CN103804158B - The manufacturing method of hindered phenol and its manufacture intermediate - Google Patents

The manufacturing method of hindered phenol and its manufacture intermediate Download PDF

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CN103804158B
CN103804158B CN201310537547.0A CN201310537547A CN103804158B CN 103804158 B CN103804158 B CN 103804158B CN 201310537547 A CN201310537547 A CN 201310537547A CN 103804158 B CN103804158 B CN 103804158B
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compound
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carboxylic acid
manufacturing
acid
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CN103804158A (en
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堀口雅弘
门本丰
楠本哲生
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Priority claimed from JP2012242720A external-priority patent/JP6302157B2/en
Priority claimed from JP2012242718A external-priority patent/JP6070079B2/en
Priority claimed from JP2012242719A external-priority patent/JP5991530B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/06—Alkylated phenols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
    • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
    • C07C49/825—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups all hydroxy groups bound to the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
    • C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition

Abstract

The present application problem to be solved is to provide in the case where making an addition to liquid crystal material, the compound for being not easy the manufacturing method for the hindered phenol for reducing the voltage retention of liquid crystal material and being obtained by the manufacturing method.Further it is provided that when making the polymer that polymerizable composition, polymerizable composition is polymerize and obtained, the heat resistance of polymer will not be made reduce, be not easy that polymer is made to generate non-uniform polymerization inhibitor.Further it is provided that pass through the polymer for obtaining polymerizable composition, polymerizable composition polymerization and the optically anisotropic body for having used the polymer.The method for solving problem of the present invention is to provide a kind of manufacturing method and the compound obtained by the manufacturing method, it is further provided using the compound as the compound of intermediate and has used the composition of the compound；The manufacturing method is using phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) and the manufacturing method of the Acylphenol (D) of progress, and when phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) are reacted, there are organic solvents.Further it is provided that leading to formula (IV) compound represented and having used the polymerizable composition, polymerizable composition of the compound, in formula, Sp represents the alkylidene of carbon number 6~25.Further, it provides and one or more carbonyls at least one carbonyl and the compound (A) of at least one phenolic group that is obstructed is converted into methylene so as to the manufacturing method of the compound (B) at least one methylene and at least one phenolic group that is obstructed of progress and the compound obtained by the manufacturing method by contacting hydro-reduction, it further provides for the compound using the compound as intermediate and has used the composition of the compound.

Description

The manufacturing method of hindered phenol and its manufacture intermediate
Technical field
Manufacturing method the present invention relates to the compound with hindered phenol skeleton, the change by being obtained by the manufacturing method Close compound, the composition containing the compound obtained by the manufacturing method and the tree for having used said composition of object manufacture Fat, oil, oil filter, grease, ink, drug, cosmetics, lotion, liquid crystal material, pesticide, polymer, pigment, dyestuff, adhesion Agent, bonding agent, printed article, food, optically anisotropic body, display element or electronic device.
In addition, polymerization inhibitor the present invention relates to the structure with bisphenol derivative, being made using the polymerization inhibitor as intermediate Compound, the polymerizable composition, polymerizable composition containing the polymerization inhibitor and the optically anisotropic body for having used the polymerizable composition, polymerizable composition made.
Background technology
As the 1st background technology, as the problem of TFT liquid crystal display elements, have and be carried out continuously identical display for a long time In the case of the reliabilities such as " the image reservation " that occurs the problem of.A variety of causes can be enumerated for image reservation, one of them has The reduction of voltage retention caused by the deterioration as caused by light, heat of liquid crystal material.In general, with TFT as inhibition For the purpose of the deterioration of liquid crystal material, antioxidant is added in liquid crystal material.
Antioxidant as easy to manufacture, it is known that be connected with the hindered phenol of carbonyl.These antioxidants are to use 2,6- Di-t-butyl phenol and carboxylic acid in the presence of acid anhydrides, are manufactured by paying gram (Friedel-Crafts) reaction.However, it closes In the antioxidant manufactured by previously reported reaction condition, the situation of progress panelization in liquid crystal material is made an addition to Under, have be easy to due to heat or light and make panel voltage retention reduce the problem of (patent document 1, non-patent literature 1~2). It as its reason, can enumerate in the case where manufacturing antioxidant by previous reaction condition, generation is difficult to by usual The refined and by-product (patent document 1, non-patent literature 1~2) of denier that removes.As a result, it is possible to think wanting In the TFT materials used for liquid crystal display element for seeking special high-quality, voltage retention is caused due to the influence of the micro impurity Reduction.
Since the reaction is intermolecular reaction, shorten the reaction time in order to improve productivity, for this purpose, it is preferred that reaction solution Concentration is high.
Although in addition, the reagent used in the reaction, particularly dissolubility of the carboxylic acid in acid anhydrides is higher, It is extremely low for the dissolubility in inactive organic solvent compared with acid anhydrides.It is understood that with pure (neat) is carried out The situation of mixing is compared, and in the case where using organic solvent, makes the concentration for the carboxylic acid that dissolving is present in reaction system significantly It reduces, from the viewpoint of productivity, not preferably.Therefore be only it is known in the reaction by each reagent it is pure mix And after being made paste mixture, in order to stirring is made easily to add manufacturing method of the minimal amount of dichloromethane as lubricant (patent document 1) and by each reagent it is pure mixed and form the manufacture being directly stirred after paste mixture Method (non-patent literature 1~2).
In this way, since the antioxidant manufactured by well known preparation method has problem as described above, adding In the case of TFT materials used for liquid crystal display element, it is desirable that exploitation only can just be manufactured by common refining step, be not easy Make the preparation method for the antioxidant that the voltage retention of panel reduces.
As the 2nd background technology, polymerizable liquid crystal compound is used in various films.For example, by make said composition with It is polymerize after mesomorphic state arrangement, so as to make the film for having and being uniformly directed.The film so made can be used for liquid crystal Polarizer, polarizer needed for display etc..In addition, polymerizable liquid crystal compound can be used for having cholesteric texture The making of film.In most cases, in order to meet required optical characteristics, polymerization speed, dissolubility, fusing point, glass transition Temperature, the transparency of film, mechanical strength, case hardness, heat resistance and light resistance, and use comprising plural polymerizable compound and The composition of additive.
The known film with cholesteric texture selectively reflects the light of wavelength corresponding with the cholesteric pitch.It attempts The selection reflection characteristic is used for the reflection polarizing plate of display.For this purpose, in order to expand selection reflection wavelength region and into Capable research is necessary.As a kind of method, it is known that it is effective to add polymerization inhibitor in polymerism cholesteric liquid crystal compositions (patent document 2).
However, if by usually used polymerization inhibitor addition in the composition, the heat resistance of rewarding film is significantly The problem of reduction.In addition, if the composition added with previous polymerization inhibitor is coated on film, then non-uniform ask of mostly occurring It inscribes (patent document 3~4).If such film is used in display product, the display quality of product can be greatly reduced, Therefore in the purposes, it is desirable that exploitation will not reduce the heat resistance of film, be not easy to cause film non-uniform polymerization inhibitor.
As the 3rd background technology, liquid-crystal compounds used in TFT liquid crystal materials and additive preferably do not contain pair certainly Display causes the impurity that image retains, also, is preferably as far as possible high-purity.
