CN107108541A - The manufacture method of butyrolactone compound - Google Patents
The manufacture method of butyrolactone compound Download PDFInfo
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- CN107108541A CN107108541A CN201580058138.XA CN201580058138A CN107108541A CN 107108541 A CN107108541 A CN 107108541A CN 201580058138 A CN201580058138 A CN 201580058138A CN 107108541 A CN107108541 A CN 107108541A
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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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- 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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- 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
The novel method that useful polymerizable compound for liquid crystal represents element is manufactured inexpensively with good yield is provided.The manufacture method of compound shown in a kind of formula (3) (n represents following meanings), wherein, making formula (1), (n is 1~10 integer, PG is the dialkyl acetal base that carbon number is 1~2,1,3 alkyl dioxins or 1,3 dioxolanyls, Ar1For biphenylene etc.) shown in compound reacted in acid condition in metallic tin or sn-containing compound and in the presence of palladium catalyst with compound shown in formula (2) (R is the alkyl of carbon number 1~6).
Description
Technical field
The present invention relates to the manufacture method of the compound with butyrolactone ring.
Background technology
The mode for being responded the liquid crystal molecule vertical orientated relative to substrate using electric field is (also referred to as vertical orientated
(VA) mode) liquid crystal represent among element, include one side in its manufacturing process and apply voltage to liquid crystal molecule to irradiate on one side
The step of ultraviolet.
For the liquid crystal of this vertical orientation mode represents element, it is known that by advance to liquid-crystal composition
Middle addition photopolymerizable compound, and be used together with the vertical alignment layer of polyimides etc., while applying electricity to liquid crystal cells
One side irradiation ultraviolet radiation is pressed, ((polymer is persistently orientated (Polymer to PSA so as to accelerate the technology of liquid crystal response speed
Sustained Alignment) type liquid crystal display) (with reference to patent document 1 and non-patent literature 1).
Generally, the incline direction in response to the liquid crystal molecule of electric field is arranged on substrate projection, it is arranged at expression and uses
Slit of electrode etc. is controlled, but it is said that：By adding photopolymerizable compound into liquid-crystal composition, and while to liquid crystal list
Member applies voltage one side irradiation ultraviolet radiation, so that the polymerization that the incline direction that liquid crystal molecule is formed on liquid crystal orientation film is remembered
Thing works, therefore, compared with the method in liquid crystal molecules tilt direction is only controlled by projection, slit, liquid crystal represents element
Response speed accelerate.
In addition, there is report to claim：By the way that photopolymerizable compound is added in liquid crystal orientation film, without added to liquid crystal group
In compound, liquid crystal represents that the response speed of element can also accelerate (SC-PVA types liquid crystal display) (with reference to non-patent literature 2).
Be used as the example of above-mentioned addition photopolymerizable compound, it is known to certain polymerizable monomer (with reference to patent document 2~
6).In addition, being used as the construction method of the lactonic ring in polymerizable monomer, it is known to the method for using palladium catalyst, but these examples
Son remains room for improvement in terms of yield (with reference to non-patent literature 3).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-307720 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-239873 publications
Patent document 3：Japanese Unexamined Patent Publication 2011-84477 publications
Patent document 4：Japanese Unexamined Patent Publication 2012-240945 publications
Patent document 5：Japanese Unexamined Patent Application Publication 2013-509457 publications
Patent document 6：UK Patent Application discloses GB2297549A publications
Non-patent literature
Non-patent literature 1：K.Hanaoka,SID 04 DIGEST、P.1200-1202
Non-patent literature 2：K.H Y.-J.Lee,SID 09 DIGEST、P.666-668
Non-patent literature 3：Tetrahedron Letters,Vol.32,No.2,pp225-228,1991
The content of the invention
Problems to be solved by the invention
The conventional compound using costliness of photopolymerizable compound is manufactured as raw material.Therefore, as require cut down cost
Electronic instrument raw material, there is problem in terms of its supply.Thus, seek that photopolymerizable compound can be manufactured inexpensively
Novel manufacturing method.
It is an object of the invention to solve above-mentioned problem of the prior art point.
Specifically, it is an object of the present invention to provide representing element for being manufactured inexpensively liquid crystal with good yield
The novel manufacturing method of the middle photopolymerizable compound used.
The solution used to solve the problem
The present inventor etc. have made intensive studies to achieve these goals, as a result find：Make methacrylic acid hydroxyl
Ester and acetal or ketal compound in the presence of sn-containing compound when reacting, by the way that palladium catalyst has further coexisted,
Photopolymerizable compound can be manufactured with good efficiency.
The present invention is based on the opinion, with following purports.
