RU2846765C1 - Ester compound - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to an ester compound of formula (1), which is an ester compound of general formula (5) or general formula (31). In formula (1), each of R¹-R²⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom; R¹-R¹⁰, R²³ and R²⁴ are optionally linked to each other to form a ring or optionally to form a multiple bond, wherein adjacent substituents are directly linked; R¹¹-R²⁴ are optionally bonded to each other to form a ring, or adjacent substituents are optionally bonded to each other to form a multiple bond; at least one set in R¹- R²⁴ is connected to each other to form an annular structure; each of n2-n5 is independently integer from 0 to 2; each of n1 and n6 is independently integer 0 or 1; and in formula (5) each of R¹ and R² independently represents a hydrogen atom, each of R⁴ and R⁹ is independently a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom, each of R¹¹, R¹⁵, R¹⁷ and R²¹ independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom; R¹¹, R¹⁵, R¹⁷ and R²¹ optionally connected to each other to form a ring; in formula (31), each of R³¹-R³⁴ represents a hydrogen atom, each of R⁴, R⁹, R²¹ and R²² independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom, R⁴, R⁹, R²¹ and R²² are optionally connected to each other to form a ring. In formulas (1), (5) and (31), X is a hydrocarbon group, a heteroatom or a hydrocarbon group containing a heteroatom; and each of L¹ and L² is independently a hydrocarbon group or a hydrocarbon group containing a heteroatom. Hydrocarbon group has 1–20 carbon atoms.

EFFECT: disclosed ester compound having a specific cyclic structure is suitable as a Lewis base for a solid Ziegler-Natta titanium catalyst component and enables to obtain a catalyst having excellent stereoregularity and efficiency during polymerisation of polypropylene.

15 cl, 71 ex

Description

Field of technology

[0001] The present invention relates to a new ester compound.

Background of the invention

[0002] Regarding traditional methods related to ester compounds, there are many descriptions concerning applications, such as resin additives, cosmetics and external skin preparations, microbicidal compositions, antioxidants and chelators. As one of such applications, the aspect of using a titanium catalyst on a support of a Mg compound for use in the polymerization of olefins is known.

[0003] The catalyst for olefin polymerization is one of the methods that has been widely developed to date, which was prompted by the discovery of the so-called Ziegler-Natta catalysts, for which Ziegler reported in 1953 that ethylene was polymerized even at low pressures using a combination of titanium tetrachloride and an organoaluminum compound, and Natta subsequently reported the first polymerization of propylene using a combination of titanium trichloride and a halogen-containing organoaluminum compound. Meanwhile, it was found that catalysts containing titanium tetrachloride, a magnesium compound, and a Lewis base, which belong to the third generation catalysts, can achieve both high polymerization activity (high productivity) and high stereoregularity in propylene polymerization. This made it possible to spread propylene polymers (polypropylene) throughout the world.

[0004] It has been found that the Lewis base (hereinafter also referred to as the "internal donor"), one of the main components of the above-mentioned third-generation catalyst component (hereinafter also referred to as the "solid titanium catalyst component"), greatly influences the catalyst performance, and various Lewis bases have been developed to date.

[0005] As Lewis bases for use in Ziegler-Natta catalysts, ethyl benzoate, phthalic acid esters, 1,3-diketone (Patent Literature 1), malonic ester (Patent Literature 2), succinic ester (Patent Literature 3), 2,4-pentanediol diester (Patent Document 4), for example, naphthalenediol diester (Patent Document 5) and catechol diester (Patent Document 6) have become known. Basically, enterprises are actively conducting research and development in this field even today.

[0006] Regarding the elementary reactions for synthesizing various esters, a large number of approaches have been disclosed (for example, Patent Documents 7 to 11 and Non-Patent Documents 1 to 19).

BIBLIOGRAPHY

Patent literature

[0007] Patent Document 1: JP 2005-226076 A

Patent Document 2: JP 2000-516987 A

Patent Document 3: JP 2002-542347 A

Patent Document 4: JP 2005-517746 A

Patent Document 5: JP 2011-529888 A

Patent Document 6: JP 2014-500390 A

Patent Document 7: JP 2008-247796 A

Patent Document 8: WO 2008/062553

Patent Document 9: US 2018/0149973 A1

Patent Document 10: US 2002/0162991 A1

Patent Document 11: JP 2008-037756 A

Non-patent literature

[0008] Non-patent literature 1: Journal of the American Chemical Society, 1952, 74, 1027-1029.

Non-patent literature 2: Journal of Organic Chemistry, 1971, 36, 3979-3987.

Non-patent literature 3: Fundamentals of organics, 2004, 6, 1589-1592.

Non-patent literature 4: Journal of the American Chemical Society, 1957, 79, 2822-2824.

Non-patent Literature 5: Organic Synthesis 1991, 70, 47-53

Non-patent Literature 6: Organic Synthesis 1997, 75, 153-160

Non-Patent Literature 7: Fundamentals of Catalysis 2012, 142, 124-130

Non-patent Literature 8: Organic Synthesis 1997, 74, 91-100

Non-Patent Literature 9: Fourth Issue of Experimental Chemistry, Vol. 20, Organic Compound Synthesis II, Alcohols and Amines, p. 39

Non-patent literature 10: Journal of Organic Chemistry 1959, 24, 54-55.

Non-patent Literature 11: International Journal of Applied Chemistry, 1978, 17, 522-524.

Non-patent Literature 12: Bulletin of the Chemical Society of Japan, 1967, 40, 2380-2382.

Non-patent literature 13: Organic synthesis, 1952, 32, 41.

Non-Patent Literature 14: Macromolecules, 2017, 50, 580–586

Non-patent Literature 15: Journal of Organic Chemistry, 1980, 45, 2301–2304.

Non-patent Literature 16: Journal of Organic Chemistry, 2009, 74, 405–407.

Non-patent Literature 17: Journal of Organic Chemistry, 1988, 53, 2120–2122.

Non-patent literature 18: Journal of Organic Chemistry, 1963, 28, 2572–2577.

Non-Patent Literature 19: European Journal of Organic Chemistry, 2017, 24, 3501–3504.

The essence of the invention

Technical problem

[0009] Propylene polymers, although having heat resistance and toughness similar to those of general-purpose engineering plastics, have the advantage of releasing less toxic gas even when processed by combustion, since they are composed primarily of only carbon and hydrogen.

[0010] Recent advances in molding technology have made it possible to develop higher physical properties (such as rigidity and thermal stability) using a propylene polymer with higher stereoregularity. Therefore, the market is demanding propylene polymers with higher stereoregularity. From a resource conservation and environmental perspective, methods for producing propylene polymer with high productivity are also needed.

[0011] Thus, the object of the present invention is to provide an internal donor component suitable for a solid titanium catalyst component capable of producing a propylene polymer having extremely high stereoregularity with high productivity (high activity), when used mainly for the solid titanium catalyst component.

Solution to the problem

[0012] As a result of careful studies aimed at solving the above-mentioned problems, the inventors of the present invention have found that an ester compound having a specific cyclic structure is suitable as a Lewis base for a solid titanium catalyst component, for example, by implementing the present invention. The present invention relates to, for example, the following [1]-[28].

[0013] [1] An ester compound represented by the following general formula (1):

[0014] [Chemical formula 1]

[0015] wherein in formula (1), each of R ¹ -R ²⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹ -R ¹⁰ , R ²³ and R ²⁴ are optionally bonded to each other to form a ring or optionally to form a multiple bond in which adjacent substituents are bonded directly; R ¹¹ -R ²⁴ are optionally bonded to each other to form a ring, or adjacent substituents are optionally bonded to each other to form a multiple bond; at least one set of R ¹ -R ²⁴ is bonded to each other to form a ring structure; each of n2 -n5 is independently an integer from 0 to 2; each of n1 and n6 is independently an integer of 0 or 1; and L ¹ and L ² , each independently, represent a hydrocarbon group or a hydrocarbon group containing a heteroatom.

[2] The ester compound according to [1], wherein each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group containing from 1 to 20 carbon atoms.

[0016] [3] The ester compound according to [1], wherein each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[4] An ester compound according to [1], represented by any one of the following general formulas (2) to (4):

[0017] [Chemical formula 2]

[0018] wherein in formulas (2)-(4), each of R ¹ -R ²⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹ -R ¹⁰ , R ²³ and R ²⁴ are optionally bonded to each other to form a ring or optionally to form a multiple bond in which adjacent substituents are bonded directly; R ¹¹ -R ²⁴ are optionally bonded to each other to form a ring, or adjacent substituents are optionally bonded to each other to form a multiple bond; each of X and Y independently represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom; each of n2 -n5 independently represents an integer from 0 to 2; each of n1 and n6 independently represents an integer of 0 or 1; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[5] An ester compound according to [3] or [4] in which n1 and n6 are all 1 and n2 through n5 are all 0.

[0019] [6] The ester compound according to [1], represented by the following general formula (5) or (6):

[0020] [Chemical formula 3]

[0021] wherein, in the formula (5), each of R ¹ and R ² independently represents a hydrogen atom or a hydrocarbon group, each of R ⁴ and R ⁹ independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom, R ¹¹ , R ¹⁵ , each of R ¹⁷ and R ²¹ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹¹ , R ¹⁵ , R ¹⁷ and R ²¹ are optionally bonded to each other to form a ring; X represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms;

[0022] [Chemical formula 4]

[0023] wherein in formula (6), each of R ¹ and R ² independently represents a hydrogen atom or a hydrocarbon group, each of R ⁴ , R ⁹ , R ¹¹ , R ¹² , R ¹⁵ -R ¹⁸ , R ²¹ and R ²² independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹¹ , R ¹² , R ¹⁵ -R ¹⁸ , R ²¹ and R ²² are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; X represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[7] An ester compound according to [1], represented by the following general formula (7) or (8):

[0024] [Chemical formula 5]

[0025] wherein in formula (7), each of ^R4 , ^R9 , ^R12 , ^R15 - ^R18 and ^R21 independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom; ^R15 - ^R18 are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; Y represents a hydrocarbon group, a heteroatom or a hydrocarbon group containing a heteroatom; and each of ^L1 and ^L2 independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms;

[0026] [Chemical formula 6]

[0027] in which, in formula (8), each of R ¹ and R ² independently represents a hydrogen atom or a hydrocarbon group, each of R ³ , R ⁴ , R ⁹ , R ¹⁰ , R ¹² , R ¹⁵ -R ¹⁸ and R ²¹ independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹⁵ -R ¹⁸ are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; Y represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[8] An ester compound according to [1], represented by the following general formula (9):

[0028] [Chemical formula 7]

[0029] wherein, in formula (9), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group, R ⁴ , R ⁹ , R ¹² , R ¹⁵ -R ¹⁸ and R ²¹ each independently represent a hydrogen atom, a hydrocarbon group or a heteroatom-containing hydrocarbon groups; R ¹⁵ -R ¹⁸ are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; each of X and Y independently represents a hydrocarbon group, a heteroatom or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[9] The ester compound according to [1], represented by the following general formula (31):

[0030] [Chemical formula 8]

[0031] wherein, in formula (31), each of ^R31 to ^R34 independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom, each of ^R4 , ^R9 , ^R21 , and ^R22 independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom, ^R4 , ^R9 , ^R21 , ^R22 , and ^R31 to ^R34 are optionally bonded to each other to form a ring; ^L1 and ^L2 each independently represent a hydrocarbon group or a hydrocarbon group containing a heteroatom; and X represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom.

[10] An ester compound according to any one of [4] and [6] to [9], wherein X and Y each independently represent a divalent group selected from the following general formula for group (10):

[0032] [Chemical formula 9]

[0033] wherein in group (10), each of R ¹ '-R ⁷ ' independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom, and R ² '-R ⁷ ' are optionally bonded to each other to form a ring, or adjacent substituents are optionally directly bonded to form a multiple bond.

[11] An ester compound according to any one of [4] and [6] to [9], wherein Y and Y represent a divalent group selected from the following general formula of Group (11):

[0034] [Chemical formula 10]

[0035] wherein in group (11), each of R ¹ '-R ⁵ ' independently represents a hydrogen atom, a hydrocarbon group containing from 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group containing from 1 to 20 carbon atoms, and R ² '-R ⁵ ' are optionally bonded to each other to form a ring, or adjacent substituents are optionally directly bonded to form a multiple bond.

[12] The ester compound according to [9], in which X is a divalent group represented by the following general formula (13):

[0036] [Chemical formula 11]

[0037] wherein in formula (13), each of R ² ' and R ³ ' independently represents a hydrogen atom, a hydrocarbon group containing from 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group containing from 1 to 20 carbon atoms, and R ² ' and R ³ ' are optionally bonded to each other to form a ring.

[13] The ester compound according to item [10], wherein each of R ¹ ' to R ⁷ ' independently represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms.

[0038] [14] The ester compound according to item [11], wherein each of R ¹ ' to R ⁵ ' independently represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms.

[15] The ester compound according to item [12], wherein each of R ² ' and R ³ ' independently represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms.

[0039] [16] The ester compound according to [12], in which all R ² ' and R ³ ' are hydrogen atoms.

[17] The ester compound according to any one of items [1] to [16], wherein each of R ¹ to R ²⁴ independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms.

[0040] [18] The ester compound according to any one of items [1] to [16], wherein each of R ¹ to R ²⁴ independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group containing a heteroatom having 1 to 10 carbon atoms.

[0041] [19] The ester compound according to item [9], wherein each of R ³¹ to R ³⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms.

[0042] [20] The ester compound according to item [9], wherein each of R ³¹ to R ³⁴ independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

[21] The ester compound according to [9], wherein ^R31 to ^R34 are all hydrogen atoms, ^R4 , ^R9 , ^R21 and ^R22 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 6 carbon atoms, and each of ^L1 and ^L2 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a heteroatom-containing hydrocarbon group having 1 to 10 carbon atoms.

[0043] [22] The ester compound according to [9], wherein R ³¹ -R ³⁴ , R ²¹ and R ²² are all hydrogen atoms, R ⁴ and R ⁹ each independently represent a hydrogen atom or a hydrocarbon group containing from 1 to 6 carbon atoms, and L ¹ and L ² are each independently selected from hydrocarbon groups containing from 1 to 10 carbon atoms.

[0044] [23] The ester compound according to any one of items [1] to [8], wherein R ¹ and R ² are hydrogen atoms.

[24] The ester compound according to any one of items [1] to [8], wherein R ¹ , R ² , R ²³ and R ²⁴ are all hydrogen atoms, and each of R ³ to R ²² independently represents a hydrogen atom or a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms.

[0045] [25] The ester compound according to any one of items [1] to [8], wherein each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having from 4 to 20 carbon atoms.

[26] The ester compound according to any one of items [1] to [8], wherein each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group containing from 4 to 10 carbon atoms.

[0046] [27] The ester compound according to [4], [6] or [8], wherein R ⁴ and/or R ⁹ represent a hydrocarbon group or a hydrocarbon group containing a heteroatom.

[28] The ester compound according to [4], [6] or [8], wherein R ⁴ and/or R ⁹ represent a hydrocarbon group or a hydrocarbon group containing an oxygen atom.

Beneficial effects of the invention

[0047] The ester compound of the present invention can be used, for example, in resin additives, cosmetics and external skin preparations, bactericidal compositions, antioxidants, chelators and Ziegler-Natta catalysts.

Description of the embodiment

[0048] The ester compound of the present invention will now be described in detail.

The ester compound of the present invention (hereinafter also referred to as “ester compound (A)”) is represented by the following general formula (1).

[0049] [Chemical formula 12]

[0050] In formula (1), each of R ¹ -R ²⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom. R ¹ -R ¹⁰ , R ²³ and R ²⁴ may be bonded to each other to form a ring or may form a multiple bond in which adjacent substituents are bonded directly. R ¹¹ -R ²⁴ may be bonded to each other to form a ring, or adjacent substituents may be bonded to each other to form a multiple bond. At least one set in R ² -R ²⁴ is bonded to each other to form a ring structure. From n2 to n5, each independently represents an integer from 0 to 2. Each of n1 and n6 independently represents an integer from 0 or 1. Each of L ¹ and L ² independently represents a hydrocarbon group or a hydrocarbon group containing a heteroatom. Of the above, any one of n4, n5 and n6 is preferably 1 or 2. In particular, when any two or more of R ²¹ to R ²⁴ are bonded to form an aromatic ring structure, any one of n4, n5 and n6 is preferably 1 or 2.

[0051] An example of a preferred aspect of the ester compound (A) of the present invention includes compounds represented by the following general formulas (2) to (4).

[0052] [Chemical formula 13]

[0053] wherein in formulas (2)-(4), each of R ¹ -R ²⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹ -R ¹⁰ , R ²³ and R ²⁴ are optionally bonded to each other to form a ring or optionally to form a multiple bond in which adjacent substituents are bonded directly; R ¹¹ -R ²⁴ are optionally bonded to each other to form a ring, or adjacent substituents are optionally bonded to each other to form a multiple bond; each of X and Y independently represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom; each of n2 -n5 independently represents an integer from 0 to 2; each of n1 and n6 independently represents an integer of 0 or 1; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[0054] An example of a more preferred aspect of the ester compound (A) of the present invention also includes compounds represented by the following general formulas (5) to (9).

[0055] [Chemical formula 14]

[0056] wherein in formula (5), each of R ¹ and R ² independently represents a hydrogen atom or a hydrocarbon group, each of R ⁴ and R ⁹ independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom, R ¹¹ , R ¹⁵ , each of R ¹⁷ and R ²¹ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom; R ¹¹ , R ¹⁵ , R ¹⁷ and R ²¹ are optionally bonded to each other to form a ring; X represents a hydrocarbon group, a heteroatom or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[0057] [Chemical formula 15]

[0058] wherein in formula (6), each of R ¹ and R ² independently represents a hydrogen atom or a hydrocarbon group, each of R ⁴ , R ⁹ , R ¹¹ , R ¹² , R ¹⁵ -R ¹⁸ , R ²¹ and R ²² independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹¹ , R ¹² , R ¹⁵ -R ¹⁸ , R ²¹ and R ²² are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; X represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[0059] [Chemical formula 16]

[0060] wherein in formula (7), each of ^R4 , ^R9 , ^R12 , ^R15 - ^R18 and ^R21 independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom; ^R15 - ^R18 are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; Y represents a hydrocarbon group, a heteroatom or a hydrocarbon group containing a heteroatom; and each of ^L1 and ^L2 independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[0061] [Chemical formula 17]

[0062] wherein in formula (8), each of R ¹ and R ² independently represents a hydrogen atom or a hydrocarbon group, each of R ³ , R ⁴ , R ⁹ , R ¹⁰ , R ¹² , R ¹⁵ -R ¹⁸ and R ²¹ independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹⁵ -R ¹⁸ are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; Y represents a hydrocarbon group, a heteroatom, or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[0063] In the case of the structure in formula (8), R ³ , R ⁴ , R ⁹ and R ¹⁰ each independently are preferably a substituent selected from a hydrogen atom, a halogen atom, a hydrocarbon group and a halogen-containing hydrocarbon group, more preferably selected from a hydrogen atom, a hydrocarbon group and a halogen-containing hydrocarbon group, and particularly preferably selected from hydrogen and a hydrocarbon group. More particularly, preferred examples of the hydrocarbon group described above are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, and substituted or unsubstituted aryl groups having 6 to 20 carbon atoms. Preferred examples of the halogen-containing hydrocarbon group described above are substituents in which one or more hydrogen atoms in a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms are replaced by a halogen atom.

[0064] [Chemical formula 18]

[0065] wherein in formula (9), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group, R ⁴ , R ⁹ , R ¹² , R ¹⁵ -R ¹⁸ and R ²¹ each independently represent a hydrogen atom, a hydrocarbon group or heteroatom-containing hydrocarbon groups; R ¹⁵ -R ¹⁸ are optionally bonded to each other to form a ring or optionally form a multiple bond in which adjacent substituents are bonded to each other; each of X and Y independently represents a hydrocarbon group, a heteroatom or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms.

[0066] Of these ester compounds, the ester compounds represented by formulas (5), (8) and (9) are preferred, the compounds represented by formulas (5) and (9) are more preferred, and the ester compounds represented by formula (5) are most preferred.

[0067] An example of a preferred aspect of the ester compound (A) of the present invention also includes a compound represented by the following general formula (31).

[0068] [Chemical formula 19]

[0069] A detailed description of the structure of the substituents in formula (31) will be given below.

<R ¹ -R ²⁴ >

In formulas (1) and the like, each of R ² -R ²⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom.

[0070] Examples of the hydrocarbon group may include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.

[0071] Examples of the heteroatom-containing hydrocarbon group may include substituted or unsubstituted alkyl groups containing a heteroatom and substituted or unsubstituted heteroaryl groups.

Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. These groups preferably contain 1 to 20 carbon atoms. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, the preferred lower limit in the case of the aryl group is 6. Meanwhile, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. The heteroaryl group preferably has one or more 5-membered or more ring structures, more preferably has one or more 5-7-membered ring structures, and more preferably has one or more 5-membered ring or 6-membered ring structures.

[0072] At least one substituent R ¹ -R ²⁴ may preferably be a substituent other than hydrogen. In addition, one or more carbon atoms forming the cyclic structure may preferably be a quaternary carbon. In the aspect, as described above, when the ester compound of the present invention is used as a component of an olefin polymerization catalyst, the balance of performance can be improved.

[0073] As described above, R ¹ -R ¹⁰ , R ²³ and R ²⁴ may be bonded to each other to form a ring, and R ¹¹ -R ²⁴ may be bonded to each other to form a ring. The ring-forming moiety may be formed by a single bond or may include a double bond. A structure including a carbon-carbon double bond may be preferred. The ring-forming moiety may preferably be a structure,

further comprising a ring structure, and an aspect in which a double bond, particularly preferably a carbon-carbon double bond, is included in the ring structure may be preferable. Specific examples of the structure of a moiety forming a ring like this are the same as the examples of structure X and Y mentioned below. In the present invention, the carbon-carbon double bond includes an aromatic structure.

[0074] To the carbon to which the substituents which are bonded to each other to form a ring are bonded (hereinafter, this carbon may be referred to as "B4C"), an "other substituent" (hereinafter, may be referred to as "B4S") is usually bonded (for example, when ^R3 is directly bonded to ^R10 to form a ring, ^R4 and ^R9 correspond to it). In the present invention, the "other substituent" may preferably be a hydrocarbon group and/or a heteroatom-containing hydrocarbon group mentioned below. As the heteroatom-containing hydrocarbon group, an oxygen-containing hydrocarbon group is particularly preferable. The hydrocarbon group is more specifically an aliphatic group having 1 to 10 carbon atoms, an alicyclic group, or an aromatic group, and more preferably an aliphatic group having 1 to 6 carbon atoms, an alicyclic group, or an aromatic group. The heteroatom-containing hydrocarbon group is more particularly an aliphatic group containing a heteroatom having 1 to 10 carbon atoms, an alicyclic group, or an aromatic group, and more preferably an aliphatic group containing a heteroatom having 1 to 6 carbon atoms, an alicyclic group, or an aromatic group. The heteroatom is preferably oxygen. The oxygen-containing hydrocarbon group is also preferably an alkoxy group. More specific examples of the position of such a substituent may include R ⁴ and/or R ⁹ in formulas (2), (4), (5), (6), and (9), and R ¹² and/or R ²¹ in formulas (3), (4), (7), and (8). More preferred are R ⁴ and/or R ⁹ . When the substituent at such a position is a group having the structure indicated above and is used as a component of an olefin polymerization catalyst, the molecular weight of the resulting polymer can be easily controlled by hydrogen, in addition to the polymerization activity and stereoregularity.

[0075] In R ¹ -R ^{24 ,} adjacent substituents may be bonded directly to form a multiple bond, such as a double bond or a triple bond. In addition, an aromatic ring structure in which these substituents are bonded is also within the scope of the present invention. Examples thereof may include aromatic ring structures represented by formulas (5) and (7).

[0076] When R ¹ and the like form a ring structure, the substituents forming the ring are selected from substituents other than a hydrogen atom and halogen atoms, and are preferably hydrocarbon groups. At least one set in R ¹ to R ²⁴ is bonded to each other to form a ring structure. Inside the formed ring, the substituents for forming the ring of at least one set are preferably separated by 2 or more carbon atoms, and more preferably separated by 3 or more carbon atoms. Such a structure is preferably a ring structure including X or Y in formulas (2) to (4), and more preferably a ring structure including X or Y in formulas (5) to (9).

[0077] When adjacent substituents are bonded to form a ring, substituents selected from ^R3 - ^R6 , ^R7 - ^R10 and ^R11 - ^R22 are preferably bonded to each other to form a ring. At this time, the substituents forming the ring preferably do not contain carbon atoms at a bridging position from a synthetic viewpoint. Carbon atoms at a bridging position refer to carbon atoms having two or more rings. For example, in the case of formula (2), refer to a carbon atom to which X and ^R4 are bonded, a carbon atom to which X and ^R9 are bonded, a carbon atom to which ^R23 is bonded and a carbon atom to which ^R24 is bonded. Preferred examples of such structures include the structures included in formulas (5)-(9). As the structure included in the formula (5), a ring structure formed by bonding R ¹¹ and R ¹⁵ to each other, a ring structure formed by bonding R ¹⁵ and R ¹⁷ to each other, a ring structure formed by bonding R ¹⁷ and R ²¹ to each other, and a structure consisting of these combinations are particularly preferable. As the structure included in the formula (6), a ring structure formed by bonding R ¹¹ or R ¹² and R ¹⁵ or R ¹⁶ , a ring structure formed by bonding R ¹⁵ or R ¹⁶ and R ¹⁷ or R ¹⁸ , a ring structure formed by bonding R ¹⁷ or R ¹⁸ and R ²¹ or R ²² , and a structure consisting of these combinations are particularly preferable. With respect to the structure included in formulas (7) to (9), a ring structure formed by bonding R ¹⁵ or R ¹⁶ and R ¹⁷ or R ¹⁸ is particularly preferable.

[0078] One example of an ester compound (A) having a structure in which R ¹¹ and R ¹⁵ are linked to each other to form a ring in formula (5) is shown below.

[0079] [Chemical formula 20]

[0080] One example of an ester compound (A) having a structure in which R ¹⁵ and R ¹⁷ are linked to each other to form a ring in formula (5) is shown below.

[0081] [Chemical formula 21]

[0082] One example of an ester compound (A) having a structure in which R ¹⁷ and R ²¹ are linked to each other to form a ring in formula (5) is shown below.

[0083] [Chemical formula 22]

[0084] One example of an ester compound (A) having a structure in which R ¹¹ or R ¹² are bonded to R ¹⁵ or R ¹⁶ to form a ring in formula (6) is shown below.

[0085] [Chemical formula 23]

[0086] One example of an ester compound (A) having a structure in which R ¹⁵ or R ¹⁶ is bonded to R ¹⁷ or R ¹⁸ to form a ring in formula (6) is shown below.

[0087] [Chemical formula 24]

[0088] One example of an ester compound (A) having a structure in which R ¹⁷ or R ¹⁸ is bonded to R ²¹ or R ²² to form a ring in formula (6) is shown below.

[0089] [Chemical formula 25]

[0090] One example of an ester compound (A) having both a structure in which R ¹¹ or R ¹² is bonded to R ¹⁵ or R ¹⁶ to form a ring and a structure in which R ¹⁷ or R ¹⁸ is bonded to R ²¹ or R ²² to form a ring in formula (6) is shown below.

[0091] [Chemical formula 26]

[0092] One example of an ester compound (A) having a structure in which R ¹⁵ or R ¹⁶ is bonded to R ¹⁷ or R ¹⁸ to form a ring in formula (7) is shown below.

[0093] [Chemical formula 27]

[0094] One example of an ester compound (A) having a structure in which R ¹⁵ or R ¹⁶ is bonded to R ¹⁷ or R ¹⁸ to form a ring in formula (8) is shown below.

[0095] [Chemical formula 28]

[0096] One example of an ester compound (A) having a structure in which R ¹⁵ or R ¹⁶ is bonded to R ¹⁷ or R ¹⁸ to form a ring in formula (9) is shown below.

[0097] [Chemical formula 29]

[0098] Preferably, each of R ¹⁵ to R ¹⁸ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group containing from 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group containing from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group containing from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms, a substituted or unsubstituted alkyl group containing a heteroatom having from 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 20 carbon atoms. Each of ^R3 , ^R4 , ^R9 and ^R10 independently preferably represents a substituent selected from a hydrogen atom, a halogen atom, a hydrocarbon group and a halogen-containing hydrocarbon group, more preferably selected from a hydrogen atom, a hydrocarbon group and a halogen-containing hydrocarbon group, particularly preferably selected from hydrogen and a hydrocarbon group. Preferred examples of the hydrocarbon group include substituted or unsubstituted alkyl groups containing from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups containing from 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups containing from 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups containing from 2 to 20 carbon atoms, and substituted or unsubstituted aryl groups containing from 6 to 20 carbon atoms. Preferred examples of the halogen-containing hydrocarbon group include substituents in which one or more hydrogen atoms in a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms are replaced by a halogen atom.

