CN107108541B - Method for producing butyrolactone compound - Google Patents
Method for producing butyrolactone compound Download PDFInfo
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- CN107108541B CN107108541B CN201580058138.XA CN201580058138A CN107108541B CN 107108541 B CN107108541 B CN 107108541B CN 201580058138 A CN201580058138 A CN 201580058138A CN 107108541 B CN107108541 B CN 107108541B
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- 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
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Abstract
Provided is a novel method for producing a polymerizable compound useful for a liquid crystal display element at a low cost with a good yield. A process for producing a compound represented by the formula (3) (n represents an integer of 1 to 10), wherein the compound represented by the formula (1) (n is a dialkyl acetal group having 1 to 2 carbon atoms, a 1, 3-dioxane group or a 1, 3-dioxolane group, Ar is used as PG), and a salt thereof1Biphenylene group, etc.) with a compound represented by the formula (2) (R is an alkyl group having 1 to 6 carbon atoms) in the presence of a palladium catalyst under acidic conditions.
Description
Technical Field
The present invention relates to a method for producing a compound having a butyrolactone ring.
Background
In a liquid crystal display element of a system (also referred to as a Vertical Alignment (VA) system) in which liquid crystal molecules aligned vertically with respect to a substrate are caused to respond to an electric field, a manufacturing process thereof includes a step of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules.
As such a vertical Alignment type liquid crystal display element, there is known a technique (PSA (polymer sustained Alignment) type liquid crystal display) in which a photopolymerizable compound is added to a liquid crystal composition in advance and is used together with a vertical Alignment film of polyimide or the like, and ultraviolet rays are irradiated while applying a voltage to a liquid crystal cell to accelerate a liquid crystal response speed (see patent document 1 and non-patent document 1).
In general, the tilt direction of the liquid crystal molecules in response to an electric field is controlled by a protrusion provided on a substrate, a slit provided on a display electrode, or the like, but it is said that: since a polymer structure in which the tilt direction of the liquid crystal molecules is memorized is formed on the liquid crystal alignment film by adding a photopolymerizable compound to the liquid crystal composition and irradiating ultraviolet rays while applying a voltage to the liquid crystal cell, the response speed of the liquid crystal display element is faster than that of a method in which the tilt direction of the liquid crystal molecules is controlled only by protrusions or slits.
Further, there are reports that: the response speed of the liquid crystal display element is also increased by adding the photopolymerizable compound to the liquid crystal alignment film without adding it to the liquid crystal composition (SC-PVA type liquid crystal display) (see non-patent document 2).
As an example of adding a photopolymerizable compound, a polymerizable monomer is known (see patent documents 2 to 6). Further, as a method for constructing a lactone ring in a polymerizable monomer, a method using a palladium catalyst is known, but these examples have room for improvement in terms of yield and the like (see non-patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-307720
Patent document 2: japanese laid-open patent publication No. 2008-239873
Patent document 3: japanese patent laid-open publication No. 2011-84477
Patent document 4: japanese patent laid-open No. 2012-240945
Patent document 5: japanese Kohyo publication (Kohyo publication) No. 2013-509457
Patent document 6: UK patent application publication No. GB2297549A
Non-patent document
Non-patent document 1: k. Hanaoka, SID 04 DIGEST, P.1200-1202
Non-patent document 2: K.H Y. -J.Lee, SID 09 DIGEST, P.666-668
Non-patent document 3: tetrahedron Letters, Vol.32, No.2, pp225-228,1991
Disclosure of Invention
Problems to be solved by the invention
Photopolymerizable compounds have been conventionally produced from expensive compounds as raw materials. Therefore, there is a problem in terms of the supply property as a raw material for electronic equipment which is required to reduce the cost. Therefore, a novel production method capable of producing a photopolymerizable compound at low cost has been demanded.
The present invention aims to solve the problems of the prior art described above.
Specifically, an object of the present invention is to provide a novel method for producing a photopolymerizable compound used for a liquid crystal display element at a low cost with a good yield.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: when a hydroxy methacrylate and an acetal or ketal compound are reacted in the presence of a tin-containing compound, a photopolymerizable compound can be produced with good efficiency by further coexistence of a palladium catalyst.
