JP6726521B2 - Substituted polyacetylene having optically active group and method for producing the same - Google Patents

Description

The present invention relates to a substituted polyacetylene having an optically active group and a method for producing the same.

Polymer compounds exhibit various functions and are used as useful materials. Against this background, attempts have been actively made in recent years to introduce a conjugated structure into a polymer and to develop an optical/electrical function due to the conjugated structure.

Substituted polyacetylene is a typical conjugated polymer, and has been widely researched as a functional material showing useful properties such as gas permeability as well as photoelectric functions such as photoelectroluminescence and hole transportability. Among them, disubstituted acetylene polymers are said to exhibit higher thermal stability and optical properties than monosubstituted polymers. On the other hand, an optically active polymer is expected to be applied as an asymmetric resolution material because it exhibits an asymmetric induction catalytic ability and an asymmetric recognition ability. It is known that optically active conjugated polymers have asymmetric recognition ability in addition to optical and electrical properties. For example, the following Patent Documents 1 to 3 propose a polyacetylene derivative having an optically active group, which is useful as an optical resolving agent, a liquid crystal, a non-linear optical material and the like.
As described above, polyacetylene having an optically active group has a unique function and is expected to be applied to various uses.

Regarding the synthesis of conjugated polymers, a method of polymerizing acetylenes and forming a conjugated double bond in the resulting polymer is of interest. From such a viewpoint, when a functional group is introduced into the αβ-position of acetylene as a monomer to form a 2-substituted acetylene, in addition to the conjugation due to the polymer main chain after polymerization, the function of the functional group is synergistically. By adding these, further improvement in functionality can be expected. However, regarding the polymerization of disubstituted acetylene having a substituent at the αβ-position of acetylene, there are several examples of synthesis by metathesis polymerization (see, for example, Non-Patent Documents 1 and 2 below), and there are very few synthetic examples of chain polymerization.

The present applicant has previously proposed a method of producing a substituted polyacetylene from a disubstituted acetylene by chain polymerization using a phosphine-palladium complex as a substituted acetylene polymerization initiator (Patent Document 4 below).

JP, 7-292037, A JP-A-8-133991 Japanese Unexamined Patent Publication No. 8-21698 JP, 2014-162745, A

Polymer Chemistry Volume 2 Page 1044 2011 "Quarterly Chemistry Review No. 17 (Organic Chemistry of Previous Transition Metals)", Academic Publishing Center, 1993

The present inventors are investigating a method for producing a substituted polyacetylene from a disubstituted acetylene by chain polymerization, and in the presence of a specific polymerization initiator, use a disubstituted acetylene having a novel optically active group. It was found that a substituted polyacetylene having a novel optically active group useful as an optical resolving agent, a liquid crystal, a non-linear optical material, a photoelectroluminescent material, etc. can be obtained by carrying out the reaction, and the present invention has been completed.

That is, the present invention is to provide a substituted polyacetylene having a novel optically active group, which is useful as an optical resolving agent, a liquid crystal, a non-linear optical material, a photoelectroluminescent material, and the like, and an industrially advantageous production method thereof.

The first invention to be provided by the present invention is the following general formula (1)
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. X is a halogen atom and * is an asymmetric carbon atom.), and is a substituted polyacetylene having an optically active group.

The second invention to be provided by the present invention is the following general formula (2)
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. X represents a halogen atom, * represents an asymmetric carbon atom, and the polymerization reaction of a disubstituted acetylene having an optically active group represented by the following general formula (3)

(In the formula, R ³ , R ⁴ and R ⁵ represent a group selected from an alkyl group and an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. Wherein Me represents a methyl group, Z represents a group selected from a halogen group, a tosyl group, a triflate group and a mesyl group, and y represents an integer of 1 to 2) of the substituted acetylene polymerization initiator. The following general formula (1) characterized by being carried out in the presence of
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. X is a halogen atom and * is an asymmetric carbon atom.) is a process for producing a substituted polyacetylene having an optically active group containing a repeating structural unit represented by the formula:

A third invention which the present invention is to provide is the following general formula (2)
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. X is a halogen atom, and * is an asymmetric carbon atom.) is a disubstituted acetylene.