1. the manufacture method of compound shown in a kind of formula (3), it is characterised in that make compound shown in following formula (1) with
Compound shown in formula (2) is stated in metallic tin or sn-containing compound and in the presence of palladium catalyst in acid condition to occur instead
Should.
(in formula, n be 1~10 integer, PG be carbon number be 1~2 dialkyl acetal base, 1,3- alkyl dioxins or
DOX base, Ar1For the divalent group shown in following formula (4), (5) or (6).)
(in formula (4), (5) and (6), X represents to be selected from halogen atom, the alkoxy of carbon number 1~6, carbon independently of one another
Substituent in the haloalkyl of atomicity 1~6, the halogenated alkoxy and cyano group of carbon number 1~6, m1~m6Independently of one another
For 0~4 integer, m7And m8It is each independently 0~3 integer, when X number is more than 2, X is optionally identical each other or not
Together.)
(in formula, R is the alkyl of carbon number 1~6.)
(in formula, Ar1Above-mentioned meaning is represented with n.)
The effect of invention
The polymerism that is used in element is represented in accordance with the invention it is possible to be manufactured inexpensively using good yield as liquid crystal
Compound etc. is the compound with alpha-methylene-gamma-butyrolactone base shown in useful formula (3).
Embodiment
<Compound shown in formula (3)>
By making acetal or ketal compound and the first as compound shown in formula (2) as compound shown in formula (1)
Base crylic acid hydroxy ester reacts in metallic tin or sn-containing compound and in the presence of palladium catalyst, can manufacture as formula
(3) the alpha-methylene-gamma-butyrolactone compound of compound shown in.
In above-mentioned formula, n is 1~10 integer, and R is the alkyl of carbon number 1~6, and PG is two that carbon number is 1~2
Alkyl acetal base, 1,3- dioxane -2- bases or DOX -2- bases, Ar1For 2 shown in following formula (4), (5) or (6)
Valency group.
It is used as n, preferably 1~4, more preferably 3~4.The n of left and right can be the same or different, from the sight in synthesis
Point sets out, and preferably left and right is identical.
As PG, preferably dimethylacetal base or DOX -2- bases, left and right can be the same or different,
From the viewpoint of synthesis is upper, preferably left and right is identical.
R is preferably the alkyl of carbon number 1~5, can be that straight-chain can also be branched, preferably straight-chain.It is special
You Xuanwei not methyl or ethyl.
In formula (4), (5) and (6), X represents to be selected from halogen atom, the alkoxy of carbon number 1~6, carbon independently of one another
Substituent in the haloalkyl of atomicity 1~6, the halogenated alkoxy and cyano group of carbon number 1~6, m1~m6Independently of one another
For 0~4 integer, m7And m8It is each independently 0~3 integer, when X number is more than 2, X is optionally identical each other or not
Together.
As halogen atom, fluorine, chlorine, bromine etc. can be included.
It is used as X, preferably methoxyl group, trifluoromethyl, trifluoromethoxy etc..Particularly preferably methoxyl group.
m1~m6Independently of one another be preferably 0~1 integer.
m7And m8Independently of one another be preferably 0~1 integer.
As metallic tin or the example of sn-containing compound, tin powder, anhydrous stannic chloride, the hydration of stannic chloride two can be used
The tin based compounds such as thing, stannic chloride pentahydrate.Wherein, preferably anhydrous stannic chloride or stannic chloride dihydrate.
As metallic tin or the consumption of sn-containing compound, relative to compound, preferably 2~4 shown in the formula (1) of 1 equivalent
Equivalent, it is desirable to when further improving the yield of object, preferably 3~4 equivalents.
Reaction is carried out in acid condition, and the pH of acid condition is preferably 1~3, more preferably 1~2.As in order to realize
Acid condition and the acid used, can use the inorganic acid aqueous solutions such as hydrochloric acid, sulfuric acid, phosphoric acid, ammonium chloride, Amberlyst 15 etc.
The organic acids such as acidic resins, p-methyl benzenesulfonic acid, acetic acid, formic acid.Wherein, preferably hydrochloric acid, sulfuric acid or acetic acid.
