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WO2019111853A1 - Procédé de fabrication de corps de monoester d'acide dicarboxylique, sel de monoester d'acide dicarboxylique, et procédé de fabrication de composé de cristaux liquides polymérisable - Google Patents

Procédé de fabrication de corps de monoester d'acide dicarboxylique, sel de monoester d'acide dicarboxylique, et procédé de fabrication de composé de cristaux liquides polymérisable Download PDF

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Publication number
WO2019111853A1
WO2019111853A1 PCT/JP2018/044414 JP2018044414W WO2019111853A1 WO 2019111853 A1 WO2019111853 A1 WO 2019111853A1 JP 2018044414 W JP2018044414 W JP 2018044414W WO 2019111853 A1 WO2019111853 A1 WO 2019111853A1
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group
dicarboxylic acid
compound
acid monoester
formula
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Japanese (ja)
Inventor
賢 島村
英知 古山
慶太 高橋
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/16—Monomers containing no hetero atoms other than the ether oxygen
    • C08F16/22—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/16—Esters having free carboxylic acid groups

Definitions

  • the present invention relates to a method for producing a dicarboxylic acid monoester, a dicarboxylic acid monoester salt, and a method for producing a polymerizable liquid crystal compound.
  • Optical films such as an optical compensation sheet and a retardation film are used in various image display devices for the purpose of decoloring an image and enlarging a viewing angle.
  • a stretched birefringent film has been used as an optical film, but in recent years, it has been proposed to use an optical film having an optically anisotropic layer made of a liquid crystalline compound in place of the stretched birefringent film.
  • the liquid crystal compound used to form such an optically anisotropic layer is, for example, a hydroxy compound for forming a skeleton located at the molecular center of the liquid crystal compound (hereinafter also referred to as “core portion”), It is known that synthesis is performed utilizing an esterification reaction with a carboxylic acid compound to form a side chain portion of a liquid crystal compound (see, for example, Patent Documents 1 to 4).
  • the present inventors examined the synthesis methods of the liquid crystal compounds described in Patent Documents 1 to 4. With regard to the carboxylic acid compound for forming the side chain, the productivity depending on the structure of the target side chain Revealed that there is room for improvement.
  • this invention makes it a subject to provide the manufacturing method of the dicarboxylic acid monoester body excellent in production efficiency, the manufacturing method of a polymeric liquid crystal compound, and a novel dicarboxylic acid monoester salt.
  • the present inventors hydrolyze a dicarboxylic acid diester having a predetermined structure with a base in a solvent containing a secondary or tertiary alcohol to obtain a monoester. It turned out that it could produce dicarboxylic acid monoester body by a high yield, and completed the present invention. That is, it discovered that the above-mentioned subject could be achieved by the following composition.
  • a dicarboxylic acid compound represented by the formula (1) described later and a hydroxyl group-containing vinyl compound represented by the formula (2) described later are reacted, and a dicarboxylic acid diester represented by the formula (3) described later Diesterizing step to form a body, A monoesterification step of hydrolyzing a dicarboxylic acid diester body using a base in a solvent containing a secondary or tertiary alcohol to form a dicarboxylic acid monoester salt represented by the formula (4) described later; The manufacturing method of the dicarboxylic acid monoester body which has.
  • a dicarboxylic acid monoester salt represented by the formula (4-1) described later [8] A dicarboxylic acid monoester salt represented by the formula (4-1) described later. [9] A dicarboxylic acid monoester salt according to [8], wherein Ma in formula (4-1) described later represents any of sodium, potassium and lithium.
  • a polymerizable compound represented by the formula (6) described later prepared by the method for producing a dicarboxylic acid monoester according to [3] and a compound having a hydroxyl group are reacted to obtain a polymerizable liquid crystal compound And a method of producing a polymerizable liquid crystal compound.
  • the present invention it is possible to provide a method for producing a dicarboxylic acid monoester body excellent in production efficiency, a method for producing a polymerizable liquid crystal compound, and a novel dicarboxylic acid monoester salt.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the method for producing a dicarboxylic acid monoester of the present invention (hereinafter simply referred to as “the production method of the present invention”) is represented by a dicarboxylic acid compound represented by the following formula (1), and the following formula (2) And a hydroxyl group-containing vinyl compound to produce a dicarboxylic acid diester represented by the following formula (3).