[0099] Preferably, each of R ¹ to R ²⁴ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group containing from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group containing from 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group containing from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms, a substituted or unsubstituted alkyl group containing a heteroatom having from 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 20 carbon atoms.

[0100] More preferably, each of R ¹ to R ²⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group containing from 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group containing from 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group containing from 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group containing from 2 to 10 carbon atoms, a substituted or unsubstituted aryl group containing from 6 to 15 carbon atoms, a substituted or unsubstituted alkyl group containing a heteroatom having from 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group containing from 2 to 10 carbon atoms.

[0101] More preferably, each of R ¹ -R ²⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 3 to 10 carbon atoms.

[0102] More preferably, each of R ¹ -R ²⁴ independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms.

It is particularly preferred that all of R ¹ , R ² , R ²³ and R ²⁴ represent hydrogen atoms and each of R ³ -R ²² independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms.

[0103] The carbon to which R ¹ -R ²⁴ are bonded forms 2 or more ring structures as shown by the general formula (1). One or more ring structures are preferably alicyclic structures. That is, preferably, at least not all of the rings are aromatic rings.

[0104] <R ³¹ -R ³⁴ >

In formula (31), each of R ³¹ to ^{R 34} independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

[0105] Examples of the hydrocarbon group may include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.

[0106] Examples of the heteroatom-containing hydrocarbon group may include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.

Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. These groups preferably have 1 to 20 carbon atoms. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, the preferred lower limit in the case of the aryl group is 6. Meanwhile, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. The heteroaryl group preferably has one or more 5-membered or more ring structures, more preferably has one or more 5-7-membered ring structures, and more preferably has one or more 5-membered ring or 6-membered ring structures.

[0107] Preferably, each of R ³¹ to R ³⁴ independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 20 carbon atoms.

[0108] More preferably, each of R ³¹ to R ³⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 10 carbon atoms.

[0109] Furthermore, it is preferred that each of R ³¹ to R ³⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 1 to 6 carbon atoms.

[0110] R ³¹ -R ³⁴ may have a ring structure formed by linking R ³¹ -R ³⁴ with each other.

Particularly preferably, each of ^R31 - ^R34 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, and most preferably, all of ^R31 - ^R34 represent hydrogen atoms. ^R31 - ^R34 , ^R21 , ^R22 , ^R4 and ^R9 may be bonded to each other to form a ring, or adjacent substituents may be directly bonded to form a multiple bond.

[0111] The structure of the ester compound represented by formula (31) will now be described in detail.

As described above, ^R31 - ^R34 , ^R21 , ^R22 , ^R4 and ^R9 may form a ring in which the substituents are bonded to each other, or adjacent substituents are bonded directly to form a multiple bond, such as a double bond or a triple bond. In addition, an aromatic ring structure in which these substituents are bonded is also within the scope of the present invention. An example thereof may include an aromatic ring structure in which ^R34 , ^R21 and ^R22 are bonded.

[0112] When ^R31 - ^R34 , ^R21 , ^R22 , ^R4 and ^R9 are bonded to each other to form a ring structure, the substituents forming the ring are selected from substituents other than a hydrogen atom and halogen atoms, and are preferably hydrocarbon groups. ^R31 - ^R34 , ^R21 and ^R22 are preferably bonded to each other to form a ring, and a structure selected from a ring structure formed by bonding ^R31 and ^R32 to each other, a ring structure formed by bonding ^R32 and ^R33 to each other, a ring structure formed by bonding ^R33 and ^R34 to each other, a ring structure formed by bonding ^R21 and ^R22 to each other, a structure in which ^R34 , ^R21 and ^R22 are bonded to each other, and combinations thereof is more preferable.

[0113] One example of an ester compound (A) having a structure in which R ³¹ and R ³² are linked to each other to form a ring is shown below.

[0114] [Chemical formula 30]

[0115] One example of an ester compound (A) having a structure in which R ³² and R ³³ are linked to each other to form a ring is shown below.

[0116] [Chemical formula 31]

[0117] One example of an ester compound (A) having a structure in which R ³³ and R ³⁴ are linked to each other to form a ring is shown below.

[0118] [Chemical formula 32]

[0119] One example of an ester compound (A) having a structure in which R ²¹ and R ²² are linked to each other to form a ring is shown below.

[0120] [Chemical formula 33]

[0121] One example of an ester compound (A) having a structure in which R ³⁴ , R ²¹ and R ²² are linked to each other to form a ring is shown below.

[0122] [Chemical formula 34]

[0123] Preferably, each of R ²¹ , R ²² , R ⁴ and R ⁹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 20 carbon atoms.

[0124] More preferably, each of R ²¹ , R ²² , R ⁴ and R ⁹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 10 carbon atoms.

[0125] Furthermore, preferably, each of R ²¹ , R ²² , R ⁴ and R ⁹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having from 2 to 6 carbon atoms, a substituted or unsubstituted alkynyl group having from 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 6 carbon atoms.

[0126] R ²¹ , R ²² , R ⁴ and R ⁹ may have a structure in which R ²¹ , R ²² , R ⁴ and R ⁹ are bonded to each other to form a ring, and an example of this may include a ring structure formed by bonding R ²¹ and R ²² to each other.

Particularly preferably, each of R ²¹ , R ²² , R ⁴ and R ⁹ independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, and most preferably, all of R ²¹ , R ²² , R ⁴ and R ⁹ represent hydrogen atoms.

[0127] <L ¹ and L ² >

In formulas (1) and others, each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.

[0128] Examples of the hydrocarbon group may include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.

[0129] Examples of the heteroatom-containing hydrocarbon group may include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.

Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. These groups preferably contain 1 to 20 carbon atoms. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, the preferred lower limit in the case of the aryl group is 6. Meanwhile, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. The heteroaryl group preferably has one or more 5-membered or more ring structures, more preferably has one or more 5-7-membered ring structures, and more preferably has one or more 5-membered ring or 6-membered ring structures.

[0130] The preferred number of carbon atoms described above is selected from the range of 4 or more or 1 to 20. In the latter case, the number is more preferably from 1 to 10. In the former case, the number is more preferably from 4 to 20.

[0131] Preferred L ¹ and L ² in the first case independently represent a substituted or unsubstituted alkyl group having from 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 4 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having from 4 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having from 4 to 20 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 4 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 4 to 20 carbon atoms.

[0132] More preferably, each of L ¹ and L ² independently represents a substituted or unsubstituted alkyl group having from 4 to 10 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 4 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having from 4 to 15 carbon atoms.

[0133] Furthermore, preferably, each of L ¹ and L ² independently represents a substituted or unsubstituted aryl group having 6 to 10 carbon atoms and a substituted or unsubstituted heteroaryl group having 4 to 10 carbon atoms, and particularly preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. Particularly preferred are aryl groups containing a substituent other than hydrogen. The substituents other than hydrogen are hydrocarbon groups having 1 to 10 carbon atoms and heteroatom-containing hydrocarbon groups having 1 to 10 carbon atoms. The heteroatom is in particular an element of group 16 of the periodic table, more precisely oxygen. Specific examples of the hydrocarbon group may include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group, and specific examples of the heteroatom-containing hydrocarbon group may include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, and a t-butoxy group, as preferred examples.

[0134] <n1-n6>

In formulas (1) and others, n2-n5 represent integers from 0 to 2, and n1 and n6 represent integers from 0 or 1.

[0135] n2-n5 are preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

n1 and n6 are preferably equal to 0 or 1, and more preferably 1.

[0136] <X and Y>

In formulas (2) to (9) and (31), each of X and Y independently represents a hydrocarbon group, a heteroatom, or a heteroatom-containing hydrocarbon group, and, preferably, each independently represents a divalent group selected from the groups shown in the following general group (10) of formulas.

[0137]

[Chemical formula 35]

[0138] wherein in group (10), each of R ¹ '-R ⁷ ' independently represents a hydrogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R ² '-R ⁷ ' are optionally bonded to each other to form a ring, or adjacent substituents are optionally directly bonded to form a multiple bond.

[0139] Preferably, each of R ¹ '-R ⁷ ' independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having from 1 to 10 carbon atoms, or a substituted or unsubstituted heteroatom-containing hydrocarbon group having from 1 to 10 carbon atoms.

[0140] More preferably, each of R ¹ '-R ⁷ ' independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having from 1 to 6 carbon atoms, and most preferably, all of R ¹ '-R ⁷ ' represent hydrogen atoms.

As described previously, R ² '-R ⁷ ' can be linked to each other to form a monocyclic ring or a polycyclic ring. Alternatively, R ¹ '-R ⁷ ' can be linked to R ¹ -R ²⁴ to form a ring structure.

[0141] X and Y are preferably divalent groups selected from the groups shown in the following general group (11) of formulas.

[0142] [Chemical formula 36]

[0143] wherein in group (11), each of R ¹ '-R ⁵ ' independently represents a hydrogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having from 1 to 20 carbon atoms, and R ² '-R ⁵ ' are optionally bonded to each other to form a ring, or adjacent substituents are optionally directly bonded to form a multiple bond.

[0144] When X and Y are divalent groups selected from the groups shown in the general formula (11), each of R ¹ '-R ⁵ ' preferably independently represents a hydrogen atom or a hydrocarbon group having from 1 to 10 carbon atoms.

X and Y are also preferably divalent groups selected from the groups shown in the following general group (12) of formulas.

[0145] [Chemical formula 37]

[0146] In the formula (12), each of R ² '-R ⁵ ' independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms, and R ² '-R ⁵ ' may be bonded to each other to form a ring.

[0147] X and Y are particularly preferably divalent groups shown in the following general formula (13).

[0148] [Chemical formula 38]

[0149] In formula (13), each of R ² ' and R ³ ' is independently selected from a hydrogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, or a heteroatom-containing hydrocarbon group having from 1 to 20 carbon atoms, and R ² ' and R ³ ' may be bonded to each other to form a ring.

[0150] In the ester compound (A) represented by the formula (31), when X is a divalent group shown in the formula (13), each of R ² ' and R ³ ' is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably both are hydrogen atoms.

[0151] As mentioned above, in the formulas (10), (11) and (12), R ² '-R ⁷ ' may be preferably bonded to each other to further form a ring, or adjacent substituents may be preferably directly bonded to form a multiple bond. A carbon-carbon double bond is preferred as the multiple bond. A moiety further forming a ring by bonding R ² '-R ⁷ ' to each other preferably has a structure including a carbon-carbon double bond. Of those described above, R ² '-R ⁵ ' are preferably bonded to each other to form a ring, and more preferably, a substituted or unsubstituted aryl group is included in the multiple bond. An example of a substituent of such X and Y is shown below.

[0152] [Chemical formula 39]

[0153] Examples of the hydrocarbon group may include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted aryl groups.

[0154] Examples of the heteroatom-containing hydrocarbon group may include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.

Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. These groups preferably have 1 to 20 carbon atoms. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, in the case of an aryl group, the preferred lower limit is 6, and the upper limit is preferably 20, more preferably 15, even more preferably 10, and particularly preferably 6. The heteroaryl group preferably has one or more 5-membered or more ring structures, more preferably has one or more 5-7-membered ring structures, and more preferably has one or more 5-membered ring or 6-membered ring structures.

[0155] More specific examples of groups and atoms exemplified for R ¹ -R ²⁴ , R ³¹ -R ³⁴ , L ¹ , L ² , and R ¹ ' -R ⁷ ' are shown below.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of hydrocarbon groups include a variety of structures, such as aliphatic, branched aliphatic, alicyclic, and aromatic structures, as described below.

[0156] Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a neopentyl group, an n-hexyl group, a hexyl group, a cumyl group, and a trityl group.

[0157] Examples of the substituted or unsubstituted alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group.

[0158] Examples of the substituted or unsubstituted alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group.

[0159] Examples of the substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a cyclopentadienyl group, an indenyl group, and a fluorenyl group.

[0160] Examples of the substituted or unsubstituted aryl group include aromatic hydrocarbon groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a diisopropylphenyl group, a dimethylisopropylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group and an anthracenyl group, and heteroatom-substituted aryl groups such as a methoxyphenyl group, a dimethylaminophenyl group, a nitrophenyl group and a trifluoromethylphenyl group.

[0161] Examples of the substituted or unsubstituted heteroatom-containing hydrocarbon group include heteroatom-containing alkyl groups such as a methoxymethyl group, a methoxyethyl group, a benzyloxy group, an ethoxymethyl group, and an ethoxyethyl group, and heteroaryl groups such as a furyl group, a pyrrolyl group, a thienyl group, a pyrazolyl group, a pyridyl group, a carbazolyl group, an imidazolyl group, a dimethylfuryl group, an N-methylpyrrolyl group, an N-phenylpyrrolyl group, a diphenylpyrrolyl group, a thiazolyl group, a quinolyl group, a benzofuryl group, a triazolyl group, and a tetrazolyl group. The number of carbon atoms contained in the substituent containing carbon as described above is, as described previously, preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 6, and particularly preferably from 1 to 4. The number of carbon atoms when the substituent has an aryl group structure is preferably from 4 to 20, more preferably from 4 to 10, and even more preferably from 6 to 10. R ¹ to R ²⁴ , when they are substituents other than a hydrogen atom, are preferably selected from the hydrocarbon groups and oxygen-containing hydrocarbon substituents described above. An alkoxy group is preferred as the oxygen-containing hydrocarbon group. When using such a structure as an internal donor of an olefin polymerization catalyst, effects such as obtaining an olefin polymer having a broader molecular weight distribution can be exhibited.

[0162] <Specific Examples of the Ester Compound (A)>

Specific examples of the ester compound (A) of the present invention will be shown below, but the ester compound (A) of the present invention is not limited to them.

[0164] [Chemical formula 41]

[0165] [Chemical formula 42]

[0166] [Chemical formula 43]

[0167] [Chemical formula 44]

[0168] [Chemical formula 45]

[0169] [Chemical formula 46]

[0170] [Chemical formula 47]

[0171] [Chemical formula 48]

[0172] [Chemical formula 49]

[0173] [Chemical formula 50]

[0174] [Chemical formula 51]

[0175] [Chemical formula 52]

[0176] [Chemical formula 53]

[0177] [Chemical formula 54]

[0178] [Chemical formula 55]

[0179] [Chemical formula 56]

[0180] [Chemical formula 57]

[0181] [Chemical formula 58]

[0182] [Chemical formula 59]

[0183] [Chemical formula 60]

[0184] [Chemical formula 61]

[0185] [Chemical formula 62]

[0186] [Chemical formula 63]

[0187] [Chemical formula 64]

[0188] [Chemical formula 65]

[0189] [Chemical formula 66]

[0190] [Chemical formula 67]

[0191] [Chemical formula 68]

[0192] [Chemical formula 69]

[0193] [Chemical formula 70]

[0194] [Chemical formula 71]

[0195] [Chemical formula 72]

[0196] [Chemical formula 73]

[0197] [Chemical formula 74]

[0198] [Chemical formula 75]

[0199] [Chemical formula 76]

[0200] [Chemical formula 77]

[0201] [Chemical formula 78]

[0202] [Chemical formula 79]

[0203] [Chemical formula 80

[0204] [Chemical formula 81]

[0205] [Chemical formula 82]

[0204] [Chemical formula 83]

[0207] [Chemical formula 84]

[0208] [Chemical formula 85]

[0209] [Chemical formula 86]

[0210] Examples of a compound in which a moiety forming a ring by bonding R ¹ -R ²⁴ has a ring structure further including a double bond or a ring structure, in particular, the double bond may include compounds of the following structures.

[0211] [Chemical formula 87]

[0212] [Chemical formula 88]

[0213] [Chemical formula 89]

[0214] [Chemical formula 90]

[0215] [Chemical formula 91]

[0216] [Chemical formula 92]

[0217] [Chemical formula 93]

[0218] [Chemical formula 94]

[0219] [Chemical formula 95]

[0220] [Chemical formula 96]

[0221] In the structural formulas described above, the methyl group is denoted as "Me", the ethyl group is denoted as "Et", the propyl group is denoted as "Pr", the butyl group is denoted as "Bu", and the phenyl group is denoted as "Ph", and [n] represents "normal", [i] represents "iso", and "t" represents "tertiary".

[0222] In the ester compound (A) of the present invention, the OCOL ¹ group and the OCOL ² group bonded to the alicyclic structure may form a cis structure or a trans structure derived from the alicyclic structure, and the ester compound of the cis structure is preferably a major component. The major component herein refers to a content of the compound of the cis structure exceeding 50 mol % and, preferably, a content of 70 mol % or more.

[0223] Although the reason why the ester compound (A) of the present invention is suitable as a Lewis base component (internal donor) of the solid titanium catalyst component is currently unknown, the present inventors suggest the following reason.

The ester compound (A) of the present invention has a structure in which the rings are linked and, preferably, also has a cross-linked structure (a structure corresponding to X or Y, as described above). This requirement limits the conformation of the compound and fixes the distance between two adjacent ester groups linked to the rings and the orientation of the ester groups. Consequently, when the ester coordinates with magnesium chloride, the ester coordination mode is limited, and a rigid polymerization environment is presumably formed, comprising atoms of titanium, magnesium chloride, and the ester compound. It is believed that when polymerization occurs in an ambient environment, the orientation of the polymer chain and the direction of propylene insertion are significantly regulated, resulting in the formation of a catalyst suitable for highly stereoregular polymerization. The circuit in which the ester is linked to the ring including the cross-linked structure (e.g. formulas (5), (6) and (9)) is subject to limitation of the distance and orientation of the ester moieties, and thus, it is a more excellent circuit as an internal donor for the Ziegler catalyst. It is assumed that even in the case of a circuit in which the ester moieties are directly linked to the cyclohexane circuit (e.g. formula (8)), the fusion of the ring structure including the cross-linked structure with the cyclohexane circuit results in a change in the conformation of the cyclohexane circuit to be limited, and thus, a similar effect is achieved. As mentioned above, a structure having a 6-membered ring structure was described here. Based on this assumption, a similar effect can be expected from an ester compound having a structure represented by formula (1), more preferably a polycyclic structure represented by formulas (2) to (4), even if the compound is different from the compounds specifically exemplified. It is obvious that a similar effect occurs even when moving from a 5-membered ring to a 10-membered ring.

[0224] The ester compound (A) of the present invention, which has a structure in which the rings are connected as described above, is expected to have moderate rigidity and relatively less structure shift. For this reason, when used in the olefin polymerization catalyst mentioned below, it is expected that a stable structure is maintained while moderate interaction is ensured when the compound (A) containing the ester group is coordinated with a titanium compound or a magnesium compound. Therefore, the interaction is expected to have a positive effect on stereospecificity and activity. Meanwhile, the epicyclic structure as described above will have various structures that can be shifted relative to the local structure, for example, a chair type or a boat type. Accordingly, a polymer with a wide molecular weight distribution can be expected to be obtained.

[0225] The ester compound (A) of the present invention represented by formula (31) has a specific polycyclic structure as described above. The compound also has a specific asymmetric structure. The presence of such a structure allows the compound to have moderate rigidity. Therefore, when active particles for olefin polymerization are formed by reacting with a magnesium compound or a titanium compound and a polymerization reaction occurs, it is expected that less displacement or fluctuation of the structures is possible. Meanwhile, in the case of the ester compound (A) having an asymmetric structure such as the structure of formula (31), there may be more conformations in the case of reacting with a magnesium compound or a titanium compound than in a symmetric compound. Therefore, it is possible to form active particles having different microstructures. It is expected that this may be advantageous for achieving aspects including a polymer having a wide molecular weight distribution or a polymer having high stereoregularity. Since the compound preferably has a specific asymmetric structure including an aryl structure, this compound can enable a strong coordination structure to be obtained with a magnesium compound or a titanium compound.

[0226] From the viewpoint shown above, the ester compound (A) of the present invention is presumably suitable as a Lewis base component (internal donor) of a solid titanium catalyst component.

<Method for producing an ester compound (A)>

The method for producing the ester compound (A) according to the present invention is not particularly limited. For example, the ester compound (A) can be obtained by dihydroxylating the corresponding olefin followed by esterifying the diol obtained by dihydroxylation. In addition, the ester compound (A) can also be obtained by sequentially introducing a carbonate group into a specific polycyclic compound such as anthracene, hydrolyzing the carbonate group, and then esterifying the diol obtained by hydrolysis. More specifically, the ester compound (A) can be produced as follows.

[0227] "Olefin Synthesis"

The olefin represented by the following formula (21) can be synthesized, for example, by the Diels-Alder reaction of cyclopentadiene and norbornene (Non-Patent Literature 1). The olefin represented by the following general formula (33) can be synthesized by the Diels-Alder reaction of substituted indene and substituted diene (Patent Literature 11). For the diene, a diene dimer (e.g., dicyclopentadiene), which is a precursor, can also be used as a starting material. The product obtained by the Diels-Alder reaction is often a mixture of the endo form and the exo form (see the following formulas (22) and (34)), but any of the isomers can be used in the present invention. That is, any mixture, only the endo form or only the exo form can be used. These structures of the endo form and the structures of the exo form are often reflected also in the structure of the ester compound as a final product.

[0228] The reaction of gasoline with a diene can produce an olefin (Non-Patent Documents 2, 3 and 14). A cyclic olefin can be produced by decarbonylation and decarboxylation of an alicyclic dicarboxylic acid anhydride in the presence of a nickel complex (e.g., tetrakistriphenylphosphine nickel) with a reagent that can act as a ligand (e.g., triphenylphosphine) to the nickel complex (Patent Literatures 7 and 8).

"Synthesis of Anthracene"

When a compound in which a moiety forming a ring by bonding R ¹ -R ²⁴ has a cyclic structure having a ring structure including a double bond, or a ring structure, especially one including a double bond, the compound can be synthesized by subjecting anthracene to a Diels-Alder reaction with vinylene carbonate to obtain a carbonate compound, and then hydrolyzing the carbonate compound, followed by esterification of the diol.

[0229] Anthracene can be synthesized, for example, by reacting anthraquinone with an organometallic reagent (e.g., an alkyl lithium or a Grignard reagent) and then carrying out reduction (e.g., a reaction using tin(II) chloride or sodium hypophosphite) (the following formula (14(1)), see Patent Literature 9 and Non-Patent Literatures 15 and 16).

[0230] Anthracene can also be synthesized by subjecting dihaloanthracene to a substitution reaction with a metal reagent (e.g., lithium or magnesium) and a halogenated alkyl, and a coupling reaction using a transition metal catalyst (e.g., nickel or palladium) and an organometallic reagent (e.g., a boronic ester or a Grignard reagent) (formulas (14(2)) and (14(3)), see Patent Literature 10 and Non-Patent Literature 17). In addition, dialkoxyanthracene can be obtained by reacting an anthraquinone with a reducing agent (e.g., zinc) and an electrophile (e.g., a halogenated alkyl or sulfoether) (formula (14(4)), see Non-Patent Literature 18).

[0231] [Chemical formula 97]

[0232] In formula (14(1)) R ²⁵ M is an organometallic reagent, R ²⁵ is an alkyl group, and M is a metal or metal halide. Examples of M include Li, MgBr, MgCl, and MgI.

[0233] [Chemical formula 98]

[0234] In the formula (14(2)) R ²⁶ Z is an electrophile, Z is a halogen atom and R ²⁶ is an alkyl group.

[0235] [Chemical formula 99]

[0236] In the formula (14(3)) Z represents a halogen atom, R27 represents an alkyl group or an aryl group, and A and A' represent a hydroxyl group or a crosslinked structure in which A and A' are bonded. An example of a structural formula of a boric acid compound and a boric acid ester (preferably a cyclic boric acid ester compound), which are boron-containing compounds, including the structures of the above ^R27 , A and A', may include structures represented by the following groups (15) of the formula.

[0237] [Chemical formula 100]

[0238] [Chemical formula 101]

[0239] In formula 14(4), R ²⁸ Z is an electrophile, Z is a halogen atom, and R ²⁸ is an alkyl group.

Diol Synthesis

Diol forms (formula (23) and formula (35)), which are ester precursors, can be prepared with the corresponding olefins (formula (21) and formula (33)) as feedstock. For example, the reaction of olefin with potassium permanganate (Non-patent Literature 4) or osmium tetroxide (Non-patent Literature 5) produces the diol form (formula (23) and formula (35)).

[0240] As another method, the diol forms (formula (23) and formula (35)) can be prepared by epoxidizing the olefin moiety using m-chloroperoxybenzoic acid (Non-patent Literature 6); tert-butyl peroxide (Non-patent Literature 7); dimethyldioxirane (Non-patent Literature 8); a solution of formic acid and hydrogen peroxide (Non-patent Literature 9); a solution of hydrogen peroxide and a molybdenum catalyst; or a solution of hydrogen peroxide and a tungsten catalyst (Non-patent Literature 10), followed by an acidic or alkaline hydrolysis reaction.

[0241] [Chemical formula 102]

[0242] [Chemical formula 103]

[0243] A diol compound can also be obtained after hydrolysis of a cyclic carbonate obtained from the above-mentioned diene or anthracene compound. The details are as follows.

A cyclic carbonate (formula (24)), which is a precursor to the diol form (formula (23)), can be prepared by the Diels-Alder reaction of the corresponding diene and vinylene carbonate (Non-Patent Literature 19). As described above, the diene dimer, which is the precursor, can also be used as the starting material for the diene. The product obtained by the Diels-Alder reaction is often a mixture of the endo form and the exo form, and even the true Diels-Alder isomer can be used. In this reaction, a polycyclic carbonate of a certain structure, as shown in the examples mentioned below, can be prepared using a polycyclic aromatic compound such as anthracene instead of the diene.

[0244] Acid or alkaline hydrolysis of the cyclic carbonate of formula (24) allows the diol form (formula (23)) to be obtained (Non-patent Literature 19).

[0245] [Chemical formula 104]

[0246] "Synthesis of Ester"

The ester form corresponding to the formula (1) can be synthesized by reacting the diol form (formula (23)) and the acid chloride in the presence of a base (formula 25). Examples of the base that can be used include, but are not limited to, sodium hydroxide, potassium hydroxide and amine bases. The ester form can also be synthesized by a synthetic method in which the diol form and the carboxylic acid are reacted in the presence of an acid catalyst or using a condensing agent such as DCC (Non-Patent Literature 11) (formula (26)). When one equivalent of the acid chloride or carboxylic acid is allowed to react with the diol form (formula (3')), an isomer corresponding to the formula (24) can be formed, but then by allowing the acid chloride or carboxylic acid to react, a compound corresponding to the formula (1) can be obtained. At this time, L ¹ and L ² may be the same or different. The ester form can also be synthesized by allowing the diol form to react with a carboxylic acid in the presence of an azocarboxylic acid ester of triphenylphosphine (Non-patent Literature 12).

[0247] The ester form corresponding to formula (31) can be synthesized by adding the diol form (formula (35)) and an acid chloride in the presence of a base, as shown in the following formula (37). Examples of a base that can be used include, but are not limited to, sodium hydroxide, potassium hydroxide, and amine bases. The ester form can also be synthesized by a synthetic method in which the diol form and a carboxylic acid are reacted in the presence of an acid catalyst or using a condensing agent such as DCC (Non-Patent Literature 11) (see formula (38)). When one equivalent of an acid chloride or carboxylic acid reacts with the diol form (formula (35)), an isomer corresponding to formula (36) may be formed, but subsequent reaction of the acid chloride or carboxylic acid yields a compound corresponding to formula (31). At this time, L1 and L2 may be the same or different. The ester form can also be synthesized by allowing the diol form to react with the carboxylic acid in the presence of an ester of an azocarboxylic acid and triphenylphosphine (Non-patent Literature 12).

[0248] [Chemical formula 105]

[0249] [Chemical formula 106]

[0250] In the method for synthesizing the ester compound as described above, the ester compound can be obtained as a mixture of the endo form and the exo form, as described previously. From a structural point of view, the endo form tends to be easily obtained. The ratio of isomers when the compound is obtained as a mixture thereof is not particularly limited, and a preferable example may include an endo form/exo form ratio of 100/0 to 50/50, preferably 95/5 to 60/40, and more preferably 90/10 to 65/35.