On one of the species as TFT liquid crystal display elements PSA (Polymer Sustained Alignment, gather Close object stable orientations) type liquid crystal display element, have for controlling the polymer architecture of pre-tilt angle in unit, height can be carried out Contrast is shown and high-speed response.The element by that will be added in the liquid-crystal composition injection unit of polymerizable compound, It is applied in the state of voltage and carries out UV irradiations, make polymerizable compound polymerization.Therefore, for used in the element Liquid-crystal compounds and additive, special requirement do not contain due to UV irradiation and counter plate bring image retain etc. it is dysgenic miscellaneous Matter.
In general, for the purpose of preventing the deterioration of TFT liquid crystal materials, antioxidant is added in liquid crystal material.It is anti-as this Oxidant, based on it is easy to manufacture, high to the compatibility of liquid-crystal composition, the reasons such as harmful effect are not brought to the orientation of liquid crystal By, therefore it is frequently utilized that the phenol derivatives (patent document 5~6) with alkylidene.
Manufacturing method as the phenol derivatives with alkylidene, it is known that by the benzene with corresponding carbonyl alkylen group The method (non-patent literature 3) that carbonyl present in amphyl is reduced by contacting hydrogenation.If however, use the party The core reduction of aromatic rings then occurs while the reduction of carbonyl and generates each seed nucleus Reduction Body for method, and therefore, it is difficult in high yield Obtain the target substance of high-quality.In order to solve this problem, it was recently reported that will deposited in the phenol derivatives that there is carbonyl alkylen group Carbonyl be reduced into hydroxyl in advance after, by contact hydrogenation and reduce step synthesis (patent document 7).According to the party Method then can significantly inhibit the secondary generation of the hexamethylene alcohol among each seed nucleus Reduction Body.However, carbonyl is being reduced into advance , it is necessary to post-process, refining step after hydroxyl, therefore process number becomes more, not preferably.In addition, suitable on phenol aromatic rings In the case of hindered phenol with bulky group, although there is hexamethylene among the secondary each seed nucleus Reduction Body generated can be inhibited The generation of the core Reduction Body of alcohol structure, it can be difficult to inhibiting the generation of the core Reduction Body with cyclohexanone structure.
Therefore, in the field of the compound of the special requirement high-purity such as TFT liquid crystal materials, in the carbonyl being connected with hindered phenol In the reduction process of base, contact hydrogenation will not be used, and has used Clemensen reduction or hydride reduction (non-patent text Offer 4~6).If this method is used for the manufacture of hindered phenol, as anti-oxidant in the TFT liquid crystal material purposes of previous type Agent obtains the antioxidant effect of fully high-quality.On the other hand, if as described above, using contact hydro-reduction, produce The aromatic rings at raw hindered phenol position is difficult to the by-product removed obtained from being reduced by core, the purity drop of the compound finally obtained It is low, therefore the purposes cannot be used in.
However, compared with PSA type display element liquid crystal material, if addition passes through Clemensen reduction or hydride also Former and manufacture hindered phenol, then have the panel after manufacture to be prone to the problem of image retains.Speculate this is because by this also The impurity of former method and the denier contained by the hindered phenol that manufactures in the UV irradiation process when panel manufactures, goes bad as to figure As leave strip carrys out dysgenic substance.
In addition to above reaction path, the well known manufacturing method as the hindered phenol with alkylidene, it is known that make Phenol with alkylidene is in the presence of sulfuric acid or lewis acid, the method with tertiary butyl alcohol, tertiary butyl chloride or isobutene reaction (patent document 5, non-patent literature 7).However, for these reaction paths, there is the reaction time to take a long time or in order to incite somebody to action The problem of gas is blown into reaction solution and needs special installation.Furthermore it is known that method (the patent document using benzoquinones as raw material 8), but have raw material synthesis it is complicated the problems such as.
It is therefore desirable to develop do not contain harmful effect is come to image leave strip as impurity there is alkylidene to be obstructed The manufacturing method of phenol.
Prior art literature
Patent document
Patent document 1：US5684204 publications
Patent document 2：Japanese Unexamined Patent Publication 2011-247934 publications
Patent document 3：DE1811322A1 publications
Patent document 4：Japanese Unexamined Patent Publication 05-301865 publications
Patent document 5：Japanese Unexamined Patent Publication 9-124529 publications
Patent document 6：Japanese Unexamined Patent Publication 2006-169472 publications
Patent document 7：Japanese Unexamined Patent Publication 2001-233811 publications
Patent document 8：US3660505 publications
Non-patent literature
Non-patent literature 1：The Journal of Organic Chemistry, nineteen eighty-two, volume 47, No. 12,2278- Page 2285
Non-patent literature 2：Tetrahedron Letters, 1981, volume 22, No. 52,5293-5296 pages
Non-patent literature 3：Organic Reactions periodicals, nineteen fifty-three, volume 17,263-326 pages
Non-patent literature 4：Synthetic Communications periodicals, 2003, volume 33, No. 2,199-205 pages
Non-patent literature 5：Journal of Medicinal Chemistry periodicals, 1989, volume 32,100-104 pages
Non-patent literature 6：The Journal of Organic Chemistry periodicals, 2005, volume 70,4338- Page 4345
Non-patent literature 7：Chemische Berichte periodicals, 1985, volume 118, No. 5,1782-1797 pages
The content of the invention
Problems to be solved by the invention
The present application problem to be solved is to provide the manufacturing method of the hindered phenol of high-quality and by the manufacture Method and the compound obtained.
Further it is provided that when making the polymer that polymerizable composition, polymerizable composition is polymerize and obtained, the heat-resisting of polymer will not be made Property reduce, be not easy to make polymer to generate non-uniform polymerization inhibitor.Further it is provided that by obtaining polymerizable composition, polymerizable composition polymerization Polymer and used the optically anisotropic body of the polymer.
Means for solving the problems
1st, provide a kind of manufacturing method and the compound obtained by the manufacturing method, it is further provided with the change Object is closed as the compound of intermediate and has used the composition of the compound, the method for making is to use phenol (A), carboxylic The manufacturing method of sour (B) and carboxylic acid anhydrides (C) and the Acylphenol (D) of progress, phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) into There are organic solvents during row reaction.
2nd, logical formula (IV) compound represented is provided and has used the polymerizable composition, polymerizable composition of the compound.
(in formula, Sp represents the alkylidene of carbon number 6~25.).
3rd, it provides one or more carbonyls at least one carbonyl and the compound (A) of at least one phenolic group that is obstructed What base was converted into methylene and carried out by contacting hydro-reduction has at least one methylene and at least one phenolic group that is obstructed Compound (B) manufacturing method and the compound that is obtained by the manufacturing method, it is further provided using the compound as The compound of intermediate and the composition for having used the compound.
The effect of invention
The compound with hindered phenol skeleton manufactured on the manufacturing method by the present application, is making an addition to liquid In the case of the composition of brilliant material etc., the anti-metamorphic effect of composition is high, therefore the member of formation as various compositions is Useful.In addition, the composition of the compound manufactured containing the manufacturing method by the present application is in resin, oil, oil strain Device, grease, ink, drug, cosmetics, lotion, liquid crystal material, pesticide, polymer, pigment, dyestuff, sticker, bonding agent, print Brush object, food, optically anisotropic body, display element or electronic device purposes in be useful.