The present invention has the following gist based on the above findings.
1. A method for producing a compound represented by the formula (3), characterized in that a compound represented by the formula (1) and a compound represented by the formula (2) are reacted under acidic conditions in the presence of a palladium catalyst and metallic tin or a tin-containing compound.
(wherein n is an integer of 1 to 10, PG is a C1-2 dialkyl acetal group, a C1, 3-dioxan group or a C1, 3-dioxolan group, Ar is1Is represented by the following formula (4), (5) or (6)The 2-valent radical shown. )
In the formulae (4), (5) and (6), X independently represents a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms and a cyano group, and m represents1～m6Each independently an integer of 0 to 4, m7And m8Each independently is an integer of 0 to 3, and when the number of X is 2 or more, X's are optionally the same or different from each other. )
(wherein R represents an alkyl group having 1 to 6 carbon atoms.)
(wherein Ar is1And n represents the above meaning. )
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a compound having α -methylene- γ -butyrolactone group represented by formula (3), which is useful as a polymerizable compound used in a liquid crystal display device, or the like, can be produced at a good yield and at a low cost.
Detailed Description
< Compound represented by formula (3) >
The α -methylene- γ -butyrolactone compound which is the compound represented by formula (3) can be produced by reacting an acetal or ketal compound which is the compound represented by formula (1) with a hydroxy methacrylate which is the compound represented by formula (2) in the presence of metallic tin or a tin-containing compound and a palladium catalyst.
In the above formula, n is1 to 10, R is an alkyl group having 1 to 6 carbon atoms, PG is a dialkyl acetal group, 1, 3-dioxane-2-yl or 1, 3-dioxolan-2-yl group having 1 to 2 carbon atoms, Ar is1Is a 2-valent group represented by the following formula (4), (5) or (6).
N is preferably 1 to 4, more preferably 3 to 4. The n may be the same or different on the left and right sides, and from the viewpoint of synthesis, the n is preferably the same on the left and right sides.
The PG is preferably a dimethylacetal group or a 1, 3-dioxolan-2-yl group, and may be the same or different from each other on the left and right sides, and is preferably the same on the left and right sides from the viewpoint of synthesis.
R is preferably an alkyl group having 1 to 5 carbon atoms, and may be linear or branched, preferably linear. Particularly preferred is methyl or ethyl.
In the formulas (4), (5) and (6), X independently represents a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms and a cyano group, and m represents1～m6Each independently an integer of 0 to 4, m7And m8Each independently is an integer of 0 to 3, and when the number of X is 2 or more, X's are optionally the same or different from each other.
Examples of the halogen atom include fluorine, chlorine, bromine and the like.
X is preferably methoxy, trifluoromethyl, trifluoromethoxy or the like. Methoxy is particularly preferred.
m1～m6Each independently is preferably an integer of 0 to 1.
m7And m8Each independently is preferably an integer of 0 to 1.
Examples of the metallic tin or tin-containing compound include tin-based compounds such as tin powder, anhydrous tin chloride, tin chloride dihydrate, and tin chloride pentahydrate. Among them, anhydrous tin chloride or tin chloride dihydrate is preferable.
The amount of the metallic tin or tin-containing compound is preferably 2 to 4 equivalents based on 1 equivalent of the compound represented by the formula (1), and when the yield of the target compound is to be further improved, it is preferably 3 to 4 equivalents.
The reaction is carried out under an acidic condition, and the pH value of the acidic condition is preferably 1-3, more preferably 1-2. As the acid used for realizing the acidic condition, an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or ammonium chloride, an acidic resin such as Amberlyst 15, or an organic acid such as p-toluenesulfonic acid, acetic acid, or formic acid can be used. Among them, hydrochloric acid, sulfuric acid, or acetic acid is preferable.