[0251] These endo forms and exo forms can often be separated by known column chromatography using silica gel. In this way, the endo form and the exo form can be isolated. The isomer ratio can also be changed by an isomerization reaction using a solid acid catalyst such as zeolite. Of course, it is possible to adjust the desired isomer ratio by combining each of the compounds isolated in a certain ratio. Depending on the applications in which the ester compound of the present invention is used, it is expected that either the endo form or the exo form can exhibit a suitable effect, or that a suitable effect can be exhibited at a certain isomer ratio. In such cases, it is only necessary to adjust the isomer ratio within the range of 100/0 to 0/100 in the manner described above, for example, before use.

[0252] As the ester compound (A) of the present invention, each endo form and exo form can be used individually, or a mixture of isomers can be used in various applications as described above.

The ester compound (A) of the present invention is suitable as a Lewis base component of a solid titanium catalyst component, as mentioned previously, but is not limited to this application. Naturally, the ester compound can be used in known additive applications, such as additives to various resins, cosmetics and topical skin care products, microbicidal compositions, antioxidants, and chelators.

Examples

[0253] The method for synthesizing the ester compound of the present invention will be illustrated in the following examples. The compounds with the structural formulas disclosed in the following examples and comparative examples represent the structures of the main component of stereoisomers and may include other stereoisomers. In the present invention, the main component refers to a component exceeding 50 mol%, preferably 7 mol% or more.

[0254] (Method of measuring the melting point of a compound)

When the obtained ester compound was solid, using a differential scanning calorimeter model DSC7020 manufactured by Hitachi High-Tech Science Corporation, an appropriate amount of the sample was placed in an aluminum pan and the melting behavior was measured under the following conditions.

[0255] Initial temperature: 25°C

Final temperature: 300°C

Temperature increase rate: 10°C/minute

The peak temperature, considered the melting point, was observed. When the peak temperature was difficult to determine, perhaps due to the influence of a mixture of isomers or a compound beginning to decompose, for example, at high temperature, the temperature at which heat absorption ceased was defined as the melting point.

[0256] (Method for determining isomeric composition)

The isomers were separated using conventional silica gel column chromatography. NMR analysis of the isolated isomers and NMR analysis of the mixture were used to identify the chemical shifts characteristic of the isomers, and the ratio of the isomers was determined using the ratio of their absorption intensities.

[0257] (Structural Analysis Method by CN NMR) A JNM-EX270 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. and a small amount of tetramethylsilane were added to deuterated chloroform as a solvent. The conditions included: a measurement temperature of room temperature, an observed 1H nucleus (270 MHz), a single pulse sequence, a 45° pulse, a repetition time of 5.5 seconds or more, and an integrated frequency of 16 to 64 times or more. As a reference chemical shift, the hydrogen of tetramethylsilane was set to 0 ppm. ^1H peaks obtained from an organic acid compound, for example, were determined by a conventional method.

[0258] [Example A1]

<Synthesis of compound 1>

Compound 1 shown below was synthesized by the following method according to the following reaction formula.

[0259] [Chemical formula 107]

[0260] 8.62 g (53.8 mmol) of the endo form of tetracyclododecene, 240 ml of tert-butyl alcohol and 50 ml of water were added to a 1 L three-necked flask, and the internal temperature was lowered to 0 °C with stirring. 12.0 g of potassium permanganate, 250 ml of water and 2.68 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared solution of tetracyclododecene so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for one hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The resulting precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate 3 times.

The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator, yielding 7.24 g of crude compound 1. The resulting compound 1 was used without further purification.

[0261] <Synthesis of Compound 2>

Compound 2 shown below was synthesized by the following method according to the following reaction formula.

[0262] [Chemical formula 108]

[0263] In a 100 mL three-necked flask, 5 g (25.7 mmol) of compound 1 and 31 mL of dehydrated pyridine were added under nitrogen atmosphere and stirred. While cooling in an ice bath, 6.3 mL of benzoyl chloride was slowly added thereto. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 mL of methanol was added. The organic layer was separated by adding chloroform and water to the reaction solution. The organic layer was washed 3 times with water, saturated aqueous ammonium chloride solution and brine and dried over magnesium sulfate. Magnesium sulfate was filtered off and the resulting organic layer was concentrated on a rotary evaporator to give 10.37 g of crude product. The crude product was purified by silica gel column chromatography to give 6.67 g (16.6 mmol, white solid) of compound 2. The 1H NMR data of the obtained compound 2 are shown below.

[0264] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 0.97-1.28 (m, 3H), 1.32-1.70 (m, 4H), 1.90 (br s, 2H), 2.15 (d, J=10.2 Hz, 1H), 2.39 (br s, 2H), 2.53 (br s, 2H), 5.53-5.59 (m, 2H), 7.19-7.33 (m, 4H), 7.40-7.49 (m, 2H), 7.80-7.92 (m, 4 h).

The melting point of the obtained compound 2 was 141°C.

[02 65] [Example A2]

<Synthesis of compound 3>

Compound 3 shown below was synthesized by the method given below.

[0266] [Chemical formula 109]

[0267] 10.18 g (63.5 mmol) of tetracyclododecene exoform, 240 ml of tert-butyl alcohol and 60 ml of water were added to a 1 L three-necked flask, and the internal temperature was lowered to 0 °C with stirring. 13.81 g of potassium permanganate, 300 ml of water and 3.00 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared tetracyclododecene solution so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for one hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The resulting precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate three times. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator, yielding 3.42 g (17.6 mmol) of crude compound 3. The resulting compound 3 was used without further purification.

[0268] <Synthesis of Compound 4>

Compound 4 shown below was synthesized by the method given below.

[0269] [Chemical formula 110]

[0270] Under a nitrogen atmosphere, 4.0 g (20.6 mmol) of compound 3, 4.2 ml of dehydrated pyridine and 100 ml of dehydrated chloroform were added to a 200 ml three-necked flask and stirred. While cooling in an ice bath, 4.9 ml of benzoyl chloride were slowly added thereto. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 ml of methanol were added. The organic layer was separated by adding chloroform and water to the reaction solution. The organic layer was washed 3 times with water, saturated aqueous ammonium chloride solution and brine and dried over magnesium sulfate. Magnesium sulfate was filtered off and the resulting organic layer was concentrated on a rotary evaporator to give 11.3 g of crude product. The crude product was purified by silica gel column chromatography to give 4.44 g (11.0 mmol, white solid) of compound 4. The ¹ H-NMR data of the obtained compound 4 are shown below.

[0271] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 0.96 (d, J=10.6 Hz, 1H), 1.13-1.22 (m, 2H), 1.43-1.60 (m, 5H), 1.77-2.05 (m, 2H), 2.23 (br s, 2H), 2.41 (br s, 2H), 4.99-5.01 (m, 2H), 7.21-7.29 (m, 4H), 7.42-7.49 (m, 2H), 7.81-7.87 (m, 4H).

The melting point of the obtained compound 4 was 163°C.

[0272] [Example A3]

<Synthesis of compound 5>

Compound 5 shown below was synthesized by the method given below.

[0273] [Chemical formula 111]

[0274] 15.53 g (110.8 mmol) of benznorbornadiene, 425 ml of tert-butyl alcohol and 105 ml of water were added to a 2 L three-necked flask, and the internal temperature was lowered to 0 °C with stirring. 23.7 g of potassium permanganate, 527 ml of water and 5.07 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared benznorbornadiene solution so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for 1 hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The resulting precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate three times. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator, yielding 8.19 g of compound 5. The ¹ H NMR data for the resulting compound 5 are shown below.

[0275] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.89-1.97 (m, 1H), 2.20-2.27 (m, 1H), 2.74-2.82 (m, 2H), 3.20-3.25 (m, 2H), 3.80-3.87 (m, 2H), 7.06-7.13 (m, 2H), 7.15-7.22 (m, 2H).

<Synthesis of compound 6>

Compound 6 shown below was synthesized by the method given below.

[027 6] [Chemical formula 112]

[0277] Under a nitrogen atmosphere, 9.57 g (54.3 mmol) of compound 5 and 70 ml of dehydrated pyridine were added to a 300 ml three-necked flask and stirred. While cooling in an ice bath, 13.4 ml of benzoyl chloride were slowly added thereto. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 ml of methanol were added. 200 ml of water were added to a beaker, the reaction solution was added with stirring, and the formed precipitate was filtered off. The precipitate was washed with hexane and then recrystallized with ethanol to obtain 16.36 g of a solid. A small amount of residual pyridine was removed by silica gel column chromatography to give 15.48 g (40.3 mmol, white solid) of compound 6. The ¹ H-NMR data of the obtained compound 6 are shown below.

[0278] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.12-2.20 (m, 1H), 2.57-2.64 (m, 1H), 3.57 (br s, 2H), 5.18 (d, J=1.6 Hz, 2H), 7.12-7.22 (m, 2H), 7.24-7.37 (m, 6H), 7.44-7.53 (m, 4H), 7.87-7.96 (m, 2H).

The melting point of the obtained compound 6 was 139°C.

[0279] [Example A4]

<Synthesis of compound 7>

Compound 7 shown below was synthesized by the following method according to the following reaction formula.

[0281] Under nitrogen atmosphere, 200 ml of anhydrous toluene, 6.36 ml of 1-bromo-2-iodobenzene and 10.5 ml of 2,5-dimethylfuran were added to a 1-liter three-necked flask and cooled to -20°C with stirring. 47 ml of n-butyl lithium solution in hexane (1.6 M) was slowly added dropwise and after dropwise addition, stirring was carried out at -20°C for 1 hour. The temperature was gradually raised to room temperature and stirring was continued overnight. Under cooling in an ice bath, water was slowly added dropwise and ethyl acetate was added to separate the organic layer. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off and the resulting organic layer was concentrated on a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain 4.05 g (23.5 mmol) of compound 7. The ¹ H-NMR data of the obtained compound 7 are shown below.

[0282] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.90 (s, 6H), 6.77 (s, 2H), 6.97 (dd, J=5.3, 3.0 Hz, 2H), 7.13 (dd, J=5.3, 3.0 Hz, 2H).

<Synthesis of compound 8>

Compound 8 shown below was synthesized by the method given below.

[0283] [Chemical formula 114]

[0284] 4.05 g (23.5 mmol) of compound 7, 129 ml of tert-butyl alcohol and 32 ml of water were added to a 2 L three-necked flask, and the internal temperature was lowered to 0 °C with stirring. 7.23 g of potassium permanganate, 161 ml of water and 1.61 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared solution of compound 7 so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for 1 hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The resulting precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate 3 times. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator to yield 3.03 g of crude product. The crude product was purified by silica gel column chromatography to yield 2.02 g (10.7 mmol) of compound 8. ^{The 1} H NMR data of the resulting compound 8 are shown below.

[0285] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.76 (s, 6H), 2.84 (br s, 2H), 3.76 (br s, 2H), 7.15-7.25 (m, 4H).

<Synthesis of compound 9>

Compound 9 shown below was synthesized by the method given below.

[028 6] [Chemical formula 115]

[0287] In a 50 mL three-necked flask under nitrogen atmosphere, 2.15 g (10.4 mmol) of compound 8 and 10 mL of dehydrated pyridine were added and stirred. While cooling in an ice bath, 2.8 mL of benzoyl chloride was slowly added thereto. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 mL of methanol was added. In a beaker, 100 mL of water and 100 mL of ethyl acetate were added to separate the organic layer. The organic layer was washed with water 3 times, washed with a saturated aqueous solution of ammonium chloride and brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator to obtain 4.78 g of crude product. The crude product was purified by silica gel column chromatography to give 3.29 g (7.9 mmol, white solid) of compound 9. The ¹ H-NMR data of the obtained compound 9 are shown below.

[0288] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.85 (s, 6H), 5.34 (s, 2H), 7.22-7.55 (m, 10H), 7.91-8.02 (m, 4H).

The melting point of the obtained compound 9 was 196°C.

[028 9] [Example A5]

<Synthesis of compound 10>

Compound 10 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0290] [Chemical formula 116]

[0291] Under a nitrogen atmosphere, 16.0 g of 3,4-dibromotoluene, 120 ml of anhydrous toluene, and 4.23 g of cyclopentadiene were added to a 500 ml three-necked flask and stirred. Regarding the cyclopentadiene used for the reaction, as reported in non-patent literature 13, dicyclopentadiene was pyrolyzed at a temperature of 160 to 170°C, and the component distilled at a temperature of 40°C to 67°C was quickly used. The internal temperature was lowered to 0°C, and 40 ml of n-butyl lithium solution in hexane (1.6 M) was slowly added dropwise. After the dropwise addition, the temperature was gradually raised to room temperature, and stirring was carried out at room temperature for 4 hours. After the reaction, a saturated aqueous solution of ammonium chloride was added, followed by diethyl ether. The organic layer was separated, and the organic layer was washed with water and brine. After drying the organic layer over magnesium sulfate, magnesium sulfate was filtered, and the resulting organic layer was concentrated on a rotary evaporator to obtain 14.32 g of crude product. The crude product was purified by silica gel column chromatography to obtain 4.19 g (26.8 mmol) of compound 10. The ¹ H NMR data of the obtained compound 10 are shown below.

[0292] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.19-2.24 (m, 1H), 2.27-2.33 (m, 4H), 3.85 (s, 2H), 6.71-6.81 (m, 2H), 7.06-7.12 (m, 3H).

<Synthesis of compound 11>

Compound 11 shown below was synthesized by the method given below.

[0293] [Chemical formula 117]

[0294] 4.19 g (26.8 mmol) of compound 10, 107 ml of tert-butyl alcohol and 27 ml of water were added to a 500 ml three-necked flask, and the internal temperature was lowered to 0 °C with stirring. 6.40 g of potassium permanganate, 135 ml of water and 1.42 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared solution of compound 10 so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for 1 hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator to yield 3.80 g of crude product. The crude product was purified by silica gel column chromatography to yield 3.04 g (16.0 mmol) of compound 11. ^{The 1} H NMR data of the resulting compound 11 are shown below.

[0295] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.86-1.93 (m, 1H), 2.18-2.24 (m, 1H), 2.30 (s, 3H), 2.78-2.86 (m, 2H), 3.15-3.19 (m, 2H), 3.78-3.84 (m, 2H), 6.90 (d, J=7.3 Hz, 1H), 7.02 (s, 1H), 7.07 (d, J=7.3 Hz, 1H).

<Synthesis of compound 12>

Compound 12 shown below was synthesized by the method given below.

[0296] [Chemical formula 118]

[0297] Under a nitrogen atmosphere, 2.94 g (15.5 mmol) of compound 11, 80 ml of dehydrated chloroform and 4.6 g of benzoyl chloride were added to a 200 ml three-necked flask and stirred. While cooling in an ice bath, 2.6 ml of anhydrous pyridine were slowly added dropwise. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 ml of methanol were added. After adding water and chloroform to the reaction solution and stirring, the organic layer was separated. The organic layer was washed with brine and then dried over magnesium sulfate. Magnesium sulfate was filtered off and the resulting organic layer was concentrated on a rotary evaporator to give 7.91 g of a crude product. The crude product was purified by silica gel column chromatography to give 4.82 g (12.1 mmol, white solid) of compound 12. The ¹ H-NMR data of the obtained compound 12 are shown below.

[0298] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.08-2.17 (m, 1H), 2.35 (s, 3H), 2.55-2.63 (m, 1H), 3.49-3.55 (m, 2H), 5.13-5.18 (m, 2H), 6.96-7.04 (m, 1H), 7.15-7.39 (m, 6H), 7.44-7.52 (m, 2H), 7.87-7.95 (m, 4H).

The melting point of the resulting compound 12 was 155°C.

[02 99] [Example A6]

<Synthesis of compound 13>

Compound 13 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0300] [Chemical formula 119]

[0301] Under a nitrogen atmosphere, 21.7 g of sodium hydride (64.6% liquid paraffin dispersion) was added to a 200 ml three-necked flask, 135 ml of anhydrous tetrahydrofuran was added thereto and stirred. While cooling in an ice bath, 19.3 g of cyclopentadiene was slowly added dropwise. Regarding the cyclopentadiene used for the reaction, as reported in non-patent literature 13, dicyclopentadiene was pyrolyzed at a temperature of 160 to 170 °C, and the component distilled at a temperature of 40 °C to 67 °C was quickly used. After the dropwise addition, the mixture was stirred at room temperature for 20 minutes. Then, while cooling in an ice bath, 28.9 g of 1,2-dichloroethane was slowly added dropwise. After dropwise addition, the temperature was raised to room temperature and stirred for 8 hours. 100 ml of tetrahydrofuran and 10.5 g of water were added to a beaker to obtain an aqueous tetrahydrofuran (THF) solution. While the flask was cooled in an ice bath after the reaction, the aqueous tetrahydrofuran solution was slowly added dropwise. Ice water was placed in another flask, and the reaction solution was transferred to ice water. After this, pentane was added, and the organic layer was separated. Then, the organic layer was washed twice with 0.5 N hydrochloric acid, twice with water, and once with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, the resulting organic layer was distilled, and the component was collected at a pressure of 664 to 665 Torr and a distillation temperature of 88 to 92°C, which gave 18.09 g of compound 13.

[0302] <Synthesis of Compound 14>

Compound 14 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0303] [Chemical formula 120]

[0304] Under a nitrogen atmosphere, 15.1 g (64.0 mmol) of 1,2-dibromobenzene, 130 ml of anhydrous toluene, and 5.90 g of compound 13 were added to a 500 ml three-necked flask and stirred. The internal temperature was lowered to 0 °C, and 40 ml of a solution of n-butyl lithium in hexane (1.6 M) were slowly added dropwise. After the dropwise addition, the temperature was gradually raised to room temperature, and stirring was carried out at room temperature for 4 hours. After the reaction, a saturated aqueous solution of ammonium chloride was added, and then diethyl ether was added. The organic layer was separated and washed with water and brine in that order. After drying the organic layer over magnesium sulfate, magnesium sulfate was filtered off and the resulting organic layer was concentrated on a rotary evaporator to yield 15.44 g of crude product. The crude product was purified by silica gel column chromatography to yield 7.70 g (45.8 mmol) of compound 14.

[0305] <Synthesis of Compound 14-2>

Compound 14-2 shown below was synthesized by the method given below.

[0306] [Chemical formula 121]

[0307] To a 500 mL three-necked flask were added 7.7 g (45.8 mmol) of compound 14, 178 mL of tert-butyl alcohol and 44 mL of water, and the internal temperature was lowered to 0 °C with stirring. To another flask were added 10.6 g of potassium permanganate, 222 mL of water and 2.32 g of sodium hydroxide and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared solution of compound 14 so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for 1 hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The resulting precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator to yield 5.63 g of crude product. The crude product was purified by silica gel column chromatography to yield 3.85 g (19.0 mmol) of compound 14-2. The ¹ H NMR data of the obtained compound 14-2 are shown below.

[0308] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 0.29-0.35 (m, 2H), 0.89-0.95 (m, 2H), 2.69-2.79 (m, 4H), 3.91-3.96 (m, 2H), 7.08-7.22 (m, 4H).

<Synthesis of compound 15>

Compound 15 shown below was synthesized by the method given below.

[0309] [Chemical formula 122]

[0310] Under a nitrogen atmosphere, 4.06 g (24.1 mmol) of compound 14-2, 105 ml of dehydrated chloroform and 5.95 g of benzoyl chloride were added to a 200 ml three-necked flask and stirred. While cooling in an ice bath, 3.4 ml of anhydrous pyridine were slowly added dropwise. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 ml of methanol was added. After adding water and chloroform to the reaction solution and stirring, the organic layer was separated. The organic layer was washed with brine and then dried over magnesium sulfate. Magnesium sulfate was filtered off and the resulting organic layer was concentrated on a rotary evaporator to give 9.65 g of a crude product. The crude product was purified by silica gel column chromatography to give 3.88 g (9.5 mmol, white solid) of compound 15. The ¹ H-HMP data of the obtained compound 15 are shown below.

[0311] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 0.46-0.56 (m, 2H), 1.05-1.14 (m, 2H), 3.04 (s, 2H), 5.28 (s, 2H), 7.17-7.37 (m, 8H), 7.44-7.53 (m, 2H), 7.88-7.96 (m, 4H).

The melting point of the resulting compound 15 was 111°C.

[0312] [Example A7]

<Synthesis of compound 16>

Compound 16 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0313] [Chemical formula 123]

[0314] Under a nitrogen atmosphere, 20.0 g (68.5 mmol) of 1,2-dibromo-4-tert-butylbenzene, 130 ml of dehydrated toluene and 4.54 g of cyclopentadiene were added to a 500 ml three-necked flask and stirred. Regarding the cyclopentadiene used for the reaction, as reported in non-patent literature 13, dicyclopentadiene was pyrolyzed at a temperature of 160 to 170°C, and the component distilled at a temperature of 40°C to 67°C was quickly used. The internal temperature was lowered to 0°C, and 43 ml of a hexane solution of n-butyl lithium (1.6 M) was slowly added dropwise. After the dropwise addition, the temperature was gradually raised to room temperature, and stirring was carried out at room temperature for 12 hours. After the reaction, a saturated aqueous solution of ammonium chloride was added, followed by diethyl ether. The organic layer was separated and washed with water and brine in that order. After drying the organic layer over magnesium sulfate, magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator to yield 19.67 g of crude product. The crude product was purified by silica gel column chromatography to yield 5.57 g (28.1 mmol) of compound 16. The ¹ H NMR data of the obtained compound 16 are shown below.

[0315] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.30 (s, 9H), 2.21-2.33 (m, 2H), 3.83-3.87 (m, 2H), 6.76-6.80 (m, 2H), 6.93 (dd, J=7.2, 1.6 Hz, 1H), 7.13 (d, J=7.2 Hz, 1H), 7.29 (d, J=1.6 Hz, 1H).

<Synthesis of compound 17>

Compound 17 shown below was synthesized by the method given below.

[0316] [Chemical formula 124]

[0317] 5.57 g (28.1 mmol) of compound 16, 109 ml of tert-butyl alcohol and 27 ml of water were added to a 500 ml three-necked flask, and the internal temperature was lowered to 0 °C with stirring. 6.55 g of potassium permanganate, 135 ml of water and 1.55 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared solution of compound 16 so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for one hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The resulting precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate four times. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator. The crude product was purified by silica gel column chromatography to yield 4.11 g (17.7 mmol) of compound 17. The ¹ H NMR data for the resulting compound 17 are shown below.

[0318] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.29 (s, 9H), 1.88-1.95 (m, 1H), 2.19-2.25 (m, 1H), 2.89 (br s, 2H), 3.17-3.20 (m, 2H), 3.80-3.84 (m, 2H), 7.09-7.12 (m, 2H), 7.22-7.24 (m, 1H).

<Synthesis of compound 18>

Compound 18 shown below was synthesized by the method given below.

[0319] [Chemical formula 125]

[0320] Under nitrogen atmosphere, 4.11 g (9.3 mmol) of compound 17 and 17.7 ml of dehydrated pyridine were added to a 50 ml three-necked flask and stirred. While cooling in an ice bath, 4.3 ml of benzoyl chloride was slowly added thereto. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 ml of methanol was added. 100 ml of water and 100 ml of ethyl acetate were added to a beaker to separate the organic layer. The organic layer was washed with water 3 times and once each with a saturated aqueous solution of ammonium chloride and brine in that order and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator to give 9.34 g of crude product. The crude product was purified by silica gel column chromatography to yield 6.13 g of a solid component. The resulting solid was recrystallized from hexane to yield 4.0 g (9.0 mmol, white solid) of compound 18. ^{The 1} H-NMR data of the resulting compound 18 are shown below.

[0321] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.33 (s, 9H), 2.11-2.19 (m, 1H), 2.56-2.63 (m, 1H), 3.53 (s, 2H), 5.15-5.19 (m, 2H), 7.18-7.32 (m, 6H), 7.37-7.39 (m, 1H), 7.44-7.53 (m, 2H), 7.88-7.94 (m, 4H).

The melting point of the resulting compound 18 was 115°C.

[0322] [Example A8]

<Synthesis of compound 19>

Compound 19 shown below was synthesized by the method given below.

[0323] [Chemical formula 126]

[0324] Under a nitrogen atmosphere, 20.0 g (75.8 mmol) of 1,2-dibromo-4,5-dimethylbenzene, 150 ml of dehydrated toluene and 5.01 g of cyclopentadiene were added to a 500 ml three-necked flask and stirred. Regarding the cyclopentadiene used for the reaction, as reported in non-patent literature 13, dicyclopentadiene was pyrolyzed at a temperature of 160 to 170°C, and the component distilled at a temperature of 40°C to 67°C was quickly used. The internal temperature was lowered to 0°C, and 47.5 ml of a hexane solution of n-butyl lithium (1.6 M) was slowly added dropwise. After the dropwise addition, the temperature was gradually raised to room temperature, and stirring was carried out at room temperature for 12 hours. After the reaction, a saturated aqueous solution of ammonium chloride was added, followed by diethyl ether. The organic layer was separated and washed with water and brine in that order. After drying the organic layer over magnesium sulfate, magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator to yield 18.64 g of crude product. The crude product was purified by silica gel column chromatography to yield 3.89 g (22.8 mmol) of compound 19. ^{The 1} H-NMR data of the obtained compound 19 are shown below.

[0325] ¹ H NMR (270 MHz, CDCL3, TMS as internal standard): δ 2.17-2.22 (m, 7H), 2.29 (dt, J=6.9, 1.6 Hz, 1H), 3.81-3.85 (m, 2H), 6.77 (t, J=2.0 Hz, 2H), 7.03 (s, 2H).

<Synthesis of compound 20>

Compound 20 shown below was synthesized by the method given below.

[0326] [Chemical formula 127]

[0327] 5.57 g (22.8 mmol) of compound 19, 89 ml of tert-butyl alcohol and 22 ml of water were added to a 500 ml three-necked flask, and the internal temperature was lowered to 0 °C with stirring. 5.33 g of potassium permanganate, 111 ml of water and 1.22 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was slowly added dropwise to the previously prepared solution of compound 19 so that the internal temperature did not exceed 5 °C. After dropwise addition, stirring was continued at 0 °C for 1 hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The formed precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times. The organic layer was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator. The crude product was purified by silica gel column chromatography to yield 2.25 g (11.0 mmol) of compound 20. The ¹ H NMR data of the resulting compound 20 are shown below.

[0328] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.83-1.90 (m, 1H), 2.17-2.23 (m, 7H), 2.70-2.77 (m, 2H), 3.12-3.17 (m, 2H), 3.77-3.83 (m, 2H), 6.98 (s, 2H).

<Synthesis of compound 21>

Compound 21 shown below was synthesized by the method mentioned below.

[0329] [Chemical formula 128]

[0330] Under nitrogen atmosphere, 2.25 g (11.0 mmol) of compound 20 and 11.0 mL of dehydrated pyridine were added to a 50 mL three-necked flask and stirred. While cooling in an ice bath, 2.7 mL of benzoyl chloride was slowly added thereto. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 mL of methanol was added. 100 mL of water and 100 mL of ethyl acetate were added to a beaker to separate the organic layer. The organic layer was washed with water 3 times, once each with a saturated aqueous solution of ammonium chloride and brine in that order and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator to give 4.82 g of crude product. The crude product was purified by silica gel column chromatography to give 4.44 g (10.8 mmol, pale yellow solid) of compound 21. The ¹ H-NMR data of the obtained compound 21 are shown below.

[0331] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.09 (d, J=9.8 Hz, 1H), 2.26 (s, 6H), 2.57 (d, J=9.8 Hz, 1H), 3.49 (s, 2H), 5.13 (d, J=1.3 Hz, 2H), 7.13 (s, 2H), 7.20-7.31 (m, 4H), 7.44-7.52 (m, 2H), 7.87-7.93 (m, 4H).

The melting point of the resulting compound 21 was 152°C.

[0332] [Example A9]

<Synthesis of compound 22>

Compound 22 shown below was synthesized by the method given below.

[0333] [Chemical formula 129]

[0334] A 1 L three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was equipped with a dropping funnel, a thermometer, and a three-way stopcock. Under a nitrogen atmosphere, 6.00 mL (44.1 mmol, 1 equivalent) of 2-isopropylphenol was charged, followed by the addition of 100 mL of dichloromethane and 0.62 mL (4.41 mmol, 0.1 equivalent) of diisopropylamine. Then, under a nitrogen atmosphere, to the reaction solution prepared earlier at room temperature. The completed addition was stirred dropwise for an hour at room temperature. After the completion of the reaction, hydrochloric acid (2 M) was added until the pH reached 1, and after adding 100 mL of water, extraction was performed with dichloromethane 3 times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane) to obtain 9.40 g (43.7 mmol, yield 91%) of compound 22. The obtained compound showed good agreement with the spectrum of the identical compound synthesized in "J. Med. Chem. 2017, 60, 3618-3625". The ¹ H-NMR data of the obtained compound 22 are shown below.

