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WO2011132479A1 - Procédé de préparation de composé - Google Patents

Procédé de préparation de composé Download PDF

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Publication number
WO2011132479A1
WO2011132479A1 PCT/JP2011/056140 JP2011056140W WO2011132479A1 WO 2011132479 A1 WO2011132479 A1 WO 2011132479A1 JP 2011056140 W JP2011056140 W JP 2011056140W WO 2011132479 A1 WO2011132479 A1 WO 2011132479A1
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Prior art keywords
ring
group
formula
compound represented
aromatic
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English (en)
Japanese (ja)
Inventor
栄 高橋
研 吉村
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the present invention relates to a method for producing a compound having a specific structure.
  • organic elements using organic semiconductor materials such as organic electroluminescence elements, organic thin film solar cells, and organic thin film transistors
  • the organic semiconductor material include a material having a structure in which an aromatic ring is condensed through an oxygen atom and a carbon atom.
  • the present invention provides a method for producing a compound as a raw material for a polymer material having a tricyclic structure in which two aromatic rings are condensed via an oxygen atom and a carbon atom in a high yield. That is, the present invention is a compound of formula (1): In formula, A ring and B ring are the same or different, and represent an aromatic ring. A compound represented by formula (2): In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group.
  • Formula (3) in which a compound represented by the formula is reacted with hydrogen peroxide In formula, A ring and B ring represent the same meaning as the above-mentioned. The manufacturing method of the compound represented by these is provided.
  • the present invention relates to a method for producing a compound represented by formula (3) in which a compound represented by formula (1), a compound represented by formula (2), and hydrogen peroxide are reacted in a solvent.
  • a ring and B ring are the same or different and represent an aromatic ring.
  • the aromatic ring may be an aromatic carbocyclic ring or an aromatic heterocyclic ring.
  • aromatic carbocycle examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pentacene ring, chrysene ring, triphenylene ring, pyrene ring, picene ring and perylene ring which may have a substituent. Is mentioned.
  • aromatic heterocycle examples include a pyridine ring, quinoline ring, isoquinoline ring, pyrazine ring, quinoxaline ring, acridine ring, pyrimidine ring, quinazoline ring, pyridazine ring, cinnoline ring and furan ring which may have a substituent.
  • Examples of the substituent of the aromatic carbocycle and the aromatic heterocycle include a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, and An arylalkoxy group is mentioned. These alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group and arylalkoxy group may be substituted.
  • halogen atom chlorine atom, bromine atom, fluorine atom, iodine atom
  • substituents examples include a halogen atom (chlorine atom, bromine atom, fluorine atom, Iodine atom), a cyano group, a nitro group, and an alkoxy group having 1 to 12 carbon atoms.
  • the alkyl group may be linear or branched, and may be a cyclic alkyl group.
  • the alkyl group usually has 1 to 30 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl.
  • hexyl group isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group
  • chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cyclic alkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.
  • the alkoxy group may be linear or branched, and may be a cyclic alkyloxy group.
  • the carbon number of the alkoxy group is usually 1 to 20, and specific examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group. Cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group.
  • Examples of the substituted alkoxy group include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methoxymethoxy group, and a 2-methoxyethoxy group.
  • the aryl group is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is usually 6 to 60. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a C1-C12 alkylphenyl group.
  • Examples of the substituted aryl group include a C1 to C12 alkoxyphenyl group (C1 to C12 indicates that having 1 to 12 carbon atoms, the same applies hereinafter) and a pentafluorophenyl group.
  • the aryloxy group usually has 6 to 60 carbon atoms, and specific examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a C1-C12 alkylphenoxy group.
  • Examples of the substituted aryloxy group include a C1-C12 alkoxyphenoxy group and a pentafluorophenyloxy group.
  • the arylalkyl group usually has 7 to 60 carbon atoms, and specific examples thereof include phenyl-C1 to C12 alkyl group, 1-naphthyl-C1 to C12 alkyl group, 2-naphthyl-C1 to C12 alkyl group, and C1 to C12. Examples include alkylphenyl-C1 to C12 alkyl groups. Examples of the substituted arylalkyl group include C1-C12 alkoxyphenyl-C1-C12 alkyl groups. The arylalkoxy group usually has 7 to 60 carbon atoms.
  • phenyl-C1 to C12 alkoxy groups 1-naphthyl-C1 to C12 alkoxy groups, 2-naphthyl-C1 to C12 alkoxy groups, and C1 to C12.
  • alkylphenyl-C1 to C12 alkoxy groups examples include alkylphenyl-C1 to C12 alkoxy groups.
  • substituted arylalkoxy group include C1-C12 alkoxyphenyl-C1-C12 alkoxy groups.