In addition, the compound of the present application is making an addition to polymerizable composition, polymerizable composition in the case of film is made, heat resistance is high, It is uneven few, therefore the member of formation as polymerizable composition, polymerizable composition is useful.In addition, use the chemical combination containing the present application The polymerizable composition, polymerizable composition of object and the optically anisotropic body made, heat resistance is high, uneven few, therefore in the purposes of optical film etc. In be useful.
Specific embodiment
A kind of manufacturing method is provided, is using phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) and the Acylphenol (D) of progress Manufacturing method, wherein, when phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) are reacted, there are organic solvents.
In these embodiments, preferably in 2 kinds of the mixture in phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) (E) and in organic solvent, add among phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) not as mixture (E) ingredient 1 Kind.In a kind of the ingredient for not becoming mixture (E) among adding in phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C), Ke Yi It is directly added into, can also can also be added in being dissolved in the addition of the solution of solvent with suspension in the state of pure.It uses at this time Solvent can in order to be mixed with mixture (E) and the organic solvent that uses is identical, can not also be same.
In addition in these embodiments, preferably as a kind in phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) Compound (F) and organic solvent in, add in 2 among phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) in addition to compound (F) Kind.In 2 kinds in addition to compound (F) among adding in phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C), 2 kinds of chemical combination can not be made Object is mixed and sequentially added, and can not also be made 2 kinds of compound mixing and be added in simultaneously, can also mix 2 kinds of compounds and add Enter.Furthermore, it is possible to which 2 kinds of compounds are directly added into the state of pure, can also be added in being dissolved in the solution of solvent, It can be added in suspension.The solvent used at this time can in order to be mixed with compound (F) and the organic solvent that uses is identical, It can not also be same.
In addition in these embodiments, from the viewpoint of the easiness of operation, preferably for phenol (A), carboxylic acid (B) Carboxylic acid anhydrides (C) is added in organic solvent, carboxylic acid (B) is added in or for carboxylic for phenol (A), carboxylic acid anhydrides (C) and organic solvent Sour (B), carboxylic acid anhydrides (C) and organic solvent add in phenol (A), are more preferably added in for phenol (A), carboxylic acid (B) and organic solvent Carboxylic acid anhydrides (C).
Further, phenol (A) is preferably the following general formula (I) compound represented.
(in formula, Y1、Y2、Y3、Y4And Y5Each independently represent hydrogen atom, the alkyl of carbon number 1~18, carbon number 1 ~18 alkenyl or the alkynyl of carbon number 1~18, the hydrogen atom in these groups independently can be by fluorine atom, chlorine 1-CH in atom, bromine atoms, iodine atom, cyano, nitro, hydroxyl substitution, and/or these groups2- or non-conterminous 2 A above-CH2- independently can by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,- S-CO- ,-O-CO-O- ,-CO-NH- ,-NH-CO- substitutions, Y1、Y2、Y3、Y4And Y5In at least one group table Show hydrogen atom.)
In addition, carboxylic acid (B) is preferably the following general formula (II) compound represented.
(in formula, G represents the organic group of 4 valencys, and R represents the group shown in the following general formula (III), m represent 1~4 it is whole Number, R there are can be the same or different in the case of multiple,
(in formula, Sp represents 1-CH2- or non-conterminous 2 or more-CH2- independently can be by-O- Or the alkylidene or singly-bound of the carbon number 1~20 of-S- substitutions, X expressions-O- ,-S- ,-OCH2- ,-CH2O- ,- CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O-CO-O- ,-CO-NH- ,-NH- CO- ,-CF2O- ,-OCF2- ,-CF2S- ,-SCF2- ,-CH2CF2- ,-CF2CH2- ,-CF2CF2- ,-CH= CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,- OCO-CH2CH2- ,-CH2CH2- COO- ,-CH2CH2- OCO- ,-COO-CH2- ,-OCO-CH2- ,-CH2- COO- ,-CH2- OCO- ,-CY11=CY11- (in formula, Y11Each independently represent hydrogen atom, carbon number 1~12 Alkyl, fluorine atom, chlorine atom or cyano.),-C ≡ C- or singly-bound, A represents Isosorbide-5-Nitrae-phenylene, naphthalene -2,6- diyl, 1, 4- cyclohexylenes, 1,4- cycloethylenes alkenyl, bis- rings of 1,4- [2.2.2] octamethylene, decahydronaphthalene -2,6- diyls, 1,2,3, 4- naphthane -2,6- diyls, pyridine -2,6- diyls, pyrimidine -2,5- diyls, 1,3- dioxane -2,5- two Base, these groups for it is unsubstituted or independently can by halogen, cyano, nitro, Pentafluorosulfanyl or carbon number 1~ 10 alkyl substitutes, and 1 or more hydrogen atom can be substituted by fluorine atom or chlorine atom independently in the alkyl, on the alkyl 1-CH2- or non-conterminous 2 or more-CH2- independently can by-O- ,-S- ,-CO- ,- COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O-CO-O- ,-CO-NH- ,-NH-CO- ,-CH= CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-CY21=CY21- (in formula, Y21Each independently represent hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.) or-C ≡ C- take Generation, Z expressions-O- ,-S- ,-OCH2- ,-CH2O- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S- CO- ,-O-CO-O- ,-CO-NH- ,-NH-CO- ,-SCH2- ,-CH2S- ,-CF2O- ,-OCF2- ,- CF2S- ,-SCF2- ,-CH2CF2- ,-CF2CH2- ,-CF2CF2- ,-CH=CH-COO- ,-CH=CH- OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,- CH2CH2- COO- ,-CH2CH2- OCO- ,-COO-CH2- ,-OCO-CH2- ,-CH2- COO- ,-CH2- OCO- ,-CY31=CY31- (in formula, Y31Each independently represent hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine Atom or cyano.) ,-C ≡ C-, 1-CH2- or non-conterminous 2 or more-CH2- independently can by- O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O-CO-O- ,-CO- NH- ,-NH-CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH- ,-CY41=CY41- (in formula, Y41Each independently represent hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine Atom or cyano.) or-C ≡ C- substitutions carbon number 1~20 alkylidene or singly-bound, n represents 0~5 integer, and A depositing In the case of multiple they can be the same or different Z there are in the case of multiple they can it is identical can not also Together.).)
Further, on logical formula (I) compound represented, from the easiness of synthesis, reaction efficiency and it is used in liquid crystal material In the case of material with from the viewpoint of the compatibility of liquid crystal material, preferably Y1It is more excellent for the situation of the alkyl of carbon number 1~8 Select Y1And Y5For the situation of the alkyl of carbon number 1~8, further preferred Y1For isopropyl or tertiary butyl, Y5For carbon number 1 The situation of~8 alkyl, even more preferably Y1For isopropyl or tertiary butyl, Y5Alkyl, Y for carbon number 1~83Represent hydrogen The situation of atom, further preferred Y1And Y5For isopropyl or tertiary butyl, Y3Represent the situation of hydrogen atom, even more preferably Y1 And Y5For isopropyl or tertiary butyl, Y2、Y3And Y4Represent the situation of hydrogen atom, particularly preferred Y1And Y5For tertiary butyl, Y2、Y3And Y4 Represent the situation of hydrogen atom.