As palladium catalyst, independent catalyst, supported catalyst or the complex compound catalyst of palladium (0) can be included, anti-
Answer the compound for becoming palladium (0) catalyst in liquid.Specifically, such as thunder Buddhist nun palladium, the palladium of nonloaded silica can be included to urge
Agent, the palladium catalyst of Supported alumina, the palladium catalyst for loading carbon, palladium catalyst, the palladium of loaded zeolite for loading barium sulfate
Catalyst, the palladium catalyst of nonloaded silica aluminum oxide or its solid or supported catalyst；Dichloro double (triphenylphosphines) is closed
Palladium, dichloro double (trimethyl-phosphines) close palladium, dichloro double (tributylphosphines) and close palladium, double (tricyclohexyl phosphines) conjunction palladium, four (triethyl group phosphorous
Acid esters) close palladium, double (ring octyl- 1,5- diene) conjunction palladium, four (triphenylphosphines) conjunction palladium, dicarbapentaborane double (triphenylphosphines) conjunction palladium, carbonyl
Three (triphenylphosphines) close palladium, dichloro double (benzonitriles) and close the complex compound catalysts such as palladium, dichloro (1,5- cyclo-octadiene) conjunction palladium；Chlorination
The uniformly or non-uniformly catalyst etc. such as palladium, acid chloride, palladium oxide.
Palladium catalyst may be used alone, can also be used in combination two or more.
The consumption of palladium catalyst is usually 0.0001~20 mole of % relative to the compound shown in formula (1), is preferably
0.001~10 mole of %.
Ligand can also be added into above-mentioned palladium catalyst as needed.As ligand, such as front three can be included
Base phosphine, triethyl phosphine, tributylphosphine, triphenylphosphine, three (p-methylphenyl) phosphines, three (2,6- 3,5-dimethylphenyls) phosphines, diphenylphosphine
Double (diphenylphosphino) ethane of base benzene -3- sodium sulfonates, double (3- sulfonyl-phenyls) phosphino- benzene sodium salts, 1,2-, the double (diphenylphosphines of 1,3-
Base) propane, single part such as 1,4- double (diphenylphosphino) butane, three (3- sulfonyl-phenyls) phosphine sodium salts or multiple ligand tertiary phosphine class；
The phosphite esters such as triethyl phosphite, tributyl phosphite, triphenyl phosphite, three (2,6- 3,5-dimethylphenyls) phosphite esters
Class；Trityl group phosphonium iodide, triphenyl first base phosphonium bromide, triphenylmethylphospchloride chloride, triphenyl pi-allyl phosphonium iodide, triphen
The phosphorus such as base pi-allyl phosphonium bromide, the third base of triphenyl alkene phosphonium chloride, tetraphenyl phosphonium iodide, 4-phenyl phosphonium bromide, tetraphenyl phosphonium chloride
Salt；The phosphoric acid esters such as triphenyl phosphate, trimethyl phosphate, triethyl phosphate, TAP；The nitriles such as benzonitrile, acetonitrile
Class；The ketones such as acetylacetone,2,4-pentanedione；The dienes such as cyclopentadiene, pentamethylcyclopentadiene, 1,5- cyclo-octadiene；Pyridine, 2- methyl pyrroles
Pyridine, 3- picolines, 4- picolines, 2,2- bipyridyls, terpyridyl, 1,10- phenanthroline, 8-hydroxyquinoline, bis- oxazole pyrroles
The nitrogen-containing hetero ring system ligand such as pyridine (Pybox), 1,4- dimethyl pyrazoles, 1,3,5- trimethylpyrazols, pyrimidine, pyrazine；As anti-
Answer carbon monoxide of atmosphere gas etc..
The consumption of above-mentioned ligand is usually 0.1~10000 mole of % relative to palladium catalyst, preferably 1~5000 rubbed
You are %.
As the methacrylic acid hydroxy ester compound for belonging to compound shown in formula (2), specifically, methyl can be included
Dihydroxypropyl methyl esters, hydroxyethyl methacrylate, methacrylic acid hydroxyl isopropyl ester, the methacrylic acid hydroxyl tert-butyl ester
Deng.Preferably methacrylic acid hydroxyl methyl esters or hydroxyethyl methacrylate.
The consumption of compound is not particularly limited shown in formula (2), excellent relative to compound (1) shown in the formula (1) of 1 equivalent
Choosing uses 2.0~2.5 equivalents, more preferably 2.2~2.5 equivalents.
In above-mentioned reaction, solvent is preferably used, the solvent of stable and nonactive without prejudice to reaction can be used.For example may be used
To use water, ethers (Et2O、i-Pr2O, TBME (methyl tertiary butyl ether(MTBE)), CPME (cyclopentyl methyl ether), tetrahydrofuran, dioxanes
Deng) etc..These solvents can contemplate reaction easness etc. and suitably select, and can use single a kind, can also be used in mixed way
Two or more.Preferably tetrahydrofuran or water.
Reaction temperature is not particularly limited, usually 0~100 DEG C, preferably 20~70 DEG C.
Reaction time is usually 1~100 hour, is preferably 1~12 hour.