  • Preferred embodiments of the A ring and the B ring are both aromatic heterocycles. Examples of the group obtained by removing two hydrogen atoms from the aromatic carbocycles of the A ring and the B ring include groups represented by the following formulas (101) to (125).
  • Examples of the group obtained by removing two hydrogen atoms from the aromatic heterocyclic ring include groups represented by the following formulas (201) to (267).
  • R ′ is the same or different and is a hydrogen atom, halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group or arylalkoxy.
  • R ′′ and R ′ ′′ are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an arylalkyl group.
  • the carbon number of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group and an arylalkoxy group specific examples are alkyls which are substituents that the aforementioned A ring and B ring may have
  • the number of carbon atoms of the group, alkoxy group, aryl group, aryloxy group, arylalkyl group and arylalkoxy group is the same as the specific example.
  • these alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group and arylalkoxy group are a halogen atom, a cyano group, a nitro group or a carbon number of 1 to It may be substituted with 12 alkoxy groups.
  • Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (301) to (335). In the formulas (301) to (335), R ′ and R ′′ represent the same meaning as described above. Other examples of the compound represented by formula (1) include compounds represented by formula (301) to formula (335) having a substituent.
  • substituents examples include a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, and arylalkoxy group.
  • halogen atom chlorine atom, bromine atom, fluorine atom, iodine atom
  • alkyl group alkoxy group, aryl group, aryloxy group, arylalkyl group, and arylalkoxy group.
  • the carbon number of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group and an arylalkoxy group and specific examples thereof are a halogen which is a substituent that the above-mentioned A ring and B ring may have.
  • the number of carbon atoms of an atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, and an arylalkyloxy group are the same as in the specific examples.
  • these alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group and arylalkoxy group are a halogen atom, a cyano group, a nitro group or a carbon number of 1 to It may be substituted with 12 alkoxy groups.
  • R 1 and R 2 are the same or different, and are a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group. Represents.
  • the alkyl group represented by R 1 and R 2 may be linear or branched, and may be a cyclic alkyl group.
  • Carbon number of the alkyl group is usually 1-20, and specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, Isopentyl group, 2-methylbutyl group, 1-methylbutyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group , 3,7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, eicosyl group and other chain alkyl groups, cycl
  • the aryl group represented by R 1 and R 2 usually has 6 to 60 carbon atoms, and specific examples thereof include a phenyl group, a C1 to C12 alkylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Specific examples of the substituted aryl group include a C1-C12 alkoxyphenyl group.
  • Examples of the substituent that the alkyl group and aryl group represented by R 1 and R 2 may have include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, and C1 to C12 alkoxy groups may be mentioned.
  • Preferred substituents are a chlorine atom and a fluorine atom, and particularly preferred substituents are a fluorine atom.
  • Specific examples of the compound represented by the formula (2) include compounds represented by the following formulas (401) to (430).
  • the compound represented by formula (401) to formula (430) from the viewpoint of increasing the yield of the compound represented by formula (3), the compound represented by formula (401), represented by formula (410) And a compound represented by formula (421) are preferred, a compound represented by formula (401) (acetic anhydride) and a compound represented by formula (421) (trifluoroacetic anhydride) are more preferred,
  • the compound represented by Formula (421) is preferable.
  • the hydrogen peroxide used in the present invention is usually diluted with water. That is, hydrogen peroxide water is used.
  • the concentration of hydrogen peroxide used is usually 1 to 50% by weight, preferably 5 to 40% by weight.
  • the solvent used in the present invention may be any solvent that does not react with the compound represented by the formula (2) or the hydrogen peroxide solution, and includes aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic halogenated hydrocarbons, and aromatics.
  • Halogenated hydrocarbons are preferred.
  • the aliphatic hydrocarbon include pentane, hexane, heptane, octane, decane, dodecane and cyclohexane.
  • the aromatic hydrocarbon include benzene, toluene, ethylbenzene, xylene, and cumene.
  • Examples of the aliphatic halogenated hydrocarbon include chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane.
  • Examples of the aromatic halogenated hydrocarbon include chlorobenzene, o-chlorobenzene, and 1,2,4-trichlorobenzene.
  • halogenated hydrocarbons are preferable and aliphatic halogenated hydrocarbons are more preferable from the viewpoint of increasing the yield of the compound represented by Formula (3). Chloroform and dichloromethane are more preferred, and dichloromethane is particularly preferred.