According to the present invention, it is possible to provide a substituted polyacetylene having a novel optically active group, which is useful as an optical resolving agent, a liquid crystal, a non-linear optical material, a photoelectroluminescence material, and the like.
Further, according to the production method of the present invention, the substituted polyacetylene having the optically active group can be produced by an industrially advantageous method.

The CD spectrum and UV-vis spectrum figure of the substituted polyacetylene obtained in Examples 4, 5 and 6.

The present invention will be described below based on its preferred embodiments.
The substituted polyacetylene having an optically active group of the present invention (hereinafter sometimes simply referred to as “substituted polyacetylene”) includes a repeating structural unit represented by the following general formula (1).


(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. (X represents a halogen atom, * represents an asymmetric carbon atom.)

R ¹ and R ² in the general formula (1) are an alkyl group having 1 to 10 carbon atoms or an aryl group.

Examples of the alkyl group include an acyclic alkyl group and an alicyclic alkyl group.
The acyclic alkyl group includes a linear alkyl group and a branched alkyl group. Examples of the linear alkyl group include those having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-heptyl group. .. The branched alkyl group has 3 to 10 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isoheptyl group, isohexyl group, 1,1,3,3-tetramethylbutyl group, etc. Are listed.
The alicyclic alkyl group includes a monocyclic alkyl group and a bicyclic alkyl group. Examples of the monocyclic alkyl group include those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Examples of the polycyclic alkyl group include those having 4 to 10 carbon atoms such as an adamantyl group.
Examples of the aryl group for R ¹ and R ² include a phenyl group, a biphenyl group, a tolyl group, a xylyl group, and a naphthyl group.
The alkyl group and aryl group for R ¹ and R ² may have a substituent. Examples of the substituent include an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, and a general formula; -N(A ¹ )(A ² ) (in the formula, A ¹ and A ² represents a linear alkyl group having 1 to 8 carbon atoms).

In the present invention, R ¹ and R ² in the formula (1) are different groups, and R ¹ and R ² are a combination of a methyl group and an ethyl group or a methyl group and a phenyl group. It is preferably a combination.

X in the formula of the general formula (1) is a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and among these, a chlorine atom is preferable.

The substituted polyacetylene according to the present invention has a number average molecular weight of 1,000 to 1,000,000, preferably 5,000 to 500,000, and particularly preferably 5,000 to 200,000. In the present invention, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 15 or less, preferably 6 or less, and particularly preferably 1.1 to 2.

Hereinafter, a method for producing a substituted polyacetylene having an optically active group according to the present invention will be described.
The method for producing a substituted polyacetylene having an optically active group represented by the general formula (1) according to the present invention is a polymerization reaction of a disubstituted acetylene having an optically active group represented by the general formula (2). It is characterized in that it is carried out in the presence of a substituted acetylene polymerization initiator represented by the general formula (3).

The 2-substituted acetylene having an optically active group as a raw material is represented by the following general formula (2).
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. (X represents a halogen atom, * represents an asymmetric carbon atom.)

R ¹ , R ² and X in the formula of the general formula (2) are groups respectively corresponding to R ¹ , R ² and X in the formula of the general formula (1).

In the formula of the general formula (2), R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms or an aryl group.

Examples of the alkyl group include an acyclic alkyl group and an alicyclic alkyl group.
The acyclic alkyl group includes a linear alkyl group and a branched alkyl group. Examples of the linear alkyl group include those having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-heptyl group. .. The branched alkyl group has 3 to 10 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isoheptyl group, isohexyl group, 1,1,3,3-tetramethylbutyl group, etc. Are listed.
The alicyclic alkyl group includes a monocyclic alkyl group and a bicyclic alkyl group. Examples of the monocyclic alkyl group include those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Examples of the polycyclic alkyl group include those having 4 to 10 carbon atoms such as an adamantyl group.
Examples of the aryl group for R ¹ and R ² include a phenyl group, a biphenyl group, a tolyl group, a xylyl group, and a naphthyl group.
The alkyl group and aryl group for R ¹ and R ² may have a substituent. Examples of the substituent include an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, and a general formula; -N(A ¹ )(A ² ) (in the formula, A ¹ and A ² represents a linear alkyl group having 1 to 8 carbon atoms).