  • the dicarboxylic acid diester body represented by the following formula (3) is hydrolyzed using a base in a solvent containing a secondary or tertiary alcohol, and the following formula (4) It has a monoesterification step to produce the dicarboxylic acid monoester salt represented.
  • n represents an integer of 0 to 2; R 1 and R 2 each independently represent a ring structure, L 1 represents a single bond or a divalent linking group, and when n is 2, plural L 1 s may be identical to each other It may be different, and multiple R 2 s may be the same or different.
  • SP 1 one or more of —CH 2 — constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms is — It represents a divalent linking group substituted by O-, -S-, -NH-, -N (Q)-or -CO-, and Q represents a substituent.
  • M represents an alkali metal atom or an alkaline earth metal atom
  • m represents a valence of M.
  • the dicarboxylic acid diester represented by the above formula (3) is hydrolyzed using a base in a solvent containing a secondary or tertiary alcohol, and the above formula (4)
  • the dicarboxylic acid monoester body can be produced
  • the reaction selectivity is improved, and it becomes possible to isolate it only by the filtration operation. Therefore, in the present invention, when monoesterification to generate a dicarboxylic acid monoester salt from a dicarboxylic acid diester body, a monoester salt having high purity could be recovered by a simple method, and thus the dicarboxylic acid monoester is produced. It is believed that the body could be produced in high yield.
  • water or an organic solvent can be used in each step as necessary.
  • the solvent for example, ethers such as tetrahydrofuran (THF), 1,4-dioxane; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene; chlorinated solvents such as methylene chloride, chloroform, trichloroethylene Ketones such as acetone and 2-butanone; aprotic polar solvents such as N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and hexamethylphosphoric triamide; acetonitrile And nitriles such as propionitrile; esters such as ethyl acetate and n-buty
  • the dicarboxylic acid compound used for the said diesterization process is a compound represented by following formula (1).
  • n represents an integer of 0 to 2, preferably 0 or 1.
  • R 1 and R 2 each independently represent a ring structure.
  • L 1 represents a single bond or a divalent linking group, and is preferably a single bond.
  • n 2
  • plural L 1 s may be the same or different
  • plural R 2 s may be the same or different.
  • the C3-C20 bivalent alicyclic hydrocarbon group which may have a substituent, and a substituent are mentioned, for example Examples thereof include C6-20 divalent aromatic hydrocarbon groups which may be possessed.
  • a C3-C20 bivalent alicyclic hydrocarbon group a C3-C20 cycloalkylene group etc. are mentioned, for example, Specifically, a cyclohexylene group, a cyclo pentylene group, norbornylene group And an adamantylene group.
  • examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an arylene group having 6 to 12 carbon atoms, and specific examples include a phenylene group and a naphthylene group.
  • an alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group) N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group and the like are more preferable, an alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group or an ethyl group is more preferable Is particularly preferred.
  • an alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group) N-butyl group, isobutyl group
  • the alkoxy group is, for example, preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) More preferably, it is an alkoxy group of the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that it is a fluorine atom and a chlorine atom.
  • examples of the divalent linking group include a linear or branched alkylene group having 1 to 12 carbon atoms, And one or more of —CH 2 — constituting a linear or branched alkylene group having 1 to 12 carbon atoms is —O—, —S—, —NH—, —N (Q) — or — Examples thereof include a divalent linking group substituted by CO- and the like.
  • Q represents a substituent, and examples thereof include the same substituents as the above-mentioned alicyclic hydrocarbon group and the like may have.
  • linear or branched alkylene group having 1 to 12 carbon atoms for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylhexylene group, heptylene group and the like are preferable. It can be mentioned.
  • the dicarboxylic acid compound represented by the above formula (1) has the following formula from the viewpoint of the ease of precipitation of the dicarboxylic acid monoester salt, and the usefulness of the polymerizable liquid crystal compound to be derived:
  • the compound is preferably a compound represented by (1-1a), and more preferably a compound represented by the following formula (1-1).
  • s represents an integer of 1 to 3 and is preferably an integer of 1 to 2.
  • P represents an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.