In addition, on logical formula (II) compound represented, from the easiness of synthesis, reaction efficiency and liquid crystal material is used in With from the viewpoint of the compatibility of liquid crystal material, on G, preferably representing the situation of carbon atom in the case of material, on Sp, preferably Represent 1-CH2- or non-conterminous 2 or more-CH2- the carbon number 1~20 that can be substituted independently by-O- Alkylidene or singly-bound situation, more preferably represent 1-CH2- or non-conterminous 2 or more-CH2- independently may be used With by the alkylene of the situation of the alkylidene of the carbon number 1~20 of-O- substitutions, further preferably expression carbon number 1~20 The situation of base even more preferably represents the situation of the alkylidene of carbon number 1~12, even more preferably represents carbon number The situation of 1~7 alkylidene particularly preferably represents the situation of the alkylidene of carbon number 1~3, preferably each independent on X Ground expression-O- ,-OCH2- ,-CH2O- ,-COO- ,-OCO- ,-CH=CH-COO- ,-CH=CH- OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,- CH2CH2- COO- ,-CH2CH2The situation of-OCO- or singly-bound, more preferably each independently expression-O- ,-OCH2- ,- CH2O- ,-COO- ,-OCO- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,- CH2CH2The situation of-OCO- or singly-bound further preferably each independently represent-O- ,-COO- ,-OCO- or singly-bound Situation, on A, preferably represent unsubstituted independently or independently can be by halogen, cyano, nitro, five fluorine sulphur Alkyl or independently 1 or more hydrogen atom can be substituted by fluorine atom or chlorine atom and 1-CH2- or non-conterminous 2 A above-CH2- independently can by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,- S-CO- ,-O-CO-O- ,-CO-NH- ,-NH-CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,- (in formula, Y each independently represents hydrogen atom, carbon number 1 by COO-CH=CH- ,-OCO-CH=CH- ,-CY=CY- ~12 alkyl, fluorine atom, chlorine atom or cyano.) or-C ≡ C- substitution carbon number 1~10 it is alkyl-substituted, 1, 4- phenylenes, naphthalene -2,6- diyls, 1,4- cyclohexylenes, 1,4- cycloethylenes alkenyl, bis- rings of 1,4- [2.2.2] octamethylene, Decahydronaphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls, pyridine -2,6- diyls, pyrimidine -2,5- diyls, The situation of 1,3- dioxane -2,5- diyl more preferably represents unsubstituted independently or independently can be by Fluorine atom, chlorine atom or 1 or more hydrogen atom can be replaced by fluorine atoms and 1-CH independently2- or non-conterminous 2 A above-CH2- can be taken independently by the alkyl of-O- ,-COO- ,-the OCO- carbon number 1~10 substituted Generation, 1,4- phenylenes, naphthalene -2,6- diyls, 1,4- cyclohexylenes, 1,4- cycloethylenes alkenyl, bis- rings of 1,4- [2.2.2] Octamethylene, decahydronaphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls, pyridine -2,6- diyls, pyrimidine -2, The situation of 5- diyls, 1,3- dioxane -2,5- diyls further preferably represents unsubstituted independently or respective It 1 or more hydrogen atom can independently be replaced by fluorine atoms and 1-CH by fluorine atom or independently2- or not phase 2 or more adjacent-CH2- independently can be by-O- ,-COO- ,-the OCO- carbon number 1~10 substituted Alkyl-substituted, Isosorbide-5-Nitrae-phenylene, the situation of Isosorbide-5-Nitrae-cyclohexylene, even more preferably represent it is unsubstituted independently, Or can be substituted by the alkyl, alkoxy or alkanoyl of carbon number 1~5, the feelings of 1,4- phenylenes, 1,4- cyclohexylenes Condition, particularly preferably represent it is unsubstituted independently or can by methyl, methoxy substitution, Isosorbide-5-Nitrae-phenylene or unsubstituted Isosorbide-5-Nitrae-cyclohexylene situation, on Z, preferably each independently represent-O- ,-OCH2- ,-CH2O- ,- COO- ,-OCO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,-CH2CH2- OCO- ,-CY=CY- (in formula, Y each independently represents hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.) ,-C ≡ C-, 1-CH2- or non-conterminous 2 or more-CH2- can be taken independently by-O- ,-COO- ,-OCO- The alkylidene of carbon number 1~20 in generation or the situation of singly-bound, more preferably each independently expression-OCH2- ,-CH2O- ,- COO- ,-OCO-, 1-CH2- or non-conterminous 2 or more-CH2- independently can by-O- ,- The alkylidene of carbon number 1~20 or the situation of singly-bound of COO- ,-OCO- substitution, further preferably table independently Show-OCH2- ,-CH2O- ,-COO- ,-OCO-, the situation of the alkylidene of carbon number 1~20 or singly-bound, further more It is preferred that the situation of-COO- ,-OCO-, the alkylidene of carbon number 1~10 or singly-bound is each independently represented, further more It is preferred that the situation of-COO- ,-OCO-, the alkylidene of carbon number 2~8 or singly-bound is each independently represented, it is further more excellent Choosing each independently represents-COO- ,-OCO-, the alkylidene of even number of carbon number 2~6 or the situation of singly-bound, further The more preferably each independently situation of expression-COO- ,-OCO- or singly-bound, particularly preferably each independently represents singly-bound Situation on n, preferably represents the situation of 0~3 integer, more preferably represents the situation of 0~2 integer, further preferably represent 0 or 1 situation even more preferably represents 0 situation, on m, preferably represents the situation of 1~3 integer, more preferably represents 1 Or 2 situation.
Carboxylic acid anhydrides (C) is preferably that can be more preferably fluoroalkyl carboxylic acids' acid anhydride by the alkyl carboxylic acid acid anhydride that halogen atom substitutes, into One step is preferably trifluoroacetic anhydride.
More specific embodiment is recorded below.
Reaction temperature is preferably -100 DEG C~200 DEG C, from the viewpoint of yield and reaction speed, more preferably -20 DEG C~100 DEG C, further preferably 0 DEG C~60 DEG C, be even more preferably 0 DEG C~40 DEG C, particularly preferably 0 DEG C~room temperature with Under.
It is preferably organic solvent as reaction dissolvent, is more preferably the organic solvent of aprotic.As specific reaction Solvent, for example, chloroform, carbon tetrachloride, dichloromethane, 1,2- dichloroethanes, 1,2-dichloroethene, 1,1,2,2- can be enumerated Tetrachloroethanes, trichloro ethylene, 1-chlorobutane, carbon disulfide, acetone, acetonitrile, benzonitrile, DMAC N,N' dimethyl acetamide, diformazan Sulfoxide, Anaesthetie Ether, ethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, o-dichlorohenzene, dimethylbenzene, ortho-xylene, Paraxylene, meta-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, second Propyl propionate, pentyl acetate, methyl acetate, 2-Methoxyethyl acetate, hexamethylphosphoramide, three (dimethylamino) phosphines, ring Hexanone, 1,4- dioxane, tetrachloro-ethylene, tetrahydrofuran, pyridine, 1-Methyl-2-Pyrrolidone, tri- chloroethenes of 1,1,1- Alkane, toluene, hexane, pentane, hexamethylene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), t-butyl methyl ether, methyl ethyl ketone, Methyl cyclohexanone, methyl butyl ketone, metacetone, gasoline, coal tar naphtha, petroleum ether, naphtha, light petroleum, turpentine Oil, mineral spirits, but be preferably chloroform, carbon tetrachloride, dichloro from the viewpoint of yield, the easiness for post-processing and obtaining Methane, 1,2- dichloroethanes, 1,2- dichloroethylene, 1,1,2,2- tetrachloroethanes, trichloro ethylene, 1-chlorobutane, diethyl Ether, diethylene glycol diethyl ether, 1,4- dioxane, tetrachloro-ethylene, tetrahydrofuran, 1,1,1- trichloroethanes, hexane, penta Alkane, hexamethylene, pentamethylene, heptane, t-butyl methyl ether, gasoline, coal tar naphtha, petroleum ether, naphtha, light petroleum, Turpentine oil, mineral spirits, more preferably chloroform, carbon tetrachloride, dichloromethane, 1,2- dichloroethanes, 1,2-dichloroethene, 1, 1,2,2- tetrachloroethanes, 1-chlorobutane, Anaesthetie Ether, diethylene glycol diethyl ether, 1,4- dioxane, tetrachloro-ethylene, four Hydrogen furans, 1,1,1- trichloroethanes, hexane, pentane, hexamethylene, pentamethylene, heptane, t-butyl methyl ether, further preferably Chloroform, carbon tetrachloride, dichloromethane, 1,2- dichloroethanes, 1,2- dichloroethylene, 1,1,2,2- tetrachloroethanes, 1- neoprenes Alkane, tetrachloro-ethylene, 1,1,1- trichloroethanes, hexane, pentane, hexamethylene, pentamethylene, heptane.In addition, reaction dissolvent can be Above-mentioned solvent two or more can also be used in mixed way by single solvent.