The palladium catalyst includes a palladium (0) catalyst alone, a supported catalyst or a complex catalyst, and a compound which becomes a palladium (0) catalyst in the reaction solution. Specific examples thereof include raney palladium, a silica-supported palladium catalyst, an alumina-supported palladium catalyst, a carbon-supported palladium catalyst, a barium sulfate-supported palladium catalyst, a zeolite-supported palladium catalyst, a silica-alumina-supported palladium catalyst, and a solid or supported catalyst thereof; complex catalysts such as dichlorobis (triphenylphosphine) palladium, dichlorobis (trimethylphosphine) palladium, dichlorobis (tributylphosphine) palladium, bis (tricyclohexylphosphine) palladium, tetrakis (triethylphosphite) palladium, bis (cycloocta-1, 5-diene) palladium, tetrakis (triphenylphosphine) palladium, dicarbonylbis (triphenylphosphine) palladium, carbonyltris (triphenylphosphine) palladium, dichlorobis (benzonitrile) palladium, and dichloro (1, 5-cyclooctadiene) palladium; palladium chloride, palladium acetate, palladium oxide, and the like.
The palladium catalyst may be used alone, or two or more kinds may be used in combination.
The amount of the palladium catalyst to be used is usually 0.0001 to 20 mol%, preferably 0.001 to 10 mol%, based on the compound represented by the formula (1).
If necessary, a ligand may be added to the palladium catalyst. Examples of the ligand include mono-or multi-ligand tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tri (p-tolyl) phosphine, tris (2, 6-dimethylphenyl) phosphine, diphenylphosphine-3-sulfonic acid sodium salt, bis (3-sulfonylphenyl) phosphinobenzene sodium salt, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane and tris (3-sulfonylphenyl) phosphine sodium salt; phosphites such as triethyl phosphite, tributyl phosphite, triphenyl phosphite, and tris (2, 6-dimethylphenyl) phosphite; phosphorus salts such as triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride, triphenylallylphosphonium iodide, triphenylallylphosphonium bromide, triphenylallylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, etc.; phosphoric acid esters such as triphenyl phosphate, trimethyl phosphate, triethyl phosphate, and triallyl phosphate; nitriles such as benzonitrile and acetonitrile; ketones such as acetylacetone; dienes such as cyclopentadiene, pentamethylcyclopentadiene, and 1, 5-cyclooctadiene; nitrogen-containing heterocyclic ligands such as pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-bipyridine, terpyridine, 1, 10-phenanthroline, 8-hydroxyquinoline, bisoxazolopyridine (Pybox), 1, 4-dimethylpyrazole, 1,3, 5-trimethylpyrazole, pyrimidine, and pyrazine; carbon monoxide as a reaction atmosphere gas, and the like.
The amount of the ligand to be used is usually 0.1 to 10000 mol%, preferably 1 to 5000 mol%, based on the palladium catalyst.
Specific examples of the hydroxy methacrylate compound belonging to the compound represented by the formula (2) include hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxyisopropyl methacrylate, and hydroxy-t-butyl methacrylate. Preferably hydroxymethyl methacrylate or hydroxyethyl methacrylate.
The amount of the compound represented by the formula (2) to be used is not particularly limited, but is preferably 2.0 to 2.5 equivalents, more preferably 2.2 to 2.5 equivalents, based on 1 equivalent of the compound (1) represented by the formula (1).
In the above reaction, a solvent is preferably used, and a solvent which is stable, inactive and does not inhibit the reaction can be used. For example, water and ethers (Et) can be used2O、i-Pr2O, TBME (methyl tert-butyl ether), CPME (cyclopentyl methyl ether), tetrahydrofuran, dioxane, etc.), and the like. These solvents may be appropriately selected in consideration of the ease of reaction and the like, and may be usedThe number of the single species may be 1 or more, and 2 or more may be used in combination. Tetrahydrofuran or water is preferred.
The reaction temperature is not particularly limited, but is usually 0 to 100 ℃ and preferably 20 to 70 ℃.
The reaction time is usually 1 to 100 hours, preferably 1 to 12 hours.
The compound represented by formula (3) obtained as described above can be purified to high purity by removing an excessive amount of acid by adding a base to the reaction solution after the reaction, and then washing with water and recrystallizing or the like.