  • the hydroxyl group-containing vinyl compound used in the above-described diesterization step is a compound represented by the following formula (2).
  • SP 1 is —CH 2 constituting a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms
  • Examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP 1 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group and a heptylene group. Etc. are mentioned suitably.
  • substituents represented Q is, in the description of R 1 and R 2 of formula (1) described above, similarly to the illustrated alicyclic hydrocarbon substituent which may be have such groups as the ring structure
  • any of the compounds represented by the following formulas (2-1) to (2-3) is preferably mentioned from the viewpoint of the ease of obtaining and deprotection.
  • reaction conditions for the dicarboxylic acid compound and the hydroxyl group-containing vinyl compound described above are not particularly limited, and conventionally known reaction conditions for esterification can be appropriately adopted.
  • the reaction temperature is preferably ⁇ 10 to 150 ° C., more preferably ⁇ 5 to 120 ° C., and still more preferably ⁇ 5 to 100 ° C.
  • the reaction time is preferably 10 minutes to 24 hours, more preferably 30 minutes to 10 hours, and still more preferably 1 hour to 8 hours.
  • the dicarboxylic acid diester body represented by the above formula (3) is hydrolyzed using a base in a solvent containing a secondary or tertiary alcohol, and the above formula This is a step of producing a dicarboxylic acid monoester salt represented by (4).
  • a solvent containing a secondary or tertiary alcohol is used.
  • the ratio of the secondary or tertiary alcohol in the solvent is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and still more preferably 50 to 100% by mass.
  • the secondary alcohol include 2-propanol (isopropanol), sec-butanol, cyclopentanol, cyclohexanol and the like.
  • the tertiary alcohol include 1-ethynyl-1-cyclopropanol, 1-adamantanol, tert-butanol, t-amyl alcohol and the like.
  • solvents other than secondary alcohol or tertiary alcohol can be used together.
  • solvents exemplified as the organic solvent which can be used in each step solvents other than primary alcohols are preferably mentioned as the solvent to be used in combination.
  • the base used in the monoesterification step is preferably a Bronsted base from the viewpoints of availability, solubility, suppression of side reactions, and the like.
  • a Br ⁇ ⁇ ⁇ ⁇ ⁇ nsted base inorganic Br ⁇ ⁇ ⁇ ⁇ nsted bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate and the like; pyridine, triethylamine, dimethylaminopyridine, diisopropylethylamine, N-methylmorpholine etc.
  • Organic Br ⁇ ⁇ ⁇ ⁇ ⁇ nsted bases are preferable, and from the viewpoint of availability and solubility, sodium hydroxide, potassium hydroxide and lithium hydroxide are more preferable.
  • a metal alkoxide t-butoxy potassium, t-butoxy sodium, sodium methoxide and the like can be used.
  • reaction conditions for producing the dicarboxylic acid monoester salt represented by the above formula (4) are not particularly limited except that the above-described solvent and base are used, and conventionally known hydrolysis reaction conditions are appropriately employed. be able to.
  • the reaction temperature is preferably ⁇ 30 to 100 ° C., more preferably ⁇ 20 to 50 ° C., and still more preferably ⁇ 10 to 40 ° C.
  • the reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.
  • n, R 1 , R 2 , L 1 and SP 1 are all the same as those described in the above formulas (1) and (2).
  • M represents an alkali metal atom or an alkaline earth metal atom
  • m represents a valence number of M.
  • alkali metal atom represented by M in the above formula (4) include sodium, potassium, lithium and cesium. Among them, sodium, potassium and lithium are preferable. Further, specific examples of the alkaline earth metal atom represented by M include, for example, calcium, strontium and barium. Among them, calcium and barium are preferable.
  • the compound represented by a following formula is mentioned suitably, for example.
  • Ma represents an alkali metal atom.
  • the production method of the present invention imparts an acid to the dicarboxylic acid monoester salt represented by the above formula (4) after the above monoesterification step to form a devinylized compound represented by the formula (5) described later It is preferable to have a deprotecting step.