On the amount of reaction dissolvent, as long as the amount that the reaction heat generated by reacting can be made fully to escape, then do not have There is special limitation, but if the amount of solvent is very few, then reaction heat accumulation is easy to generate by-product in the reaction system.Especially It is, if since the reaction heat of accumulation reacts so as to which reaction product is further superfluous, the secondary impurity for generating high molecular weight.By It is extremely micro in these macromolecule impurities, therefore direct quantitative is difficult to by common analysis method.Further, since molecular structure Similar with target substance, therefore, it is difficult to be removed by common purification operations.Even however, extremely micro, making an addition to In the case of liquid crystal material, also due to heat or light and voltage retention is greatly reduced, therefore be preferably as far as possible not secondary generation The reaction condition of high molecular weight impurity.Furthermore, it is possible to think to be previously added solvent for height before by reaction reagent all mixing The inhibition of molecular weight impurity is effective.On the other hand, if the amount of solvent is excessive, the concentration of reactant reduces, reaction speed Degree significantly decreases.Consider from view of the above, be suitably for compared with 1 gram of phenol (A), the amount of solvent is 0.01 milliliter~100 liters, It is more suitable for for compared with 1 gram of phenol (A), solvent is 0.1 milliliter~10 liters, is further adapted for as compared with 1 gram of phenol (A), it is molten Agent is 0.15 milliliter~1 liter, and preferably compared with 1 gram of phenol (A), solvent is 0.2 milliliter~500 milliliters, more preferably opposite In 1 gram of phenol (A), solvent is 0.4 milliliter~100 milliliters, and further preferably compared with 1 gram of phenol (A), solvent is 0.5 milli Rise~50 milliliters, even more preferably for compared with 1 gram of phenol (A), solvent is 1 milliliter~20 milliliters, even more preferably for Compared with 1 gram of phenol (A), solvent is 2 milliliters~15 milliliters, even more preferably for compared with 1 gram of phenol (A), solvent 2.5 Milliliter~10 milliliters, particularly preferably compared with 1 gram of phenol (A), solvent is 3 milliliters~8 milliliters.
As for implementing the mode of the 2nd invention, the present application provide lead to formula (IV) compound represented, along with The polymerizable composition, polymerizable composition of the compound, by make the polymerizable composition, polymerizable composition polymerization and obtain polymer and used the polymer Optically anisotropic body.
In logical formula (IV), Sp represents the alkylidene of carbon number 6~25, but the viewpoint of the easiness in obtaining from raw material is examined Consider, be preferably the straight-chain alkyl-sub of the straight-chain alkyl-sub of carbon number 6~25, more preferably carbon number 6~18, from adding In polymerizable composition, polymerizable composition and in the case of film is made it is uneven it is few from the viewpoint of, further preferably carbon number for 6~ The straight-chain alkyl-sub of even number among 18, from from the viewpoint of the compatibility of other ingredients, being particularly preferably carbon number as 6 The straight-chain alkyl-sub of even number among~10.
It is preferably following formula (IV-1)~formula (IV-12) institutes specifically as logical formula (I) compound represented The compound shown.
The compound of the present application can be manufactured by following preparation method.
The manufacture of (preparation method 1) following formula (S-3) compound represented
By formula (S-1) compound represented in presence of an acid, reacted with formula (S-2) compound represented, it can be with Acquisition formula (S-3) compound represented.As acid, as long as formula (S-3) compound represented is obtained during the reaction Acid is then not particularly limited, but can enumerate such as aluminium chloride, aluminium isopropoxide, aluminium ethylate, aluminum chloride hydrate, aluminium bromide, trifluoro Change boron, dibutyl boron trifluoromethanesulfonic acid, trifluoromethanesulfonic acid dicyclohexyl boron, boron chloride, boron chloride methyl sulfide to match somebody with somebody Position compound, boron trifluoride tetrahydrofuran complex, boron trifluoride t-butyl methyl ether complex, boron trifluoride Methanol complex, boron trifluoride dihydrate, boron trifluoride Anaesthetie Ether compound, boron trifluoride dibutyl compound, three Boron fluoride phenol complex, boron trifluoride propyl alcohol complex, boron trifluoride methyl ether compound, boron trifluoride diethyl Etherate, boron trifluoride methyl sulfide complex, boron trifluoride acetic acid complex, metal trifluoroacetate mesylate, Trifluoroacetic anhydride, silicon compound etc..Formula (S-1) compound represented is used directly for reacting, and can also protect hydroxyl It is used further to react after shield.As protecting group, such as preferably GREENE ' S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((fourth edition), PETER G.M.WUTS, THEODORA W.GREENE write altogether, A John Wiley＆Sons, Inc., Publication) in the group enumerated.Formula (S-2) compound represented is used directly for reacting, and can also derive It is reused into acetyl halide compound, ester, aldehyde or mixed acid anhydride.As the reaction condition, it is preferably for example, experimental chemistry lecture (day This chemistry can be compiled, Wan Shan Co., Ltd. distribution), Organic Syntheses (A John Wiley＆Sons, Inc., Publication), Beilstein Handbook of Organic Chemistry (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH＆ Co.K), the documents such as Fiesers ' Reagents for Organic Synthesis (John Wiley＆Sons, Inc.) or The condition enumerated in the databases such as SciFinder or Reaxys.Furthermore, it is possible to reaction dissolvent is used as needed.As reaction Solvent as long as obtaining the reaction dissolvent of formula (S-3) compound represented during the reaction, is then not particularly limited, but makees For preferred reaction dissolvent, can enumerate for example, chloroform, carbon tetrachloride, dichloromethane, 1,2- dichloroethanes, 1,2-, bis- chloroethenes Alkene, 1,1,2,2- tetrachloroethanes, trichloro ethylene, 1-chlorobutane, carbon disulfide, acetone, acetonitrile, benzonitrile, N, N- dimethyl Formamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, Anaesthetie Ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetic acid It is ester, ethylene glycol monobutyl ether, ethylene glycol single methyl ether, diethylene glycol diethyl ether, o-dichlorohenzene, dimethylbenzene, ortho-xylene, right Dimethylbenzene, meta-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, acetic acid Propyl ester, pentyl acetate, methyl acetate, 2-Methoxyethyl acetate, hexamethylphosphoramide, three (dimethylamino) phosphines, hexamethylene Ketone, 1,4- dioxane, dichloromethane, styrene, tetrachloro-ethylene, tetrahydrofuran, pyridine, 1-Methyl-2-Pyrrolidone, 1,1,1- trichloroethanes, toluene, hexane, pentane, hexamethylene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), tertbutyl methyl Ether, methyl ethyl ketone, methyl cyclohexanone, methyl butyl ketone, metacetone, gasoline, coal tar naphtha, petroleum ether, naphtha, Light petroleum, turpentine oil, mineral spirits.