  • First aspect A compound represented by formula (2) and hydrogen peroxide are mixed in a solvent to produce a mixture, and then the compound represented by formula (1) is mixed with the mixture. How to react by doing.
  • Second aspect A compound represented by formula (1) and hydrogen peroxide are mixed in a solvent to produce a mixed solution, and then the compound represented by formula (2) is mixed with the mixed solution. How to react by doing.
  • Third aspect A compound represented by formula (1) and a compound represented by formula (2) are mixed in a solvent to produce a mixture, and then hydrogen peroxide is mixed with the mixture. To make it react, Is mentioned. From the viewpoint of improving the yield of the compound represented by formula (3), the first embodiment is preferable.
  • the temperature at which the compound represented by formula (2) and hydrogen peroxide are mixed to produce a mixture, and the compound represented by formula (1) is mixed with the mixture The temperature and the reaction temperature are preferably -20 to 50 ° C, more preferably -10 to 20 ° C.
  • the holding time is preferably 1 minute to 5 hours, more preferably 5 minutes to 1 hour.
  • the reaction time after the compound represented by the formula (1) is mixed with the mixed solution is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours.
  • the reaction mixture obtained by the above reaction is subjected to usual post-treatment such as, for example, extracting the product with an organic solvent after diluting with water, and distilling off the solvent in the organic layer, and is represented by the formula (3).
  • the compounds represented can be obtained.
  • the compound represented by the formula (3) can be isolated and purified by a method such as fractionation by chromatography or recrystallization.
  • the formula (2-2) In the method of the present invention, the formula (2-2) In the formula, A ring and B ring have the same meaning as described above.
  • the compound represented by may be by-produced.
  • the compound represented by Formula (2-2) is by-produced, it is represented by Formula (3) by dehydrating the compound represented by Formula (2-2) using a dehydrating agent in a solvent. It can be converted to a compound.
  • the dehydrating agent sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, tetrafluoroboric acid and polyphosphoric acid are preferably used. Trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid are more preferred, and p-toluenesulfonic acid is particularly preferred.
  • the solvent for performing the dehydration reaction include aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic halogenated hydrocarbons, and aromatic halogenated hydrocarbons.
  • Examples of the aliphatic hydrocarbon include pentane, hexane, heptane, octane, decane, dodecane and cyclohexane.
  • Examples of the aromatic hydrocarbon include benzene, toluene, ethylbenzene, xylene, and cumene.
  • Examples of the aliphatic halogenated hydrocarbon include chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane.
  • Examples of the aromatic halogenated hydrocarbon include chlorobenzene, o-chlorobenzene, and 1,2,4-trichlorobenzene.
  • the temperature of the dehydration reaction is usually 20 to 200 ° C., preferably 50 to 150 ° C.
  • the time for the dehydration reaction is usually 10 minutes to 5 hours, preferably 30 minutes to 2 hours.
  • the compound represented by the formula (3) is used as a raw material for producing an organic semiconductor material, and the obtained organic semiconductor material is used for an electroluminescence element, an organic thin film solar cell element, an organic thin film transistor element or the like. It becomes possible to obtain an organic element having high characteristics.
  • reaction solution was cooled to ⁇ 25 ° C., and a solution in which 60 g (236 mmol) of iodine was dissolved in 1000 mL of diethyl ether was added dropwise over 30 minutes. After dropping, the mixture was stirred at room temperature (25 ° C.) for 2 hours, and 50 mL of 1N aqueous sodium thiosulfate solution was added to stop the reaction. After extracting the reaction product with diethyl ether, the ether solution was dried with magnesium sulfate and concentrated to obtain 35 g of a crude product. The crude product was purified by recrystallization using chloroform to obtain 28 g of Compound 1.
  • Example 1 (Synthesis of Compound 4-Br) In a 2 L flask, 500 mL of dichloromethane and 50 g of hydrogen peroxide (35 wt%) were placed, and the flask was kept at 0 ° C. Thereafter, 382.5 g of trifluoroacetic anhydride was dropped into the flask over 40 minutes. After dropping, the mixture was stirred at 0 ° C. for 30 minutes.
  • the obtained product was extracted with chloroform, and the chloroform solution was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled off to obtain 38.2 g of a crude product 4-Br 2.
  • 38.2 g of the obtained crude 4-Br 3 0.5 g of p-toluenesulfonic acid, and 450 mL of toluene were added to obtain a uniform solution.
  • the flask was heated in an oil bath at 120 ° C. and stirred for 1 hour. Then, it cooled to room temperature (25 degreeC).
  • the fused ring compound represented by the formula (3) which is a raw material for producing an organic semiconductor material, can be produced in high yield, and thus the present invention is useful.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Thin Film Transistor (AREA)