  • Examples of the acid to be imparted to the dicarboxylic acid monoester salt include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid or salts thereof; formic acid, acetic acid, propionic acid, oxalic acid Organic acids such as trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid or salts thereof; lithium tetrafluoroborate, boron trifluoride, boron trichloride, boron tribromide , Lewis acids such as aluminum trichloride, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, tin dichloride, titanium tetrachloride, titanium te
  • generating the intendylization compound represented by Formula (5) mentioned later are not specifically limited,
  • the reaction conditions of the deprotection reaction of the conventionally well-known vinyl group using an acid can be employ
  • the reaction temperature is preferably ⁇ 30 to 100 ° C., more preferably ⁇ 20 to 50 ° C., and still more preferably ⁇ 10 to 40 ° C.
  • the reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.
  • n, R 1 , R 2 and L 1 and SP 1 are all the same as described in the above formulas (1) and (2).
  • the manufacturing method of this invention has a polymeric group introduce
  • n, R 1 , R 2 and L 1 and SP 1 are all the same as described in the above formulas (1) and (2).
  • R 3 represents a hydrogen atom or a methyl group.
  • the reaction for forming the polymerizable compound represented by the above formula (6) is not particularly limited.
  • a method of reacting acryloyl chloride or methacryloyl chloride with the intendyl compound represented by the above formula (5) A method in which 3-chloropropionic acid chloride is reacted with a istylized compound represented by the formula (5), and then dehydrochlorinated to give an acryloyl group or a methacryloyl group;
  • the reaction temperature is preferably ⁇ 30 to 100 ° C., more preferably ⁇ 20 to 50 ° C., and still more preferably ⁇ 10 to 40 ° C.
  • the reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.
  • the dicarboxylic acid monoester salt of the present invention is a dicarboxylic acid monoester salt represented by the following formula (4-1).
  • s represents an integer of 1 to 3 and is preferably an integer of 1 to 2.
  • P represents an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.
  • Ma represents an alkali metal atom, and preferably represents any of sodium, potassium and lithium.
  • SP 1 is the same as that described in the above equation (2).
  • Examples of the compound represented by the above formula (4-1) include the same compounds as those exemplified as the compound represented by the above formula (4).
  • Method of producing polymerizable liquid crystal compound In the method for producing a polymerizable liquid crystal compound of the present invention, a polymerizable compound represented by the above formula (6) produced by the above-mentioned production method of the present invention is reacted with a compound having a hydroxyl group to obtain a polymerizable liquid crystal compound. It is a manufacturing method of a polymerizable liquid crystal compound to obtain.
  • the compound having a hydroxyl group to be reacted with the polymerizable compound represented by the formula (6) is preferably a compound represented by the following formula (7).
  • Ar represents a divalent aromatic group.
  • the divalent aromatic group include, for example, an arylene group having 6 to 12 carbon atoms, and specific examples include a phenylene group and a naphthylene group.
  • Ar in the above formula (7) is preferably any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5) .
  • * represents a bonding position to a hydroxyl group in the above formula (7).
  • Q 1 represents N or CH
  • Q 2 represents -S-, -O-, or -N (R 5 )-
  • R 5 represents R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Y 1 is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or an aromatic complex having 3 to 12 carbon atoms Represents a ring group.
  • alkyl group having 1 to 6 carbon atoms represented by R 5 include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. And n-pentyl and n-hexyl groups.
  • aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y 1 include aryl groups such as phenyl group, 2,6-diethylphenyl group and naphthyl group.
  • Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 include heteroaryl groups such as thienyl group, thiazolyl group, furyl group and pyridyl group. Moreover, as a substituent which Y 1 may have, an alkyl group, an alkoxy group, a halogen atom etc. are mentioned, for example.
  • alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group) N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group and the like are more preferable, an alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group or an ethyl group is more preferable Is particularly preferred.
  • an alkyl group having 1 to 8 carbon atoms eg, methyl group, ethyl group, propyl group, isopropyl group
  • N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group and the like are more preferable
  • the alkoxy group is, for example, preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) More preferably, it is an alkoxy group of the number 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that it is a fluorine atom and a chlorine atom.
  • Z 1 , Z 2 and Z 3 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon A monovalent alicyclic hydrocarbon group of 3 to 20, a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR 6 , -NR 7 R 8 , or represents -SR 9, R 6 ⁇ R 9 each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 ⁇ 6, Z 1 and Z 2, also form an aromatic ring bonded to each other Good.