Compound shown in formula obtained from operating as above (3) was removed by adding alkali into reaction solution after the reaction
After the acid of amount, washed and recrystallized etc. to refine, so as to realize high purity.
As the solvent used in recrystallization, the compound shown in a solemnity (3) dissolves in heating and analysed in cooling
Go out, be just not particularly limited.The hydro carbons such as hexane, heptane, toluene can be included；The halogen such as chloroform, 1,2- dichloroethanes, chlorobenzene
Prime system hydro carbons；The ethers such as diethyl ether, tetrahydrofuran, 1,4- dioxanes；The esters such as ethyl acetate；The ketones such as acetone, MEK；First
The alcohols such as alcohol, ethanol, 2- propyl alcohol；Their mixture etc..Preferably tetrahydrofuran, toluene, methanol, ethanol, 2- propyl alcohol, oneself
Alkane, heptane or their mixture.
<Compound shown in formula (1)>
Compound (1) is as follows can be by making the aromatic compound (A) with phenolic hydroxyl group and the halogen shown in formula (B)
Element substitution acetal or ketal compound react to obtain in the presence of base.
In above-mentioned formula, n, PG and Ar1Represent above-mentioned meaning, J1For halogen atom.It is used as J1, preferably Cl, Br or I.
As the alkali used in above-mentioned reaction, sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, phosphoric acid can be used
Inorganic bases such as sodium, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate etc..Preferably sodium carbonate or potassium carbonate.
In order to promote reaction speed, additive can be further used.As additive, KI, iodate can be used
Sodium, quaternary ammonium salt, crown ether etc..
In above-mentioned reaction, solvent is preferably used, the solvent of stable and nonactive without prejudice to reaction can be used.For example may be used
To use the ketones such as water, alcohols, amine, acetone or MEK；Aprotic polar organic solvent (DMF, DMSO, DMAc, NMP
Deng)；Aromatic hydrocarbon (benzene,toluene,xylene, mesitylene, chlorobenzene, dichloro-benzenes, nitrobenzene, naphthane etc.)；Halogen system hydrocarbon
Class (chloroform, dichloromethane, carbon tetrachloride, dichloroethanes etc.)；Nitrile (acetonitrile, propionitrile, butyronitrile etc.) etc..These solvents can be examined
Consider reaction easness etc. suitably to select, single a kind can be used, can also be mixed with two or more.It is preferably non-proton
Property polar organic solvent (DMF, DMSO, DMAc, NMP etc.).
Reaction temperature is not particularly limited, usually 40~200 DEG C, preferably 40~150 DEG C.Reaction time is usually 20
~100 hours, preferably 20~60 hours.
Compound shown in formula obtained from operating as above (1) is refined by washing and recrystallizing etc. after the reaction, from
And high purity can be realized.
As the solvent used in recrystallization, the compound shown in a solemnity (1) dissolves in heating and analysed in cooling
Go out, be just not particularly limited.The hydro carbons such as hexane, heptane or toluene can be included；Chloroform, 1,2- dichloroethanes, chlorobenzene etc.
Halogen system hydro carbons；The ethers such as diethyl ether, tetrahydrofuran, 1,4- dioxanes；The esters such as ethyl acetate；The ketones such as acetone, MEK；
The nitriles such as acetonitrile, propionitrile；The alcohols such as methanol, ethanol, 2- propyl alcohol；Their mixture etc..Preferably toluene, methanol, ethanol, 2-
Propyl alcohol, hexane, heptane or their mixture.
<Compound shown in formula (A)>
Compound shown in formula (A) can also obtain commercially available product, but as follows such, can be by making halogenated aryl [2-
A] using metallic catalyst progress crosslinking coupling reaction, (Suzuki-palace Pu is anti-in the presence of base with organometallic reagent [3-A]
Should) obtain.
In above-mentioned formula, X, m1And m2Foregoing meaning is represented, Hal represents Br, I or OTf (Tf is p-toluenesulfonyl), M tables
Show B (OH)2Or 4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases.
Use ratio (the equivalent of the halogenated aryl [2-A] used in above-mentioned crosslinking coupling reaction and boronic acid derivatives [3-A]
Than) be not particularly limited, relative to the halogenated aryl [2-A] of 1 equivalent, preferably use the boronic acid derivatives of 1.0~1.5 equivalents
[3-A].In addition, relative to the boronic acid derivatives [3-A] of 1 equivalent, the halogenated aryl [2-A] of 1.0~1.5 equivalents can be used.
