+

WO2016072366A1 - Composé de butyrolactone et son procédé de production - Google Patents

Composé de butyrolactone et son procédé de production Download PDF

Info

Publication number
WO2016072366A1
WO2016072366A1 PCT/JP2015/080805 JP2015080805W WO2016072366A1 WO 2016072366 A1 WO2016072366 A1 WO 2016072366A1 JP 2015080805 W JP2015080805 W JP 2015080805W WO 2016072366 A1 WO2016072366 A1 WO 2016072366A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
compound represented
compound
group
following formula
Prior art date
Application number
PCT/JP2015/080805
Other languages
English (en)
Japanese (ja)
Inventor
裕一 後藤
雅久 遠藤
軍 孫
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2016557748A priority Critical patent/JP6760075B2/ja
Priority to CN201580058217.0A priority patent/CN107108540B/zh
Priority to KR1020177014716A priority patent/KR102508578B1/ko
Publication of WO2016072366A1 publication Critical patent/WO2016072366A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing a compound having a butyrolactone ring, and a novel intermediate compound used therein.
  • a voltage is applied to the liquid crystal molecules during the manufacturing process.
  • Some of them include a step of irradiating ultraviolet rays.
  • a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell.
  • a PSA (Polymer sustained Alignment) type liquid crystal display (PSA) that increases the response speed of liquid crystal is known.
  • the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a photopolymerizable compound is added to the liquid crystal composition, By irradiating ultraviolet rays while applying voltage to the liquid crystal cell, a polymer structure in which the tilted direction of the liquid crystal molecules is stored is formed on the liquid crystal alignment film. It is said that the response speed of the liquid crystal display element is faster than the method of controlling the above. It has also been reported that the response speed of the liquid crystal display element is increased by adding a photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (non-patented). Reference 2). As the additive photopolymerizable compound, several polymerizable compounds are known (see Patent Documents 2 to 6).
  • Japanese Unexamined Patent Publication No. 2003-307720 Japanese Unexamined Patent Publication No. 2008-239873 Japanese Unexamined Patent Publication No. 2011-84477 Japanese Unexamined Patent Publication No. 2012-240945 Japanese special table 2013-509457 gazette British Patent Application GB 2297549A
  • Photopolymerizable compounds have heretofore been manufactured using expensive compounds as raw materials. Therefore, as a raw material for electronic equipment that requires cost reduction, there has been a problem in its supplyability. Therefore, there is a need for a novel production method that can produce a photopolymerizable compound at low cost.
  • An object of the present invention is to solve the problems of the prior art described above. Specifically, an object of the present invention is to provide a novel production method and a novel intermediate for producing a photopolymerizable compound used in a liquid crystal display element at a low cost and in a high yield.
  • the present inventors use an expensive raw material selected from a hydroxyphenyl group and a hydroxynaphthyl group in the final step by using a ⁇ -butyrolactone compound substituted with a hydroxyalkyl group as an intermediate.
  • a ⁇ -butyrolactone compound substituted with a hydroxyalkyl group as an intermediate.
  • the intermediate can be obtained from an inexpensive unsaturated heterocyclic compound in a single step with a good yield, and that the storage stability of the intermediate is good, which is extremely advantageous industrially. It was.
  • the photopolymerizable compound useful in a liquid crystal display element could be manufactured using the said intermediate body.
  • the present invention is based on such knowledge and has the following gist. 1.
  • the compound represented by the following formula (A) and the compound represented by the following formula (C) are reacted in the presence of metal tin or a tin-containing compound under acidic conditions.
  • a method for producing the represented compound In the formula, n represents 1 or 2.
  • J 1 represents a halogen atom, and R represents an alkyl group having 1 to 6 carbon atoms.
  • n represents the above meaning.
  • a compound represented by the following formula (1) and a compound represented by the following formula (D) are reacted in the presence of a base, and then obtained when R 1 in the formula (2) is a halogen atom.