[0335] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.24 (d, J=6.9 Hz, 6H), 3.32 (segment, J=6.9 Hz, 1H), 5.57 (s, 1H), 6.77 (t), J=7.5 Hz, 1H), 7.14 (dd, J=7.5, 1.7 Hz, 1H), 7.29 (dd, J=7.5, 1.7 Hz, 1H).

Synthesis link: Bull. Chem. Soc. Jpn. 1993, 66, 1576-1579.

<Synthesis of compound 23>

Compound 23 shown below was synthesized by the method given below.

[0336] [Chemical formula 130]

[0337] A 500 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was equipped with a reflux condenser, a flat stopper, and a three-way valve. Under a nitrogen atmosphere, 9.40 g (43.7 mmol, 1 equivalent) of the compound, 22.85 mL of THF, and 12.0 mL (56.8 mmol, 1.3 equivalents) of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) were added to the flat stopper, followed by stirring while heating in an oil bath at 80 °C. After stirring overnight, followed by cooling to room temperature, the pressure was released under a nitrogen atmosphere, and THF and unreacted HMDS were removed from the reaction system. The product of this reaction was not purified and used in the next reaction.

[0338] The container containing the product of the above reaction was equipped with a dropping funnel and cooled to -78°C after adding 120 mL of THF. 38.3 mL (1.6 M, 61.2 mmol, 1.4 equiv) of n-BuLi solution in hexane was slowly added dropwise and after the dropwise addition was complete, stirring was maintained at -78°C for 30 minutes. Then, 10.0 mL (61.0 mmol, 1.4 equivalents) of trifluoromethanesulfonic anhydride (Tf2O) was slowly added dropwise under -78°C. After the dropwise addition was complete, stirring was maintained at -78°C for 30 minutes and then the reaction solution was allowed to reach room temperature. The reaction solution was again cooled to 0 °C, and saturated aqueous sodium hydrogen carbonate solution was slowly added until the pH reached approximately 7-8. The solution was extracted with ethyl acetate 3 times, and the collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane) to obtain 9.93 g (29.2 mmol, yield 67%) of compound 23. The obtained compound 23 showed good agreement with the spectrum of the identical compound synthesized in "Angew. Chem. Int. Ed. 2011, 50, 5674-5677". The ¹ H-NMR data of the obtained compound 23 are shown below.

[0339] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 0.38 (s, 9H), 1.24 (d, J=6.9 Hz, 6H), 3.31 (break, J=6.9 Hz, 1H), 7.31-7.43 (m, 3H).

Link to synthesis: Org. Lett. 2013, 15, 5722-5725.

<Synthesis of compound 24>

Compound 24 shown below was synthesized by the method given below.

[0340] [Chemical formula 131]

[0341] A 1 L, 3-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a reflux condenser, a flat stopper, and a three-way valve. Under a nitrogen atmosphere, 22.2 g (146 mmol, 5 equivalents) of cesium fluoride and 290 mL of acetonitrile were added thereto. Then, 12.3 mL (146 mmol, 5 equivalents) of cyclopentadiene, obtained by pyrolysis of dicyclopentadiene immediately before, were added to the reaction solution. Immediately thereafter, 9.93 g (29.2 mmol, 1 equivalent) of compound 23 were added thereto. After replacing the flat stopper with a thermometer, the solution was heated in an oil bath to 40°C and stirred with heating for 16 hours. After completion of the reaction and subsequent cooling to room temperature, the reaction solution was passed through silica gel (eluent: ethyl acetate) and concentrated on a rotary evaporator. The resulting crude product was purified by column chromatography on silica gel (eluent: hexane) to yield 5.32 g of a solution containing compound 24 and a small amount of impurities. The solution was used in the next reaction without further purification. The ¹ H NMR data of the resulting compound 24 are shown below.

[0342] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.20 (d, J=6.9 Hz, 3H), 1.28 (d, J=6.9 Hz, 3H), 2.17-2.21 (m, 1H), 2.26-2.30 (m, 1H), 3.13 (cleavage, J=6.9 Hz, 1H), 3.86-3.88 (m, 1H), 4.08-4.09 (m, 1H), 6.77-6.93 (m, 4H), 7.07 (d, J=6.3 Hz, 1H).

Synthesis reference: Macromolecules 2017, 50, 580-586.

<Synthesis of compound 25>

Compound 25 shown below was synthesized by the method given below.

[0343] [Chemical formula 132]

[0344] A 500 mL three-necked flask including a magnetic stirrer was equipped with a dropping funnel, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 120 mL of ^t BuOH, 35 mL of water, and 5.32 g (1 equivalent) of the mixed solution of compound 24 obtained in the <synthesis of compound 24>3 were charged thereto, and the reaction solution was cooled to 0°C. 1.45 g (36.2 mmol, 1.25 equiv.) of NaOH and 6.86 g (43.4 mmol, 1.5 equiv.) _of KMnO4 were dissolved in 130 mL of water and slowly added dropwise to the reaction solution. After the dropwise addition was completed, stirring was continued at 0°C for another 30 minutes, and then the unreacted _KMnO4 was quenched with a saturated aqueous solution of sodium metabisulfite. After stirring for some time at room temperature, sodium hydrogen carbonate was added until the pH of the reaction solution reached approximately 7-8, and the formed white precipitate was removed by filtration. The filtered solution was extracted with ethyl acetate 3 times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (after development with 1 L of eluent: hexane, development with a mixture of hexane:ethyl acetate = 3:1) to give 5.31 g (24.3 mmol, yield 84%) of compound 25. The ¹ H-NMR data of the obtained compound 25 are shown below.

[0345] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.22 (d, J=6.9 Hz, 3H), 1.27 (d, J=6.9 Hz, 3H), 1.86-1.92 (m, 1H), 2.20-2.24 (m, 1H), 2.71 (d, J=4.9 Hz, 1H), 2.86 (d, J=4.9 Hz, 1H), 3.09 (split, J=6.9 Hz, 1H), 3.20 (br s, 1H), 3.40 (br s, 1H), 3.78-3.87 (m, 2H), 6.99-7.10 (m, 3H).

Synthesis reference: J. Org. Chem. 2017, 82, 9715-9730.

<Synthesis of compound 2b>

Compound 26 shown below was synthesized by the method given below.

[0346] [Chemical formula 133]

[0347] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way stopcock. Under a nitrogen atmosphere, 5.31 g (24.3 mmol, 1 equivalent) of compound 25 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 7.0 mL (60.3 mmol, 2.5 equivalents) of benzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 1 hour. After adding approximately 20 ml of water and approximately 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 20:1) and recrystallization from hexane to obtain 5.19 g (12.2 mmol, yield 50%, white solid) of compound 26. The ¹ H-NMR data of the obtained compound 26 are shown below.

[0348] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.32 (d, J = 6.9 Hz, 3H), 1.33 (d, J = 6.9 Hz, 3H), 2.10-2.15 (m, 1H), 2.57-2.61 (m, 1H), 3.19 (segment, J = 6.9 Hz, 1H), 3.56 (br s, 1H), 3.75 (br s, 1H), 5.12-5.19 (m, 2H), 7.08-7.17 (m, 3H), 7.22-7.35 (overlap with CHCl ₃ signal, m, 4H), 7.45-7.54 (m, 2H), 7.87-7.96 (m, 4H).

The melting point of the resulting compound 26 was 114°C.

[0349] [Example A10]

<Synthesis of compound 27>

Compound 27 shown below was synthesized by the method given below.

[0350] [Chemical formula 134]

[0351] 7.26 g (23.2 mmol, yield 48%) of compound 27 was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 23> except that 6.00 ml (48.4 mmol) of 6-bromo-o-cresol was used instead of 9.40 g (43.7 mmol) of compound 22 in <Synthesis of Compound 23>. The obtained compound 27 showed good agreement with the spectrum of the identical compound synthesized in "J. Org. Chem. 2015, 80, 11618-11623". The ¹ H-NMR data of the obtained compound 27 are shown below.

[0352] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 0.38 (s, 9H), 2.38 (s, 3H), 7.28-7.30 (m, 2H), 7.38-7.47 (m, 1H).

<Synthesis of compound 28>

Compound 28 shown below was synthesized by the method mentioned below.

[0353] [Chemical formula 135]

[0354] 3.39 g (17 mmol, yield 74%) of compound 28 contaminated with a small amount of hexane were obtained according to the operation and equivalence ratio described in <synthesis of compound 24> except that 7.26 g (23.2 mmol) of compound 27 was used instead of 9.93 g (29.2 mmol) of compound 23 in <synthesis of compound 24>. The ¹ H-NMR data of the obtained compound 28 are shown below.

[0355] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.17-2.21 (m, 1H), 2.26-2.31 (m, 4H), 3.85-3.88 (m, 1H), 3.99-4.00 (m, 1H), 6.73-6.85 (m, 4H), 7.05 (d, J=6.9 Hz, 1H).

<Synthesis of compound 29>

Compound 29 shown below was synthesized by the method given below.

[0356] [Chemical formula 136]

[0357] A 500 mL three-necked flask equipped with a magnetic stirrer was fitted with a dropping funnel, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 70 mL of ^tBuOH , 20 mL of water, and 3.39 g (17 mmol, 1 equivalent) of compound 28 contaminated with a small amount of hexane obtained in the <synthesis of compound 28> were charged thereto, and the reaction solution was cooled to 0 °C. 0.85 g (21.3 mmol, 1.25 equivalents) of NaOH and 4.03 g (25.5 mmol, 1.5 equivalents) of KMnO ₄ were dissolved in 80 mL of water and slowly added dropwise to the reaction solution. After the dropwise addition was complete, stirring was continued at 0°C for another 30 minutes, and then the unreacted _KMnO4 was quenched with a saturated aqueous solution of sodium metabisulfite. After stirring for some time at room temperature, sodium hydrogen carbonate was added until the pH of the reaction solution reached approximately 7-8, and the formed white precipitate was removed by filtration. The filtered solution was extracted with ethyl acetate 3 times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 3:1) to obtain 2.19 g (11.5 mmol, yield 68%) of compound 29. The ¹ H-NMR data of the obtained compound 29 are shown below.

[0358] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.86-1.91 (m, 1H), 2.19-2.24 (m, 1H), 2.31 (s, 3H), 2.72-2.74 (m, 1H), 2.83-2.85 (m, 1H), 3.19-3.20 (m, 1H), 3.31-3.32 (m, 1H), 3.77-3.84 (m, 2H), 6.89-7.07 (m, 3H).

<Synthesis of compound 30>

Compound 30 shown below was synthesized by the method given below.

[0359] [Chemical formula 137]

[0360] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.19 g (11.5 mmol, 1 equivalent) of compound 29 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 2.94 mL (25.3 mmol, 2.2 equivalents) of benzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was continued for 3 hours. After completion of the reaction, the solution was cooled to 0 °C, 20 mL of methanol was added, and stirring was continued for an hour. After adding approximately 20 ml of water and approximately 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) to obtain 3.19 g (8.01 mmol, yield 70%, white solid) of compound 30. The ¹ H-NMR data of the obtained compound 30 are shown below.

[0361] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.09-2.14 (m, 1H), 2.41 (s, 3H), 2.56-2.60 (m, 1H), 3.55 (br s, 1H), 3.67 (br s, 1H), 5.10-5.18 (m, 2H), 6.99-7.17 (m, 3H), 7.24-7.33 (overlap with CHCl ₃ signal, m, 4H), 7.45-7.53 (m, 2H), 7.88-7.95 (m, 4H).

The melting point of the resulting compound 30 was 131°C.

[0362] [Example A11]

<Synthesis of compound 31>

Compound 31 shown below was synthesized by the method given below.

[0363] [Chemical formula 138]

[0364] 10.8 g (53.9 mmol, yield 90%) of compound 31 was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 22> except that 7.33 g (60.0 mmol) of 2,5-dimethylphenol was used instead of 6.00 ml (44.1 mmol) of 2-isopropylphenol in <Synthesis of Compound 22>. The obtained compound showed good agreement with the spectrum of the identical compound synthesized in "Adv. Synth. Catal. 2008, 350, 1309-1315". ^{The 1} H-NMR data of the obtained compound 31 are shown below.

[0365] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.27 (s, 3H), 2.36 (s, 3H), 5.65 (s, 1H), 6.71 (d, J=7.6 Hz, 1H), 6.95 (g, J=7.6 Hz, 1H).

<Synthesis of compound 32>

Compound 32 shown below was synthesized by the method given below.

[0366] [Chemical formula 139]

[0367] 13.0 g of compound 32 containing a small amount of impurities was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 23> except that 10.8 g (53.9 mmol) of compound 31 was used instead of 9.40 g (43.7 mmol) of compound 22 from <Synthesis of Compound 23>. The product of this reaction was used in the next reaction without further purification and identification.

[0368] <Synthesis of Compound 33>

Compound 33 shown below was synthesized by the method given below.

[0369] [Chemical formula 140]

[0370] 5.58 g (32.8 mmol) of compound 33 was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 24> except that 13.0 g (39.9 mmol as 1 equivalent) of compound 32 containing a small amount of impurities was used instead of 9.93 g (29.2 mmol) of compound 23 from <Synthesis of Compound 24>. The ¹ H-NMR data of the obtained compound 33 are shown below.

[0371] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.13-2.17 (m, 1H), 2.23-2.27 (m, 7H), 3.97-4.00 (m, 2H), 6.66 (s, 2H), 6.78-6.79 (m, 2H).

<Synthesis of compound 34>

Compound 34 shown below was synthesized by the method given below.

[0372] [Chemical formula 141]

[0373] A 500 mL three-neck flask equipped with a magnetic stirrer was fitted with a dropping funnel, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 135 mL of ^tBuOH , 40 mL of water, and 5.58 g (32.8 mmol, 1 equiv) of compound 33 were charged, and the reaction solution was cooled to 0 °C. 1.64 g (41.0 mmol, 1.25 equiv) of NaOH and 7.78 g (49.2 mmol, 1.5 equiv) of KMnO ₄ were dissolved in 150 mL of water and slowly added dropwise to the reaction solution. After completion of the dropwise addition, stirring was continued at 0 °C for another 30 min, and then unreacted KMnO ₄ was quenched with a saturated aqueous solution of sodium metabisulfite. After stirring for some time at room temperature, sodium hydrogen carbonate was added until the pH of the reaction solution reached approximately 7-8, and the resulting white precipitate was removed by filtration. The filtered solution was extracted with ethyl acetate 3 times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 5:1) to obtain 5.29 g (25.9 mmol, yield 79%) of compound 34. The ¹ H-NMR data of the obtained compound 34 are shown below.

[0374] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.82-1.87 (m, 1H), 2.18-2.22 (m, 1H), 2.27 (s, 6H), 2.73-2.78 (m, 2H), 3.29-3.03 (m, 2H), 3.76-3.80 (m, 2H), 6.81 (s, 2H).

<Synthesis of compound 35>

Compound 35 shown below was synthesized by the method given below.

[0375] [Chemical formula 142]

[0376] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 5.29 g (25.9 mmol, 1 equivalent) of compound 34 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 6.60 mL (57.0 mmol, 2.2 equivalents) of benzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was continued for 4 hours. After completion of the reaction, the solution was cooled to 0 °C, 20 mL of methanol was added, and stirring was continued for an hour. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 20:1) and recrystallized from hexane to obtain 5.49 g (13.3 mmol, yield 51%, white solid) of compound 35. The ¹ H-NMR data of the obtained compound 35 are shown below.

[0377] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.04-2.10 (m, 1H), 2.36 (s, 6H), 2.54-2.58 (m, 1H), 3.66 (br s, 2H), 5.10-5.11 (m, 2H), 6.91 (s, 2H), 7.26-7.32 (overlaps with CHCl ₃ signal, m, 4H), 7.46-7.53 (m, 2H), 7.91-7.94 (m, 4H).

The melting point of the resulting compound 35 was 138°C.

[0378] [Example A12]

<Synthesis of compound 36>

Compound 36 shown below was synthesized by the method given below.

[0379] [Chemical formula 143]

[0380] A 500 mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a thermometer, and a three-way valve was added. Under nitrogen atmosphere, 110 mL of tBuOH, 35 mL of water, and 5.00 g (26.0 mmol, 1 equivalent) of 1,4-dihydro-1,4-methanoanthracene were added, and the reaction solution was cooled to 0 °C. 1.30 g (32.5 mmol, 1.25 equivalent) of NaOH and 6.16 g (39.0 mmol, 1.5 equivalent) of KMnO ₄ were dissolved in 120 mL of water and slowly added dropwise to the reaction solution. After the dropwise addition was completed, stirring was continued at 0°C for another hour, and then the unreacted _KMnO4 was quenched with a saturated aqueous solution of sodium metabisulfite. After stirring for some time at room temperature, sodium hydrogen carbonate was added until the pH of the reaction solution reached approximately 7-8, and the formed white precipitate was removed by filtration. The filtered solution was extracted with ethyl acetate 3 times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) to obtain 2.57 g (11.4 mmol, yield 44%) of compound 36. The ¹ H-NMR data of the obtained compound 36 are shown below.

[0381] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.94-1.99 (m, 1H), 2.33-2.37 (m, 1H), 2.82 (br s, 2H), 3.37 (s, 2H), 3.92 (br s, 2H), 7.39-7.43 (m, 2H), 7.60 (br s, 2H), 7.74-7.77 (m, 2H).

<Synthesis of compound 37>

Compound 37 shown below was synthesized by the method given below.

[0382] [Chemical formula 144]

[0383] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.57 g (11.4 mmol, 1 equivalent) of compound 36 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 2.90 mL (25.1 mmol, 2.2 equivalents) of benzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 1 hour. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The obtained crude product was purified twice by silica gel column chromatography (eluent: the first time: hexane:ethyl acetate = 20:1, then only ethyl acetate, the second time: hexane:ethyl acetate = 5:1) and washed with hexane to give 3.09 g (7.1 mmol, yield 62%, pale yellow solid) of compound 37. The ¹ H-NMR data of the obtained compound 37 are shown below.

[0384] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.19 (d, J=9.9 Hz, 1H), 2.71 (d, J=9.2 Hz, 1H), 3.72 (br s, 2H), 5.26 (d, J=9.2 Hz, 1H), m, 2H), 7.27-7.32 (m, 4H), 7.45-7.53 (m, 4H), 7.76 (br s, 2H), 7.80-7.83 (m, 2H), 7.91-7.94 (m, 4H).

The melting point of the resulting compound 37 was 164°C.

[0385] [Example A13]

<Synthesis of compound 38>

Compound 38 shown below was synthesized by the method given below.

[0386] [Chemical formula 145]

[0387] A 500 mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a thermometer, and a three-way valve was charged under nitrogen atmosphere with 150 mL of tBuOH, 50 mL of water, and 4.33 g (30.0 mmol, 1 equivalent) of 1,4-epoxy-1,4-dihydronaphthalene, and the reaction solution was cooled to 0 °C. 1.50 g (37.5 mmol, 1.25 equivalent) of NaOH and 7.11 g (45.0 mmol, 1.5 equivalent) of KMnO ₄ were dissolved in 150 mL of water and slowly added dropwise to the reaction solution. After the dropwise addition was complete, stirring was continued at 0°C for another hour, and then the unreacted _KMnO4 was quenched with a saturated aqueous solution of sodium metabisulfite. After stirring for some time at room temperature, sodium hydrogen carbonate was added until the pH of the reaction solution reached approximately 7-8, and the formed white precipitate was removed by filtration. The filtered solution was extracted with ethyl acetate 3 times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain 2.79 g (15.7 mmol, yield 53%) of compound 38. The ¹ H-NMR data of the obtained compound 38 are shown below.

[0388] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.71-2.77 (m, 2H), 3.93-3.98 (m, 2H), 5.17 (s, 2H), 7.19-7.24 (m, 2H), 7.27-7.31 (m, 2H).

<Synthesis of compound 39>

Compound 39 shown below was synthesized by the method given below.

[0389] [Chemical formula 146]

[0390] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way stopcock. Under a nitrogen atmosphere, 3.10 g (17.4 mmol, 1 equivalent) of compound 38 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 4.50 mL (38.3 mmol, 2.2 equivalents) of benzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 30 minutes. After adding approximately 20 mL of water and approximately 30 mL of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by recrystallization from acetone to give 3.92 g (10.1 mmol, yield 58%, colorless crystals) of compound 39. The ¹ H NMR data of the obtained compound 39 are shown below.

[0391] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 5.30 (s, 2H), 5.55 (s, 2H), 7.26-7.33 (overlaps with CHCl ₃ signal, m, 6H), 7.43-7.54 (m, 4H), 7.94-7.97 (m, 4H).

The melting point of the resulting compound 39 was 188°C.

[0392] [Example A14]

<Synthesis of compound 40>

Compound 40 shown below was synthesized by the method given below.

[0393] [Chemical formula 147]

[0394] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.13 g (12.1 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 3.42 mL (26.8 mmol, 2.2 equivalents) of o-toluoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 30 minutes. After adding approximately 20 mL of water and approximately 30 mL of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 5:1, then ethyl acetate only) to obtain 3.75 g (9.08 mmol, yield 75%, white solid) of compound 40. The ¹ H-NMR data of the obtained compound 40 are shown below.

[0395] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.13-2.17 (m, 1H), 2.49 (s, 6H), 2.54-2.59 (m, 1H), 3.55 (s, 2H), 5.15-5.16 (m, 2H), 7.02 (t, J=7.6 Hz, 2H), 7.15-7.20 (m, 4H), 7.30-7.36 (m, 4H), 7.77-7.80 (m, 2H).

The final melting point of the obtained compound 40 was 119°C.

[0396] [Example A15]

<Synthesis of compound 41>

Compound 41 shown below was synthesized by the method given below.

[0397] [Chemical formula 148]

[0398] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.15 g (12.2 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 3.54 mL (26.8 mmol, 2.2 equivalents) of m-toluoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 30 minutes. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified twice by silica gel column chromatography (eluent: hexane:ethyl acetate = 5:1) and recrystallization with ethanol to obtain 2.60 g (6.30 mmol, yield 52%, white solid) of compound 41. The ¹ H-NMR data of the obtained compound 41 are shown below.

[0399] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.13-2.21 (m, 7H), 2.59-2.63 (m, 1H), 3.57 (s, 2H), 5.15-5.16 (m, 2H), 7.17-7.24 (m, 4H), 7.29-7.36 (m, 4H), 7.68 (bride s, 2H), 7.76-7.79 (m, 2H).

The final melting point of the obtained compound 41 was 84°C.

[0400] [Example A16]

<Synthesis of compound 42>

Compound 42 shown below was synthesized by the method given below.

[0401] [Chemical formula 149]

[0402] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.23 g (12.6 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 4.20 mL (28.4 mmol, 2.3 equivalents) of 3,5-dimethylbenzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 1 hour. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The obtained crude product was purified twice by silica gel column chromatography (eluent: the first time: hexane:ethyl acetate = 10:1, the second time: hexane:ethyl acetate = 20:1) to obtain 5.13 g (11.6 mmol, yield 92%), white solid) of compound 42. ^{The 1} H-NMR data of the obtained compound 42 are shown below.

[0403] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.12-2.19 (m, 13H), 2.59-2.63 (m, 1H), 3.56 (s, 2H), 5.11-5.12 (m, 2H), 7.12 (br s, 2H), 7.17-7.20 (m, 2H), 7.32-7.35 (m, 2H), 7.53 (br s, 4H).

The final melting point of the obtained compound 42 was 118°C.

[0404] [Example A17]

<Synthesis of compound 43>

Compound 43 shown below was synthesized by the method given below.

[0405] [Chemical formula 150]

[0406] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was equipped with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.26 g (12.8 mmol, 1 equivalent) of compound 5 and about 10 mL of pyridine were added thereto. After cooling the reaction solution to 0 °C, 5.00 g (29.3 mmol, 2.3 equivalents) of 4-methoxybenzoyl chloride were slowly charged. After completion of the charging, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirred for 1 hour. After adding about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by washing with ethanol to yield 4.67 g (10.5 mmol, 82% yield, pale yellow solid) of compound 43. ^{The 1} H-HMP data of the resulting compound 43 are shown below.

[0407] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.11-2.16 (m, 1H), 2.56-2.61 (m, 1H), 3.54 (s, 2H), 3.83 (s, 6H), 5.12-5.13 (m, 2H), 6.75-6.80 (m, 4H), 7.16-7.19 (m, 2H), 7.31-7.34 (m, 2H), 7.84-7.89 (m, 4H).

The melting point of the resulting compound 43 was 167°C.

[0408] [Example A18]

<Synthesis of compound 44>

Compound 44 shown below was synthesized by the method given below.

[0409] [Chemical formula 151]

[0410] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.26 g (12.8 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 3.81 mL (27.9 mmol, 2.2 equivalents) of 3-methoxybenzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 1 hour. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) and recrystallized with a two-layer system of acetone-hexane to obtain 3.07 g (6.91 mmol, yield 54%, white solid) of compound 44. The ¹ H-NMR data of the obtained compound 44 are shown below.

[0411] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.13-2.18 (m, 1H), 2.57-2.61 (m, 1H), 3.56 (s, 2H), 3.66 (s, 6H), 5.16-5.17 (m, 2H), 7.01-7.06 (m, 2H), 7.17-7.23 (m, 4H), 7.32-7.35 (m, 2H), 7.41-7.42 (m, 2H), 7.52-7.56 (m, 2H).

The final melting point of the obtained compound 44 was 113°C.

[0412] [Example A19]

<Synthesis of compound 45>

Compound 45 shown below was synthesized by the method given below.

[0413] [Chemical formula 152]

[0414] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 1.78 g (10.1 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 3.30 mL (22.3 mmol, 2.2 equivalents) of 3-(trifluoromethyl)benzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 1 hour. After adding approximately 20 ml of water and approximately 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) and recrystallization from hexane to obtain 3.63 g (6.98 mmol, yield 70%, colorless crystals) of compound 45. The ¹ H-NMR data of the obtained compound 45 are shown below.

[0415] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.19-2.24 (m, 1H), 2.60-2.65 (m, 1H), 3.59 (br s, 2H), 5.22-5.23 (m, 2H), 7.19-7.24 (m, 2H), 7.34-7.37 (m, 2H), 7.46 (t, J=7.6 Hz, 2H), 7.73-7.77 (m, 2H), 8.09-8.12 (m, 4H).

The melting point of the resulting compound 45 was 124°C.

[0416] [Example A20]

<Synthesis of compound 46>

Compound 46 shown below was synthesized by the method given below.

[0417] [Chemical formula 153]

[0418] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.06 g (11.7 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 3.80 mL (25.3 mmol, 2.2 equivalents) of 1-naphthoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 1 hour. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) and washed with hexane to obtain 4.73 g (9.76 mmol, yield 85%, white solid) of compound 46. The ¹ H-NMR data of the obtained compound 46 are shown below.

[0419] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.19-2.24 (m, 1H), 2.65-2.69 (m, 1H), 3.67 (s, 2H), 5.34-5.35 (m, 2H), 7.06-7.12 (m, 2H), 7.21-7.24 (m, 2H), 7.33-7.46 (m, 6H), 7.76-7.80 (m, 2H), 7.86 (d, J=8.2, 2H), 8.01-8.05 (m, 2H), 8.79-8.82 (m, 2H).

The melting point of the resulting compound 46 was 158°C.

[0420] [Example A21]

<Synthesis of compound 47>

Compound 47 shown below was synthesized by the method given below.

[0421] [Chemical formula 154]

[0422] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.03 g (11.5 mmol, 1 equivalent) of compound 5 and about 10 mL of pyridine were added. After cooling the reaction solution to 0 °C, 4.80 g (25.2 mmol, 2.2 equivalents) of 2-naphthoyl chloride were slowly added. After complete addition, the temperature was raised to room temperature and stirring was continued overnight. After completion of the reaction, about 10 mL of dichloromethane was added and stirring was continued for another 3 hours. The solution was then cooled to 0 °C, 10 mL of methanol was added, and stirring was continued for an hour. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The obtained crude product was purified twice by silica gel column chromatography (eluent: the first time: hexane:ethyl acetate = 7:1, the second time: hexane:ethyl acetate = 5:1) and washed with hexane to obtain 2.05 g (4.23 mmol, yield 37%, white solid) of compound 47. ^{The 1} H-NMR data of the obtained compound 47 are shown below.

[0423] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.21-2.26 (m, 1H), 2.71-2.76 (m, 1H), 3.67 (br s, 2H), 5.26-5.27 (m, 2H), 7.20-7.23 (m, 2H), 7.30-7.40 (m, 6H), 7.48-7.54 (m, 2H), 7.71 (d, J=8.6 Hz, 2H), 7.77-7.80 (m, 2H), 7.96-8.00 (m, 2H), 8.39 (br s, 2H).