It is preferable to use in nematic liquid-crystal composition, smectic liquid crystal composition, chiral smectic liquid for the compound of the present application Crystal composite and cholesteric liquid crystal compositions.It, can also in liquid-crystal composition using the reactive compounds of the present application Add the compound beyond the present application.
As other reactive compounds that the reactive compounds with the present application are mixed and used, specifically, The P of preferably general formula (2II) compound represented, particularly preferably general formula (2II)1And P2For acryloyl group or methacryl The situation of base.
(in formula, P1And P2The group in following formulas (P-1)~formula (P-17) is each independently represented,
S1And S2Each independently represent the alkylidene of singly-bound or carbon number 1~18,1-CH2- or it is non-conterminous 2 or more-CH2- can be substituted by oxygen atom ,-COO- ,-OCO- ,-OCOO-, X3And X4Each independently represent list Key ,-O- ,-S- ,-OCH2- ,-CH2O- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,- O-CO-O- ,-OCOOCH2- ,-CH2OCOO- ,-CO-NH- ,-NH-CO- ,-SCH2- ,-CH2S- ,- CH=N- ,-SCH2- ,-CH2S- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,- OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,-CH2CH2- OCO- ,- COO-CH2- ,-OCO-CH2- ,-CH2- COO- ,-CH2- OCO- ,-CF2- ,-CF2O- ,-OCF2- ,- CH2CH2- ,-CF2CH2- ,-CH2CF2- ,-CF2CF2-, (in formula, Y is independently by-CY=CY- or-C ≡ C- Represent hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.), Z1Each independently represent singly-bound ,- O- ,-S- ,-OCH2- ,-CH2O- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O- CO-O- ,-OCOOCH2- ,-CH2OCOO- ,-CO-NH- ,-NH-CO- ,-SCH2- ,-CH2S- ,-CH= N- ,-SCH2- ,-CH2S- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO- CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,-CH2CH2- OCO- ,-COO- CH2- ,-OCO-CH2- ,-CH2- COO- ,-CH2- OCO- ,-CF2- ,-CF2O- ,-OCF2- ,- CH2CH2- ,-CF2CH2- ,-CH2CF2- ,-CF2CF2-, (in formula, Y is independently by-CY=CY- or-C ≡ C- Represent hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.), A1And A2Each independently represent 1,4- Phenylene, 1,4- cyclohexylenes, pyridine -2,5- diyls, pyrimidine -2,5- diyls, naphthalene -2,6- diyls, naphthane -2, 6- diyls or 1,3- dioxane -2,5- diyl, A1And A2It is each independently unsubstituted or can be by alkyl, alkyl halide Base, alkoxy, halogenated alkoxy, halogeno-group, cyano or nitro substitution, m1 represent 0,1,2 or 3, and 2 or 3 situation is represented in m1 Under, existing 2 or 3 A1And/or Z1It can be the same or different.).
Specifically, it is preferably general formula (2III) compound represented, is particularly preferably following formula (2III-1)~formula (2III-8) compound represented.
(in formula, S3And S4Each independently represent alkylidene, the X of carbon number 2~183And X4Each independently represent- O- ,-COO- ,-OCO- or singly-bound, Z3And Z4Each independently represent-COO- or-OCO-, A3、A4And A5Each solely On the spot represent 1,4- Asias benzene that is unsubstituted or being substituted by fluorine atom, the alkyl of chlorine atom or carbon number 1~4 or alkoxy Base.).
(in formula, S3It represents and the S in general formula (2III)3Identical meaning, S4It represents and the S in general formula (2III)4It is identical Meaning.) in above-mentioned formula (2III-1)~formula (2III-8), further preferably S3And S4It is each independently carbon atom The compound of the alkylidene of number 2~8.
Furthermore it is preferred that being general formula (2IV) compound represented, following formula (2IV-1)~formula (2IV-8) is particularly preferably Compound represented.
(in formula, S5And S6Each independently represent the alkylidene of carbon number 2~18, X5And X6Each independently represent- O- ,-COO- ,-OCO- or singly-bound, Z5Expression-COO- or-OCO-, A6、A7And A8It each independently represents unsubstituted Or by fluorine atom, the alkyl of chlorine atom or carbon number 1~4 or alkoxy instead of 1,4- phenylenes.).
(in formula, S5It represents and the S in general formula (2IV)5Identical meaning, S6It represents and the S in general formula (2IV)6Identical Meaning.) it is preferably formula (2IV- from the viewpoint of heat resistance and durability in above-mentioned formula (2IV-1)~formula (2IV-8) 2), formula (2IV-5), formula (2IV-6), formula (2IV-7) and formula (2IV-8) compound represented, further preferably formula (2IV-2) compound represented, particularly preferably S5And S6It is each independently the compound of the alkylidene of carbon number 2~8.
In addition, as preferred 2 function polymerizable compound, can enumerate shown in the following general formula (2V-1)~formula (2V-5) Compound.
(in formula, S7And S8Each independently represent the alkylidene of carbon number 2~18.) in above-mentioned formula (2V-1)~formula It is preferably formula (2V-2), formula (2V-3) and formula (2V-5) compound represented, particularly preferably S in (2V-5)7And S8Respectively From the compound for the alkylidene for independently being carbon number 2~8.
In the polymerizable liquid crystal compound of compound containing the present application, also said composition can not be significantly being damaged The degree of liquid crystal liquid crystal property, addition do not show the polymerizable compound of liquid crystal liquid crystal property.Specifically, as long as being recognized in the technical field To be the compound of macromolecule formative monomer or macromolecule formative oligomer, then it is not particularly limited, can uses.
In addition, make an addition to the Photoepolymerizationinitiater initiater in the polymerizable liquid crystal compound of the compound containing the present application Concentration is preferably 0.1~10 mass %, further preferably 0.2~5 mass %.As Photoepolymerizationinitiater initiater, benzene can be used Acyloin ethers, benzophenone, acetophenones, benzil ketals class, acylphosphine oxide etc..
In addition, for the polymerizable liquid crystal compound of the compound containing the present application, stablize to improve the preservation Property, stabilizer can also be added.As stabilizer, can enumerate for example, quinhydrones, quinhydrones monoalkyl ethers, tert-butyl catechol Class, 1,2,3,-thrihydroxy-benzene class, benzenethiol class, nitro compound species, beta-naphthylamine class, betanaphthol class, nitroso compound etc..It is using Additive amount in the case of stabilizer is, is preferably 0.005~1 mass %, further preferably compared with liquid-crystal composition 0.02~0.5 mass %.