  • a method for producing a compound represented by the following formula (3), wherein a reaction product is reacted with a metal halide. In the formula, n represents 1 or 2.
  • J 2 represents a halogen atom
  • Y 1 represents —SO 2 —R 2
  • R 2 represents a hydrocarbon group.
  • R 1 represents OY 1 or a halogen atom
  • Y 1 represents —SO 2 —R 2
  • R 2 represents a hydrocarbon group.
  • each X independently represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • 6 represents a substituent selected from a haloalkoxy group and a cyano group
  • m 1 to m 6 each independently represents an integer of 0 to 4
  • m 7 and m 8 each independently represents 0 to 3 (It is an integer, and when the number of X is 2 or more, Xs may be the same or different.)
  • n and Ar 1 represent the above meanings.
  • a compound represented by the following formula (2) (In the formula, n represents 1 or 2, R 1 represents OY 1 , chlorine, bromine or iodine, Y 1 represents —SO 2 —R 2 , and R 2 represents a hydrocarbon group.)
  • a compound represented by the formula (3) having a divalent organic group having an aromatic ring having at least one halogen substituent and two ⁇ -methylene- ⁇ -butyrolactone groups A novel production method for producing at low cost and in a high yield, and a compound represented by formula (1) and a novel intermediate of the compound represented by formula (2) used in the production method and the like A compound is provided.
  • the compound represented by the formula (3) obtained by the production method of the present invention is highly oriented when used as a polymerizable compound in a liquid crystal display element, particularly as a polymerizable compound added to a liquid crystal alignment film material. It has immobilization ability, and storage stability in varnish is improved, and further solubility in liquid crystal is improved.
  • the present invention comprises an unsaturated heterocyclic compound represented by the following formula (A) and a compound represented by the following formula (C) in the presence of metal tin or a tin-containing compound. It is a manufacturing method of the compound represented by Formula (1) by making it react on acidic conditions.
  • n 0 or 1
  • J 1 represents a halogen atom
  • R represents an alkyl group having 1 to 6 carbon atoms.
  • J 1 is preferably chlorine, bromine or iodine, and preferably chlorine or bromine.
  • R is preferably an alkyl group having 1 to 5 carbon atoms, which may be linear or branched, but is preferably linear. In particular, a methyl group or an ethyl group is preferable.
  • the compound represented by the formula (A) is a known compound and can be obtained commercially.
  • the compound represented by the formula (C) is also a known compound and can be obtained commercially.
  • metal tin or tin-containing compounds examples include tin compounds such as tin powder, anhydrous tin chloride, tin chloride dihydrate, and tin chloride pentahydrate.
  • tin compounds such as tin powder, anhydrous tin chloride, tin chloride dihydrate, and tin chloride pentahydrate.
  • anhydrous tin chloride or tin chloride dihydrate is preferred.
  • an inorganic acid aqueous solution such as hydrochloric acid, sulfuric acid or phosphoric acid, an acidic resin such as Amberlyst®15, or an organic acid such as p-toluenesulfonic acid, acetic acid or formic acid can be used.
  • Hydrochloric acid, sulfuric acid or acetic acid is particularly preferable.
  • acrylic acid derivative which is the above compound (C)
  • 2- (chloromethyl) acrylic acid, 2- (chloromethyl) methyl acrylate, 2- (chloromethyl) ethyl acrylate, 2- (bromomethyl) acrylic acid 2- (Bromomethyl) methyl acrylate, 2- (bromomethyl) ethyl acrylate, and the like are preferable, and 2- (bromomethyl) acrylic acid or 2- (bromomethyl) ethyl acrylate is particularly preferable.
  • the amount of the compound (C) used is preferably 1.0 to 1.2 equivalents relative to 1 equivalent of the unsaturated heterocyclic compound, which is the compound represented by the formula (A), and 1.1 to 1. Two equivalents are more preferred.
  • the above reaction is carried out under acidic conditions, and the pH in the reaction is preferably 1 to 3, more preferably 1 to 2.
  • a solvent that is stable and inert and does not interfere with the reaction is preferable.
  • a solvent that is stable and inert and does not interfere with the reaction is preferable.
  • water, ethers Et 2 O, i-Pr 2 O
  • TBME tert-butyl methyl ether
  • CPME cyclopentyl methyl ether
  • tetrahydrofuran dioxane, etc.
  • solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. Tetrahydrofuran or water is preferable.
  • the reaction temperature is not particularly limited, but is usually 0 to 100 ° C., preferably 20 to 70 ° C.
  • the reaction time is usually 1 to 100 hours, preferably 1 to 12 hours.
  • the ⁇ -methylene- ⁇ -butyrolactone compound (1) obtained as described above is purified by silica gel column chromatography after the reaction, after adding a base to the reaction solution to remove excess acid. The purity can be increased.
  • Solvents used for silica gel column chromatography used for purification are not particularly limited, but include, for example, hydrocarbons such as hexane, heptane, and toluene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, and chlorobenzene; And ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate; mixed solutions thereof; and the like.
  • it is a mixed liquid of esters such as ethyl acetate and hydrocarbons such as hexane or heptane.
  • n 1 or 2
  • R 1 represents OY 1 or a halogen atom
  • Y 1 represents —SO 2 —R 2
  • R 2 represents a hydrocarbon group.
  • the hydroxy group of the compound represented by the formula (1) obtained above is a sulfonic acid halide which is a compound represented by the formula (D). By making it react, it can be converted into a leaving group.
  • n represents the same meaning as described above, J 2 represents a halogen atom, Y 1 represents —SO 2 —R 2 , and R 2 represents a hydrocarbon group. Examples of J 2 include chlorine, bromine and iodine.
  • hydrocarbon group for R 2 a linear or branched C 1-12 alkyl group, a C 3-12 cycloalkyl group, a C 2-12 haloalkyl group, a benzyl group optionally substituted with R a , or Examples thereof include a phenyl group which may be substituted with Ra .
  • R a halogen, C 1-6 alkyl group, C 1-6 haloalkyl group, C 3-6 cycloalkyl group, C 1-6 alkoxy group, C 1-6 alkoxy C 1-6 alkyl group, C 1 And a substituent selected from a -6 haloalkoxy group, NO 2 , CN, a formyl group, and a phenyl group.
  • a methyl group or an ethyl group is preferable.
  • the reaction between compound (1) and compound (D) is preferably carried out in the presence of a base.
  • the base is preferably used in an amount of 1.2 to 10 equivalents, more preferably 1.2 to 3 equivalents, relative to compound (1).
  • bases include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride; pyridine, 4-dimethylaminopyridine, triethylamine, tributylamine , Organic bases such as N, N-dimethylaniline and 1,8-diazabicyclo [5.4.0] -7-undecene; Among them, bases such as 4-dimethylaminopyridine, pyridine and triethylamine can be used. Pyridine or triethylamine is preferable.
  • a solvent that is stable and inert and does not interfere with the reaction.
  • ketones such as acetone and methyl ethyl ketone
  • aprotic polar organic solvents DMF, DMSO, DMAc, NMP, etc.
  • ethers Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.
  • Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate) , Ethyl acetate, butyl acetate, methyl propionate,
  • the reaction temperature is not particularly limited, but is usually 0 to 100 ° C., preferably 40 to 70 ° C.
  • the reaction time is usually 1 to 100 hours, preferably 1 to 12 hours.
  • the compound (2-A) obtained above can be highly purified by purifying with silica gel column chromatography after the reaction.
  • Solvents used for silica gel column chromatography are not particularly limited, but include, for example, hydrocarbons such as hexane, heptane and toluene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene; diethyl ether, tetrahydrofuran, Ethers such as 1,4-dioxane; esters such as ethyl acetate; mixed solutions thereof; and the like.
  • a mixture of an ester such as ethyl acetate and a hydrocarbon such as hexane or heptane is used. is there.
  • the compound represented by the formula (2-A) obtained above is preferably combined with a metal halide in a solvent.
  • a compound represented by the formula (2-B) in which —OY 1 is converted to halogen can be obtained. (Wherein J 3 represents a halogen atom, and Y 1 represents the above meaning.)
  • the metal halide sodium iodide, potassium iodide, sodium bromide, potassium bromide and the like can be used.
  • the amount of the metal halide to be used is preferably 1 to 2 mol, more preferably 1 to 1.2 mol, relative to 1 mol of compound (2-A).
  • a solvent for this reaction a solvent that is stable under reaction conditions, inert and does not interfere with the reaction is used.
  • ketones such as acetone and methyl ethyl ketone
  • aprotic polar organic solvents DMF, DMSO, DMAc, NMP, etc.