In the present invention, R ¹ and R ² in the formula (2) are different groups, and R ¹ and R ² are a combination of a methyl group and an ethyl group or a methyl group and a phenyl group. It is preferably a combination.

X in the formula of the general formula (2) is a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and among these, a chlorine atom is preferable.

The 2-substituted acetylene having an optically active group represented by the general formula (2) can be produced, for example, according to the following reaction scheme (1).

(In the formula, R ¹ and R ² are as defined above. Bu ₄ NF represents tetrabutylammonium fluoride.)

The substituted acetylene polymerization initiator used in the present production method is represented by the following general formula (3).

(In the formula, R ³ , R ⁴ and R ⁵ represent a group selected from an alkyl group and an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. Among them, Me represents a methyl group, Z represents a group selected from a halogen group, a tosyl group, a triflate group and a mesyl group, and y represents an integer of 1 to 2.)

In the formula of the general formula (3), R ³ , R ⁴ and R ⁵ are an alkyl group having 1 to 10 carbon atoms or an aryl group.

Examples of the alkyl group include an acyclic alkyl group and an alicyclic alkyl group.
The acyclic alkyl group includes a linear alkyl group and a branched alkyl group. Examples of the linear alkyl group include those having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-heptyl group. .. The branched alkyl group has 3 to 10 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isoheptyl group, isohexyl group, 1,1,3,3-tetramethylbutyl group, etc. Are listed.
The alicyclic alkyl group includes a monocyclic alkyl group and a bicyclic alkyl group. Examples of the monocyclic alkyl group include those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Examples of the polycyclic alkyl group include those having 4 to 10 carbon atoms such as an adamantyl group.
Examples of the aryl group for R ^{3 to} R ⁵ include a phenyl group, a biphenyl group, a tolyl group, a xylyl group, and a naphthyl group.
The alkyl group and aryl group related to R ^{3 to} R ⁵ may have a substituent. And the substituent is an alkyl group having 1 to 8 carbon atoms, alkyl groups and the general formula 1 to 8 carbon atoms which is substituted with a halogen ^{atom; -N (A 3) (A} 4) ( wherein, A ³ and A ⁴ represents a group selected from a linear alkyl group having 1 to 8 carbon atoms).

In the present invention, R ³ , R ⁴ and R ^{5 in} the formula of the general formula (3) may be the same group or different groups, and among R ^{3 to} R ⁵ Two may be the same group. In the present production method, it is particularly preferable that each of R ³ , R ⁴ and R ⁵ is a tert-butyl group.

In the formula of the general formula (3), Me represents a methyl group, Z represents a group selected from a halogen group, a tosyl group, a triflate group and a mesyl group, and among these, Z is preferably a halogen group.

Further, y in the formula of the general formula (3) is an integer of 1 to 2, and y is preferably 1.

In the present production method, the substituted acetylene polymerization initiator represented by the general formula (3) is preferably the following compound, particularly the compound (3a) (hereinafter, referred to as [(t-Bu ₃ P)PdMeCl]). preferable.

(In the formula, tBu represents a tert-butyl group and iPr represents an isopropyl group.)

The substituted acetylene polymerization initiator represented by the general formula (3) is a known compound and can be produced, for example, according to the following reaction scheme (2) (JP-A-2014-162745, JP-A-2006-241325). JP, JP-A-2006-241326, ACS
Macro Lett. , 3, 51-54 (2014)).

(In the formula, R ³ , R ⁴ , R ⁵ , X and y have the same meanings as described above. cod represents a 1,5-cyclooctadiene group.)

The polymerization reaction of the disubstituted acetylene having an optically active group represented by the general formula (2) according to the present invention is carried out in the presence of the substituted acetylene polymerization initiator represented by the general formula (3). The polymerization reaction of a disubstituted acetylene having an optically active group represented by 2) is performed in a reaction solvent to obtain a substituted polyacetylene having an optically active group represented by the general formula (1).