In addition, the polymerizable liquid crystal compound of the compound containing the present application is being used in film class, optical element It, can also basis in the case of the purposes such as class, functional pigment class, drug class, toiletries, smears class, synthetic resin Its purpose and add metal, metal complex, dyestuff, pigment, pigment, fluorescent material, phosphor material, surfactant, Levelling agent, thixotropic agent, gelating agent, polysaccharide, ultra-violet absorber, infrared absorbent, antioxidant, amberlite Metal oxides such as fat, titanium oxide etc..
Pass through the polymer for polymerizeing to obtain by the polymerizable liquid crystal compound of the compound containing the present application It can utilize in a variety of applications where.For example, by the way that the polymerizable liquid crystal compound of the compound containing the present application is made not take To and polymerize the polymer so as to obtain, light diffuser plate can be used as, polarisation eliminates plate, Moire fringe prevent plate (モ ア レ Onyx prevent plate) and utilize.In addition, the polymer obtained by being polymerize after being orientated, has optical anisotropy, is to have .Such optically anisotropic body can manufacture as follows, for example, making the polymerism liquid of the compound containing the present application Crystal composite is supported in the substrate that friction treatment has been carried out with cloth etc., the substrate for being formed with organic film or is deposited with tilting There is SiO2Alignment films substrate or after being held between substrate, which is polymerize, so as to manufacture.
As polymerizable liquid crystal compound is made to support method when on substrate, can enumerate rotary coating, die coating, Extrusion coated, roller coat cloth, the coating of silk bar type, intaglio plate coating, injection coating, dipping, print process etc..When being coated in addition, Ke Yi Organic solvent is added in polymerizable liquid crystal compound.As organic solvent, hydrocarbon system solvent, halogenated hydrocarbon system solvent, ether can be used Series solvent, alcohol series solvent, ketone series solvent, ester series solvent, non-protonic solvent etc., such as can enumerate toluene as hydrocarbon system solvent Or hexane, dichloromethane can be enumerated as halogenated hydrocarbon system solvent, tetrahydrofuran, acetyl oxygen can be enumerated as ether series solvent Base -2- Ethoxyethanes or propylene glycol monomethyl ether can enumerate methanol, ethyl alcohol or isopropyl as alcohol series solvent Alcohol can enumerate acetone, methyl ethyl ketone, cyclohexanone, gamma-butyrolacton or N-Methyl pyrrolidone class as ketone series solvent, Ethyl acetate or cellosolve can be enumerated as ester series solvent, dimethylformamide or second can be enumerated as non-protonic solvent Nitrile.They may be used alone, can also be used in combination, as long as considering its vapour pressure and the dissolubility of polymerizable liquid crystal compound And it carries out suitable for selection.As the method that the organic solvent of addition is made to volatilize, can use natural drying, heat drying, It is dried under reduced pressure, vacuum drying under reduced pressure.In order to which the coating for making polymerizable liquid crystal material further improves, polyamides is set on substrate The interlayers such as imines film, addition levelling agent is also effective in polymerizable liquid crystal material.Polyimides is set on substrate The method in the interlayers such as film makes the polymer and substrate by the way that polymerizable liquid crystal material to polymerize to obtain for raising Adaptation be effective.
As orientation process other than the above, the utilization of the flow orientation of liquid crystal material, electric field or magnetic field can be enumerated It utilizes.These orientation means can be used alone, and can also combine and use in addition.Further, as the orientation for replacing friction Processing method can also use optical alignment method.As the shape of substrate, in addition to tablet, there can be curved surface as composition Part.Forming the material either organic material or inorganic material of substrate can use.As the material as substrate Organic material can be enumerated for example, polyethylene terephthalate, makrolon, polyimides, polyamide, polymethyl Sour methyl esters, polystyrene, polyvinyl chloride, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene, polyarylate, polysulfones, triacetyl cellulose, fibre Element, polyether-ether-ketone etc. are tieed up, in addition, as inorganic material, can be enumerated such as silicon, glass, calcite.
When polymerizeing the polymerizable liquid crystal compound of the compound containing the present application, it is expected promptly to polymerize into Row, therefore be preferred by irradiating ultraviolet light or electron ray isoreactivity energy-ray and the method for polymerization.It is using In the case of ultraviolet light, polarization light source can be used, non-polarized light source can also be used.In addition, clamp liquid-crystal composition In the case of being polymerize in the state of between 2 pieces of substrates, the substrate at least irradiating surface side must be compared with active energy beam With the appropriate transparency.In addition it is possible to use following methods：Only made using mask when light is irradiated specific partially polymerized Afterwards, by changing the conditions such as electric field, magnetic field or temperature, and change the state of orientation of unpolymerized part, further irradiation is lived Property energy-ray and polymerize.In addition, temperature during irradiation is preferably to keep the polymerizable liquid crystal compound of the present invention Within the temperature range of mesomorphic state.Particularly, in the case where to manufacture optically anisotropic body by photopolymerization, from avoiding The meaning of the induction of unintentional thermal polymerization considers, is preferably also as closely as possible to the temperature of room temperature, i.e. typically with 25 DEG C Temperature polymerize.The intensity of active energy beam is preferably 0.1mW/cm2~2W/cm2.It is 0.1mW/cm in intensity2Below In the case of, photopolymerization is made to complete the needs substantial amounts of time, productivity deteriorates, in 2W/cm2In the case of above, there is polymerism Liquid-crystal compounds or the danger of polymerizable liquid crystal compound deterioration.
On the optically anisotropic body obtained by polymerizeing, with the characteristic variations at the initial stage of mitigating, stabilization is realized Characteristic shows as a purpose, can also implement to be heat-treated.The temperature of heat treatment is preferably 50~250 DEG C of scope, during heat treatment Between be preferably 30 seconds~12 it is small when scope.
The optically anisotropic body manufactured by such method, can make from strippable substrate as sole body With can not also remove and use.Furthermore, it is possible to which the optically anisotropic body of gained is stacked, it can also be fitted in Its substrate and use.
A kind of one or by at least one carbonyl and the compound (3A) of at least one hindered phenol skeleton is provided more A carbonyl is converted into the manufacturing method of the compound of methylene (3B) by contacting hydro-reduction.Wherein, so-called hindered phenol, Be represent hydrogen atom on phenol aromatic rings by the substituent group of large volume instead of compound.In addition, by such structure table It is shown as hindered phenol skeleton.
In these embodiments, compound (3A) preferably have with hindered phenol skeleton directly in conjunction at least one carbonyl Base, as catalyst, it is preferable to use homogeneous series catalysts or heterogeneous series catalysts, and preferably hydrogen pressure is below 10MPa, preferably instead It is -100 DEG C~200 DEG C to answer temperature.
In addition, compound (3A) is preferably the following general formula (V) compound represented.
(in formula, G represents the organic group of 4 valencys, and R represents the following general formula (VI), and m represents 1~4 integer, and R is in the presence of more They can be the same or different in the case of a.