The solvent used for recrystallization is not particularly limited as long as the compound represented by formula (3) dissolves when heated and precipitates when cooled. Examples thereof include hydrocarbons such as hexane, heptane and toluene; halogen 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; mixtures thereof and the like. Preferably tetrahydrofuran, toluene, methanol, ethanol, 2-propanol, hexane, heptane, or mixtures thereof.
< Compound represented by formula (1) >
The compound (1) can be obtained by reacting an aromatic compound (a) having a phenolic hydroxyl group with a halogen-substituted acetal or ketal compound represented by the formula (B) in the presence of a base.
In the above formula, n, PG and Ar1Denotes the above meaning, J1Is a halogen atom. As J1Preferably Cl, Br or I.
As the base used in the above reaction, 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. Preferably sodium or potassium carbonate.
To accelerate the reaction rate, additives may be further used. As the additive, potassium iodide, sodium iodide, quaternary ammonium salt, crown ether, or the like can be used.
In the above reaction, a solvent is preferably used, and a solvent which is stable, inactive and does not inhibit the reaction can be used. For example, ketones such as water, alcohols, amines, acetone, methyl ethyl ketone, etc.; aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.); halogen-based hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.) and the like. These solvents may be appropriately selected in consideration of ease of reaction, etc., and 1 kind alone may be used, or 2 or more kinds may be used in combination. Aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.) are preferred.
The reaction temperature is not particularly limited, but is usually 40 to 200 ℃ and preferably 40 to 150 ℃. The reaction time is usually 20 to 100 hours, preferably 20 to 60 hours.
The compound represented by formula (1) obtained in the above manner can be purified by washing with water and recrystallization after the reaction, thereby achieving high purity.
The solvent used for recrystallization is not particularly limited as long as the compound represented by formula (1) dissolves when heated and precipitates when cooled. Examples thereof include hydrocarbons such as hexane, heptane and toluene; halogen 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; mixtures thereof and the like. Preferably toluene, methanol, ethanol, 2-propanol, hexane, heptane, or mixtures thereof.
< Compound represented by formula (A) >
The compound represented by the formula (A) is commercially available, but can be obtained by a crosslinking coupling reaction (Suzuki-Miyaura reaction) of a haloaryl group [2-A ] with an organometallic reagent [3-A ] in the presence of a base using a metal catalyst, as shown below.
In the above formula, X, m1And m2Denotes the aforementioned meanings, Hal denotes Br, I or OTf (Tf is p-toluenesulfonyl), M denotes B (OH)2Or 4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl.
The ratio (equivalent ratio) of the halogenated aryl group [2-A ] to the boric acid derivative [3-A ] used in the crosslinking coupling reaction is not particularly limited, and it is preferable to use 1.0 to 1.5 equivalents of the boric acid derivative [3-A ] to 1 equivalent of the halogenated aryl group [2-A ]. Furthermore, 1.0 to 1.5 equivalents of the halogenated aryl [2-A ] may be used with respect to 1 equivalent of the boric acid derivative [3-A ].
The metal catalyst used in the coupling reaction is preferably a metal complex and a ligand, but in the case where the reaction proceeds without using a ligand, the ligand may not be used. As the metal complex, complexes having various structures can be used, and a palladium complex or a nickel complex is preferably used. As the metal complex, a low-valence palladium complex or nickel complex is preferably used, and particularly a zero-valence complex having a tertiary phosphine or a tertiary phosphite as a ligand is preferred. In addition, suitable precursors that are easily converted to zero-valent complexes in the reaction system may also be used.
Further, a complex containing no tertiary phosphine and no tertiary phosphite as ligands may be mixed with tertiary phosphine and tertiary phosphite in the reaction system to produce a low valence complex containing tertiary phosphine and tertiary phosphite as ligands. Examples of the tertiary phosphine or tertiary phosphite include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1' -bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, and triphenyl phosphite. It is also suitable to use a complex in which 2 or more of them are mixed and contained in the form of a ligand.