  • ethers Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.
  • Aromatic hydrocarbons benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.
  • halogenated hydrocarbons chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.
  • lower fatty acid esters methyl acetate) , Ethyl acetate, butyl acetate, methyl propionate, etc.
  • the reaction temperature is not particularly limited, but is usually 0 to 100 ° C., preferably 30 to 45 ° C.
  • the reaction time is usually 1 to 100 hours, preferably 1 to 12 hours.
  • the compound represented by the formula (2-B) can be highly purified by purifying it by silica gel column chromatography after the reaction.
  • Y 1 in OY 1 in the compound (2-A) is ⁇
  • a compound that is SO 2 —R 2 and R 2 is a phenyl group optionally substituted by R a is preferred.
  • Ar 1 is a divalent group represented by the following formula (4), (5) or (6).
  • each X independently represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • m 1 to m 6 are each independently an integer of 0 to 4, and m 7 and m 8 are each independently an integer of 0 to 3.
  • X is 2 or more, Xs may be the same or different.
  • the halogen atom include fluorine, chlorine, bromine and the like.
  • X is preferably a methoxy group, a trifluoromethyl group, a trifluoromethoxy group, or the like.
  • m 1 to m 6 are preferably 0 to 1.
  • m 7 and m 8 are preferably 0 to 1.
  • inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate can be used.
  • it is sodium carbonate or potassium carbonate.
  • Additives can be used for the purpose of accelerating the reaction rate.
  • potassium iodide, sodium iodide, quaternary ammonium salts, crown ethers and the like can be used.
  • a solvent is preferable, and a stable and inert solvent that does not hinder the reaction is used.
  • ketones such as acetone and methyl ethyl ketone; aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.), Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate) , Ethyl acetate, butyl acetate, methyl propionate, etc.);
  • the reaction temperature is not particularly limited, but is usually 40 to 200 ° C, preferably 40 to 150 ° C.
  • the reaction time is usually 20 to 100 hours, preferably 20 to 60 hours.
  • the compound (3) obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
  • the solvent used for washing is not particularly limited.
  • hydrocarbons such as hexane, heptane and toluene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene; diethyl ether, tetrahydrofuran, 1,4 -Ethers such as dioxane; esters such as ethyl acetate; ketones such as acetone or methyl ethyl ketone; alcohols such as methanol or ethanol and 2-propanol; mixtures thereof; Preferred are alcohols such as methanol, ethanol and 2-propanol.
  • the solvent used for recrystallization is not particularly limited as long as the compound (3) dissolves during heating and precipitates during cooling.
  • hydrocarbons such as hexane, heptane and toluene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate Ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and 2-propanol; and mixtures thereof.
  • Tetrahydrofuran, toluene, methanol, ethanol, 2-propanol, hexane, heptane or a mixture thereof is preferable.
  • X, m 1 and m 2 represent the above meanings
  • Hal represents Br, I or OTf (Tf is a paratoluenesulfonyl group)
  • M represents B (OH) 2 or 4, 4, 5, Represents 5-tetramethyl-1,3,2-dioxaborolan-2-yl.
  • the amount of the aryl halide [2-A] and boronic acid derivative [3-A] used in the cross-coupling reaction is not particularly limited, but the boronic acid derivative is equivalent to 1 equivalent of the halogenated aryl [2-A]. It is preferable to use 1.0 to 1.5 equivalents of [3-A]. Further, 1.0 to 1.5 equivalents of aryl halide [2-A] may be used per 1 equivalent of boronic acid derivative [3-A].
  • metal catalyst used in the above coupling reaction it is preferable to use a metal complex and a ligand. However, if the reaction proceeds without a ligand, the ligand may not be used.
  • metal complexes those having various structures can be used, but palladium complexes and nickel complexes are preferably used.
  • the metal complex a low-valent palladium complex or nickel complex is preferably used, and a zero-valent complex having tertiary phosphine or tertiary phosphite as a ligand is particularly preferable.
  • an appropriate precursor that can be easily converted into a zero-valent complex in the reaction system can also be used.
  • a complex containing no tertiary phosphine or tertiary phosphite as a ligand is mixed with a tertiary phosphine or tertiary phosphite, and the tertiary phosphine or tertiary phosphite is converted into a ligand. It is also possible to generate a low valence complex.