As the metallic catalyst used in above-mentioned coupling reaction, metal complex and ligand are preferably used, but do not make
, can also be without using ligand in the case that reaction can also be carried out during ligand.As metal complex, it can use various
The complex compound of structure, preferably uses palladium complex, nickel complex.As metal complex, the palladium network of low valence is preferably used
Compound or nickel complex, particularly preferably using tertiary phosphine, tertiary phosphite ester as ligand zero valent complex.Further, it is also possible to make
The appropriate precursor of zero valent complex is readily converted in reaction system.
And then, in reaction system, using the complex compound and tertiary phosphine without tertiary phosphine, tertiary phosphite ester as ligand, uncle Asia
Phosphate is mixed, can also produce using tertiary phosphine, tertiary phosphite ester as ligand low valence complex compound.It is used as tertiary phosphine
Or tertiary phosphite ester, such as triphenylphosphine, tri-o-tolyl phosphine, diphenyl methyl phosphine, phenyldimethylphosphine, 1,2- can be included
Double (diphenylphosphino) butane of double (diphenylphosphino) propane of double (diphenylphosphino) ethane, 1,3-, 1,4-, 1,1 '-bis- (hexichol
Base phosphino-) ferrocene, Trimethyl phosphite, triethyl phosphite, triphenyl phosphite etc..Use in them with being also suitable for
Two or more complex compound for mixing and being included in ligand form.
As metallic catalyst, without tertiary phosphine, the palladium complex of tertiary phosphite ester, nickel complex and tertiary phosphine, uncle will be included
It is also preferred mode that the complex compound of phosphite ester is applied in combination with aforementioned coordinative body.It is above-mentioned without uncle as what is be applied in combination
Phosphine, the palladium complex of tertiary phosphite ester, nickel complex, can include double (benzalacetones) and close palladium, three (benzylidenes third
Ketone) two palladiums, double (acetonitrile) dichloro palladiums, double (benzonitrile) dichloro palladiums, acid chloride, palladium bichloride, palladium bichloride-acetonitrile complex compound, palladium-work
Property charcoal, nickel chloride, nickel iodide etc..In addition, as the above-mentioned complex compound comprising tertiary phosphine, tertiary phosphite ester, dimethyl can be included
Double (triphenylphosphines) closes palladium, dimethyl double (diphenyl methyl phosphines) and closes palladium, ethylenebis (triphenylphosphine) conjunction palladium, four (triphenyls
Phosphine) close palladium, double (triphenylphosphine) dichloro palladiums, [double (diphenylphosphino) propane of 1,3-] Nickel Chloride (II), [double (hexichol of 1,2-
Base phosphino-) ethane] Nickel Chloride (II) etc..They are not limited to above-mentioned substance.
The consumption of these palladium complexs and nickel complex can be arbitrary catalytic amount, in general, relative to matrix
For 20 moles of below % just enough, usually 10 moles of below %.
As alkali, can also use sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium acid carbonate, saleratus, sodium phosphate,
The inorganic bases such as potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate；Methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, three
Ethamine, propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, tri-isopropyl amine, butylamine, dibutyl amine, tri-n-butylamine, diisopropyl
The amines such as ethamine, pyridine, imidazoles, quinoline, trimethylpyridine；Sodium acetate, potassium acetate, lithium acetate etc..
In above-mentioned reaction, solvent is preferably used, the solvent of stable and nonactive without prejudice to reaction can be used.It can make
With such as water, alcohols, amine, aprotic polar organic solvent (DMF, DMSO, DMAc, NMP), ethers (Et2O、i-Pr2O、
TBME, CPME, tetrahydrofuran, dioxanes etc.), it is aliphatic hydrocarbon (pentane, hexane, heptane, petroleum ether etc.), aromatic hydrocarbon
(benzene,toluene,xylene, mesitylene, chlorobenzene, dichloro-benzenes, nitrobenzene, naphthane etc.), halogen system hydro carbons (chloroform, dichloromethane
Alkane, carbon tetrachloride, dichloroethanes etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate
Deng), nitrile (acetonitrile, propionitrile, butyronitrile etc.) etc..These solvents can contemplate reaction easness etc. and suitably select, and can use
Single a kind, it can also be mixed with two or more.
Reaction temperature is not particularly limited, be usually -90~200 DEG C, be preferably -50~150 DEG C, more preferably 40~
120℃。
Reaction time is usually 0.05~100 hour, is preferably 0.5~40 hour, is more preferably 0.5~24 hour.
Biphenol compound obtained from operating as above [4-A] is cleaned by using slurry, recrystallized after the reaction, silicagel column color
Spectrometry etc. is refined, and can realize high purity.