In the present production method, the addition ratio of the disubstituted acetylene to the substituted acetylene polymerization initiator is 10 to 1,000 times, preferably 50 to 500 times, in molar ratio.

The reaction solvent that can be used is not particularly limited as long as it can dissolve the raw materials and is inert to the product. Examples thereof include tetrahydrofuran, toluene, dichloromethane, acetonitrile and the like, which may be used alone or in combination of two or more.

In the present production method, the disubstituted acetylene is polymerized efficiently and smoothly by carrying out the polymerization reaction in the presence of an activator capable of abstracting the Z group in the formula (3). The reaction can be carried out.

Examples of the activator that can be used include sodium hexafluorophosphate, ammonium hexafluorophosphate, silver hexafluorophosphate, sodium tetrafluoroborate, ammonium tetrafluoroborate, silver tetrafluoroborate, and trifluoromethanesulfone. Examples thereof include silver acid salts, and among these, silver trifluoromethanesulfonate is preferably used.

The addition amount of the activator is 1 to 5 times, preferably 1 to 1.5 times the molar ratio of the substituted acetylene polymerization initiator.

The reaction temperature of the polymerization reaction is preferably selected as appropriate depending on the type of disubstituted acetylene used for the polymerization, but in many cases it is 0 to 100°C, preferably 20 to 90°C. The reaction time varies depending on the type of the substituted acetylene to be polymerized, but in many cases is 6 hours or longer, preferably 12 to 36 hours.

After the completion of the polymerization reaction, the reaction solvent is removed by a conventional method, and purification such as reprecipitation is carried out if necessary, whereby the desired substituted polyacetylene represented by the general formula (1) can be obtained.

Thus, the obtained substituted polyacetylene represented by the general formula (1) has a number average molecular weight of 1,000 to 1,000,000, preferably 5,000 to 500,000, particularly preferably 5,000 to 200, It is 000. In the present invention, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 15 or less, preferably 6 or less, and particularly preferably 1.1 to 2.

The substituted polyacetylene having an optically active group represented by the general formula (1) according to the present invention is particularly useful as an optical resolving agent, a liquid crystal, a non-linear optical material, a photoelectroluminescence material, and the like. Other desired functional groups can be introduced by substituting the halogen atom of X in the formula).

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

{Example 1}
<Preparation of Disubstituted Acetylene (1P) Having Optically Active Group>
As 2-substituted acetylene, the following chemical formula (1p) was synthesized according to the following reaction scheme (3).
(In the formula, Et represents an ethyl group.)

(Synthesis of (R)-1-(2-butoxy)-4-iodobenzene (a3))
Diisopropylazodicarboxylate (61.1 ml) and THF (100 ml) were charged in the reaction vessel. PPh ₃ (30.5 g, 116 mmol), p-iodophenol (25.5 g, 116 mmol), (S)-2-butanol (8.60 g, 116 mmol) were dissolved in THF (300 ml), and the mixture was heated at 0° C. in argon. Then, the mixture was stirred at room temperature under N ₂ for 2 days. After completion of the reaction, the solvent THF was distilled off with a rotary evaporator, and the residue was dried under reduced pressure. The residue was dissolved with diethyl ether and the solution was filtered under reduced pressure. The solvent was distilled off with a rotary evaporator and dried under reduced pressure to obtain a gum-like yellow viscous substance. This was purified by silica gel column chromatography (hexane/chloroform = 10/1) to obtain a colorless transparent liquid (13.98 g, 50.6 mmol) (yield 44%).
(Identification data)
¹ H NMR (400MHz, CDCl ₃ ): d 0.95 (t, J = 7.6 Hz, 3H, CH ₃ ), 1.26 (d, J = 6.0Hz, 3H, CH ₃ ), 1.56-1.73 (m, 2H, CH ₂ ),4.19-4.26 (m, 1H,CH), 6.64-7.53(m, 4H).