  • the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group or an ethyl group , Isopropyl, tert-pentyl (1,1-dimethylpropyl), tert-butyl and 1,1-dimethyl-3,3-dimethyl-butyl are more preferable, and methyl, ethyl, tert-butyl Groups are particularly preferred.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, ethylcyclohexyl Monocyclic saturated hydrocarbon group such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, cyclodeca Monocyclic unsaturated hydrocarbon groups such as dienes; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tri
  • Polycyclic saturated hydrocarbon groups such as dodecyl and adamantyl; and the like.
  • Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, 2,6-diethylphenyl group, naphthyl group and biphenyl group, and the like.
  • Aryl groups (especially phenyl groups) are preferred.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that it is a fluorine atom, a chlorine atom, a bromine atom.
  • alkyl group having 1 to 6 carbon atoms represented by R 6 to R 8 include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group. Groups, tert-butyl group, n-pentyl group, and n-hexyl group.
  • a 1 and A 2 are each independently selected from —O—, —N (R 10 ) —, —S— and —CO—
  • R 10 represents a hydrogen atom or a substituent. Examples of the substituent represented by R 10 include the same as the substituent which Y 1 in the formula (Ar-1) may have.
  • X represents a hydrogen atom or a nonmetallic atom of Group 14 to 16 to which a substituent may be bonded.
  • examples of the non-metallic atoms of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent.
  • substituents include Is, for example, an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (eg, phenyl group, naphthyl group etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group etc. Can be mentioned.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
  • SP 3 and SP 4 each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms.
  • Q represents a substituent.
  • the substituent include those similar to the substituent which Y 1 in the formula (Ar-1) may have.
  • L 3 and L 4 each independently represent a monovalent organic group.
  • a monovalent organic group an alkyl group, an aryl group, heteroaryl group etc. can be mentioned, for example.
  • the alkyl group may be linear, branched or cyclic, preferably linear.
  • the carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
  • the aryl group may be monocyclic or polycyclic, but is preferably monocyclic. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable.
  • the heteroaryl group may be monocyclic or polycyclic.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
  • the hetero atom which comprises a heteroaryl group has a preferable nitrogen atom, a sulfur atom, and an oxygen atom.
  • the carbon number of the heteroaryl group is preferably 6 to 18, and more preferably 6 to 12.
  • the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include those similar to the substituent which Y 1 in the formula (Ar-1) may have.
  • Ax is an organic having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring Represents a group.
  • Ay is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic group
  • the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
  • Q 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • Ax and Ay those described in paragraphs [0039] to [0095] of Patent Document 3 (WO 2014/010325) can be mentioned.
  • Specific examples of the alkyl group having 1 to 6 carbon atoms represented by Q 3 include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. -Butyl group, n-pentyl group, n-hexyl group and the like, and as the substituent, those similar to the substituent which may be possessed by Y 1 in the above formula (Ar-1) It can be mentioned.
  • reaction conditions The reaction conditions for the polymerizable compound represented by the above formula (6) and the compound having a hydroxyl group described above are not particularly limited, and conventionally known reaction conditions for esterification can be appropriately adopted.
  • the reaction temperature is preferably ⁇ 30 to 150 ° C., more preferably ⁇ 20 to 100 ° C., and still more preferably ⁇ 10 to 50 ° C.
  • the reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and still more preferably 30 minutes to 8 hours.
  • Example 1 Compound (I-1), which is a dicarboxylic acid monoester, was synthesized according to the scheme shown below.
  • Example 2 Compound (I-2), which is a dicarboxylic acid monoester, was synthesized according to the scheme shown below.
  • Example 4 The above compound (I-1) synthesized also in Example 1 was synthesized by the following procedure.
  • Example 5 The compound (I-1-c) was synthesized in the same manner as in Example 4 and used. 50 mL of t-butanol, 50 mL of acetonitrile, 2.99 g (26.6 mmol) of potassium t-butoxide, and 0.5 mL of water were mixed, heated and dissolved, and then cooled to room temperature. To this reaction solution, 10.0 g (22.2 mmol) of compound (I-1-c) was added at room temperature (23 ° C.), and the mixture was stirred at 25 ° C. for 3 hours.