The solvent used in being cleaned as slurry, is not particularly limited, and can include the hydrocarbon such as hexane, heptane, toluene
Class；The halogen system such as chloroform, 1,2- dichloroethanes, chlorobenzene hydro carbons；The ethers such as diethyl ether, tetrahydrofuran, 1,4- dioxanes；Acetic acid second
The esters such as ester；The ketones such as acetone, MEK；The nitriles such as acetonitrile, propionitrile；The alcohols such as methanol, ethanol, 2- propyl alcohol；Their mixing
Thing etc..
As the solvent used in recrystallization, as long as biphenol compound [4-A] dissolves in heating and separated out in cooling,
Just it is not particularly limited.The hydro carbons such as hexane, heptane, toluene can be included；The halogens such as chloroform, 1,2- dichloroethanes, chlorobenzene
It is hydro carbons；The ethers such as diethyl ether, tetrahydrofuran, 1,4- dioxanes；The esters such as ethyl acetate；The ketones such as acetone, MEK；Second
The nitriles such as nitrile, propionitrile；The alcohols such as methanol, ethanol, 2- propyl alcohol；Their mixture etc..Preferably ethyl acetate, tetrahydrofuran,
Toluene or hexane.
By this method, various compounds (A) can be manufactured.
Embodiment
Hereinafter, the present invention is further illustrated by embodiment, but being not limited to the examples property of the present invention is explained.
Embodiment 1：
To THF (tetrahydrofuran) (100.0g), 4,4 '-bis- (4- (1,3- dioxolanes -2- bases) butoxy) 1,1 '-biphenyl
(10.0g, 23mmol), methacrylic acid hydroxyl methyl esters (5.8g, 50mmol) and 5%Pd-C (50%wet；Evonik company systems)
Dissolved in the mixed solution of (2.0g) after stannous chloride dihydrate (15.3g, 68mmol), expending 30 minutes at 64 DEG C is added dropwise
0.1N aqueous hydrochloric acid solutions (35.7g).Thereafter stir 24 hours, so that obtain comprising 4,4 '-bis- (4- (3- methylene tetrahydrofuran-
2 (3H) -one -5- bases) butoxy) biphenyl reactant mixture.
Then, filtered and after removing Pd-C, toluene (60.0g) is added in reactant mixture at 50 DEG C,
After being stirred at 50 DEG C, salt acid layer is lost.Then, gained organic layer is expended 30 minutes at 50 DEG C and is added dropwise to 15.5wt%
In potassium hydroxide aqueous solution (75.0g).Thereafter, toluene (50.0g) is further added, after being stirred 10 minutes at 50 DEG C, is lost
Water layer.Then addition water (525.0g), after being stirred at 50 DEG C, loses water layer, aforesaid operations is repeated 4 times, obtain organic layer.
And then, activated carbon (1g) (special egression is added into gained reactant mixture；Japan Enviro
Chemicals, Ltd. system), stirred 30 minutes at 50 DEG C.Thereafter, activated carbon is removed by filtering, filtrate is cooled to 5
DEG C and separate out crystal.Then, filtering crystals and drying, so that obtain 4,4 '-bis- (4- (3- methylene tetrahydrofuran -2 (3H) -
Ketone -5- bases) butoxy) biphenyl (white solid, receipts amount：7.7g, yield：70%).When being confirmed with MW/ICP-OES methods, Sn
It is less than 1ppm with Pd content.
It should illustrate, the analytical equipment and analysis condition of the compound obtained in embodiment 1 are as follows.
HPLC is analyzed
Device：LC-2010 systems (Shimadzu Scisakusho Ltd's system)
Post：Inertsil ODS-3 (4.6mm Φ × 250mm, GL Sciences Inc. systems)
Detector：UV detects (wavelength is 265nm)
Eluent：Acetonitrile/0.2wt% ammonium acetate solutions (70/30 (0-5min) → 85/15 (10-30min)) [v/v]
Embodiment 2：
To THF (100.0g), 4,4 '-bis- (4,4- dimethoxys butoxy) fluoro- 1,1 '-biphenyl of -3- (20.0g,
46mmol), methacrylic acid hydroxyl methyl esters (11.7g, 101mmol), 5%Pd-C (50%wet；Evonik company systems) (4.0g)
With in the mixed solution of dibutyl hydroxy toluene (0.05g, 0.23mmol) dissolve stannous chloride dihydrate (28.9g,
After 128mmol), 30 minutes dropwise addition 0.1N aqueous hydrochloric acid solutions (35.0g) are expended at 64 DEG C.Thereafter stir 24 hours, so that
To comprising 4,4 '-reactant mixtures of bis- (3- (3- methylene tetrahydrofuran -2 (3H) -one -5- bases) propoxyl group) -3- fluorine biphenyl.