It is also preferable to use a combination of a tertiary phosphine-free palladium complex, a tertiary phosphite-free palladium complex, a nickel complex, and a tertiary phosphine-free tertiary phosphite-containing complex with the above ligand as the metal catalyst. Examples of the palladium complex and nickel complex used in combination without containing a tertiary phosphine or a tertiary phosphite include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, palladium acetate, palladium chloride-acetonitrile complex, palladium-activated carbon, nickel chloride, and nickel iodide. Examples of the complex containing a tertiary phosphine and a tertiary phosphite include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphino) palladium, ethylenebis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) dichloropalladium, [1, 3-bis (diphenylphosphino) propane ] nickel (II) dichloride, and [1, 2-bis (diphenylphosphino) ethane ] nickel (II) dichloride. They are not limited to the above-mentioned substances.
The amount of the palladium complex and the nickel complex to be used may be any amount, and is generally 20 mol% or less, usually 10 mol% or less based on the substrate.
As the base, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, and collidine; sodium acetate, potassium acetate, lithium acetate, and the like.
In the above reaction, a solvent is preferably used, and a solvent which is stable, inactive and does not inhibit the reaction can be used. Examples of the solvent include water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et)2O、i-Pr2O, TBME, CPME, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogen hydrocarbons (chloroform, dichloromethane, etc.)Carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), and the like. These solvents may be appropriately selected in consideration of ease of reaction, etc., and 1 kind alone may be used, or 2 or more kinds may be used in combination.
The reaction temperature is not particularly limited, but is usually-90 to 200 ℃, preferably-50 to 150 ℃, and more preferably 40 to 120 ℃.
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 purified to a high degree by washing with slurry, recrystallization, silica gel column chromatography, or the like after the reaction.
The solvent used for slurry washing is not particularly limited, and examples thereof include hydrocarbons such as hexane, heptane, toluene and the like; halogen 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; mixtures thereof and the like.
The solvent used for recrystallization is not particularly limited as long as the biphenyl compound [4-a ] is dissolved upon heating and precipitated upon cooling. Examples thereof include hydrocarbons such as hexane, heptane and toluene; halogen 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; mixtures thereof and the like. Preferably ethyl acetate, tetrahydrofuran, toluene or hexane.
By this method, various compounds (a) can be produced.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not to be construed as being limited thereto.
Example 1:
after dissolving stannous chloride dihydrate (15.3g, 68mmol) in a mixed solution of THF (tetrahydrofuran) (100.0g), 4 '-bis (4- (1, 3-dioxolan-2-yl) butoxy) 1, 1' -biphenyl (10.0g, 23mmol), hydroxymethyl methacrylate (5.8g, 50mmol) and 5% Pd-C (50% wet; manufactured by Evonik Co., Ltd.) (2.0g), 0.1N aqueous hydrochloric acid (35.7g) was added dropwise thereto at 64 ℃ over 30 minutes. Followed by stirring for 24 hours, thereby obtaining a reaction mixture containing 4, 4' -bis (4- (3-methylenetetrahydrofuran-2 (3H) -on-5-yl) butoxy) biphenyl.
Subsequently, after Pd-C was removed by filtration at 50 ℃, toluene (60.0g) was added to the reaction mixture, and after stirring at 50 ℃, the hydrochloric acid layer was discarded. Next, the resulting organic layer was added dropwise to a 15.5 wt% aqueous solution of potassium hydroxide (75.0g) over a period of 30 minutes at 50 ℃. Thereafter, toluene (50.0g) was further added thereto, and after stirring at 50 ℃ for 10 minutes, the aqueous layer was discarded. Water (525.0g) was then added, and after stirring at 50 ℃ the aqueous layer was discarded, and the above operation was repeated 4 times to obtain an organic layer.
Further, activated carbon (1g) (a purpose-made Egret; Japan EnviroChemicals, Ltd., manufactured) was added to the obtained reaction mixture, and the mixture was stirred at 50 ℃ for 30 minutes. Thereafter, the activated carbon was removed by filtration, and the filtrate was cooled to 5 ℃ to precipitate crystals. Subsequently, the crystals were filtered and dried to obtain 4, 4' -bis (4- (3-methylenetetrahydrofuran-2 (3H) -on-5-yl) butoxy) biphenyl (white solid, yield: 7.7g, yield: 70%). The contents of Sn and Pd were less than 1ppm as confirmed by the MW/ICP-OES method.