The final melting point of the obtained compound 47 was 201°C.

[0424] [Example A22]

<Synthesis of compound 48>

Compound 48 shown below was synthesized by the method given below.

[0425] [Chemical formula 155]

[0426] A 100 mL three-necked flask containing a magnetic stirrer that had been sufficiently dried by heating was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.15 g (12.2 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 4.00 mL (26.8 mmol, 2.2 equivalents) of 2-ethylbenzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 30 minutes. After adding approximately 20 ml of water and approximately 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 20:1) to obtain 4.34 g (9.85 mmol, yield 81%, white solid) of compound 48. The ¹ H-NMR data of the obtained compound 48 are shown below.

[0427] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.15 (t, J=7.3 Hz, 6H), 2.13-2.17 (m, 1H), 2.54-2.57 (m, 1H), 2.89 (q, J=7.3 Hz, 4H), 3.54 (br s, 2H), 5.16 (br s, 2H), 7.01 (t, J=7.6 Hz, 2H), 7.17-7.21 (m, 4H), 7.33-7.38 (m, 4H), 7.73 (d, J=8.2 Hz, 2H).

The final melting point of the obtained compound 48 was 52°C.

[0428] [Example A23]

<Synthesis of compound 49>

Compound 49 shown below was synthesized by the method given below.

[0429] [Chemical formula 156]

[0430] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.19 g (12.4 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 4.50 g (26.7 mmol, 2.2 equivalents) of 2,3-dimethylbenzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 1 hour. After adding about 20 ml of water and about 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 20:1) and recrystallized from hexane to obtain 4.62 g (10.5 mmol, yield 85%, white solid) of compound 49. The ¹ H-NMR data of the obtained compound 49 are shown below.

[0431] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.10-2.31 (m, 13H), 2.51-2.55 (m, 1H), 3.53-3.54 (m, 2H), 5.13-5.14 (m, 2H), 6.88-6.95 (m, 2H), 7.17-7.23 (m, 4H), 7.33-7.36 (m, 2H), 7.49-7.52 (m, 2H).

The melting point of the resulting compound 49 was 107°C.

[0432] [Example A24]

<Synthesis of compound 50>

Compound 50 shown below was synthesized by the method given below.

[0433] [Chemical formula 157]

[0434] 4.34 g (pale yellow solid) of compound 50 was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 6> except that 10 g of p-dimethylaminobenzoyl chloride was used instead of 13.4 ml of benzoyl chloride and the reaction was carried out at a reaction temperature after addition of reagents of 115°C for 7 days in <Synthesis of Compound 6>. The ¹ H-NMR data of the obtained compound 50 are shown below.

[0435] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.07-2.12 (m, 1H), 2.57-2.60 (m, 1H), 3.00 (s, 12H), 3.52 (br s, 2H), 5.10-5.11 (m, 2H), 6.52 (d, J=8.9 Hz, 4H), 7.14-7.17 (m, 2H), 7.30-7.33 (m, 2H), 7.81 (d, J=8.9 Hz, 4H).

The final melting point of the obtained compound 50 was 252°C.

[0436] [Example A25]

<Synthesis of compound 51>

Compound 51 shown below was synthesized by the method given below.

[0437] [Chemical formula 158]

[0438] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 2.80 g (15.9 mmol, 1 equivalent) of compound 5 and about 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 4.38 mL (32.3 mmol, 2 equivalents) of cyclohexanecarbonyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 20 mL of methanol was added, and stirring was carried out for 1 hour. After adding approximately 20 ml of water and approximately 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 20:1) to obtain 4.57 g (11.5 mmol, yield 72%, white solid) of compound 51. The ¹ H-NMR data of the obtained compound 51 are shown below.

[0439]

¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.19-1.53 (m, 10H), 1.62-1.83 (m, 6H), 1.89-2.01 (m, 5H), 2.26-2.35 (m, 3H), 3.31-3.32 (m, 2H), 4.75-4.76 (m, 2H), 7.10-7.13 (m, 2H), 7.23-7.27 (overlaps with the signal of CHCl ₃ , m, 2H).

The melting point of the obtained compound 51 was 80°C.

[0440] [Example A26]

<Synthesis of compound 52>

Compound 52 shown below was synthesized by the method given below.

[0441] [Chemical formula 159]

[0442] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 3.22 g (18.3 mmol, 1 equivalent) of compound 5 and approximately 10 mL of pyridine were added thereto, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 4.25 mL (40.3 mmol, 2.2 equivalents) of isobutyryl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. After completion of the reaction, the solution was cooled to 0 °C, 20 mL of methanol was added, and stirring was carried out for 40 minutes. After adding approximately 20 ml of water and approximately 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. After drying over sodium sulfate, the solution was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 15:1) to obtain 5.70 g (18.0 mmol, yield 98%, pale yellow liquid) of compound 52. The ¹ H-NMR data of the obtained compound 52 are shown below.

[0443] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.17-1.22 (m, 12H), 1.98-2.03 (m, 1H), 2.30-2.34 (m, 1H), 2.57 (opening, J=6.9 Hz, 2H), 3.32-3.33 (m, 2H), 4.77-4.78 (m, 2H), 7.11-7.16 (m, 2H), 7.23-7.27 (overlaps with CHCl ₃ signal, m, 2H).

[Example A27]

<Synthesis of compound 53>

Compound 53 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0444] [Chemical formula 160]

[0445] 14.8 g of tricyclo[6,2,1,0(2,7)]undec-4-ene, 500 ml of tert-butyl alcohol and 100 ml of water were added to a 1 L three-necked flask and the internal temperature was lowered to 0°C with stirring. 23.7 g of potassium permanganate, 400 ml of water and 4.8 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. The aqueous solution of potassium permanganate was added dropwise to the pre-prepared tricycloundecene solution so that the internal temperature did not exceed 5°C. After dropwise addition, stirring was continued at 0°C for 1 hour. Thereafter, a saturated aqueous solution of sodium thiosulfate was added dropwise until the red-violet color of the aqueous layer disappeared. The resulting precipitate was removed by filtration, and tert-butyl alcohol was distilled from the filtrate under reduced pressure. The filtrate was then extracted with ethyl acetate three times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. Compound 53 was allowed to react continuously without purification.

[0446] <Synthesis of Compound 54>

Compound 54 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0447] [Chemical formula 161]

[0448] Under a nitrogen atmosphere, 5.5 g of compound 53, 6.4 g of triethylamine and 100 ml of chloroform were added to a 300 ml 3-necked flask and cooled to 0°C in an ice bath with stirring. 8.9 g of benzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. After confirming the disappearance of the raw material by liquid chromatography, the solution was cooled again in an ice bath and 5 ml of methanol was added thereto. Chloroform and water were added to the reaction solution to fractionate the organic layer, and the aqueous layer was extracted with chloroform 3 times. The organic layer was washed with brine, dried over sodium sulfate and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 10/1) to obtain 3.7 g (yield: 31%, liquid) of compound 54. ^{The 1} H-NMR data of the obtained compound 54 are shown below.

[0449] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 7.97-7.91 (m, 4H), 7.55-7.47 (m, 2H), 7.39-7.33 (m, 4H), 5.49-5.47 (m, 2H), 2.19-1.14 (m, 14H).

[Example A28]

<Synthesis of compound 55>

Compound 55 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0450] [Chemical formula 162]

[0451] In a 300 mL three-necked flask, 3 g of compound 5, 5.2 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added under a nitrogen atmosphere and cooled to 0 °C with an ice bath while stirring. 7.9 g of 4-methylbenzoyl chloride was added so that the internal temperature did not exceed 5 °C. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. After confirming the disappearance of the raw material by liquid chromatography, the solution was cooled again in an ice bath and 5 mL of methanol was added thereto. Chloroform and water were added to the reaction solution to fractionate the organic layer, and the aqueous layer was extracted with chloroform 3 times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 10/1) to obtain 4.3 g (10.4 mmol, yield: 61%, white powder) of compound 55. The ¹ H-NMR data of the obtained compound 55 are shown below.

[0452] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 7.80 (d, J=8.4 Hz, 4H), 7.33 (dd, J=5.1 Hz, 3.2 Hz, 2H), 7.18 (dd, J=5.4 Hz, 3.0 Hz, 2H), 7.09 (d, J=8.4 Hz, 4H), 5.14 (d, J=1.6 Hz, 2H), 3.55 (s, 2H), 2.59 (d, J=9.5 Hz, 1H), 2.38 (s, 6H), 2.14 (d, J=9.7 Hz, 1H).

The melting point of the resulting compound 55 was 186°C.

[0453] [Example A29]

<Synthesis of compound 56>

Compound 56 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0454] [Chemical formula 163]

[0455] In a 300 mL three-necked flask, 3 g of compound 5, 5.2 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added under nitrogen atmosphere and cooled to 0 °C with an ice bath while stirring. 10.7 g of 4-trifluoromethylbenzoyl chloride was added so that the internal temperature did not exceed 5 °C. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. After confirming the disappearance of the raw material by liquid chromatography, the solution was cooled again in an ice bath and 5 mL of methanol was added thereto. Chloroform and water were added to the reaction solution to fractionate the organic layer, and the aqueous layer was extracted with chloroform 3 times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 10/1) to obtain 4.8 g (9.2 mmol, yield: 54%, white powder) of compound 56. The ¹ H-NMR data of the obtained compound 56 are shown below.

[0456] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 7.96 (d, J=8.4 Hz, 4H), 7.54 (d, J=8.4 Hz, 4H), 7.35 (dd, J=5.4 Hz, 3.0 Hz, 2H), 7.21 (dd, J=5.4 Hz, 3.0 Hz, 2H), 5.22 (d, J=1.4 Hz, 2H), 3.58 (s, 2H), 2.60 (d, J=10.0 Hz, 1H), 2.14 (d, J=10.3 Hz, 1H).

The melting point of the resulting compound 56 was 146°C.

[0457] [Example A30]

<Synthesis of compound 57>

Compound 57 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0458] [Chemical formula 164]

[0459] Under a nitrogen atmosphere, 3 g of compound 5, 5.17 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 ml of chloroform were added to a 300 ml three-necked flask and cooled to 0°C with an ice bath while stirring. 10.0 g of 4-butylbenzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. After confirming the disappearance of the raw material by liquid chromatography, the solution was cooled again in an ice bath and 5 ml of methanol was added thereto. Chloroform and water were added to the reaction solution to fractionate the organic layer, and the aqueous layer was extracted with chloroform 3 times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 10/1) to obtain 3.8 g (7.7 mmol, yield: 45%, white powder) of compound 57. The ¹ H-NMR data of the obtained compound 57 are shown below.

[0460] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 7.81 (d, J = 8.4 Hz, 4H), 7.33 (dd, J = 5.1 Hz, 3.2 Hz, 2H), 7.18 (dd, J = 5.4 Hz, 3.2 Hz, 2H), 7.07 (d, J = 8.4 Hz, 4H), 5.14 (d, J = 1.6 Hz, 2H), 3.55 (s, 2H), 2.65-2.57 (m, 5H), 2.14 (d, J = 1.6 Hz, 2H), d, J = 9.7 Hz, 1H), 1.64-1.53 (m, 4H), 1.41-1.27 (m, 4H), 0.93 (t, J=7.3 Hz, 6H).

The final melting point of the obtained compound 57 was 86°C.

[0461] [Example A31]

<Synthesis of compound 58>

Compound 58 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0462] [Chemical formula 165]

[0463] In a 300 mL three-necked flask, 3 g of compound 5, 5.2 g of triethylamine, 0.21 g of 4-dimethylaminopyridine (DMAP), and 100 mL of chloroform were added under nitrogen atmosphere and cooled to 0 °C with an ice bath while stirring. 9.3 g of 2,4,6-trimethylbenzoyl chloride was added so that the internal temperature did not exceed 5 °C. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. After confirming the disappearance of the raw material by liquid chromatography, the solution was cooled again in an ice bath and 5 mL of methanol was added thereto. Chloroform and water were added to the reaction solution to fractionate the organic layer, and the aqueous layer was extracted with chloroform 3 times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 10/1) to obtain 4.6 g (9.8 mmol, yield: 58%, white powder) of compound 58. The ¹ H-NMR data of the obtained compound 58 are shown below.

[0464] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 7.34 (dd, J=5.4 Hz, 3.2 Hz, 2H), 7.17 (dd, J=5.4 Hz, 3.0 Hz, 2H), 6.76 (s, 4H), 5.10 (d, J=1.6 Hz, 2H), 3.55 (s, 2H), 2.42 (d, J=9.5 Hz, 1H), 2.28-2.25 (m, 7H), 2.13 (s, 12H).

The melting point of the resulting compound 58 was 173°C.

[0465] [Example A32]

<Synthesis of compound 59>

Compound 59 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0466] [Chemical formula 166]

[0467] 15 ml of 30% hydrogen peroxide solution and 60 ml of 88% formic acid were added to a 300 ml three-necked flask and heated to 40°C in an oil bath with stirring. 14.8 g of tricyclo[6,2,1,0(2,7)]undec-4-ene were added dropwise to the reaction solution so that the internal temperature did not exceed 50°C. After the dropwise addition, stirring was continued at 40°C for one hour. After this, the reaction liquid was allowed to cool to room temperature and stirred for 17 hours. The reaction solution was concentrated under reduced pressure, 20 mL of a 2 mol/L aqueous sodium hydroxide solution and 50 mL of ethyl acetate were added at 50°C or lower, and stirring was carried out at 50°C for 1 h. The organic layer was fractionated, and the aqueous layer was extracted with ethyl acetate three times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. Compound 59 was allowed to react continuously without purification.

[0468] <Synthesis of Compound 60>

Compound 60 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0469] [Chemical formula 167]

[0470] Under a nitrogen atmosphere, 3.3 g of compound 59, 3.8 g of triethylamine, 0.22 g of 4-dimethylaminopyridine (DMAP), and 100 ml of chloroform were added to a 300 ml three-necked flask and cooled to 0°C with an ice bath while stirring. 5.3 g of benzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. After confirming the disappearance of the raw material by liquid chromatography, the solution was again cooled in an ice bath and 5 ml of methanol was added thereto. Chloroform and water were added to the reaction solution to fractionate the organic layer, and the aqueous layer was extracted with chloroform 3 times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 10/1) to obtain 5.3 g (13.6 mmol, yield: 74%, white powder) of compound 60. ^{The 1} H-NMR data of the obtained compound 60 are shown below.

[0471] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 8.06-8.01 (m, 4H), 7.55-7.39 (m, 6H), 5.50-5.45 (m, 1H), 5.21-5.13 (m, 1H), 2.06-1.09 (m, 14H).

The melting point of the resulting compound 60 was 125°C.

[0472] [Example A33]

<Synthesis of compound 61>

Compound 61 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0473] [Chemical formula 168]

[0474] 15 ml of 30% hydrogen peroxide solution and 60 ml of 88% formic acid were added to a 300 ml three-necked flask and heated to 40°C in an oil bath with stirring. 14.2 g of 1,4-dihydro-1,4-methanonaphthalene were added dropwise to the reaction solution so that the internal temperature did not exceed 50°C. After the dropwise addition, stirring was continued at 40°C for an hour. Thereafter, the reaction liquid was allowed to cool to room temperature and stirred for 17 hours. The reaction solution was concentrated under reduced pressure, 20 ml of a 2 mol/L aqueous sodium hydroxide solution and 50 ml of ethyl acetate were added thereto at 50°C or less, and stirring was carried out at 50°C for an hour. The organic layer was fractionated, and the aqueous layer was extracted with ethyl acetate three times. The organic layer was washed with brine, dried over sodium sulfate, and then concentrated on a rotary evaporator. Compound 61 was allowed to react continuously without purification.

[0475] <Synthesis of Compound 62>

Compound 62 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0476] [Chemical formula 169]

[0477] Under a nitrogen atmosphere, 8.8 g of compound 61, 10.63 g of triethylamine and 100 ml of chloroform were added to a 300 ml 3-necked flask and cooled to 0°C in an ice bath with stirring. 14.8 g of benzoyl chloride was added so that the internal temperature did not exceed 5°C. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. After confirming the disappearance of the raw material by liquid chromatography, the solution was cooled again in an ice bath and 5 ml of methanol was added thereto. Chloroform and water were added to the reaction solution to fractionate the organic layer, and the aqueous layer was extracted with chloroform 3 times. The organic layer was washed with brine, dried over sodium sulfate and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 10/1) to obtain 4.1 g (10.7 mmol, yield: 21%, white powder) of compound 62. ^{The 1} H-NMR data of the obtained compound 62 are shown below.

[0478] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 8.09-8.05 (m, 2H), 7.83-7.79 (m, 2H), 7.57-7.15 (m, 10H), 5.09-5.02 (m, 2H), 3.94 (s, 1H), 3.65-3.63 (m, 1H), 2.45-2.38 (m, 1H), 2.27-2.19 (m, 1H).

The melting point of the resulting compound 62 was 192°C.

[0479] [Example A34]

<Synthesis of compound 63>

Compound 63 shown below was synthesized by the method given below.

[0480] [Chemical formula 170]

[0481] Under a nitrogen atmosphere, 35.2 g (149 mmol) of 1,2-dibromobenzene, 300 ml of dehydrated toluene, and 12.0 g of 1,3-cyclohexadiene were added to a 500 ml three-necked flask and stirred. The internal temperature was lowered to 0°C, and 83 ml of a solution of n-butyl lithium in hexane (1.6 M) was slowly added dropwise. After the dropwise addition, the temperature was gradually raised to room temperature, and stirring was carried out at room temperature for 12 hours. After the reaction, a saturated aqueous solution of ammonium chloride was added, and then diethyl ether was added. The organic layer was separated and washed with water and brine in that order. After drying the organic layer over magnesium sulfate, magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator to yield 15.42 g of crude product. The crude product was purified by silica gel column chromatography to yield 4.9 g of compound 63 as a mixture with impurities.

[0482] <Synthesis of Compound 64>

Compound 64 shown below was synthesized by the method given below.

[0483] [Chemical formula 171]

[0484] 4.9 g of compound 63 with impurities obtained in the <synthesis of compound 63>, 125 ml of tert-butyl alcohol and 31 ml of water were added to a 1000 ml three-necked flask and the internal temperature was lowered to 0°C with stirring. 7.35 g of potassium permanganate, 150 ml of water and 1.70 g of sodium hydroxide were added to another flask and stirred to obtain an aqueous solution of potassium permanganate. An aqueous solution of potassium permanganate containing the previously prepared compound 63 was slowly added dropwise so that the internal temperature did not exceed 5°C. After the dropwise addition, stirring was continued at 0°C for one hour. A saturated aqueous solution of sodium metabisulfite was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed. The resulting precipitate was removed by filtration, and the filtrate was extracted with ethyl acetate four times. The organic layer was washed with brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the resulting organic layer was concentrated on a rotary evaporator. The crude product was purified by column chromatography on silica gel to yield 0.72 g of compound 64 as a mixture of isomers.

[0485] <Synthesis of compounds 65-1 and 65-2>

Compounds 65-1 and 65-2 shown below were synthesized by the method mentioned below.

[0486] [Chemical formula 172]

[0487] Under nitrogen atmosphere, 0.65 g (3.3 mmol) of compound 64 and 10.0 ml of dehydrated pyridine were added to a 50 ml three-necked flask and stirred. While cooling in an ice bath, 0.82 ml of benzoyl chloride was slowly added thereto. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 5 ml of methanol was added. 100 ml of water and 100 ml of ethyl acetate were added to a beaker to separate the organic layer. The organic layer was washed with water 3 times, washed with a saturated aqueous solution of ammonium chloride and brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography to afford 0.41 g (white solid) of compound 65-1 and 0.53 g (white solid) of compound 65-2. The stereostructures of compounds 65-1 and 65-2 were determined by NOESY. The ¹ H-NMR data of compound 65-1 and compound 65-2 are shown below.

[0488] (Compound 65-1)

¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.40-1.50 (m, 2H), 2.36-2.45 (m, 2H), 3.45 (s, 2H), 5.19 (s, 2H), 7.25-7.32 (m, 8H), 7.44-7.53 (m, 2H), 7.90-7.96 (m, 4H).

(Compound 65-2)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.52-1.62 (m, 2H), 1.92-2.00 (m, 2H), 3.41 (s, 2H), 5.55-5.57 (m, 2H), 7.08-7.16 (m, 4H), 7.22-7.38 (m, 6H), 7.52-7.57 (m, 4H).

The temperature of completion of melting of the obtained compound 65-1 was 143°C. The temperature of completion of melting of the obtained compound 65-2 was 193°C.

[0489] [Example A35]

<Synthesis of compound 66>

Compound 66 shown below was synthesized by the method given below.

[0490] [Chemical formula 173]

[0491] Under a nitrogen atmosphere, 3.8 g of anthracene, 2.9 g of vinylene carbonate, and 15 ml of toluene were added to a 30 ml pressure-resistant vessel and stirred with heating until the internal temperature reached 180°C, and stirring was continued for 45 hours. After cooling to room temperature, the solution was concentrated, and the solid was filtered off. The resulting solid was washed with hexane and then dried to obtain 3.85 g of compound 66. The ¹ H-NMR data of the obtained compound 66 are shown below.

[0492] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.40-7.37 (m, 4H), 7.27-7.22 (m, 4H), 4.88 (m, 2H), 4.70 (m, 2H).

<Synthesis of compound 67>

Compound 67 shown below was synthesized by the method given below.

[0493] [Chemical formula 174]

[0494] 3.8 g of compound 66, 7.2 ml of a 4 mol/L aqueous sodium hydroxide solution, and 28 ml of methanol were added to a 100 ml three-necked flask. After addition, stirring was carried out at room temperature for 30 minutes. After distilling off methanol, 20 ml of water was added, extracted with 30 ml of chloroform, and the organic layer was dried over sodium sulfate. Chloroform was distilled off and dried, yielding 2.88 g of compound 67. The ¹ H-NMR data of the obtained compound 67 are shown below.

[0495] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.39-7.30 (m, 4H), 7.23-7.14 (m, 4H), 4.42 (s, 2H), 4.06 (s, 2H), 2.10 (s, 2H).

<Synthesis of compound 68>

Compound 68 shown below was synthesized by the method given below.

[0496] [Chemical formula 175]

[0497] Under a nitrogen atmosphere, 2.9 g of compound 67, 3.51 ml of triethylamine and 12 ml of chloroform were added and stirred at room temperature for 10 minutes. 2.92 ml of benzoyl chloride was added at room temperature, stirring was carried out with heating so that the internal temperature reached 85°C, and stirring was continued for 12 hours. After cooling in an ice bath, 5 ml of saturated sodium hydrogen carbonate solution was added and extraction was performed with 10 ml of chloroform. The organic layer was dried over magnesium sulfate and then concentrated. The resulting solid was filtered, washed with hexane and then dried to obtain 5.0 g (11.2 mmol, yield: 92%, white powder) of compound 68. The ¹ H-NMR data of the obtained compound 68 are shown below.

[0498] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.59-7.56 (m, 4H), 7.44-7.36 (m, 6H), 7.26-7.21 (m, 4H), 7.18-7.12 (m, 4H), 5.52 (s, 2H), 4.68 (s, 2H).

The melting point of the resulting compound 68 was 174°C.

[0499] [Example A36]

<Synthesis of compound 69>

Compound 69 shown below was synthesized by the method given below.

[0500] [Chemical formula 176]

[0501] Under a nitrogen atmosphere, 3.8 g of 9-methylanthracene and 5.2 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating so that the internal temperature reached 220°C, and stirring was continued for 9 hours. After cooling to room temperature, 5 ml of methanol were added and stirred, and then the solid was filtered off. The resulting solid was washed with methanol and then dried to obtain 5.6 g of compound 69.

[0502] <Synthesis of Compound 70>

Compound 70 shown below was synthesized by the method given below.

[0503] [Chemical formula 177]

[0504] 5.6 g of compound 69, 8.0 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-necked flask and stirred with heating until the internal temperature reached 100°C and continued stirring for 6 hours. After cooling to room temperature, concentrated hydrochloric acid with a concentration of 12 mol/L at 50°C or less was added for neutralization. The solid was filtered, washed with pure water and then dried to obtain 5.0 g of compound 70.

[0505] <Synthesis of Compound 71>

Compound 71 shown below was synthesized by the method given below.

[0506] [Chemical formula 178]

[0507] Under a nitrogen atmosphere, 5.0 g of compound 70, 8.4 g of benzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L sodium hydroxide aqueous solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane and then dried to obtain 6.4 g (14.0 mmol, yield: 70%, white powder) of compound 71. The ¹ H-NMR data of the obtained compound 71 are shown below.

[0508] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.64-7.61 (m, 2H), 7.49-7.17 (m, 14H), 7.08-7.02 (m, 2H), 5.57 (dd, J=7.8 Hz, 3.0 Hz, 1H), 5.29 (d, J=7.6 Hz, 1H), 4.68 (d, J=3.0 Hz, 1H), 2.02 (s, 3H).

The melting point of the resulting compound 71 was 173°C.

[0509] [Example A37]

<Synthesis of compound 72>

Compound 72 shown below was synthesized by the method given below.

[0510] [Chemical formula 179]

[0511] Under a nitrogen atmosphere, 4.0 g of 9,10-dimethylanthracene and 5.0 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating until the internal temperature reached 220°C, and stirring was continued for 9 hours. After cooling to room temperature, 5 ml of methanol were added and stirred, and then the solid was filtered off. The resulting solid was washed with methanol and then dried to obtain 5.6 g of compound 72.

[0512] <Synthesis of Compound 73>

Compound 73 shown below was synthesized by the method given below.

[0513] [Chemical formula 180]

[0514] 5.6 g of compound 72, 7.6 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-necked flask and stirred with heating until the internal temperature reached 100°C and continued stirring for 6 hours. After cooling to room temperature, concentrated hydrochloric acid with a concentration of 12 mol/L at 50°C or less was added for neutralization. The solid was filtered, washed with pure water and then dried to obtain 5.0 g of compound 73.

[0515] <Synthesis of Compound 74>

Compound 74 shown below was synthesized by the method given below.

[0516] [Chemical formula 181]

[0517] Under a nitrogen atmosphere, 5.0 g of compound 73, 8.0 g of benzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L sodium hydroxide aqueous solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane and dried to obtain 5.2 g (11.0 mmol, yield 58%, white powder) of compound 74. The ¹ H-NMR data of the obtained compound 74 are shown below.

[0518] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.52-7.49 (m, 4H), 7.46-7.42 (m, 4H), 7.35-7.27 (m, 6H), 7.12-7.06 (m, 4H), 5.40 (s, 2H), 2.00 (s, 6H).

The final melting point of the obtained compound 74 was 218°C.

[0519] [Example A38]

<Synthesis of compound 75>

Compound 75 shown below was synthesized by the method given below.

[0520] [Chemical formula 182]

[0521] Under a nitrogen atmosphere, 8.0 g of 9,10-diethoxyanthracene and 7.7 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating so that the internal temperature reached 220°C, and stirring was continued for 9 hours. After cooling to room temperature, 5 ml of methanol were added and stirred, and then the solid was filtered off. The resulting solid was washed with methanol and then dried to obtain 10.5 g of compound 75.

[0522] <Synthesis of Compound 76>

Compound 76 shown below was synthesized by the method given below.

[0523] [Chemical formula 183]

[0524] 10.5 g of compound 75, 12.0 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-necked flask and stirred with heating until the internal temperature reached 100°C, and stirring was continued for 6 hours. After cooling to room temperature, concentrated hydrochloric acid with a concentration of 12 mol/L at a temperature of 50°C or less was added for neutralization. The solid was filtered, washed with pure water and then dried to obtain 9.8 g of compound 76.

[0525] <Synthesis of Compound 77>

Compound 77 shown below was synthesized by the method given below.

[0526] [Chemical formula 184]

[0527] Under a nitrogen atmosphere, 9.8 g of compound 76, 12.6 g of benzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane and dried to obtain 9.4 g (17.6 mmol, yield: 59%, white powder) of compound 77. The ¹ H-NMR data of the obtained compound 77 are shown below.

[0528] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.76-7.73 (m, 2H), 7.51-7.46 (m, 6H), 7.39-7.26 (m, 6H), 7.10-7.04 (m, 4H), 5.98 (s, 2H), 4.20 (dkv, J=8.4 Hz, 7.0 Hz, 2H), 3.93 (dkv, J=8.4 Hz, 7.0 Hz, 2H), 1.46 (t, J=7.0 Hz, 6H).

The melting point of the resulting compound 77 was 175°C.

[052 9] [Example A39]

<Synthesis of compound 78>

Compound 78 shown below was synthesized by the method given below.