  • tertiary phosphine or tertiary phosphite examples include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis ( And diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite and the like. Complexes containing a mixture of two or more of these ligands are also preferably used.
  • the metal catalyst it is also preferable to use a combination of a palladium complex or nickel complex that does not contain tertiary phosphine or tertiary phosphite, a complex containing tertiary phosphine or tertiary phosphite, and the above-described ligand. It is an aspect.
  • Examples of palladium complexes and nickel complexes that do not contain the tertiary phosphine or tertiary phosphite used in combination include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, and bis (benzo Nitrile) dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, nickel chloride, nickel iodide and the like.
  • Examples of the complex containing tertiary phosphine or tertiary phosphite include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenyl). Phosphine) palladium, bis (triphenylphosphine) dichloropalladium, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride Etc. These are not limited to those described above. These palladium complexes and nickel complexes may be used in so-called catalytic amounts. Generally, 20 mol% or less is sufficient relative to the substrate, and usually 10 mol% or less.
  • the base examples include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; methylamine, dimethyl Amine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, collidine, etc. And the like; sodium acetate, potassium acetate, lithium acetate; and the like can also be used.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, sodium carbon
  • a solvent is preferable, and a stable and inert solvent that does not hinder the reaction is used.
  • a solvent for example, water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.), Aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (chloroform) , Dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl,
  • the reaction temperature is not particularly limited, but is usually ⁇ 90 to 200 ° C., preferably ⁇ 50 to 150 ° C., more preferably 40 to 120 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, and more preferably 0.5 to 24 hours.
  • the biphenyl compound [4-A] obtained as described above can be highly purified by purifying by slurry washing, recrystallization, silica gel column chromatography and the like after the reaction.
  • the solvent used for the slurry washing is not particularly limited.
  • hydrocarbons such as hexane, heptane and toluene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene; diethyl ether, tetrahydrofuran, 1, Ethers such as 4-dioxane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol and 2-propanol; a mixture thereof; Etc.
  • the solvent used for recrystallization is not particularly limited as long as the biphenyl compound [4-A] dissolves upon heating and precipitates upon cooling.
  • hydrocarbons such as hexane, heptane and toluene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate Ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol and 2-propanol; and mixtures thereof.
  • Preferred is ethyl acetate, tetrahydrofuran, toluene or hexane.
  • Example 1 When the compound obtained in Example 1 is used as a starting material, for example, it can be derived into the following compounds.
  • Ms represents a methanesulfonyl group
  • I represents an iodine atom
  • Ts represents a p-toluenesulfonyl group.
  • Example 6 The following compounds were synthesized by the reaction shown in Example 6 using the compound obtained in Example 5 as a starting material.
  • the analysis apparatus and analysis conditions employed in Example 6 use UV detection (wavelength 265 nm) as a detector, and acetonitrile / 0.2 wt% ammonium acetate aqueous solution (70/30 (0 ⁇ The above HPLC analysis was used except that 5 min) ⁇ 85/15 (10-30 min)) [v / v] was used.
  • the compound having an ⁇ -methylene- ⁇ -butyrolactone group represented by the formula (3) obtained by the production method of the present invention is used in a wide range of fields such as a photopolymerizable compound used in a liquid crystal display device. .
  • the compound represented by Formula (1) and the compound represented by Formula (2) are used as an intermediate of the compound represented by Formula (3).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal (AREA)
  • Furan Compounds (AREA)