The analytical equipment and analytical conditions for the compound obtained in example 1 are as follows.
HPLC analysis
The device comprises the following steps: LC-2010 System (Shimadzu Kaisha)
Column: inertsil ODS-3(4.6 mm. phi. times.250 mm, manufactured by GL Sciences Inc.)
A detector: UV detection (wavelength 265nm)
Eluent: acetonitrile/0.2 wt% ammonium acetate aqueous solution (70/30(0-5min) → 85/15(10-30min)) [ v/v ]
Example 2:
after dissolving stannous chloride dihydrate (28.9g, 128mmol) in a mixed solution of THF (100.0g), 4 '-bis (4, 4-dimethoxybutoxy) -3-fluoro-1, 1' -biphenyl (20.0g, 46mmol), hydroxymethyl methacrylate (11.7g, 101mmol), 5% Pd-C (50% wet; manufactured by Evonik Co.) (4.0g) and dibutylhydroxytoluene (0.05g, 0.23mmol), 0.1N aqueous hydrochloric acid solution (35.0g) was added dropwise thereto at 64 ℃ over 30 minutes. Followed by stirring for 24 hours, thereby obtaining a reaction mixture containing 4, 4' -bis (3- (3-methylenetetrahydrofuran-2 (3H) -on-5-yl) propoxy) -3-fluorobiphenyl.
Subsequently, toluene (80.0g) and THF (20.0g) were added to the reaction mixture, and filtration was carried out at 50 ℃ to remove Pd-C. Thereafter, the mixture was stirred at 50 ℃ and the hydrochloric acid layer was discarded. Next, the resulting organic layer was added dropwise to a 15.5 wt% aqueous solution of potassium hydroxide (150.0g) over a period of 30 minutes at 50 ℃. Thereafter, the mixture was stirred at 50 ℃ for 10 minutes, and the aqueous layer was discarded. Next, water (750.0g) was added, and after stirring at 50 ℃, the aqueous layer was discarded, and the above operation was repeated 4 times to obtain an organic layer.
Further, activated carbon (2g) (a purpose-made Egret; manufactured by Japan EnviroChemicals, Ltd.) was added to the obtained reaction mixture, and the mixture was stirred at 50 ℃ for 30 minutes. Thereafter, the activated carbon was removed by filtration, and cooled to 5 ℃ to precipitate crystals. Subsequently, the crystals were filtered and dried to obtain 4, 4' -bis (3- (3-methylenetetrahydrofuran-2 (3H) -on-5-yl) propoxy) -3-fluorobiphenyl (white solid, yield: 14.1g, yield: 65%). The contents of Sn and Pd were less than 1ppm as confirmed by the MW/ICP-OES method.
The analytical apparatus and analytical conditions for the compound obtained in example 2 were the same as those in example 1 except that the eluent was changed to acetonitrile/0.2 wt% ammonium acetate aqueous solution (70/30) [ v/v ].
Example 3:
after dissolving stannous chloride dihydrate (15.7g, 69mmol) in a mixed solution of THF (100.0g), 4 '-bis (4- (1, 3-dioxolan-2-yl) butoxy) -3-fluoro-1, 1' -biphenyl (10.0g, 22mmol), hydroxyethyl methacrylate (6.2g, 48mmol) and 5% Pd-C (50% wet; manufactured by Evonik Co.) (2.0g), 0.1N aqueous hydrochloric acid (35.7g) was added dropwise thereto at 64 ℃ over 30 minutes. Followed by stirring for 24 hours, to obtain a reaction mixture comprising 4, 4' -bis (4- (3-methylenetetrahydrofuran-2 (3H) -on-5-yl) butoxy) -3-fluoro-biphenyl. The reaction conversion based on HPLC analysis was 99.3%.
The analytical apparatus and analytical conditions for the compound obtained in example 3 were the same as those in example 1 except that the eluent was changed to acetonitrile/0.2 wt% ammonium acetate aqueous solution (70/30(0-5min) → 85/15(10-30min)) [ v/v ].