Abstract

La présente invention concerne un procédé de préparation pour un composé représenté par la formule (3), dans lequel un composé représenté par la formule (1), un composé représenté par la formule (2), et du peroxyde d'hydrogène réagissent dans un solvant, de telle manière que le composé représenté par la formule (3), qui est un matériau de départ pour produire un matériau semi-conducteur organique, peut être préparé avec un rendement élevé. (Dans la formule, le cycle A et le cycle B sont identiques ou différents et représentent un cycle aromatique, et R1 et R2 sont identiques ou différents et représentent un atome d'hydrogène, un groupe alkyle facultativement substitué, ou un groupe aryle facultativement substitué.)
PCT/JP2011/056140 2010-04-21 2011-03-09 Procédé de préparation de composé Ceased WO2011132479A1 (fr)

Applications Claiming Priority (2)

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JP2010097603 2010-04-21
JP2010-097603 2010-04-21

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WO2011132479A1 true WO2011132479A1 (fr) 2011-10-27

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478834A (en) * 1983-02-11 1984-10-23 Usv Pharmaceutical Corporation Dihydropyridines and their use in the treatment of asthma

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478834A (en) * 1983-02-11 1984-10-23 Usv Pharmaceutical Corporation Dihydropyridines and their use in the treatment of asthma

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS 1915, "Synthesis of hydroxythiophene derivatives from aminocrotonic ester", accession no. STN Database accession no. 9:1784c-i *
DATABASE CAPLUS 1983, "The unexpected formation of a dithienopyrone (2,7-dimethyldithieno[2,3-b;2',3'-d]pyran-4- one)", accession no. STN Database accession no. 99:175618d *
KANG, H. ET AL.: "New method of generating trifluoroperoxyacetic acid for the Baeyer- Villiger oxidation", BULLETIN OF THE KOREAN CHEMICAL SOCIETY, vol. 17, no. 1, 1996, pages 5 - 6 *

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