Abstract

L'invention concerne un nouveau procédé de production permettant de produire, de façon peu coûteuse et avec un rendement élevé, un composé photopolymérisable utilisé dans des éléments d'affichage à cristaux liquides ou équivalent ; et un nouveau composé intermédiaire. Dans un procédé de production d'un composé représenté par la formule (1), un composé représenté par la formule (A) est mis à réagir avec un composé représenté par la formule (C), dans des conditions acides, en présence d'étain métallique ou d'un composé contenant de l'étain. Dans un procédé de production d'un composé représenté par la formule (2-A), le composé représenté par la formule (1) est mis à réagir avec un composé représenté par la formule (D), en présence d'une base. L'invention concerne également le composé représenté par la formule (1) et le composé représenté par la formule (2-A). Dans les formules : n représente 1 ou 2 ; J1 et J2 représentent des halogènes ; R représente un groupe alkyle en C1 à C6 ; Y1 représente -SO2-R2 ; et R représente un groupe hydrocarboné.
PCT/JP2015/080805 2014-11-04 2015-10-30 Composé de butyrolactone et son procédé de production WO2016072366A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2016557748A JP6760075B2 (ja) 2014-11-04 2015-10-30 ブチロラクトン化合物及び製造方法
CN201580058217.0A CN107108540B (zh) 2014-11-04 2015-10-30 丁内酯化合物和制造方法
KR1020177014716A KR102508578B1 (ko) 2014-11-04 2015-10-30 부티로락톤 화합물 및 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-224511 2014-11-04
JP2014224511 2014-11-04

Publications (1)

Publication Number Publication Date
WO2016072366A1 true WO2016072366A1 (fr) 2016-05-12

Family

ID=55909091

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/080805 WO2016072366A1 (fr) 2014-11-04 2015-10-30 Composé de butyrolactone et son procédé de production

Country Status (5)

Country Link
JP (1) JP6760075B2 (fr)
KR (1) KR102508578B1 (fr)
CN (1) CN107108540B (fr)
TW (1) TWI696613B (fr)
WO (1) WO2016072366A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4879420A (en) * 1988-05-06 1989-11-07 E.I. Du Pont De Nemours And Company Preparation of mixtures of butanediols
WO2005061501A2 (fr) * 2003-12-12 2005-07-07 Merck & Co., Inc. Procede de preparation de hexahydropyrimido[1,2-a]azepine-2-carboxylates et composes connexes
WO2012002513A1 (fr) * 2010-06-30 2012-01-05 日産化学工業株式会社 Composé polymérisable, agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de production de dispositif d'affichage à cristaux liquides

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2297549B (en) 1995-02-06 1999-06-30 Merck Patent Gmbh Direactive mesogenic compound
JP4175826B2 (ja) 2002-04-16 2008-11-05 シャープ株式会社 液晶表示装置
JP5168976B2 (ja) 2007-03-28 2013-03-27 Ｄｉｃ株式会社 ビフェニル及びテルフェニル化合物、該化合物を含有する重合性液晶組成物
JP5549174B2 (ja) 2009-10-13 2014-07-16 Ｄｉｃ株式会社 重合性ナフタレン化合物
DE102010047409A1 (de) 2009-10-28 2011-05-05 Merck Patent Gmbh Polymerisierbare Verbindungen und ihre Verwendung in Flüssigkristallanzeigen
KR101831006B1 (ko) * 2010-06-30 2018-02-21 닛산 가가쿠 고교 가부시키 가이샤 액정 배향제, 액정 배향막, 액정 표시 소자 및 액정 표시 소자의 제조 방법
TW201534594A (zh) * 2010-06-30 2015-09-16 Nissan Chemical Ind Ltd 液晶配向劑、液晶配向膜、液晶顯示元件及液晶顯示元件之製造方法，以及聚合性化合物
JP5834489B2 (ja) 2011-05-18 2015-12-24 Dic株式会社 重合性ナフタレン化合物
JP6212912B2 (ja) * 2012-07-03 2017-10-18 Jsr株式会社 液晶配向剤、液晶配向膜、液晶表示素子及び液晶表示素子の製造方法
TWI647226B (zh) * 2014-01-30 2019-01-11 日商日產化學工業股份有限公司 Polymeric compound substituted by halogen atom

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4879420A (en) * 1988-05-06 1989-11-07 E.I. Du Pont De Nemours And Company Preparation of mixtures of butanediols
WO2005061501A2 (fr) * 2003-12-12 2005-07-07 Merck & Co., Inc. Procede de preparation de hexahydropyrimido[1,2-a]azepine-2-carboxylates et composes connexes
WO2012002513A1 (fr) * 2010-06-30 2012-01-05 日産化学工業株式会社 Composé polymérisable, agent d'alignement de cristaux liquides, film à alignement de cristaux liquides, dispositif d'affichage à cristaux liquides, et procédé de production de dispositif d'affichage à cristaux liquides