(Synthesis of trimethylsilyl-4-((R)-2-butoxy)phenylacetylene (a4))
In a reaction vessel, (R)-1-(2-butoxy)-4-iodobenzene (a3) (13.98 g, 50.6 mmol), Pd(PPh ₃ ) ₂ Cl ₂ (3.58 g, 5.10 mmol). , PPh ₃ (5.36 g, 20.4 mmol) were charged, and THF (170 ml, 22.3 mmol), Et ₃ N (63.8 ml, 23.8 mmol), triethylsilylacetylene (8.63 ml, 61.0 mmol) were added. It was added under argon and stirred at 50° C. for 3 h. The solvent was distilled off with a rotary evaporator, the residue was dissolved in THF and filtered, and then the solvent was distilled off again. Purification by silica gel column chromatography (hexane/chloroform=5/1) gave a yellow liquid (8.05 g, 32.6 mmol) (yield 65%).
(Identification data)
¹ H NMR (400 MHz, CDCl ₃ ): d 0.22 (s, 9H, TMS), 0.95 (t,J=7.6 Hz, 3H, CH ₃ ), 1.27 (d, J = 6.0 Hz, 3H, CH ₃ ). ,1.54-1.78 (m, 2H,CH ₂ ), 4.25-4.32 (m,1H, CH), 6.79-7.38(m, 4H)

(Synthesis of chloro-4-((R)-2-butoxy)phenylacetylene (1p))
Trimethylsilyl-4-((R)-2-butoxy)phenylacetylene (a4) (8.05 g, 32.6 mmol) and potassium carbonate (4.57 g, 32.6 mmol) were charged in a reaction vessel, and carbon tetrachloride was added. (100 ml) was added. Furthermore, a THF solution of tetrabutylammonium fluoride (1.0 M, 18.7 ml, 66.0 mmol) was added, and the mixture was stirred for several minutes and then at 25° C. for 15 hours. After the reaction was completed, Et ₂ O (110 ml) was added, and NaCl was used for salting out to separate the layers. After adding MgSO ₄ to the organic layer and dehydrating for several minutes, MgSO ₄ was filtered off, the solvent was distilled off with a rotary evaporator, and dried under reduced pressure. 1.20 g of the produced liquid was weighed and purified using preparative HPLC to obtain a brown liquid (0.873 g, 4.06 mmol) (yield 73%).
(Identification data)
[a] _D = 19.7 ° (c=0.1 g/dL, THF). IR (cm ^-1 ): 832, 1249, 2221, 2878, 2936, 2974. ¹ HNMR (400 MHz, CDCl ₃ ): d 0.95( t, J = 7.6 Hz, 3H, CH ₃ ),1.27 (d, J = 6.4 Hz,3H,
CH ₃ ),1.55-1.78 (m, 2H, CH ₂ ),4.25-4.32 (m, 1H, CH), 6.78-7.35 (m, 4H). ¹³ CNMR (100 MHz, CDCl ₃ ):9.84, 19.2, 29.2, 66.2, 75.4, 76.8, 77.1,77.4, 115.8, 133.5, 158.6. Elem. Anal.Calcd for C ₁₂ H ₁₃ OCl,C: 69.07%; H 6.28%.Found C: 67.95%, H 6.20%.

{Example 2}
<Preparation of disubstituted acetylene (1 m) having an optically active group>
Disubstituted acetylene (1 m) having an optically active group was synthesized according to the following reaction scheme (4).
(In the formula, Et represents an ethyl group.)
(Synthesis of chloro-4-((R)-2-butoxy)phenylacetylene (1m))
Chloro-4, except that m-iodophenol (b1) was used in place of p-iodophenol (a1) in the synthesis of (R)-1-(2-butoxy)-4-iodobenzene (a3). Chloro-4-((R)-2-butoxy)phenylacetylene (1m) was synthesized in the same manner as in the synthesis of -((R)-2-butoxy)phenylacetylene (1p).
(Identification data)
[a] _D = 42.2 °(0.1g/dL, THF). IR (cm ^-1 ): 686, 785, 1286,1596, 2217, 1878,1935,2972. ¹ H-NMR (400 MHz, CDCl ₃ ). d0.96 (t, J = 8.0 Hz, 3H,CH3), 1.28 (d, J= 6.0 Hz, 3H, CH ₃ ), 1.60-1.75 (m, 2H, CH2), 4.23-4.32 (m, 1H, CH),6.85-7.24(m, 4H, Ar), ¹³ CNMR (100 MHz, CDCl ₃ ) 10.0, 19.5, 29.5, 67.9, 75.0, 76.8, 77.3,77.7,117.1,119.0, 123.2, 124.3, 129.5,158.2 .Elem. Anal. Calcdfor C ₁₂ H ₁₃ OCl, C: 69.07%; H: 6.28%.Found C: 67.95%, H6.20%.