Then, toluene (80.0g) and THF (20.0g) are added in reactant mixture, are filtered, gone at 50 DEG C
Except Pd-C.Thereafter, after being stirred at 50 DEG C, salt acid layer is lost.Then, gained organic layer is expended 30 minutes at 50 DEG C
It is added dropwise in 15.5wt% potassium hydroxide aqueous solutions (150.0g).Thereafter, stirred 10 minutes at 50 DEG C, lose water layer.Then,
Water (750.0g) is added, after being stirred at 50 DEG C, water layer is lost, aforesaid operations is repeated 4 times, obtain organic layer.
And then, add activated carbon (2g) (special egression into gained reaction mixing；JapanEnviroChemicals,
Ltd. make), stirred 30 minutes at 50 DEG C.Thereafter, activated carbon is removed by filtering, is cooled to 5 DEG C and separates out crystal.Connect
, filtering crystals and drying, thus obtain 4,4 '-bis- (3- (3- methylene tetrahydrofuran -2 (3H) -one -5- bases) propoxyl group) -
3- fluorine biphenyl (white solid, receipts amount：14.1g, yield：65%).When being confirmed with MW/ICP-OES methods, Sn and Pd content
Less than 1ppm.
On the analytical equipment and analysis condition of the compound obtained in embodiment 2, except by eluent be altered to acetonitrile/
It is same as Example 1 outside 0.2wt% ammonium acetate solutions (70/30) [v/v].
Embodiment 3：
To THF (100.0g), 4,4 '-bis- (4- (1,3- dioxolanes -2- bases) butoxy) the fluoro- 1,1 '-biphenyl of -3-
(10.0g, 22mmol), hydroxyethyl methacrylate (6.2g, 48mmol) and 5%Pd-C (50%wet；Evonik company systems)
Dissolved in the mixed solution of (2.0g) after stannous chloride dihydrate (15.7g, 69mmol), expending 30 minutes at 64 DEG C is added dropwise
0.1N aqueous hydrochloric acid solutions (35.7g).Thereafter stir 24 hours, so that obtain comprising 4,4 '-bis- (4- (3- methylene tetrahydrofuran-
2 (3H) -one -5- bases) butoxy) the fluoro- biphenyl of -3- reactant mixture.It is 99.3% based on the reaction conversion ratio that HPLC is analyzed.
On the analytical equipment and analysis condition of the compound obtained in embodiment 3, except by eluent be altered to acetonitrile/
It is same as Example 1 outside 0.2wt% ammonium acetate solutions (70/30 (0-5min) → 85/15 (10-30min)) [v/v].
Comparative example 1：
Except not existing as the 5%Pd-C (50%wet of catalyst；Evonik company systems) under conditions of implement it
Outside, respectively reacted into ratio same as Example 3 is divided into, but do not react and do not obtain object.
Comparative example 2：
Except using Pd (II)-hydrotalcite (Wako Pure Chemical Industries, Ltd.'s system) to replace the 5%Pd- as catalyst
C (50%wet；Evonik company systems) outside, respectively reacted into ratio same as Example 3 is divided into, but do not occur
React and do not obtain object.
Industrial applicability
The compound with alpha-methylene-gamma-butyrolactone base shown in formula (3) obtained by the manufacture method of the present invention
Photopolymerizable compound for representing to use in element as liquid crystal etc. and be applied to extensive field.
It should illustrate, the specification for the Japanese patent application 2014-224510 that on November 4th, 2014 is submitted, right
The full content of claim and summary is quoted so far, is introduced as the disclosure of description of the invention.
Claims (6)
1. the manufacture method of compound shown in a kind of formula (3), it is characterised in that make compound and following formula shown in following formula (1)
(2) compound shown in reacts in acid condition in metallic tin or sn-containing compound and in the presence of palladium catalyst,
In formula (1), n is 1~10 integer；PG is dialkyl acetal base, 1,3- alkyl dioxin or 1 of the carbon number for 1~2,
3- dioxolanyls；Ar1For the divalent group shown in following formula (4), (5) or (6),
In formula (4), (5) and (6), X represents to be selected from halogen atom, the alkoxy of carbon number 1~6, carbon atom independently of one another
Substituent in the haloalkyl of number 1~6, the halogenated alkoxy and cyano group of carbon number 1~6；m1~m6It is each independently 0
~4 integer；m7And m8It is each independently 0~3 integer；When X number is more than 2, X is optionally identical or different each other,
In formula (2), R is the alkyl of carbon number 1~6,
In formula (3), Ar1With the above-mentioned meaning of expression.