[0530] [Chemical formula 185]

[0531] Under a nitrogen atmosphere, 7.0 g of 9,10-diethylanthracene and 7.7 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating until the internal temperature reached 220°C, and stirring was continued for 9 hours. After cooling to room temperature, 5 ml of methanol were added and stirred, and then the solid was filtered off. The resulting solid was washed with methanol and then dried to obtain 9.6 g of compound 78.

[0532] <Synthesis of Compound 79>

Compound 79 shown below was synthesized by the method given below.

[0533] [Chemical formula 186]

[0534] 9.6 g of compound 78, 12.0 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-necked flask, and stirring was continued for 6 hours so that the internal temperature reached 100°C. After cooling to room temperature, concentrated hydrochloric acid with a concentration of 12 mol/L was added at 50°C or below for neutralization. The solid was filtered, washed with pure water and then dried to obtain 3.2 g of compound 79.

[0535] <Synthesis of Compound 80>

Compound 80 shown below was synthesized by the method given below.

[0536] [Chemical formula 187]

[0537] Under a nitrogen atmosphere, 3.2 g of compound 79, 4.6 g of benzoyl chloride and 50 ml of pyridine were added to a 200 ml three-necked flask and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L sodium hydroxide aqueous solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane and then dried to obtain 2.1 g (4.2 mmol, yield: 38%, white powder) of compound 80. The ¹ H-NMR data of the obtained compound 80 are shown below.

[0538] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.47-7.44 (m, 8H), 7.33-7.22 (m, 6H), 7.09-7.03 (m, 4H), 5.65 (s, 2H), 2.58 (k, J=7.3 Hz, 4H), 1.37 (t, J=7.3 Hz, 6H).

The final melting point of the obtained compound 80 was 184°C.

[053 9] [Example A40]

<Synthesis of compound 81>

Compound 81 shown below was synthesized by the method given below.

[0540] [Chemical formula 188]

[0541] Under a nitrogen atmosphere, 8.7 g of 9,10-di-n-butylanthracene and 7.7 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating so that the internal temperature reached 220°C, and stirring was continued for 9 hours. After cooling to room temperature, 5 ml of methanol were added and stirred, and then the solid was filtered off. The resulting solid was washed with methanol and then dried to obtain 11.3 g of compound 81.

[0542] <Synthesis of Compound 82>

Compound 82 shown below was synthesized by the method given below.

[0543] [Chemical formula 189]

[0544] 11.3 g of compound 81, 12.0 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-necked flask and stirred with heating until the internal temperature reached 100°C and continued stirring for 6 hours. After cooling to room temperature, concentrated hydrochloric acid with a concentration of 12 mol/L at 50°C or less was added for neutralization. The solid was filtered, washed with pure water and then dried to obtain 4.1 g of compound 82.

[0545] <Synthesis of Compound 83>

Compound 83 shown below was synthesized by the method given below.

[054 6] [Chemical formula 190]

[0547] Under a nitrogen atmosphere, 4.1 g of compound 82, 4.9 g of benzoyl chloride, and 50 ml of pyridine were added to a 200 ml 3-necked flask, and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L sodium hydroxide aqueous solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane, and then dried to obtain 5.4 g (9.7 mmol, yield: 83%, white powder) of compound 83. The ¹ H-NMR data of the obtained compound 83 are shown below.

[0548] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.48-7.21 (m, 14H), 7.08-7.02 (m, 4H), 5.62 (s, 2H), 2.55-2.35 (m, 4H), 1.98-1.47 (m, 8H), 0.99 (t, J=7.3 Hz, 6H).

The melting point of the resulting compound 83 was 176°C.

[0549] [Example A41]

<Synthesis of compound 84>

Compound 84 shown below was synthesized by the method given below.

[0550] [Chemical formula 191]

[0551] Under a nitrogen atmosphere, 7.2 g of 9,10-dimethoxyanthracene and 7.7 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating until the internal temperature reached 220°C, and stirring was continued for 9 hours. After cooling to room temperature, 5 ml of methanol were added and stirred, and then the solid was filtered off. The resulting solid was washed with methanol and then dried to obtain 9.7 g of compound 84.

[0552] <Synthesis of Compound 85>

Compound 85 shown below was synthesized by the method given below.

[0553] [Chemical formula 192]

[0554] 9.7 g of compound 84, 12.0 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-necked flask and stirred with heating until the internal temperature reached 100°C and continued stirring for 6 hours. After cooling to room temperature, concentrated hydrochloric acid with a concentration of 12 mol/L at 50°C or less was added for neutralization. The solid was filtered, washed with pure water and then dried to obtain 6.4 g of compound 85.

[0555] <Synthesis of Compound 86>

Compound 86 shown below was synthesized by the method given below.

[0556] [Chemical formula 193]

[0557] Under a nitrogen atmosphere, 6.4 g of compound 85, 9.1 g of benzoyl chloride, and 50 ml of pyridine were added to a 200 ml 3-necked flask, and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L sodium hydroxide aqueous solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane, and then dried to obtain 7.4 g (14.6 mmol, yield: 68%, white powder) of compound 86. The ¹ H-NMR data of the obtained compound 86 are shown below.

[0558] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.71-7.56 (m, 4H), 7.51-7.05 (m, 14H), 5.98 (s, 2H), 3.87 (s, 6H).

The final melting point of the obtained compound 86 was 227°C.

[0559] [Example A42]

<Synthesis of compound 87>

Compound 87 shown below was synthesized by the method mentioned below.

[0560] [Chemical formula 194]

[0561] Under a nitrogen atmosphere, 4.1 g of compound 85, 6.4 g of 4-methylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask and stirred with heating until the internal temperature reached 60°C and stirring was continued for 6 hours. After the pyridine was distilled off, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L sodium hydroxide aqueous solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane and then dried to obtain 1.3 g (2.4 mmol, yield: 18%, white powder) of compound 87. The ¹ H-NMR data of the obtained compound 87 are shown below.

[0562] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.70-7.53 (m, 4H), 7.39-7.26 (m, 8H), 6.90-6.87 (m, 4H), 5.95 (s, 2H), 3.85 (s, 6H), 2.24 (s, 6H).

The melting point of the resulting compound 87 was 220°C.

[0563] [Example A43]

<Synthesis of compound 88>

Compound 88 shown below was synthesized by the method given below.

[0564] [Chemical formula 195]

[0565] Under a nitrogen atmosphere, 4.1 g of compound 85, 8.1 g of 4-n-butylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After pyridine was distilled off, chloroform was added thereto. After washing with 2 mol/L hydrochloric acid and 2 mol/L sodium hydroxide aqueous solution, the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered, washed with hexane and then dried to obtain 1.9 g (3.1 mmol, yield: 22%, white powder) of compound 88. The ¹ H-NMR data of the obtained compound 88 are shown below.

[0566] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.70-7.55 (m, 4H), 7.39-7.25 (m, 8H), 6.89-6.86 (m, 4H), 5.95 (s, 2H), 3.86 (s, 6H), 2.51-2.45 (m, 4H), 1.56 -1.19 (m, 8H), 0.88 (t, J=7.0 Hz, 6H).

The final melting point of the obtained compound 88 was 158°C.

[0567] [Example A44]

<Synthesis of compound 89>

Compound 89 shown below was synthesized by the method given below.

[0568] [Chemical formula 196]

[0569] Under a nitrogen atmosphere, 15 g (50.3 mmol) of compound 85 and 117 ml of dehydrated pyridine were added to a 200 ml three-necked flask and cooled in an ice bath. 18.0 g (105.5 mmol) of 4-methoxybenzoyl chloride were added dropwise over about 5 minutes, and stirred while heating in an oil bath heated to 100°C for 20 hours. After completion of the reaction, followed by cooling, 10 ml of anhydrous methanol were added thereto, and quenching was performed at room temperature. After stirring at room temperature for about 30 minutes, the reaction solution was added dropwise to 600 ml of a mixed solution of hexane and water (hexane:water=5:1) to obtain fine crystals. After the resulting crystals were collected by filtration, the product collected by filtration was washed with hexane and then dissolved in 100 ml of dichloromethane. The solution was washed twice with 100 ml of 1 N hydrochloric acid and once with 100 ml of a saturated aqueous solution of sodium hydrogen carbonate and 100 ml of brine, in that order. The resulting organic layer was then dried over magnesium sulfate. After removing magnesium sulfate by filtration and then concentrating on an evaporator, the resulting solid was redissolved in 30 ml of chloroform, and the solution was added dropwise to 150 ml of methanol to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: dichloromethane:methanol = gradient from 100:0 to 97:3) to obtain 20.17 g (yield 71%, white solid) of compound 89. The ¹ H-NMR data of the obtained compound 8 9 are shown below.

[0570] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.70-7.67 (m, 2H), 7.58-7.55 (m, 2H), 7.46-7.43 (m, 4H), 7.37-7.33 (m, 2H), 7.31-7.28 (m, 2H), 6.59-6.56 (m, 4H), 5.94 (s, 2H), 3.86 (s, 6H), 3.73 (s, 6H).

The final melting point of the obtained compound 89 was 221°C.

[0571] [Example A45]

<Synthesis of compound 90>

Compound 90 shown below was synthesized by the method given below.

[0572] [Chemical formula 197]

[0573] Under a nitrogen atmosphere, 5.0 g (16.8 mmol) of compound 85 and 13 ml of dehydrated pyridine were added to a 100 ml three-necked flask and stirred at room temperature. After dropwise addition of 7.0 g (35.6 mmol) of 4-tert-butylbenzoyl chloride, stirring was carried out at 100°C in an oil bath for 24 hours. After completion of the reaction, 26 ml of methanol was added and the precipitated solid was collected by filtration. The resulting solid was washed with 13 ml of 2 N hydrochloric acid, then suspended in 20 ml of methanol and stirred at 60°C for about an hour. After cooling, the white solid was collected by filtration to obtain 10.2 g (98% yield, white solid) of compound 90. The ¹ H-NMR data of the obtained compound 90 are shown below.

[0574] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): 7.71-7.67 (m, 2H), 7.58-7.55 (m, 2H), 7.46-7.28 (m, 8H), 7.12-7.09 (4H), 5.96 (s, 2H), 3.86 (s, 6H), 1.19 (s, 18H).

The final melting point of the obtained compound 90 was 178°C.

[0575] [Example A46]

<Synthesis of compound 91>

Compound 91 shown below was synthesized by the method given below.

[0576] [Chemical formula 198]

[0577] A 300 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, fitted with a flat stopper, a thermometer, and a three-way valve. Under a nitrogen atmosphere, 3.08 g (18.8 mmol) of 3-isopropylbenzoic acid, 60 mL of dichloromethane, and 2 drops of DMF were added thereto. After cooling the reaction solution to 0 °C, 2.57 mL (30 mmol) of oxalyl chloride were slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and stirring was carried out at room temperature for 3 hours. The volatile compound from the reaction system was removed under reduced pressure to obtain compound 91. The compound was used in the <synthesis of compound 92> without further purification.

[0578] <Synthesis of Compound 92>

Compound 92 shown below was synthesized by the method given below.

[0579] [Chemical formula 199]

[0580] A 100 ml three-necked flask containing a magnetic stirrer, sufficiently dried by heating, fitted with a flat stopper, a thermometer and a three-way valve. Under a nitrogen atmosphere, 1.6 g of compound 5 and 10 ml of dehydrated pyridine were added thereto. After cooling the reaction solution to 0°C, 20 ml of a dichloromethane solution of compound 91, synthesized in <the synthesis of compound 91>, were slowly added to the pyridine solution of compound 5 and stirred overnight. After completion of the reaction, the solution was cooled to 0°C, 20 ml of methanol was added and stirred for 1 hour. After adding 20 ml of water and 30 ml of dichloromethane, the solution was extracted three times with dichloromethane and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. The organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) and recrystallization using hexane to obtain 1.54 g (yield 34%, white solid) of compound 92. ^{The 1} H-NMR data of the obtained compound 92 are shown below.

[0581] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.12 (d, J=6.9 Hz, 12H), 2.13-2.17 (m, 1H), 2.59-2.63 (m, 1H), 2.73 (segment, J=6.9 Hz, 2H), 3.57 (s, 2H), 5.16 (s, 2H), 7.13-7.26 (overlaps with CHCl ₃ signal, m, 4H), 7.33-7.36 (m, 4H), 7.76-7.79 (m, 4H).

The melting point of the obtained compound 92 was 93°C.

[0582] [Example A47]

<Synthesis of compound 93>

Compound 93 shown below was synthesized by the method given below.

[0583] [Chemical formula 200]

[0584] Compound 93 was synthesized according to the operation and equivalence ratio described in <Synthesis of Compound 91> except that 4.21 g (28.0 mmol) of 3,4-dimethylbenzoic acid was used instead of 3-isopropylbenzoic acid from <Synthesis of Compound 91>. The resulting compound 93 was used as in <Synthesis of Compound 94>.

[0585] <Synthesis of Compound 94>

Compound 94 shown below was synthesized by the method given below.

[0586] [Chemical formula 201]

[0587] A 100 ml three-necked flask containing a magnetic stirrer, sufficiently dried by heating, fitted with a flat stopper, a thermometer and a three-way valve. Under a nitrogen atmosphere, 2.13 g (12.1 mmol) of compound 5 and 10 ml of dehydrated pyridine were added thereto. After cooling the reaction solution to 0°C, 20 ml of a dichloromethane solution of compound 93, synthesized in <synthesis of compound 93>, were slowly added to the pyridine solution of compound 5 and stirred overnight. After completion of the reaction, the solution was cooled to 0°C, 20 ml of methanol was added and stirred for 1 hour. After adding 20 ml of water and 30 ml of dichloromethane, the solution was extracted three times with dichloromethane and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. The organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) to obtain 2.64 g (6.0 mmol, yield 50%, pale yellow solid) of compound 94. ^{The 1} H-NMR data of the obtained compound 94 are shown below.

[0588] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 2.07 (s, 6H), 2.11-2.17 (m, 1H), 2.27 (s, 6H), 2.58-2.62 (m, 1H), 3.56 (s, 2H), 5.12-5.13 (m, 2H), 7.09 (d, J=7.9 Hz, 2H), 7.16-7.19 (m, 2H), 7.32-7.35 (m, 2H), 7.62 (br s, 2H), 7.70-7.72 (m, 2H).

The final melting point of the obtained compound 94 was 158°C.

[0589] [Example A48]

<Synthesis of compound 95>

Compound 95 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0590] [Chemical formula 202]

[0591] Under a nitrogen atmosphere, 200 ml of anhydrous acetonitrile, 6.36 g of 1-phenylpyrrole and 6.74 g of cesium fluoride were added to a 1 L three-necked flask and stirred at room temperature. Then, 4.3 g of 2-(trimethylsilyl)phenyl triflate were slowly added thereto, and then the reaction solution was stirred under heating at 40°C for 16 hours. The reaction solution was passed through a short silica gel column (eluent: ethyl acetate) and concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=5:1) to obtain 2.31 g (10.5 mmol, yield 71%) of compound 95.

[0592] <Synthesis of compound 9b>

Compound 96 shown below was synthesized by the method given below.

[0593] [Chemical formula 203]

[0594] A 500 mL three-necked flask equipped with a magnetic stirrer was fitted with a dropping funnel, a thermometer, and a three-way valve. 60 mL of a mixed solution of tert-butyl alcohol and acetone, 20 mL of water, and 2.51 g (11.4 mmol) of compound 95 were added thereto under a nitrogen atmosphere, and the reaction solution was cooled to 0 °C. 0.57 g (14.3 mmol) of sodium hydroxide and 2.70 g (17.1 mmol) of potassium permanganate were dissolved in 60 mL of water, and this solution was slowly added dropwise to the previously prepared reaction solution. After complete dropwise addition, stirring was continued at 0 °C for another hour, and then unreacted potassium permanganate was quenched using a saturated aqueous solution of sodium metabisulfite. After stirring for some time at room temperature, sodium hydrogen carbonate was added until the pH of the reaction solution reached approximately 7-8, and the resulting white precipitate was removed by filtration.

The filtered solution was extracted with ethyl acetate three times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 1:1) to yield 2.04 g (8.1 mmol, yield 71%) of compound 96.

[0595] <Synthesis of Compound 97>

Compound 97 shown below was synthesized by the method given below.

[0596] [Chemical formula 204]

[0597] A 100 mL three-necked flask containing a magnetic stirrer, sufficiently dried by heating, was fitted with a flat stopper, a thermometer, and a three-way valve. 2.18 g (8.6 mmol) of compound 96 and 10 mL of dehydrated pyridine were added thereto under a nitrogen atmosphere, and the flat stopper was replaced with a dropping funnel. After cooling the reaction solution to 0 °C, 2.20 mL (18.9 mmol) of benzoyl chloride were slowly added dropwise. After complete dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. Upon completion of the reaction, the solution was cooled to 0 °C, 10 mL of methanol was added, and stirring was carried out for 30 minutes. After adding 20 ml of water and 30 ml of dichloromethane, the solution was extracted three times with dichloromethane, and the collected organic layer was washed twice with a saturated aqueous solution of ammonium chloride. The organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 10:1) to obtain 1.80 g (3.9 mmol, yield 45%, white solid) of compound 97. The ¹ H-NMR data of the obtained compound 97 are shown below.

[0598] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ5.27-5.29 (m, 4H), 6.77-6.82 (m, 1H), 6.89-6.92 (m, 2H), 7.11-7.17 (m, 2H), 7.20-7.30 (overlap with CHCl ₃ signal, m, 6H), 7.41-7.51 (m, 4H), 7.90-7.94 (m, 4H).

The final melting point of the obtained compound 97 was 158°C.

[0599] [Example A49]

<Synthesis of compound 98>

Compound 98 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0600] [Chemical formula 205]

[0601] Under a nitrogen atmosphere, 14.0 g of p-benzoquinone (0.130 mol) and 17.6 g of α-terpinene (0.129 mol) were added to a 2 L three-necked flask, then 700 ml of water were added and stirring was carried out at room temperature. 420 ml of acetone was slowly added dropwise and stirring was continued at room temperature overnight. After adding 700 ml of ethyl acetate and stirring, the organic layer and aqueous layer were separated. The organic layer was washed with brine and then dried over magnesium sulfate. Concentration was carried out on a rotary evaporator to obtain the crude product. The obtained crude product was combined with the obtained crude product using 5.0 g of p-benzoquinone according to the same operation and equivalence ratio (total 41.87 g), and the combined crude products were purified by silica gel column chromatography to obtain 30.0 g of compound 98.

[0602] <Synthesis of Compound 99>

Compound 99 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0603] [Chemical formula 206]

[0604] Under nitrogen atmosphere, 28.0 g (0.115 mol) of compound 98 was added to a 500 ml three-necked flask, followed by the addition of 1078 ml of anhydrous methanol and stirred for some time at room temperature. After adding 92.9 g (0.249 mol) of cerium chloride heptahydrate, the solution was cooled with ice and 9.92 g (0.262 mol) of sodium borohydride was slowly added. After complete addition, the solution was stirred under ice-cooling for 1 hour and quenched with 1 N hydrochloric acid. Saturated aqueous sodium hydrogen carbonate solution was added for neutralization, and the volatile matter was removed on a rotary evaporator. The remaining aqueous solution was extracted with ethyl acetate. The resulting organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and brine and dried over magnesium sulfate. After filtration, magnesium sulfate was concentrated on a rotary evaporator. Purification was performed by recrystallization using column chromatography on ethanol and silica gel (hexane:ethyl acetate = 90:10 → 60:40) to obtain 24.9 g (yield 88%) of compound 99 as a mixture of isomers.

Compound 100 shown below was synthesized by the method shown below according to the following reaction formula.

[0606] [Chemical formula 207]

[0607] Under a nitrogen atmosphere, 21.3 g (85.8 mmol) of compound 99 were added to a 100 mL three-necked flask, then 25.7 g (171.5 mmol) of sodium iodide and 326 mL of acetonitrile were added and stirring was carried out at room temperature for some time. 21.7 mL (171.0 mmol) of chlorotrimethylsilane were added dropwise thereto and after the dropwise addition was complete, stirring was carried out at room temperature. The solution was quenched with sodium thiosulfate solution and the resulting solution was extracted with chloroform. The organic layer was washed with water and brine and then dried over magnesium sulfate. After filtration, magnesium sulfate was concentrated on a rotary evaporator. The concentrate was combined with the crude product from another batch and purified by silica gel column chromatography (eluent: hexane) to yield 9.13 g of compound 100, containing a small amount of impurities. Without further purification, compound 100 was used in the following <synthesis of compounds 101-1 and 101-2>.

[0608] <Synthesis of compounds 101-1 and 101-2>

Compounds 101-1 and 101-2 shown below were synthesized by the method mentioned below.

[0609] [Chemical formula 208]

[0610] Under a nitrogen atmosphere, 9.13 g of B <from the synthesis of compound 100> was added to a 1 L three-necked flask, then 167 ml of tert-butyl alcohol and 42 ml of water were added and the solution was cooled in an ice bath. An aqueous solution containing 10.0 g (63.2 mmol) of potassium permanganate, 2.18 g (54.5 mol) of sodium hydroxide and 209 ml of water was prepared in another flask and slowly added dropwise to the previously prepared reaction solution. After the dropwise addition was complete, stirring was continued while cooling in an ice bath for 20 minutes. While cooling in an ice bath, sodium metabisulfite was slowly added until the color of the potassium permanganate in the reaction solution disappeared. The process of adding ethyl acetate to the reaction solution and separating only the supernatant organic layer was repeated 4 times. The collected organic layer was dried over magnesium sulfate and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate=100:0 → 60:40) to obtain 1.74 g (yield 16%) of compound 101-1 and 1.77 g (yield 17%) of compound 101-2.

[0611] <Synthesis of Compound 102>

Compound 102 shown below was synthesized by the method given below.

[0612] [Chemical formula 209]

[0613] Under a nitrogen atmosphere, 1.74 g (7.06 mmol) of compound 101-1 was added to a 200 ml three-necked flask and dissolved in 7 ml of dehydrated pyridine. While cooling in an ice bath, 1.72 ml (14.8 mmol) of benzoyl chloride was slowly added dropwise so that the internal temperature did not exceed 5°C. After the dropwise addition, the temperature was raised to room temperature and stirred for a while. After cooling the reaction solution with ice, methanol was slowly added to quench. Then, water and dichloromethane were added, and the organic layer was washed 3 times with 1N hydrochloric acid, once with a saturated aqueous solution of sodium hydrogen carbonate, and once with brine, in that order. The organic layer after washing was dried over magnesium sulfate, filtered, and then concentrated on a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain 1.10 g (yield 35%, white solid) of compound 102. The ¹ H-NMR data of the obtained compound 102 are shown below.

[0614] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ1.19-1.47 (m, 11H), 2.27-2.58 (m, 3H), 5.15 (dd, J=1.6, 8.6 Hz, 1H), 5.29 (dd, J=1.6, 8.6 Hz, 1H), 7.11-7.17 (m, 2H), 7.29-7.40 (m, 6H), 7.43-7.50 (m, 2H), 7.77-7.80 (m, 2H), 7.88 -7.92 (m, 2H).

Peaks considered to be the melting points of the obtained compound 102 were observed at 143°C and 150°C.

[0615] <Synthesis of Compound 103>

Compound 103 shown below was synthesized by the method given below.

[0616] [Chemical formula 210]

[0617] 2.36 g (yield 73%, white solid) of compound 103 was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 102> except that 1.77 g of compound 102-2 (7.18 mmol) was used instead of 1.74 g of compound 101-1 in <Synthesis of Compound 102>. The ¹ H-NMR data of the obtained compound 103 are shown below.

¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.04 (d, J = 6.9 Hz, 3H), 1.16 (d, J = 6.9 Hz, 3H), 1.41 (s, 3H), 1.48-1.58 (m, 2H), 1.77-1.94 (m, 2H), 2.73-2.83 (m, 1H), 5.55 (d, J = 7.9 Hz, 1H), 5.62 (d, J = 7.9 Hz, 1H), 6.94-7.00 (m, 2H), 7.09-7.15 (m, 2H), 7.21-7.52 (overlaps with the signal of CHCl ₃ , m, 10H)

The final melting point of the obtained compound 103 was 149°C.

[0618] [Example A50]

<Synthesis of compound 104>

Compound 104 shown below was synthesized by the method shown below according to the following reaction formula.

[0619] [Chemical formula 211]

[0620] Under a nitrogen atmosphere, 70 g (0.85 mol) of 2-cyclopenten-1-one and 900 ml of dehydrated diethyl ether were added to a 2-liter 4-necked flask and stirred while cooling the internal temperature to 0°C. Then, 94 g (1.42 mol) of cyclopentadiene was added thereto. The cyclopentadiene used in the reaction was rapidly a product obtained by pyrolysis of dicyclopentadiene in tetradecane at 160°C or higher. 48.4 g (0.34 mol) of boron trifluoride-ethyl ether complex was added dropwise over 10 minutes while maintaining the internal temperature at 0 to 5°C. After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued in this state for 17 hours. After completion of the reaction, 900 ml of pure water was added and stirred for 30 minutes. The solution was separated into an organic layer and an aqueous layer, and the collected aqueous layer was extracted three times with 500 ml of diethyl ether. The entire organic layer was collected and then subjected to liquid separation and washing with 1 L of brine. The resulting organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 50:1) to obtain 82.9 g (yield 66%) of compound 104.

[0621] <Synthesis of Compound 105>

Compound 105 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0622] [Chemical formula 212]

[0623] Under a nitrogen atmosphere, 24 g (162 mmol) of compound 104, 41.7 g (178 mmol) of a 50% aqueous solution of 4-methylmorpholine N-oxide (hereinafter referred to as "NMO"), 60 ml of pure water, 60 ml of acetone, and 120 ml of tert-butyl alcohol were added to a 500 ml 4-necked flask and stirred. After adding 12.4 mg (0.5 mmol) of osmium oxide, stirring was carried out at room temperature for 2 days. After completion of the reaction, 2 g of sodium hydrosulfite, 2.4 g of florisil, and 160 ml of pure water were added, and stirring was carried out for 30 minutes. The filtrate was collected by filtration under reduced pressure, and the pH of the filtrate was adjusted to 7 with 1 N sulfuric acid. The organic solvent was removed from the filtrate under reduced pressure at an external temperature of 40°C, and the pH of the remaining aqueous solution was adjusted to 3 again with 1 N sulfuric acid. Excess sodium chloride and 500 ml of ethyl acetate were added and stirred, the solution was filtered under reduced pressure, and insoluble sodium chloride was filtered off. The solution was separated into an organic layer and an aqueous layer by liquid, and the collected aqueous layer was extracted 3 times with 400 ml of ethyl acetate. The organic layer was collected, dried over sodium sulfate, and filtered. Then the filtrate was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (ethyl acetate:dichloromethane=1:1) to obtain 13.2 g (yield 45%) of compound 105.

[0624] <Synthesis of Compound 106>

Compound 10 6 shown below was synthesized by the method given below.

[0625] [Chemical formula 213]

[0626] Under a nitrogen atmosphere, 3.33 g (18.3 mmol) of compound 105 were added to a three-necked flask, followed by 10 mL of dehydrated pyridine, and stirring was carried out. While cooling in an ice bath, 4.68 mL (40.3 mmol) of benzoyl chloride were slowly added. After the addition, the temperature was raised to room temperature and stirring was carried out for 5 h. Again while cooling in an ice bath, 10 mL of methanol was added for quenching. After this, water and dichloromethane were added, and the solution was transferred to a separatory funnel. The solution was washed with water and a saturated aqueous solution of ammonium chloride, the organic layer was dried over magnesium sulfate and then concentrated on a rotary evaporator. 8.29 g of the obtained crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate=85:15 → 65:35) and recrystallized with acetone solvent to obtain 3.16 g (yield 44%, pale yellow solid) of compound 10 6. ^{The 1} H-NMR data of the obtained compound 10 6 are shown below.

[0627] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.63-1.67 (m, 1H), 2.08-2.62 (m, 6H), 2.76-2.82 (m, 1H), 2.89-2.99 (m, 2H), 5.11-5.13 (m, 1H), 5.45-5.48 (m, 1H), 7.17 (t, J=7.6 Hz, 2H), 7.33 (t, J=7.6 Hz, 2H), 7.42 (t, J=7.6 Hz, 1H), 7.52 (t, J=7.6 Hz, 1H). 7.74-7.77 (m, 2H), 7.90-7.92 (m, 2H).

The final melting point of the obtained compound 106 was 127°C.