{Example 3}
(Synthesis of Disubstituted Acetylene (2p) Having Optically Active Group)
Disubstituted acetylene (2p) having an optically active group was synthesized according to the following reaction scheme (5).
(In the formula, Ph represents a phenyl group.)
(Synthesis of chloro-4-((S)-1-phenylethoxy)phenylacetylene (2p))
In the synthesis of (R)-1-(2-butoxy)-4-iodobenzene (a3), (R)-1-phenylethanol (c2) is used instead of (S)-2-butanol (a2). Chloro-4-((S)-1-phenylethoxy)phenylacetylene (2p) was synthesized in the same manner as the synthesis of chloro-4-((R)-2-butoxy)phenylacetylene (1p) except that did.
(Identification data)
[a] _D = 2.92 ° (c=0.1g/dL, THF). ¹ H NMR (400 MHz, ozone-d ₆ ): d 7.46-7.22(Ar, 5H), 6.94-6.86 (Ar, 2H), 5.00 (q, 1H, J = 6.3 Hz), 1.58 (d, 3H, J = 6.3 Hz). ¹³ C
NMR (100 MHz, yeast-d ₆ ): d159.4, 143.8, 134.0, 129.4, 128.3, 126.4, 116.9, 114.3, 76.4, 70.2, 66.4, 24.6.IR (KBr): 2985.2, 2975.8, 2927.0, 1604.4, 1508.3,1287.8,1241.3, 1180.0, 1078.0,835.7, 763.1, 699.4. Elem. Anal. Calcdfor C ₁₄ H ₉ OCl, C:73.53%; H 3.93%.Found C: 72.33%, H4.02%.MS (EI ): m/z 256, 258 (M ⁺ ),256:258 = 3:1.

{Example 4}
<Preparation of Substituted Polyacetylene (Poly(1p))>

Chloro-4-((R)-2-butoxy)phenylacetylene (1p) (234 mg, 1.12 mmol) was dissolved in toluene (0.280 ml) in a reaction vessel. _{[(t-Bu 3 P)} PdMeCl] (16.0mg, 0.04mmol) and silver trifluoromethanesulfonate were mixed (AgOTf, 14.0 mg, 0.05 mmol) in a separate vessel, toluene (0.560ml) Dissolved in. After that, the two solutions were mixed and stirred under argon at 80° C. for 20 h. After the reaction, acetic acid (0.1 ml) was added and stirred for 30 minutes to stop the reaction. Then, after dissolving it in a small amount of CH ₂ Cl ₂ , it was added dropwise to MeOH (200 ml), the resulting precipitate was filtered off under reduced pressure, and THF (50 ml) was added to separate it into a THF soluble part and an insoluble part. Then, the obtained solid was collected as a THF-insoluble part. In the THF-soluble part, after the solution was collected, the solvent was distilled off with a rotary evaporator, dissolved again in a small amount of CH ₂ Cl ₂ and poured into MeOH (200 ml), and the resulting precipitate was collected by vacuum filtration. , Substituted polyacetylene (Poly(1p)) was obtained.
(Identification data)
Poly(1p): IR (cm ^-1 ): 803, 1098, 1247, 1507, 1605, 2965, 3434. ¹ H NMR (400 MHz, CDCl ₃ ): d 0.08(s), 1.57 (s).