2. manufacture method according to claim 1, wherein, palladium catalyst is thunder Buddhist nun palladium, the palladium chtalyst of nonloaded silica
Agent, the palladium catalyst of Supported alumina, the palladium catalyst for loading carbon, palladium catalyst, the palladium of loaded zeolite of load barium sulfate are urged
Agent, the palladium catalyst of nonloaded silica aluminum oxide, palladium complex catalyst, palladium bichloride, acid chloride or palladium oxide.
3. manufacture method according to claim 1 or 2, wherein, reaction condition is the acid condition that pH is 1~2.
4. according to manufacture method according to any one of claims 1 to 3, wherein, the consumption of compound shown in formula (2) relative to
Compound shown in the formula (1) of 1 equivalent is 2.0~2.5 equivalents.
5. according to manufacture method according to any one of claims 1 to 4, wherein, the consumption phase of metallic tin or sn-containing compound
It is 2~4 equivalents for compound shown in the formula (1) of 1 equivalent.
6. according to manufacture method according to any one of claims 1 to 5, wherein, the consumption of palladium catalyst is relative to formula (1) institute
It is 0.0001~20 mole of % to show compound.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2014-224510 | 2014-11-04 | ||
| JP2014224510 | 2014-11-04 | ||
| PCT/JP2015/080804 WO2016072365A1 (en) | 2014-11-04 | 2015-10-30 | Butyrolactone-compound production method |
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| CN107108541A true CN107108541A (en) | 2017-08-29 |
| CN107108541B CN107108541B (en) | 2020-06-19 |
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| CN201580058138.XA Active CN107108541B (en) | 2014-11-04 | 2015-10-30 | Method for producing butyrolactone compound |
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| JP (1) | JP6733550B2 (en) |
| KR (1) | KR102462576B1 (en) |
| CN (1) | CN107108541B (en) |
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| WO (1) | WO2016072365A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002511A1 (en) * | 2010-06-30 | 2012-01-05 | 日産化学工業株式会社 | Liquid crystal-aligning agent, liquid crystal-aligning film, liquid crystal display element and method for producing liquid crystal display elements |
| JP2012240945A (en) * | 2011-05-18 | 2012-12-10 | Dic Corp | Polymerizable naphthalene compound |
| CN103080153A (en) * | 2010-06-30 | 2013-05-01 | 日产化学工业株式会社 | Polymerizable compound, liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and method for producing liquid crystal display device |
| WO2013099937A1 (en) * | 2011-12-28 | 2013-07-04 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment membrane, liquid crystal display element, and method for manufacturing liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2297549B (en) | 1995-02-06 | 1999-06-30 | Merck Patent Gmbh | Direactive mesogenic compound |
| JP4175826B2 (en) | 2002-04-16 | 2008-11-05 | シャープ株式会社 | Liquid crystal display |
| 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 |
| JP5549174B2 (en) | 2009-10-13 | 2014-07-16 | Ｄｉｃ株式会社 | Polymerizable naphthalene compound |
| DE102010047409A1 (en) | 2009-10-28 | 2011-05-05 | Merck Patent Gmbh | Polymerizable compounds and their use in liquid crystal displays |
-
2015
- 2015-10-30 KR KR1020177014715A patent/KR102462576B1/en active IP Right Grant
- 2015-10-30 CN CN201580058138.XA patent/CN107108541B/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002511A1 (en) * | 2010-06-30 | 2012-01-05 | 日産化学工業株式会社 | Liquid crystal-aligning agent, liquid crystal-aligning film, liquid crystal display element and method for producing liquid crystal display elements |
| CN103080153A (en) * | 2010-06-30 | 2013-05-01 | 日产化学工业株式会社 | Polymerizable compound, liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and method for producing liquid crystal display device |
| JP2012240945A (en) * | 2011-05-18 | 2012-12-10 | Dic Corp | Polymerizable naphthalene compound |
| WO2013099937A1 (en) * | 2011-12-28 | 2013-07-04 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment membrane, liquid crystal display element, and method for manufacturing liquid crystal display element |
Non-Patent Citations (1)
| Title |
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| YOSHIRO MASUYAMA ET AL.: ""PALLADIUM-CATALYZED CARBONYL ALLYLATION BY 2-(HYDROXYMETHYL)ACRYLATE DERIVATIVES: SYNTHESIS OF α-METHYLENE-γ-BUTYROLACTONES"", 《TETRAHEDRON LETTERS》 * |
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| WO2016072365A1 (en) | 2016-05-12 |
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| CN107108541B (en) | 2020-06-19 |
| KR102462576B1 (en) | 2022-11-02 |
| JPWO2016072365A1 (en) | 2017-08-17 |
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