  • compound (I-1-c) used was synthesized in the same manner as in Example 4. As shown in the above scheme, 9.0 g (15.0 mmol) of compound (I-1-c), 30 mL of t-butanol, 30 mL of acetonitrile, and 0.4 mL of water are mixed and cooled to 0 to 5 ° C. It stirred. A solution of 2.52 g (22.5 mmol) of t-butoxy potassium in 45 mL of t-butanol was added dropwise to the reaction solution, and then stirred at 0-5 ° C. for 3 hours.

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Abstract

L'invention a pour objet de fournir un procédé de fabrication de corps de monoester d'acide dicarboxylique ainsi qu'un procédé de fabrication de composé de cristaux liquides polymérisable d'une excellente efficacité de production, et un nouveau sel de monoester d'acide dicarboxylique. Plus précisément, l'invention concerne un procédé de fabrication de corps de monoester d'acide dicarboxylique qui présente : une étape de diestérification au cours de laquelle un composé acide dicarboxylique représenté par la formule (1) prédéfinie, et un composé vinyle à teneur en groupe hydroxyle représenté par la formule (2) prédéfinie, sont mis en réaction, et un corps de diester d'acide dicarboxylique représenté par la formule (3) prédéfinie, est ainsi produit ; et une étape de monoestérification au cours de laquelle le corps de diester d'acide dicarboxylique est soumis a une hydrolyse à l'aide d'une base dans un solvant contenant un alcool secondaire ou tertiaire, et un sel de monoester d'acide dicarboxylique représenté par la formule (4) prédéfinie, est ainsi produit.
PCT/JP2018/044414 2017-12-08 2018-12-03 Procédé de fabrication de corps de monoester d'acide dicarboxylique, sel de monoester d'acide dicarboxylique, et procédé de fabrication de composé de cristaux liquides polymérisable Ceased WO2019111853A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020067391A1 (fr) * 2018-09-27 2020-04-02 富士フイルム株式会社 Procédé de production de monoester d'acide dicarboxylique
CN112679342A (zh) * 2020-12-31 2021-04-20 上海康鹏科技股份有限公司 一种反,反-4,4’-二环己基二甲酸的制备方法
JP2021123558A (ja) * 2020-02-05 2021-08-30 日本ゼオン株式会社 シクロヘキサンジカルボン酸モノエステルの製造方法
WO2022181518A1 (fr) * 2021-02-26 2022-09-01 富士フイルム和光純薬株式会社 Procédé de production de monoester de dicarboxylate
JPWO2022181519A1 (fr) * 2021-02-26 2022-09-01

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WO2017047674A1 (fr) * 2015-09-18 2017-03-23 富士フイルム株式会社 Composé à cristaux liquides polymérisable, composition polymérisable, et film

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020067391A1 (fr) * 2018-09-27 2020-04-02 富士フイルム株式会社 Procédé de production de monoester d'acide dicarboxylique
JPWO2020067391A1 (ja) * 2018-09-27 2021-08-30 富士フイルム株式会社 ジカルボン酸モノエステルの製造方法
JP7062783B2 (ja) 2018-09-27 2022-05-06 富士フイルム株式会社 ジカルボン酸モノエステルの製造方法
JP2021123558A (ja) * 2020-02-05 2021-08-30 日本ゼオン株式会社 シクロヘキサンジカルボン酸モノエステルの製造方法
CN112679342A (zh) * 2020-12-31 2021-04-20 上海康鹏科技股份有限公司 一种反,反-4,4’-二环己基二甲酸的制备方法
WO2022181518A1 (fr) * 2021-02-26 2022-09-01 富士フイルム和光純薬株式会社 Procédé de production de monoester de dicarboxylate
JPWO2022181519A1 (fr) * 2021-02-26 2022-09-01
WO2022181519A1 (fr) * 2021-02-26 2022-09-01 富士フイルム株式会社 Procédé de production de monoester d'acide dicarboxylique, et sel de monoester d'acide dicarboxylique
JP7727709B2 (ja) 2021-02-26 2025-08-21 富士フイルム株式会社 ジカルボン酸モノエステル体の製造方法およびジカルボン酸モノエステル塩

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