{Example 5}
<Preparation of Substituted Polyacetylene (Poly(1m))>

The same as Example 4 except that chloro- 3 -((R)-2-butoxy)phenylacetylene (1m) was used instead of chloro-4-((R)-2-butoxy)phenylacetylene (1p). The reaction was carried out to obtain a substituted polyacetylene (Poly(1m)).
(Identification data)
Poly(1m): IR (cm ^-1 ): 796, 1216, 1595,2968, 3434. ¹ H NMR (400 MHz, CDCl ₃ ): d 1.50 (br), 3.50(s).

{Example 6}
<Preparation of Substituted Polyacetylene (Poly(2p))>

Example 4 was repeated except that chloro-4-((S)-1-phenylethoxy)phenylacetylene (2p) was used instead of chloro-4-((R)-2-butoxy)phenylacetylene (1p). Reaction was carried out in the same manner to obtain a substituted polyacetylene (Poly(2p)).
(Identification data)
Poly(2p): IR (cm ^-1 ): 699, 1241, 1507, 1604, 2927, 2925, 3438. ¹ H NMR (400 MHz, CDCl ₃ ): d 1.24(br), 1.60 (br), 3.48 ( s).

<Evaluation of number average molecular weight (Mn) and weight average molecular weight (Mw)>
For the substituted polyacetylene obtained in the examples, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) were obtained. The results are shown in Table 1.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are evaluated by SEC (ShodexGPC KD-G × 2, Shodex TSK-GELa-M C0053 × 2, JASCOCO-965, JASCO UV-2075 Plus, JASCORI- 930, JASCO PU-980, JASCO DG-980-50, 10 mM DMF solution, polystyrene conversion).

<Evaluation of optical properties>
The substituted polyacetylenes obtained in Examples 4, 5 and 6 were dissolved in DMF and the specific optical rotation and UV-vis spectrum were measured. The concentration of the monomer unit of the substituted polyacetylene in DMF was 0.04 mM.
The CD spectrum and UV-vis spectrum of the substituted polyacetylenes obtained in Examples 4, 5 and 6 are shown in FIG.
From the result of FIG. 1, a CD peak was observed in the absorption region of the main chain near 350 nm obtained in Example 5, which suggests that a chiral secondary structure is formed.

Claims (8)

The following general formula (1)
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. X is a halogen atom, and * is an asymmetric carbon atom.) A substituted polyacetylene having an optically active group, the substituted polyacetylene having a repeating structural unit represented by the formula: R ¹ and R ^{2 in} the formula of the general formula (1) are a combination of a methyl group and an ethyl group or a combination of a methyl group and a phenyl group, and have the optically active group according to claim 1. Substituted polyacetylene. The following general formula (2)
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. X represents a halogen atom, * represents an asymmetric carbon atom, and the polymerization reaction of a disubstituted acetylene having an optically active group represented by the following general formula (3)
(In the formula, R ³ , R ⁴ and R ⁵ represent a group selected from an alkyl group and an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. Wherein Me represents a methyl group, Z represents a group selected from a halogen group, a tosyl group, a triflate group and a mesyl group, and y represents an integer of 1 to 2) of the substituted acetylene polymerization initiator. The following general formula (1) characterized by being carried out in the presence of
(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. X represents a halogen atom and * represents an asymmetric carbon atom.) A process for producing a substituted polyacetylene having an optically active group containing a repeating structural unit represented by X in the formula of the general formula (3) is a chlorine atom, and the method for producing a substituted polyacetylene having an optically active group according to claim 3. A substituted acetylene polymerization initiator in which R ³ , R ⁴ and R ^{5 in the} formula (3) are each a tert-butyl group and y is 1 is used. A method for producing a substituted polyacetylene having an optically active group according to any one of 1. The polymerization reaction is carried out in the presence of a substituted acetylene polymerization initiator of the general formula (3) and an activator capable of abstracting the Z group in the formula of the general formula (3). 5. A method for producing a substituted polyacetylene having the optically active group according to any one of 5 above. The method for producing a substituted polyacetylene having an optically active group according to claim 6, wherein the activator is silver trifluoromethanesulfonate. The following general formula (2)


(In the formula, R ¹ and R ² represent an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group and the aryl group may have a substituent. provided that R ¹ and R ² are the same. A disubstituted acetylene, wherein X represents a halogen atom, * represents an asymmetric carbon atom).