Comparative example 1:
the reaction was carried out at the same ratio as in example 3 except that the reaction was carried out in the absence of 5% Pd-C (50% wet; manufactured by Evonik Co., Ltd.) as a catalyst, but the reaction did not occur and the desired product was not obtained.
Comparative example 2:
the reaction was carried out at the same ratio as in example 3 except that Pd (II) -hydrotalcite (Wako pure chemical industries, Ltd.) was used instead of 5% Pd-C (50% wet; Evonik Co., Ltd.) as a catalyst, but the reaction did not occur and the target compound was not obtained.
Industrial applicability
The compound having α -methylene- γ -butyrolactone group represented by formula (3) obtained by the production method of the present invention is used in a wide range of fields as a photopolymerizable compound used in a liquid crystal display element, and the like.
The entire contents of the specification, claims and abstract of japanese patent application No. 2014-224510 filed on 11/4/2014 are incorporated herein by reference as the disclosure of the present invention specification.
Claims (6)
1. A process for producing a compound represented by the formula (3), which comprises reacting a compound represented by the formula (1) with a compound represented by the formula (2) under acidic conditions in the presence of a palladium catalyst and metallic tin or a tin-containing compound,
in the formula (1), n is an integer of 1-10; PG is a dialkyl acetal group having 1 to 2 carbon atoms, a 1, 3-dioxanyl group or a 1, 3-dioxolanyl group; ar (Ar)1Is a 2-valent group represented by the following formula (4), (5) or (6),
in the formulas (4), (5) and (6), X independently represents a substituent selected from a halogen atom, an alkoxy group having 1-6 carbon atoms, a haloalkyl group having 1-6 carbon atoms, a haloalkoxy group having 1-6 carbon atoms and a cyano group; m is1～m6Each independently is an integer of 0 to 4; m is7And m8Each independently is an integer of 0 to 3; when the number of X is 2 or more, X's may be the same or different from each other,
in the formula (2), R is an alkyl group having 1 to 6 carbon atoms,
in the formula (3), Ar1And n represents the above-mentioned meaning,
wherein the palladium catalyst is a supported catalyst of palladium (0).
2. The production process according to claim 1, wherein the palladium catalyst is a silica-supported palladium catalyst, an alumina-supported palladium catalyst, a carbon-supported palladium catalyst, a barium sulfate-supported palladium catalyst, a zeolite-supported palladium catalyst, or a silica-alumina-supported palladium catalyst.
3. The production method according to claim 1 or 2, wherein the reaction condition is an acidic condition having a pH of 1 to 2.
4. The production method according to claim 1 or 2, wherein the compound represented by formula (2) is used in an amount of 2.0 to 2.5 equivalents relative to 1 equivalent of the compound represented by formula (1).
5. The production method according to claim 1 or 2, wherein the metallic tin or the tin-containing compound is used in an amount of 2 to 4 equivalents relative to 1 equivalent of the compound represented by formula (1).
6. The production method according to claim 1 or 2, wherein the amount of the palladium catalyst used is 0.0001 to 20 mol% based on the compound represented by formula (1).
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| JP2014224510 | 2014-11-04 | ||
| JP2014-224510 | 2014-11-04 | ||
| PCT/JP2015/080804 WO2016072365A1 (en) | 2014-11-04 | 2015-10-30 | Butyrolactone-compound production method |
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| JP5168976B2 (en) | 2007-03-28 | 2013-03-27 | Ｄｉｃ株式会社 | Biphenyl and terphenyl compounds and polymerizable liquid crystal compositions containing the compounds |
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| DE102010047409A1 (en) | 2009-10-28 | 2011-05-05 | Merck Patent Gmbh | Polymerizable compounds and their use in liquid crystal displays |
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| "PALLADIUM-CATALYZED CARBONYL ALLYLATION BY 2-(HYDROXYMETHYL)ACRYLATE DERIVATIVES: SYNTHESIS OF α-METHYLENE-γ-BUTYROLACTONES";Yoshiro Masuyama et al.;《Tetrahedron Letters》;19911231;第32卷(第2期);第225-228页 * |
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