[0628] [Example A51]

<Synthesis of compound 107>

Compound 107 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0629] [Chemical formula 214]

[0630] Under a nitrogen atmosphere, 1.5 L of anhydrous diethyl ether was added to a 5 L 4-necked flask and cooled until the internal temperature reached 0 °C. Then, 22.2 g (585 mmol) of lithium aluminum hydride was added. 51 g (344 mmol) of compound 104 was dissolved in 500 mL of dehydrated diethyl ether, and the solution was added dropwise to the previously prepared solution over 30 minutes. During this time, the liquid temperature was allowed to range from 0 to 5 °C. After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 1 hour. After the reaction was complete, the liquid temperature was cooled again to 0 °C, and 200 mL of methanol was added dropwise over an hour, paying attention to the evolution of hydrogen. Then, 2 L of a saturated aqueous solution of potassium sodium tartrate was slowly added, and stirring was continued at room temperature for 2 hours. The solution was separated into an organic layer and an aqueous layer, and the combined aqueous layer was extracted three times with 500 mL of diethyl ether. The organic layer was collected, separated from the liquid, and washed with 1 L of brine. The organic layer was dried over sodium sulfate and filtered. The filtrate was then concentrated on a rotary evaporator, and the concentrate was dried under vacuum at an external temperature of 40°C for 2 hours, yielding 48.0 g (93% yield) of compound 107.

[0631] <Synthesis of Compound 108>

Compound 108 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0632] [Chemical formula 215]

[0633] Under a nitrogen atmosphere, 47.9 g (319 mmol) of compound 107, 48.5 g (479 mmol) of triethylamine and 1 L of dichloromethane were added to a 2 L 4-necked flask and cooled until the internal temperature reached 0°C. Then, 40.2 g (351 mmol) of methanesulfonyl chloride was added dropwise over 30 minutes, paying attention to maintaining the internal temperature from 0 to 5°C. After completion of the dropwise addition, stirring was carried out for 30 minutes, while the internal temperature remained at 5°C. After the completion of the reaction, 500 ml of pure water was added and stirred for 30 minutes. The organic layer was separated, added to 500 ml of 10% hydrochloric acid cooled in an ice bath, and stirred. The organic layer was then separated, added to 500 mL of saturated aqueous sodium hydrogen carbonate solution, and stirred. The organic layer was separated again, separated from the liquid, and washed with 500 mL of brine. The organic layer was dried over sodium sulfate and filtered. The filtrate was then concentrated on a rotary evaporator, and the concentrate was dried under vacuum at an external temperature of 40°C for 2 hours, yielding 70.4 g (97% yield) of compound 108.

[0634] <Synthesis of Compound 109>

Compound 10 9 shown below was synthesized by the method mentioned below according to the following reaction formula.

[0635] [Chemical formula 216]

[0636] Under a nitrogen atmosphere, 1 L of anhydrous diethyl ether was added to a 5 L 4-necked flask and the internal temperature was brought to 0 °C. Then, 17.5 g (460 mmol) of lithium aluminum hydride was added. 70.0 g (307 mmol) of compound 108 was dissolved in 500 mL of dehydrated diethyl ether and this solution was added dropwise to the previously prepared solution over 30 minutes. During this time, the internal temperature was maintained between 0 and 5 °C. After completion of the dropwise addition, stirring was carried out at room temperature for 3 hours. After completion of the reaction, the internal temperature was again cooled to 0 °C and 2 L of a saturated aqueous solution of potassium sodium tartrate was added dropwise over 2 hours, paying attention to the formation of hydrogen. Then, stirring was carried out at room temperature for another 2 hours. The solution was separated into an organic layer and an aqueous layer, and the combined aqueous layer was extracted four times with 400 mL of diethyl ether. The combined organic layer was separated from the liquid and washed with 1 L of brine. The organic layer was dried over sodium sulfate and filtered, and the filtrate was then concentrated under atmospheric pressure at an external temperature of 50°C. After concentration, distillation was performed under reduced pressure at an external temperature of 60°C and a pressure of 10 mmHg. Collection of the components distilled at 40°C yielded 37 g (90% yield, colorless liquid) of compound 109.

[0637] <Synthesis of Compound 110>

Compound 110 shown below was synthesized by the method given below.

[0638] [Chemical formula 217]

[0639] 15 g (112 mmol) of compound 109, 108 ml of pure water and 600 ml of tert-butyl alcohol were added to a 2-liter 4-necked flask and cooled with ice. 5.87 g (145 mmol) of sodium hydroxide and 19.43 g (123 mmol) of potassium permanganate were dissolved in 660 ml of water. The solution was placed in a dropping funnel and slowly added dropwise to the pre-prepared mixed solution so that the internal temperature reached 3°C or lower. After the completion of the dropwise addition, the completion of the reaction was confirmed by GC analysis. Then, a saturated aqueous solution of sodium metabisulfite was added until the color of potassium permanganate disappeared, after which the solution was filtered with celite. The filtrate was concentrated and the resulting aqueous layer was extracted with ethyl acetate 3 times. The collected organic layer was dried over sodium sulfate and filtered, and the filtrate was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (dichloromethane:ethyl acetate = 2:1) to yield 11.95 g (64% yield, white solid) of compound 110.

[0640] <Synthesis of Compound 111>

Compound 111 shown below was synthesized by the method given below.

[0641] [Chemical formula 218]

[0642] Under a nitrogen atmosphere, 3.0 g (17.8 mmol) of compound 110 were added to a three-necked flask, followed by 10 mL of dehydrated pyridine, and stirring was carried out. While cooling in an ice bath, 4.25 mL (36.6 mmol) of benzoyl chloride was slowly added over 10 min. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 3 mL of methanol was added for quenching. After this, water and ethyl acetate were added, and the solution was transferred to a separatory funnel. The solution was washed with water, saturated aqueous ammonium chloride solution, and brine in that order, the organic layer was dried over magnesium sulfate and then concentrated on a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (hexane:ethyl acetate=10:1) to obtain 6.47 g (yield 96%, white solid) of compound 111. The ¹ H-NMR data of the obtained compound 111 are shown below.

[0643] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.58-1.87 (m, 7H), 2.22-2.26 (m, 1H), 2.44 (br s, 2H), 2.58 (br s, 2H), 5.38 (d, J=1.6H, 2H), 7.22-7.28 (overlap with CHCl ₃ signal, m, 4H), 7.46 (t, J=7.6 Hz, 2H), 7.84-7.87 (m, 4H).

The melting point of the obtained compound 111 was 97°C.

[0644] [Example A52]

<Synthesis of compound 112>

Compound 112 shown below was synthesized by the method shown below according to the following reaction formula.

[0645] [Chemical formula 219]

[0646] Under a nitrogen atmosphere, 33.3 g (0.25 mol) of aluminum chloride and 1.5 L of anhydrous toluene were added to a 5 L 4-necked flask and stirred at room temperature. After dissolving 41 g (0.50 mol) of 2-cyclopenten-1-one in 1 L of anhydrous toluene, the solution was added to the pre-prepared reaction solution and stirred at room temperature for 40 minutes. Then, 240.4 g (3.0 mol) of 1,3-cyclohexadiene was added, the internal temperature was raised to 60°C, and stirring was carried out with heating for 12 hours. After completion of the reaction, the solution was cooled in an ice bath and 2 L of 1 N hydrochloric acid was added. Then, stirring was carried out at room temperature for 30 minutes. The solution was separated into an organic layer and an aqueous layer, and the collected aqueous layer was extracted twice with 500 mL of toluene. The collected organic layer was subjected to liquid separation and washed once with 1 L of brine and once with 1 L of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over sodium sulfate and filtered, and then the filtrate was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 20:1) to obtain 36 g (yield 44%) of compound 112 as a mixture of isomers.

[0647] <Synthesis of Compound 113>

Compound 113 shown below was synthesized by the method given below.

[0648] [Chemical formula 220]

[0649] Under a nitrogen atmosphere, 35.5 g (219 mmol) of compound 112, 50 ml (241 mmol) of 50% aqueous NMO solution, 81 ml of pure water, 81 ml of acetone and 162 ml of tert-butyl alcohol were dissolved and added to a 500 ml 4-neck flask and stirred. Then 170 mg (0.66 mmol) of osmium oxide were added and stirring was carried out with heating at an internal temperature of 40 °C for 40 hours. After the completion of the reaction, 2.7 g of sodium hydrosulfite, 33 g of florisil and 216 ml of pure water were added and stirred for 30 minutes. The filtrate was collected by filtration under reduced pressure and the pH of the filtrate was adjusted to 7 with 1 N sulfuric acid. The organic solvent was removed from the filtrate under reduced pressure at an external temperature of 40°C, and the pH of the remaining aqueous solution was adjusted again to 3 with 1 N sulfuric acid. Excess sodium chloride and 600 ml of ethyl acetate were added and stirred, the solution was filtered under reduced pressure, and insoluble sodium chloride was filtered off. The solution was separated into an organic layer and an aqueous layer by liquid, and the collected aqueous layer was extracted 3 times with 600 ml of ethyl acetate. The organic layer was collected, dried over sodium sulfate, and filtered. Then, the filtrate was concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (ethyl acetate:dichloromethane=1:1) and washed with hexane solvent to obtain 27.0 g (yield 64%) of compound 113.

[0650] <Synthesis of Compound 113>

Compound 114 shown below was synthesized by the method given below.

[0651] [Chemical formula 221]

[0652] Under a nitrogen atmosphere, 4.0 g (20.4 mmol) of compound 113 were added to a 100 mL three-necked flask, followed by the addition of 10 mL of dehydrated pyridine, and stirring was carried out. While cooling in an ice bath, 4.89 mL of benzoyl chloride (42.1 mmol) was slowly added. After the addition, the temperature was raised to room temperature, and stirring was carried out overnight. Again while cooling in an ice bath, 5 mL of methanol was added for quenching. Thereafter, water and ethyl acetate were added, and the solution was separated into an aqueous layer and an organic layer. The organic layer was washed once each with a saturated aqueous solution of ammonium chloride, a saturated aqueous solution of sodium hydrogen carbonate, and brine, in that order. After drying the organic layer over magnesium sulfate and filtration, the organic layer was concentrated on a rotary evaporator. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate=10:1 → 5:1) to obtain 7.49 g (yield 91%, pale yellow solid) of compound 114. ^{The 1} H-HMP data of the obtained compound 114 are shown below.

[0653] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.48-1.55 (overlaps with H ₂ O signal, m, 2H), 1.98-2.54 (m, 9H), 2.68-2.81 (m, 1H), 5.01-5.05 (m, 1H), 5.52-5.56 (m, 1H), 7.18-7.34 (overlaps with CHCl ₃ signal, m, 4H), 7.41-7.52 (m, 2H), 7.79-7.92 (m, 4H).

The final melting point of the obtained compound 114 was 122°C.

[0654] [Example A53]

<Synthesis of compound 115>

Compound 115 shown below was synthesized by the method given below.

[0655] [Chemical formula 222]

[0656] Under a nitrogen atmosphere, 2.68 g (20 mmol) of 5,6-dihydrodicyclopentadiene, 100 ml of tert-butyl alcohol and 40 ml of water were added to a 1 L three-necked flask, and the reaction solution was cooled to 0°C. 1.0 g (25 mmol) of sodium hydroxide and 4.74 g (30 mmol) of potassium permanganate were dissolved in 100 ml of water and slowly added dropwise to the previously prepared reaction solution. After completion of the dropwise addition, stirring was carried out at the same temperature for an hour, and a saturated aqueous solution of sodium metabisulfite was added dropwise until the color of the unreacted potassium permanganate disappeared. After stirring for a while at room temperature, sodium hydrogen carbonate was added until the pH of the reaction solution reached approximately 7-8, and the resulting white precipitate was removed by filtration.

The filtered solution was extracted with ethyl acetate three times. The collected organic layer was dried over sodium sulfate and then concentrated on a rotary evaporator. The crude product (2.51 g), containing compound 115, was used in the next <synthesis of compound 116> without further purification.

[0657] <Synthesis of Compound 116>

Compound 116 shown below was synthesized by the method given below.

[0658] [Chemical formula 223]

[0659] Under a nitrogen atmosphere, 2.51 g of the obtained crude product in <the synthesis of compound 115> was added to a 100 mL 3-necked flask, followed by the addition of 10 mL of dehydrated pyridine and stirring. While cooling in an ice bath, 4.04 mL (34.8 mmol) of benzoyl chloride was slowly added. After the addition, the temperature was raised to room temperature and stirring was carried out overnight. Again while cooling in an ice bath, 10 mL of methanol was added for quenching. After that, water and dichloromethane were added and the solution was separated into an aqueous layer and an organic layer. The organic layer was washed twice with a saturated aqueous solution of ammonium chloride. The organic layer was dried over sodium sulfate and filtered. Then, the organic layer was concentrated on a rotary evaporator. The crude product was purified twice by silica gel column chromatography (the first time: hexane:ethyl acetate=10:1, the second time: hexane:ethyl acetate=20:1) to obtain 3.03 g of compound 116 (colorless liquid). The ¹ H-NMR data of the obtained compound 116 are shown below.

[0660] ¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.50-1.61 (overlaps with H2O signal, m, 6H), 1.97-2.14 (m, 2H), 2.25 (br s, 1H), 2.44 (br s, 1H), 2.61-2.69 (m, 1H), 2.72-2.83 (m, 1H), 5.47 (t, J=4.0 Hz, 1H), 5.61-5.67 (m, 1H), 7.32-7.40 (m, 4H), 7.48-7.55 (m, 2H), 7.92-7.98 (m, 4H).

[Example A54]

<Preparation of solid component [α1] titanium catalyst>

After a 1 L glass vessel was sufficiently purged with nitrogen, 85.8 g of anhydrous magnesium chloride, 321 g of decane, and 352 g of 2-ethylhexyl alcohol were placed into it and heated at 130°C for 3 hours to obtain a homogeneous solution. 241 g of this solution and 6.43 g of ethyl benzoate were added to the glass vessel and stirred with stirring at 50°C for 1 hour. The resulting homogeneous solution was cooled to room temperature. Then 38.3 ml of this total homogeneous solution was added dropwise to 100 ml of titanium tetrachloride kept at -20°C under stirring at 350 rpm for 45 minutes. After the addition was complete, the temperature of this mixture was raised to 80°C for 3.8 hours. When the temperature reached 80°C, 0.97 g of compound 6 was added to the mixture. The temperature was again raised to 120°C for 40 minutes and maintained at the same temperature with stirring for 35 minutes. After completion of the reaction, the solid portion was recovered by hot filtration. This solid portion was resuspended in 100 ml of titanium tetrachloride, and then the suspension was again subjected to a heating reaction at 120°C for 35 minutes. After completion of the reaction, the solid portion was again recovered by hot filtration and sufficiently washed with decane at 100°C and decane at room temperature until free titanium compound was detected after washing the solid in the decane solution. The solid component [α1] of the titanium catalyst obtained by the above procedure was saved as a decane suspension, and a part of it was dried to study the catalyst composition. The composition of the thus obtained solid component [α1] of the titanium catalyst included 0.28% by weight of titanium, 1.7% by weight of magnesium, and 0.12% by weight of 2-ethylhexyl alcohol residues.

[0661] <Basic Polymerization>

After adding 500 g of propylene and 1 nL of hydrogen at room temperature into a 2-liter autoclave, a mixture obtained by mixing 7 ml of heptane, 0.5 mmol of triethylaluminum, 0.08 mmol of cyclohexylmethyldimethoxysilane and 0.004 mmol of the solid [α1] titanium catalyst component (in terms of titanium atom) was added thereto at 25°C for 10 minutes, and the temperature inside the autoclave was quickly raised to 70°C. After polymerization at 70°C for 1.5 hours, the reaction was stopped by adding a small amount of methanol, and then propylene was removed. Finally, the resulting polymer particles were dried under reduced pressure at 80°C overnight. The polymerization results are as follows.

[0662] Activity: 48.6 kg-PP/g-catalyst

Specific gravity: 490 kg/ ^m3

MFR (ASTM1238E, 230°C, 2.16 kg load): 0.57 g/10 minutes

Amount of decane-insoluble component: 1.87 wt.%

Tm: 163.92°C

Tmf: 172.08°C

MW/MH: 10.64

M3/MW: 4.85

The methods for measuring the physical properties described above are as follows.

[0663] (1) Volumetric specific gravity:

The bulk specific gravity was measured according to JIS K-6721.

(2) Melt Flow Rate (MFR):

In accordance with ASTM D1238E, the measurement temperature of propylene polymer was set to 230°C.

[0664] (3) Amount of decane-soluble (insoluble) component:

About 3 g of propylene polymer (measured with an accuracy of 10 ^-4 g. In the following equation, this weight is denoted by the letter b (g)), 500 ml of decane and a small amount of a heat-resistant stabilizer soluble in decane were placed in a glass measuring vessel. Under a nitrogen atmosphere, the temperature was raised to 150 °C for 2 hours while stirring with a stirrer to dissolve the propylene polymer, the temperature was maintained at 150 °C for 2 hours, and then the solution was gradually cooled to 23 °C over 8 hours. The liquid containing the resulting propylene polymer precipitate was filtered under reduced pressure using a standard 25G-4 glass filter manufactured by Tokyo Garasu Kikai Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the component soluble in decane. Their mass was weighed with an accuracy of 10 ^-4 g (this mass was designated as a(g) in the following equation). After this operation, the amount of the decane-soluble component was determined using the following equation.

[0665] Decane soluble content = 100 × (500 × a) / (100 × b)

Content of decane-insoluble component = 100 - 100 × (500 × a) / (100 × b)

(4) Molecular weight distribution: Gel permeation chromatograph: Model HLC-8321 GPC/HT manufactured by TOSOH CORPORATION

Detector: differential refractometer

Column: Series-connected TSKgel GMH6-HT×2 and TSKge1 GMH6-HTL×2 manufactured by TOSOH CORPORATION.

[0666] Mobile phase medium: o-dichlorobenzene

Flow rate: 1.0 ml/min

Measurement temperature: 140°C

Method for constructing the calibration curve: a standard polystyrene sample was used.

Sample concentration: 0.1% (w/w)

Sample solution volume: 0.4 ml. The measurement was carried out under the conditions described above. The resulting chromatogram was analyzed using a known method to calculate the mass-average molecular weight (Mw), number-average molecular weight (Mn), average molecular weight Z (Mz), as well as the Mw/Mn and Mz/Mw values as molecular weight distribution (MWD) indices. The measurement time for one sample was 60 minutes.

[0667] (5) Polymer melting temperature (Tm):

The melting point (Tm), crystallization temperature (Tg), and heat of fusion (Hof) of the polymer of the present invention were measured using a differential scanning calorimeter (DSC) in a DSC220C manufactured by Seiko Instruments Inc. From 3 to 10 mg of the sample were sealed in an aluminum crucible and heated from room temperature to 200°C at a rate of 1000°C/min. The sample was held at 200°C for 5 minutes and then cooled to 30°C at a rate of 10°C/min. The peak temperature in this cooling test was determined as the crystallization temperature (Tg). Then, after holding at 30°C for 5 minutes, the sample was subjected to a second heating to 200°C at a rate of 10°C/min. In this second heating test, the peak temperature was used as the melting point (Tm) and the amount of heat released was used as the heat of fusion (Hof).

[0668] The final melting point (Tmf) of the polymer of the present invention was measured using a differential scanning calorimeter (DSC) in a DSC220C manufactured by Seiko Instruments Inc. From 3 to 10 mg of sample were sealed in an aluminum crucible and heated from room temperature to 240°C at a rate of 80°C/min. The sample was held at 240°C for 1 minute and then cooled to 0°C at a rate of 80°C/min. After holding at 0°C for 1 minute, the sample was heated to 150°C at a rate of 80°C/min and held for 5 minutes. Finally, the sample was heated to 180°C at a rate of 1,350°C/min, and the intersection of the tangent of the inflection point on the high-temperature side of the peak obtained in this final heating test and the baseline was used as the final melting point (Tmf).

[0669] Tmf can be regarded as one parameter for evaluating the ease of crystallization and crystalline structure of, for example, a polymer in the ultra-high molecular weight region, which is said to be difficult to crystallize. More specifically, it can be considered that the higher the Tmf value, the more likely the ultra-high molecular weight polymer component is to form crystals that are strong and have high thermal stability.

[0670] [Example B1]

<Synthesis of compounds 201 and 202>

The synthesis of compounds 201 and 202 shown below was carried out by the method given below.

[0671] [Chemical formula 224]

[0672] In (compound 201), the thick line represents the near side of the paper plane, the dotted line represents the far side of the paper plane, and compound 201 corresponds to the diol compound derived from the endo form shown in formula (34) above.

[0673] [Chemical formula 225]

[0674] In (compound 202), the thick line represents the near side of the paper plane, and compound 202 corresponds to the diol compound derived from the exo form shown in formula (34) above.

A 2-liter flask was fitted with a mechanical stirrer and purged with nitrogen, allowing the nitrogen to flow in. 25.4 g of olefin ((a compound in which in formula (33) R ⁴ , R ⁹ and R ³¹ -R ³⁴ are hydrogen atoms and X is CH ₂ ), 440 ml of tert-butyl alcohol and 110 ml of water were added to the flask and the internal temperature was cooled to 0 °C. In another 1 L beaker, 30 g of potassium permanganate, 600 ml of water and 6.60 g of sodium hydroxide were added to prepare an alkaline aqueous solution of potassium permanganate. A 2 L flask was equipped with a dropping funnel into which the prepared aqueous solution of potassium permanganate was loaded. The alkaline aqueous solution of potassium permanganate was slowly added dropwise so that the internal temperature did not exceed 5 °C. After the end of the dropwise addition, stirring was carried out at an internal temperature of 0 °C for an hour. In another flask, they prepared A saturated aqueous solution of sodium metabisulfite was added dropwise to the previous reaction solution slowly until a white precipitate was formed. After the dropwise addition, the temperature was raised to room temperature to induce the precipitation of a white solid. The supernatant of the organic layer was collected, and then the aqueous layer was subjected to extraction operation with ethyl acetate twice. The organic layer was combined and washed with water and brine. The organic layer was dried over magnesium sulfate. Then, the organic layer was concentrated to obtain 27.41 g of crude product. The resulting crude product was purified by silica gel column chromatography to obtain 22.71 g of the target product (mixture of isomers). The resulting product was again purified by silica gel column to separate the isomers, and 10.9 g of compound 201 and 2.9 g of compound 202 were isolated. The ¹ H-NMR data of the obtained compounds 201 and 202 are shown below.

[0675] (Connection 201

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.39-1.51 (m, 1H), 1.89-2.01 (m, 1H), 2.19-2.27 (m, 1H), 2.30-2.38 (m, 1H), 2.47-2.58 (m, 2H), 2.70-3.08 (m, 3H), 3.21-3.32 (m, 1H), 3.58-3.76 (m, 2H), 7.06-7.36 (m, 2H), 4H).

(Compound 202)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.00-1.10 (m, 1H), 1.55-1.64 (m, 1H), 2.07 (br s, 1H), 2.23-2.35 (m, 2H), 2.50 (dd, J=14.5, 5.3 Hz, 2H) 2.63 (dd, J=17.1, 3.6 Hz, 1H), 3.06 (d, J=7.9, 1H), 3.28 (dd, J=17.4, 10.5 Hz, 1H), 3.79-3.87 (m, 1H), 3.88-3.96 (m, 1H), 7.09-7.20 (m, 4H).

<Synthesis of compound 203>

The synthesis of compound 203 shown below was carried out by the method given below.

[0676] [Chemical formula 226]

[0677] The inside of a 200 mL flask was purged with nitrogen, 5 g of compound 201 was added, followed by 30 mL of dehydrated pyridine. While cooling in an ice bath, 5.69 mL of benzoyl chloride was slowly added dropwise. After the dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. While cooling again in an ice bath, methanol was added to quench. After adding and stirring chloroform and water, the organic layer was separated. The organic layer was washed with saturated aqueous ammonium chloride solution and brine, and then dried over magnesium sulfate. The organic layer was then concentrated to give 10.61 g of crude product. The crude product was purified by silica gel column chromatography to obtain 6.83 g of compound 203. The ¹ H-NMR data of the obtained compound 203 are shown below.

[0678] (Connection 203)

^1H NMR (270 MHz, _CDCl3 , TMS as internal standard): δ 1.68-1.74 (m, 1H), 2.29-2.34 (m, 1H), 2.57-2.59 (m, 1H), 2.90-3.20 (m, 4H), 3.83 (dd, J=10.2, 5.6 Hz, 1H), 4.66 (dd, J=5.9, 1.3 Hz, 1H), 5.03 (dd, J=5.9, 1.7 Hz, 1H), 7.20-7.49 (m, 10H), 7.79-7.86 (m, 4H).

The final melting point of compound 203 was 108.7°C.

[0679] <Synthesis of Compound 204>

The synthesis of compound 204 shown below was carried out by the method mentioned below.

[0680] [Chemical formula 227]

[0681] 3.85 g (yield 89%) of compound 204 was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 203> except that 2.2 g of compound 202 was used instead of compound 201 in <Synthesis of Compound 203>. The CNMR data of the obtained compound 204 are shown below.

[0682] (Connection 204)

¹ H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1, 27-1, 33 (m, 1H), 1, 92-1, 98 (m, 1H), 2.44 (br s, 1H), 2, 57-2.76 (m, 3H), 3, 34-3.45 (m, 2H), 5.19-5.23 (m, 1H), 5.30-5.35 (m, 1H), 7.17-7.32 (m, 8H), 7, 43-7, 52 (m, 2H), 7, 84-7, 92 (m, 4H).

The final melting point of compound 204 was 168.2°C.

[0683] [Example B2]

<Preparation of solid component [α1] titanium catalyst>

After a 1 L glass vessel was sufficiently purged with nitrogen, 85.8 g of anhydrous magnesium chloride, 321 g of decane, and 352 g of 2-ethylhexyl alcohol were placed into it and heated at 130°C for 3 hours to obtain a homogeneous solution. 241 g of this solution and 6.43 g of ethyl benzoate were added to the glass vessel and stirred with stirring at 50°C for 1 hour. The resulting homogeneous solution was cooled to room temperature. Then 38.3 ml of this total homogeneous solution was added dropwise to 100 ml of titanium tetrachloride kept at -20°C under stirring at 350 rpm for 45 minutes. After the addition was complete, the temperature of this mixture was raised to 80°C for 3.8 hours. When the temperature reached 80°C, 0.91 g of compound 203 was added to the mixture. The temperature was again raised to 120°C over 40 minutes and maintained at the same temperature with stirring for 35 minutes. After completion of the reaction, the solid portion was recovered by hot filtration. This solid portion was resuspended in 100 ml of titanium tetrachloride, and then the suspension was again subjected to a heating reaction at 120°C for 35 minutes. After completion of the reaction, the solid portion was again recovered by hot filtration and washed sufficiently with decane at 100°C and decane at room temperature until free titanium compound was detected after washing the solid in decane solution. The solid component [α1] of the titanium catalyst prepared according to the above procedure was kept as a suspension in decane.

[0684] <Main polymerization>

After adding 500 g of propylene and 1 nL of hydrogen at room temperature into a 2-liter autoclave, a mixture obtained by mixing 7 ml of heptane, 0.5 mmol of triethylaluminum, 0.08 mmol of cyclohexylmethyldimethoxysilane and 0.004 mmol of the solid [α1] titanium catalyst component (in terms of titanium atom) was added thereto at 25°C for 10 minutes, and the temperature inside the autoclave was quickly raised to 70°C. After polymerization at 70°C for 1.5 hours, the reaction was stopped by adding a small amount of methanol, and then propylene was removed. Finally, the resulting polymer particles were dried under reduced pressure at 80°C overnight. The polymerization results are as follows.

[0685] Activity: 72.7 kg polypropylene/g catalyst

Specific gravity: 490 kg/ ^m3

MFR (ASTM1238E, 230°C, 2.16 kg load): 0.45 g/10 minutes

Amount of decane-insoluble component: 0.49 wt.%

Tm: 165.39°C

TMF: 172.33°C

MW/Mn: 11.25

MW/MW: 4.41

Methods for measuring physical properties are described in Example A54.

[0686] [Example B3]

<Synthesis of compound 205>

The synthesis of compound 205 shown below was carried out by the method given below.

[0687] [Chemical formula 228]

[0688] The inside of a 100 mL flask was purged with nitrogen, 3.0 g (1 equivalent) of a mixture of compound 201 and compound 202 were added, and then 15 mL of dehydrated pyridine and 15 mL of chloroform were added. While cooling in an ice bath, 4.5 g (2.1 equivalents) of 3-methylbenzoyl chloride were slowly added dropwise. After the dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. While cooling again in an ice bath, methanol was added for quenching. After adding and stirring chloroform and water, the organic layer was separated. The organic layer was washed with a saturated aqueous solution of ammonium chloride and brine, and then dried over magnesium sulfate. Then, the organic layer was concentrated to give 6.78 g of a crude product. The crude product was purified by silica gel column chromatography to afford 5.94 g (95% yield) of compound 205 (endoform:exoform=86:14) as a mixture of endoform and exoform isomers. The ¹ H-NMR data of the obtained compound 205 are shown below.