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
BALLINI, R. ET AL.: "A New Synthesis of exo- Methylene Butyrolactones from Nitroalkanes", SYNTHESIS, 2001, pages 1519 - 1522 *
CHEN, W. ET AL.: "Enantioselective Synthesis of a-exo-Methylene y-Butyrolactones via Chromium Catalysis", ORGANIC LETTERS, vol. 17, no. 21, 23 October 2015 (2015-10-23), pages 5236 - 5239 *
FOUQUET, E. ET AL.: "Reactivity of Functionalaized Allyltrihalostannanes: An Easy Entry to a-Methylene-y-lactones", TETRAHEDRON LETTERS, vol. 34, no. 48, 1993, pages 7749 - 7752 *
NOKAMI, J. ET AL.: "Facile Synthesis of 2- Methylene-4-butyrolactones", CHEMISTRY LETTERS, 1986, pages 541 - 544 *
STOWELL, J. C. ET AL.: "A Facile Procedure for Producing y-Halo Butyraldehyde Acetals", JOURNAL OF ORGANIC CHEMISTRY, vol. 57, no. 7, 1992, pages 2195 - 2196 *
WOODS, JR., G. F.: "5-Hydroxypentanal, Organic Syntheses", COLL., vol. 3, 1955, pages 470 *

Also Published As

Publication number Publication date
KR102508578B1 (ko) 2023-03-09
TW201623270A (zh) 2016-07-01
KR20170081201A (ko) 2017-07-11
CN107108540B (zh) 2019-08-02
JP6760075B2 (ja) 2020-09-23
TWI696613B (zh) 2020-06-21
JPWO2016072366A1 (ja) 2017-08-10
CN107108540A (zh) 2017-08-29

Similar Documents

Publication Publication Date Title
JP5247436B2 (ja) メチレンジスルホネート化合物の製造方法
RU2324678C2 (ru) Способ получения динитрилов фенилмалоновой кислоты
KR20020012274A (ko) 제초제 제조용 중간체로서의 치환된 아릴말론산 디니트릴
JP5008404B2 (ja) メチレンジスルホネート化合物の製造方法
JP6760075B2 (ja) ブチロラクトン化合物及び製造方法
JP5013365B2 (ja) スペーサー導入型ビス（ターピリジン）化合物の合成方法
JP5092140B2 (ja) 非対称型ビス（ターピリジン）化合物の合成方法
JP2006188449A (ja) 環式ジスルホン酸エステルの製造方法
CN115124460A (zh) 含配位单元的联萘轴手性配体及其制备方法和用途
JP4963970B2 (ja) メチレンジスルホネート化合物の製造方法
JP6733550B2 (ja) ブチロラクトン化合物の製造方法
WO2015076296A1 (fr) Dérivé de n-phényldiacrylimide contenant du brome et procédé de production associé
TWI786080B (zh) 芳香族二胺化合物前驅物之製造方法
JP2020132541A (ja) 輪状化合物の製造方法
JP5362208B2 (ja) ビニルエーテル基を有するアダマンタン誘導体
JP2012188387A (ja) キラルスピロビストリアゾール化合物、その製造方法及びその用途
JP2013189403A (ja) ジアセチレン誘導体の製造方法
KR20140103028A (ko) 인계 (메타)아크릴레이트 화합물 및 그 제조 방법
KR20210108581A (ko) 탄화수소고리 화합물의 제조방법
WO2007119402A1 (fr) Méthode de synthèse d'un 1,2-phényléthane en utilisant une réaction de couplage radicalaire par transfert d'atomes
JP2006096692A (ja) 光学活性トリフルオロメチルカルビノール誘導体の製造方法
JPWO2015178342A1 (ja) モノカップリング体の製造方法
JP2002205967A (ja) アセナフチレン環を有する新規な架橋性化合物及びその合成中間体
CN104974131A (zh) 一种制备二磺酸亚甲酯化合物的方法
JP2010168295A (ja) １‐（ペンタフルオロスルファニルベンゼン）‐２‐フェニルエタン‐１，２−ジオン化合物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15856399

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016557748

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20177014716

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 15856399

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载