[0689] (Connection 205)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.68-1.73 (m, 1H), 2.13-2.19 (m, 6H), 2.30-2.35 (m, 1H), 2.57-2.59 (m, 1H), 2.89-3.20 (m, 4H), 3.80-3.86 (dd, J=10.6, 5.9 Hz, 1H), 4.63-4.65 (m, 1H), 5.00-5.03 (m, 1H), 7.14-7.34 (m, 8H), 7.56-7.76 (m, 4H); exo form: 1.26-1.32 (m, 1H), 1.92-1.96 (m, 1H), 2.13-2.19 (m, 6H), 2.42 (br. s, 1H), 2.61-2.74 (m, 3H), 3.33 -3.43 (m, 2H), 5.16-5.18 (m, 1H), 5.27-5.30 (m, 1H), 7.14-7.34 (m, 8H), 7.56-7.76 (m, 4H).

The final melting point of compound 205 was 116.0°C.

[0690] [Example B4]

<Synthesis of compound 206>

The synthesis of compound 206 shown below was carried out by the method mentioned below.

[0691] [Chemical formula 229]

[0692] 6.37 g (yield 96%) of compound 206 (endoform:exoform=85:15) was obtained as a mixture of endoform and exoform isomers according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 4.91 g (2.1 equivalents) of 3,5-dimethylbenzoyl chloride was used instead of 3-methylbenzoyl chloride in <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 206 are shown below.

[0693] (Connection 206)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.68-1.72 (m, 1H), 2.13-2.18 (m, 12H), 2.31-2.34 (m, 1H), 2.56-2.58 (m, 1H), 2.88-3.19 (m, 4H), 3.79-3.85 (dd, J=10.6, 5.6 Hz, 1H), 4.60-4.63 (m, 1H), 4.98-5.00 (m, 1H), 7.07-7.09 (m, 2H), 7.17-7.32 (m, 4H), 7.42-7, 50 (m, 4H); exoform: 1.24-1.29 (m, 1H), 1.90-1.96 (m, 1H), 2.13-2.18 (m, 12H), 2.42 (wide s, 1H), 2.60-2.74 (m, 3H), 3.33 -3.43 (m, 2H), 5.14-5.16 (m, 1H), 5.24-5.27 (m, 1H), 7.07-7.09 (m, 2H), 7.17-7.32 (m, 4H), 7.42 -7.50 (m, 4 h).

Peaks considered to be the melting points of compound 20 6 were observed at 153.0°C and 191.4°C.

[0694] [Example B5]

<Synthesis of compound 207>

The synthesis of compound 207 shown below was carried out by the method mentioned below.

[0695] [Chemical formula 230]

[0696] 5.40 g (yield 94%) of compound 207 (endo form:exo form=86:14) was obtained as a mixture of endo form and exo form isomers according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 3.80 g (2.1 equivalents) of 2-furoyl chloride was used instead of 3-methylbenzoyl chloride in <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 207 are shown below.

[0697] (Connection 207)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.66-1.70 (m, 1H), 2.24-2.28 (m, 1H), 2.54-2.55 (m, 1H), 2.85-3.08 (m, 4H), 3.78-3.83 (dd, J=10.6, 5.6 Hz, 1H), 4.55-4.57 (m, 1H), 4.95-4.97 (m, 1H), 6.37-6.42 (m, 2H), 6.86-6.97 (m, 2H), 7.16-7.30 (m, 4H), 7, 44-7, 49 (m, 2H); exo form: 1.23-1.28 (m, 1H), 1.86-1.91 (m, 1H), 2.39 (br. s, 1H), 2.57-2.72 (m, 3H), 3.31-3.42 (m, 2H), 5.11-5.13 (m, 1H), 5.22-5.24 (m, 1H), 6.37-6.42 (m, 2H), 6.86-6.97 (m, 2H), 7.16-7.30 (m, 4H), 7.44-7.49 (m, 2 h).

Peaks considered to be the melting points of compound 207 were observed at 107.6°C and 120.5°C.

[0698] [Example B6]

<Synthesis of compound 208>

The synthesis of compound 208 shown below was carried out by the method mentioned below.

[0699] [Chemical formula 231]

[0703] [Chemical formula 232]

[0700] 5.72 g (yield 94%) of compound 208 (endoform:exoform=86:14) was obtained as a mixture of endoform and exoform isomers according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 4.27 g (2.1 equivalents) of 2-thenoyl chloride was used instead of 3-methylbenzoyl chloride in <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 208 are shown below.

[0701] (Connection 208)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.66-1.70 (m, 1H), 2.24-2.29 (m, 1H), 2.55-2.56 (m, 1H), 2.87-3.14 (m, 4H), 3.78-3, 84 (dd, J=10.2, 5.6 Hz, 1H), 4.57-4.59 (m, 1H), 4.94-4.97 (m, 1H), 6.95-7.01 (m, 2H), 7.16-7.32 (m, 4H), 7, 43-7.48 (m, 2H), 7, 58-7, 67 (m, 2H); exoform: 1.24-1.28 (m, 1H), 1.87-1.92 (m, 1H), 2.40 (wide s, 1H), 2.56-2.73 (m, 3H), 3.32-3.42 (m, 2H), 5.11 -5.14 (m, 1H), 5.23-5.25 (m, 1H), 6.95-7.01 (m, 2H), 7.16-7.32 (m, 4H), 7.43-7.48 (m, 2H), 7.58-7.67 (m, 2 h).

Peaks considered to be the melting points of compound 208 were observed at 110.9°C and 141.5°C.

[0702] [Example B7]

<Synthesis of compound 209>

The synthesis of compound 209 shown below was carried out by the method mentioned below.

[0703] [Chemical formula 232]

[0704] 5.77 g (yield 88%) of compound 209 (endoform:exoform=88:12) was obtained as a mixture of endoform and exoform isomers according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 5.0 g (2.1 equivalents) of 1-naphthoyl chloride was used instead of 3-methylbenzoyl chloride from <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 209 are shown below.

[0705] (Connection 209)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.75-1.79 (m, 1H), 2.36-2.40 (m, 1H), 2.69-2.70 (m, 1H), 2.96-3.29 (m, 4H), 3.86-3.92 (dd, J=10.2, 5.6 Hz, 1H), 4, 82-4.85 (m, 1H), 5.19-5.22 (m, 1H), 6, 98-7.43 (m, 10H), 7, 73-7.98 (m, 6H), 8, 70-8, 80 (m, 2H); exoform: 1.33-1.37 (m, 1H), 1.99-2.03 (m, 1H), 2.53 (br. s, 1H), 2.70-2.79 (m, 3H), 3.38-3.47 (m, 2H), 5.36-5.38 (m, 1H), 5.48-5.50 (m, 1H), 6.98-7.43 (m, 10H), 7.73-7.98 (m, 6H), 8.70-8.80 (m, 2H).

The final melting point of compound 209 was 149.8°C.

[070 6] [Example B8]

<Synthesis of compound 210>

The synthesis of compound 210 shown below was carried out by the method given below.

[0707] [Chemical formula 233]

[0708] 4.89 g (yield 75%) of compound 210, including only the endo form, was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 5.0 g (2.1 equivalents) of 2-naphthoyl chloride was used instead of 3-methylbenzoyl chloride from <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 210 are shown below.

[0709] (Connection 210)

^1H NMR (270 MHz, _CDCl3 , TMS as internal standard): δ 1.76-1.80 (m, 1H), 2.43-2.47 (m, 1H), 2.67-2.68 (m, 1H), 2.95-3.25 (m, 4H), 3.85-3.91 (dd, J=10.6, 5.9 Hz, 1H), 4.74-4.76 (m, 1H), 5.11-5.14 (m, 1H), 7.21-7.54 (m, 10 N), 7.64-7.80 (m, 4H), 7.88-7.95 (m, 2H), 8.27-8.35 (m, 2H).

The final melting point of compound 210 was 173.8°C.

[0710] [Example B9]

<Synthesis of compound 211>

The synthesis of compound 211 shown below was carried out by the method given below.

[0711] [Chemical formula 234]

[0712] 4.70 g (yield 70%) of compound 211 (endoform:exoform=80:20) was obtained as a mixture of endoform and exoform isomers according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 5.0 g (2.1 equivalents) of 3-methoxybenzoyl chloride was used instead of 3-methylbenzoyl chloride in <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 211 are shown below.

[0713] (Connection 211)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.69-1.72 (m, 1H), 2.28-2.32 (m, 1H), 2.57-2.58 (m, 1H), 2.88-3.18 (m, 4H), 3.60-3. 66 (m, 6H), 3.80-3.86 (dd, J=10.2, 5.6 Hz, 1H), 4.64-4.66 (m, 1H), 5.01-5.03 (m, 1H), 6.98-7.03 (m, 2H), 7.13-7.37 (m, 8H), 7.44-7.53 (m, 2H); exoform: 1.26-1.30 (m, 1H), 1.91-1.95 (m, 1H), 2.42 (wide s, 1H), 2.60-2.73 (m, 3H), 3.33-3.43 (m, 2H), 3.60 -3.66 (m, 6H), 5.18-5.20 (m, 1H), 5.29-5.31 (m, 1H), 6.98-7.03 (m, 2H), 7.13-7.37 (m, 8H), 7.44 -7.53 (m, 2 h).

The final melting point of compound 211 was 124.3°C.

[0714] [Example B10]

<Synthesis of compound 212

The synthesis of compound 212 shown below was carried out by the method given below.

[0715] [Chemical formula 235]

[0716] 1.32 g (yield 21%) of compound 212 (endoform:exoform=78:22) was obtained as a mixture of endoform and exoform isomers as a colorless liquid according to the operation and equivalence ratio described in <synthesis of compound 205> except that 5.75 g (2.7 equivalents) of phenylacetyl chloride was used instead of 3-methylbenzoyl chloride in <synthesis of compound 205>. The ¹ H-NMR data of the obtained compound 212 are shown below.

[0717] (Connection 212)

^1H NMR (270 MHz, _CDCl3 , TMS as internal standard): endo form: δ 1.52-1.55 (m, 1H), 1.98-2.02 (m, 1H), 2.29-2.33 (m, 1H), 2.63-2.65 (m, 1H), 2. 75-2, 97 (m, 3H), 3.17-3.26 (m, 4H), 3, 66-3, 72 (dd, J=10.6, 5.6 Hz, 1H), 4.27-4.30 (m, 1H), 4.64-4.67 (m, 1H), 7.13-7.33 (m, 14H); exo form: 1.09-1.13 (m, 1H), 1.60-1.64 (m, 1H), 2.15 (br. s, 1H), 2.33-2.57 (m, 3H), 3.17-3.26 (m, 6H), 5.20-5.22 (m, 1H), 5.31-5.33 (m, 1H), 7, 13-7, 33 (m, 14H).

[Example B11]

<Synthesis of compound 213>

The synthesis of compound 213 shown below was carried out by the method given below.

[0718] [Chemical formula 236]

[0719] According to the operation and equivalence ratio described in <Synthesis of Compound 205>, except that 5.14 g (2.1 equivalents) of 3,5-difluorobenzoyl chloride was used instead of 3-methylbenzoyl chloride in <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 213 are shown below.

[0720] (Connection 213)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.74-1.77 (m, 1H), 2.24-2.29 (m, 1H), 2.57-2.59 (m, 1H), 2.89-3.11 (m, 4H), 3.82-3, 88 (dd, J=10.6, 5.6 Hz, 1H), 4.62-4.64 (m, 1H), 5.00-5.02 (m, 1H), 6.87-6.99 (m, 2H), 7.18-7.38 (m, 8H); exo form: 1.30-1.35 (m, 1H), 1.87-1.91 (m, 1H), 2.43 (br. s, 1H), 2.60-2.75 (m, 3H), 3.35-3.45 (m, 2H), 5.17 -5.20 (m, 1H), 5.29-5.31 (m, 1H), 6.87-6.99 (m, 2H), 7.18-7.38 (m, 8H).

The final melting point of compound 213 was 127.7°C.

[0721] [Example B12]

<Synthesis of compound 214>

The synthesis of compound 214 shown below was carried out by the method mentioned below.

[0722] [Chemical formula 237]

[0723] A 100 mL flask was purged with nitrogen from the inside, 5.95 g (1 equivalent) of 3-phenylbenzoic acid was added, and then 60 mL of dichloromethane and 2 drops of dimethylformamide were added. Under cooling in an ice bath, 3.0 9 mL (1.2 equivalents) of oxalyl chloride were slowly added dropwise. After the dropwise addition, the temperature was raised to room temperature and stirred for 2 hours. The volatile compound from the reaction system was removed under reduced pressure to give compound 214. The compound was used in the synthesis of compound 215 without further purification.

[0724] <Synthesis of Compound 215>

The synthesis of compound 215 shown below was carried out by the method mentioned below.

[0725] [Chemical formula 238]

[072 6] 3 mL of dehydrated pyridine was added to a 100 mL flask under nitrogen atmosphere, and the flask contained the entire amount (2.2 equivalents) of compound 214 synthesized in <the synthesis of compound 214>. While cooling in an ice bath, 10 mL of a solution of 2.92 g (1 equivalent) of a mixture of compound 201 and compound 202 in dichloromethane was slowly added. After the dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. While cooling again in an ice bath, methanol was added to quench. After adding and stirring chloroform and water, the organic layer was separated. The organic layer was washed with saturated aqueous ammonium chloride solution and brine, and then dried over magnesium sulfate. Then, the organic layer was concentrated to give 9.87 g of crude product. The crude product was purified by silica gel column chromatography to afford 6.82 g (88% yield) of compound 215 (endoform:exoform=88:12) as a mixture of endoform and exoform isomers. The ¹ H-NMR data of the obtained compound 215 are shown below.

[0727] (Connection 215)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.72-1.75 (m, 1H), 2.33-2.37 (m, 1H), 2.60-2.61 (m, 1H), 2.92-3.21 (m, 4H), 3.82-3. 88 (dd, J=9.9, 5.3 Hz, 1H), 4.69-4.72 (m, 1H), 5.08-5.11 (m, 1H), 7.17-7.39 (m, 16H), 7.59-7.64 (m, 2H), 7.81-7.85 (m, 2H), 8.02-8.07 (m, 2H); exoform: 1.26-1.33 (m, 1H), 1.96-1.99 (m, 1H), 2.45 (wide s, 1H), 2.63-2.75 (m, 3H), 3.35-3.45 (m, 2H), 5.25-5.38 (m, 1H), 5.36-5.38 (m, 1H), 7.17-7.39 (m, 16H), 7.59-7.64 (m, 2H), 7.81-7.85 (m, 2H), 8.02-8.07 (m, 2 h).

Compound 215 exhibits gradual melting starting from 62.5°C.

[0728] [Example B13]

<Synthesis of compound 216>

The synthesis of compound 216 shown below was carried out by the method given below.

[0729] [Chemical formula 239]

[0730] 2.22 g (yield 32%) of compound 216 (endo form:exo form=83:17) was obtained as a mixture of endo form and exo form isomers according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 5.36 g (2.2 equivalents) of 3-chlorobenzoyl chloride and only 10 ml of pyridine were used as a solvent instead of using 3-methylene dichloride in <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 216 are shown below.

[0731] (Connection 216)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.71-1.75 (m, 1H), 2.28-2.32 (m, 1H), 2.57-2.58 (m, 1H), 2.89-3.10 (m, 4H), 3.80-3.86 (dd, J=10.2, 5.6 Hz, 1H), 4.63-4.65 (m, 1H), 5.01-5.04 (m, 1H), 7.16-7.33 (m, 6H), 7.40-7.45 (m, 2H), 7.71-7.80 (m, 4H); exoform: 1.28-1.32 (m, 1H), 1.90-1.95 (m, 1H), 2.42 (br. s, 1H), 2.60-2.74 (m, 3H), 3.32-3.42 (m, 2H), 5.17-5.20 (m, 1H), 5.29-5.31 (m, 1H), 7.16-7.33 (m, 6H), 7.40-7.45 (m, 2H), 7.71-7.80 (m, 4H).

The final melting point of compound 216 was 139.4°C.

[0732] [Example B14]

<Synthesis of compound 217>

The synthesis of compound 217 shown below was carried out by the method mentioned below.

[0733] [Chemical formula 240]

[0734] 4.50 g (yield 58%) of compound 217, including only the endo form, was obtained according to the operation and equivalence ratio described in <Synthesis of Compound 205> except that 6.41 g (2.2 equivalents) of 3,5-dichlorobenzoyl chloride and only 10 ml of pyridine were used as a solvent instead of using 3-methylbenzene chloride in <Synthesis of Compound 205>. The ¹ H-NMR data of the obtained compound 217 are shown below.

[0735] (Connection 217)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.74-1.78 (m, 1H), 2.26-2.30 (m, 1H), 2.57-2.58 (m, 1H), 2.89-3.10 (m, 4H), 3.82-3.88 (dd, J=9.9, 5.6 Hz, 1H), 4.60-4.62 (m, 1H), 4.98-5.01 (m, 1H), 7.23-7.32 (m, 4H), N), 7.45-7.48 (m, 2H), 7.62-7.67 (m, 4H).

The final melting point of compound 217 was 208.2°C.

[0736] [Example B15]

<Synthesis of compound 218>

The synthesis of compound 218 shown below was carried out by the method given below.

[0737] [Chemical formula 241]

[0738] The synthesis of compound 218 was carried out in accordance with the operation and equivalence ratio described in <Synthesis of Compound 214> except that 4.63 g (1 equivalent) of 3,4-dimethylbenzoic acid was used instead of 3-phenylbenzoic acid in <Synthesis of Compound 214>. The obtained compound 218 was used in the same way as in the synthesis of compound 219.

[0739] <Synthesis of Compound 219>

The synthesis of compound 219 shown below was carried out by the method given below.

[0740] [Chemical formula 242]

[0741] A 100 mL flask was purged with nitrogen from the inside, 2.57 g (1 equivalent) of a mixture of compound 201 and compound 202 were added, followed by 20 mL of a solution of the total amount (2.2 equivalents) of compound 218 synthesized in <the synthesis of compound 218> in dichloromethane. While cooling in an ice bath, 10 mL of anhydrous pyridine was slowly added dropwise. After the dropwise addition, the temperature was raised to room temperature and stirring was carried out overnight. While cooling again in an ice bath, methanol was added to quench. After adding and stirring dichloromethane and water, the organic layers were separated. The organic layer was washed with a saturated aqueous solution of ammonium chloride and brine, and then dried over magnesium sulfate. Then, the organic layer was concentrated to give 10.3 g of crude product. The crude product was purified by silica gel column chromatography to afford 4.80 g (83% yield) of compound 219 (endoform:exoform=87:13) as a mixture of endoform and exoform isomers. The ¹ H-NMR data of the obtained compound 219 are shown below.

[0742] (Connection 219)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.66-1.70 (m, 1H), 2.07-2.08 (m, 6H), 2.23-2.25 (m, 6H), 2.29-2.33 (m, 1H), 2.56-2. 57 (m, 1H), 2.88-3.18 (m, 4H), 3.79-3.85 (dd, J=10.9, 5.6 Hz, 1H), 4.61-4.63 (m, 1H), 4.97-5.00 (m, 1H), 7.02-7.08 (m, 2H), 7.16-7.34 (m, 4H), 7.51-7.66 (m, 4H); exo form: 1.24-1.27 (m, 1H), 1.91-1.95 (m, 1H), 2.07-2.08 (m, 6H), 2.23-2.25 (m, 6H), 2.41 (br.s, 1H), 2.59 -2.74 (m, 3H), 3.30-3.42 (m, 2H), 5.14-5.16 (m, 1H), 5.25-5.28 (m, 1H), 7.02-7.08 (m, 2H), 7.16 -7.34 (m, 4H), 7.51-7.66 (m, 4H).

The final melting point of compound 219 was 131.1°C.

[0743] [Example B16]

<Synthesis of compound 220>

The synthesis of compound 220 shown below was carried out by the method given below.

[0744] [Chemical formula 243]

[0745] Compound 220 was synthesized according to the operation and equivalence ratio described in <Synthesis of Compound 214> except that 4.85 g (1 equivalent) of 5,6,7,8-tetrahydro-2-naphthoic acid was used instead of 3-phenylbenzoic acid in <Synthesis of Compound 214>. The obtained compound 220 was used in the same way as in the synthesis of compound 221.

[0746] <Synthesis of Compound 221>

The synthesis of compound 221 shown below was carried out by the method mentioned below.

[0747] [Chemical formula 244]

[0748] 4.30 g (yield 74%) of compound 221 (endoform:exoform=86:14) was obtained as a mixture of endoform and exoform isomers according to the operation and equivalence ratio described in <Synthesis of Compound 219> except that compound 220 (2.2 equivalents) was used instead of compound 218 in <Synthesis of Compound 219>. The ¹ H-NMR data of the obtained compound 221 are shown below.

[0749] (Connection 221)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): endo form: δ 1.66-1.73 (m, 9H), 2.28-2.32 (m, 1H), 2.37-2.77 (m, 9H), 2.88-3.19 (m, 4H), 3.78-3.84 (dd, J=10.2, 5.3 Hz, 1H), 4.60-4.62 (m, 1H), 4.97-4.99 (m, 1H), 6.96-7.01 (m, 2H), 7.14-7.32 (m, 4H), 7.41-7.50 (m, 2H), 7.58-7, 63 (m, 2H); exoform: 1.23-1.27 (m, 1H), 1.66-1.73 (m, 8H), 1.90-1.94 (m, 1H), 2.37-2.77 (m, 12H), 3.30-3.42 (m, 2H), 5.13-5.15 (m, 1H), 5.24-5.27 (m, 1H), 6.96-7.01 (m, 2H), 7.14-7.32 (m, 4H), 7.41-7.50 (m, 2H), 7.58-7.63 (m, 2H).

The final melting point of compound 221 was 151.2°C.

[0750] [Example B17]

<Synthesis of compound 222>

The synthesis of compound 222 shown below was carried out by the method mentioned below.

[0751] [Chemical formula 245]

[0752] Compound 222 was synthesized according to the operation and equivalence ratio described in <Synthesis of Compound 214> except that 5.0 g (1 equivalent) of 4-methoxy-3-methylbenzoic acid was used instead of 3-phenylbenzoic acid in <Synthesis of Compound 214>. The obtained compound 222 was used in the same way as in the synthesis of compound 223.

[0753] <Synthesis of Compound 223>

The synthesis of compound 223 shown below was carried out by the method mentioned below.

[0754] [Chemical formula 246]

[0755] 2.10 g (yield 33%) of compound 223, including only the endo form, were obtained according to the operation and equivalence ratio described in <Synthesis of Compound 219> except that compound 222 (2.2 equivalents) was used instead of compound 218 in <Synthesis of Compound 219>. The ¹ H-NMR data of the obtained compound 223 are shown below.

[0756] (Connection 223)

^1H NMR (270 MHz, CDCl ₃ , TMS as internal standard): δ 1.66-1.70 (m, 1H), 1.95 (s, 3H), 2.02 (s, 3H), 2.29-2.33 (m, 1H), 2.55-2.56 (m, 1H), 2.87-3.19 (m, 4H), 3.78-3.88 (m, 7H), 4.59-4.61 (m, 1H), 4.96-4.98 (m, 1H)), 6.67-6.73 (m, 2H), 7.21-7.33 (m, 4H), 7.51-7.58 (m, 2H), 7.72-7.79 (m, 2H).

The final melting point of compound 223 was 187.1°C.

Industrial applicability

[0757] The new ester compound according to the present invention is a compound suitable for the production of resin additives, cosmetics and external preparations for the skin, microbicidal compositions, antioxidants, chelators and Ziegler-Natta catalysts. The compound can be used, in particular, as a catalytic component for Ziegler-Natta catalysts. The compound makes it possible to obtain a catalyst having excellent stereoregularity and productivity in the polymerization of polypropylene and, thus, having significant industrial value.

Claims (30)

1. An ester compound represented by the formula (1), which is an ester compound represented by the general formula (5) or the general formula (31): [Chemical formula 1] wherein in formula (1), each of R ¹ -R ²⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom; R ¹ -R ¹⁰ , R ²³ and R ²⁴ are optionally bonded to each other to form a ring or optionally to form a multiple bond in which adjacent substituents are bonded directly; R ¹¹ -R ²⁴ are optionally bonded to each other to form a ring, or adjacent substituents are optionally bonded to each other to form a multiple bond; at least one set of R ¹ -R ²⁴ is bonded to each other to form a ring structure; each of n2 -n5 is independently an integer from 0 to 2; each of n1 and n6 is independently an integer of 0 or 1; and in the formula (5), each of R ¹ and R ² independently represents a hydrogen atom, each of R ⁴ and R ⁹ independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom, each of R ¹¹ , R ¹⁵ , R ¹⁷ and R ²¹ independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom; R ¹¹ , R ¹⁵ , R ¹⁷ and R ²¹ are optionally bonded to each other to form a ring; in the formula (31), each of R ³¹ -R ³⁴ represents a hydrogen atom, each of R ⁴ , R ⁹ , R ²¹ and R ²² independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing a heteroatom, R ⁴ , R ⁹ , R ²¹ and R ²² are optionally bonded to each other to form a ring; wherein in formulas (1), (5) and (31), X represents a hydrocarbon group, a heteroatom or a hydrocarbon group containing a heteroatom; and each of L ¹ and L ² independently represents a hydrocarbon group or a hydrocarbon group containing a heteroatom; wherein the hydrocarbon group has from 1 to 20 carbon atoms. 2. The ester compound of claim 1, wherein each of L ¹ and L ² independently represents a hydrocarbon group or a heteroatom-containing hydrocarbon group having 4 or more carbon atoms. 3. An ester compound according to claim 1, wherein X is a divalent group selected from a group of the following general formula (10): [Chemical formula 10] wherein in the group (10), each of R ^1' -R ^7' independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group containing a heteroatom, and R ^2' -R ^7' are optionally bonded to each other to form a ring, or adjacent substituents are optionally directly bonded to form a multiple bond. 4. The ester compound of claim 3, wherein each of R ^1' to R ^7' independently represents a hydrogen atom or a hydrocarbon group having from 1 to 10 carbon atoms. 5. The ester compound according to claim 1, wherein X is a divalent group represented by the following general formula (11): [Chemical formula 11] wherein in formula (13), each of R ^2' and R ^3' independently represents a hydrogen atom, a hydrocarbon group containing from 1 to 20 carbon atoms, or a hydrocarbon group containing a heteroatom having 20 carbon atoms, and R ^2' and R ^3' are optionally bonded to each other to form a ring. 6. The ester compound of claim 5, wherein each of R ^1' to R ^5' independently represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms. 7. The ester compound according to claim 1, wherein in formula (31) X is a divalent group represented by the following general formula (13) wherein in formula (13), each of R ^2' and R ^3' independently represents a hydrogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, or a hydrocarbon group containing a heteroatom and having from 1 to 20 carbon atoms, and R ^2' and R ^3' are optionally bonded to each other to form a ring. 8. The ester compound according to claim 7, wherein each of R ^2' and R ^3' independently represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms. 9. The ester compound according to claim 7, wherein all R ^2' and R ^3' are hydrogen atoms. 10. The ester compound of claim 1, wherein in formula (31), all of R ³¹ -R ³⁴ are hydrogen atoms, each of R ⁴ , R ⁹ , R ²¹ and R ²² independently represents a hydrogen atom, a hydrocarbon group having from 1 to 6 carbon atoms, or a hydrocarbon group containing a heteroatom and having from 1 to 10 hydrogen atoms. 11. The ester compound of claim 1, wherein in formula (31), R ³¹ -R ³⁴ , R ²¹ and R ²² are all hydrogen atoms, each of R ⁴ and R ⁹ is independently a hydrogen atom or a hydrocarbon group having from 1 to 6 carbon atoms, and each of L ¹ and L ² is independently selected from hydrocarbon groups having from 1 to 10 carbon atoms. 12. The ester compound according to claim 1, wherein in formula (5) each of R ¹¹ , R ¹⁵ , R ¹⁷ and R ²¹ independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms. 13. The ester compound of claim 1, wherein in formula (5) each of L ¹ and L ² independently represents a hydrocarbon group or a hydrocarbon group containing a heteroatom and having from 4 to 10 carbon atoms. 14. The ester compound according to claim 1, wherein in formula (5) R ⁴ and/or R ⁹ represent a hydrocarbon group or a hydrocarbon group containing a heteroatom. 15. The ester compound according to claim 1, wherein in formula (5) R ⁴ and/or R ⁹ represent a hydrocarbon group or a hydrocarbon group containing an oxygen atom.