(in formula, Y1And Y2Each independently represent hydrogen atom, the alkyl of carbon number 1~18, the alkane of carbon number 1~18 The alkanoyl of oxygroup or carbon number 1~18, Sp represent 1-CH2- or non-conterminous 2 or more-CH2- independently Can by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O-CO-O- ,- CO-NH- ,-NH-CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH (in formula, it is former that Y each independently represents hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine by=CH- ,-CY=CY- Son or cyano.) or-C ≡ C- substitution carbon number 1~20 alkylidene or singly-bound, X each independently represent-O- ,- S- ,-OCH2- ,-CH2O- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O-CO- O- ,-CO-NH- ,-NH-CO- ,-SCH2- ,-CH2S- ,-CF2O- ,-OCF2- ,-CF2S- ,- SCF2- ,-CH2CF2- ,-CF2CH2- ,-CF2CF2- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO- CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,- CH2CH2- OCO- ,-COO-CH2- ,-OCO-CH2- ,-CH2- COO- ,-CH2- OCO- ,-CY11=CY11- (in formula, Y11Each independently represent hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.) ,-C ≡ C- or singly-bound, A each independently represent Isosorbide-5-Nitrae-phenylene, naphthalene -2,6- diyl, Isosorbide-5-Nitrae-cyclohexylene, Isosorbide-5-Nitrae-cycloethylene Alkenyl, bis- rings of 1,4- [2.2.2] octamethylene, decahydronaphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls, pyrrole Pyridine -2,6- diyl, pyrimidine -2,5- diyl, 1,3- dioxane -2,5- diyls, these groups are unsubstituted or each From can independently be substituted by the alkyl of halogen, cyano, nitro, Pentafluorosulfanyl or carbon number 1~10, in the alkyl each Independently 1 or more hydrogen atom can be substituted by fluorine atom or chlorine atom, 1 on the alkyl-CH2- or it is 2 non-conterminous - CH above2- independently can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S- CO- ,-O-CO-O- ,-CO-NH- ,-NH-CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,- (in formula, Y each independently represents hydrogen atom, carbon number 1 by COO-CH=CH- ,-OCO-CH=CH- ,-CY=CY- ~12 alkyl, fluorine atom, chlorine atom or cyano.) or-C ≡ C- substitution, Z each independently represent-O- ,-S- ,- OCH2- ,-CH2O- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O-CO-O- ,-CO- NH- ,-NH-CO- ,-SCH2- ,-CH2S- ,-CF2O- ,-OCF2- ,-CF2S- ,-SCF2- ,- CH2CF2- ,-CF2CH2- ,-CF2CF2- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH= CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,-CH2CH2- OCO- ,-COO-CH2- ,-OCO-CH2- ,-CH2- COO- ,-CH2- OCO- ,-CY12=CY12- (in formula, Y12Each independently represent hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.) ,-C ≡ C-, 1 A-CH2- or non-conterminous 2 or more-CH2- independently can by-O- ,-S- ,-CO- ,-COO- ,- OCO- ,-CO-S- ,-S-CO- ,-O-CO-O- ,-CO-NH- ,-NH-CO- ,-CH=CH- COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-CY13=CY13- (in formula, Y13Respectively From independently expression hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.) or-C ≡ C- substitutions The alkylidene or singly-bound of carbon number 1~20, n represent 0~5 integer, and A is can be identical there are they in the case of multiple Can be different, Z there are in the case of multiple they can be the same or different.).).
In addition, compound (3B) is preferably the following general formula (VII) compound represented.
(in formula, G and m represent that, with leading to the same meaning of formula (V), R ' represents the following general formula (VIII).
(in formula, Y1、Y2, Sp, X, A, Z and n represent the meaning identical with leading to formula (VI), when these groups are in formula (VI) is led to Expression-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-CY= CY- ,-CY11=CY11- ,-CY12=CY12- ,-CY13=CY13- (in formula, Y, Y11、Y12、Y13It each independently represents Hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom or cyano.) or-C ≡ C- in the case of, in logical formula (IV) In respective expression-CH2- CH2- COO- ,-CH2- CH2- OCO- ,-COO-CH2- CH2- ,-OCO-CH2- CH2- ,-CHY-CHY- ,-CHY11- CHY11- ,-CHY12- CHY12- ,-CHY13- CHY13- or-CH2- CH2-.).)
Further, when liquid-crystal composition is made in logical formula (V) and logical formula (VI) compound represented, from the phase with other ingredients From the viewpoint of capacitive, preferably Y1And Y2It is each independently hydrogen atom, the alkyl of carbon number 1~18 or carbon number 1~18 Alkoxy situation, be more preferably each independently hydrogen atom, the alkane of the alkyl of carbon number 1~8 or carbon number 1~8 The situation of oxygroup, further preferred Y1And Y2Among a side represent hydrogen atom, the opposing party for hydrogen atom, the alkane of carbon number 1~8 The situation of the alkoxy of base or carbon number 1~8, particularly preferred Y1And Y2For the situation of tertiary butyl, Sp is preferably 1-CH2- Or non-conterminous 2 or more-CH2- the carbon number 1 that can be substituted independently by-O- ,-COO- or-OCO- ~20 alkylidene or the situation of singly-bound, more preferably 1-CH2- or non-conterminous 2 or more-CH2- independently It can be by-O- the alkylidenes of carbon number 1~20 substituted or the situation of singly-bound, further preferably carbon number 1~20 Alkylidene or singly-bound situation, be even more preferably the alkylidene of carbon number 1~10 or the situation of singly-bound, further more The situation of the preferably situation of the alkylidene of carbon number 1~5 or singly-bound, the particularly preferably alkylidene of carbon number 1~5, X It is preferred that it is each independently-O- ,-OCH2- ,-CH2O- ,-COO- ,-OCO- ,-CH=CH-COO- ,-CH= CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,- CH2CH2- COO- ,-CH2CH2(in formula, Y each independently represents hydrogen atom, carbon number 1 by-OCO- ,-CY=CY- ~12 alkyl, fluorine atom, chlorine atom or cyano.), the situation of-C ≡ C- or singly-bound, more preferably each independently for- O- ,-COO-, the situation of-OCO- or singly-bound are even more preferably each independently the situation of-O- or singly-bound, special The not preferred situation of singly-bound independently, A are preferably each independently unsubstituted or independently can be by halogen or each From can independently be substituted by 1 or more hydrogen atom by fluorine atom or chlorine atom and 1-CH2- or it is 2 non-conterminous - CH above2- can be taken independently by the alkyl of-O- ,-COO- or-the OCO- carbon number 1~10 substituted Isosorbide-5-Nitrae-the phenylene in generation, naphthalene -2,6- diyl, Isosorbide-5-Nitrae-cyclohexylene, the situation of 1,3- dioxane -2,5- diyls, more It is preferred that it is each independently unsubstituted or independently can be by fluorine atom or chlorine atom or independently can be by 1 A-CH2- or non-conterminous 2 or more-CH2- can be substituted independently by-O- ,-COO- or-OCO- Alkyl-substituted 1,4- phenylenes, naphthalene -2,6- diyls, 1,4- cyclohexylenes, the 1,3- dioxies six of carbon number 1~10 The situation of ring -2,5- diyl, it is further preferably unsubstituted independently or be each independently and can be taken by fluorine atom In generation, independently can be by 1-CH2- or non-conterminous 2 or more-CH2- can be taken independently by-O- Alkyl-substituted Isosorbide-5-Nitrae-phenylene of the carbon number 1~5 in generation or the situation of Isosorbide-5-Nitrae-cyclohexylene, even more preferably each Independently be it is unsubstituted or independently can by the 1,4- phenylenes of fluorine atom, methyl, ethyl or methoxy substitution or The situation of Isosorbide-5-Nitrae-cyclohexylene is particularly preferably each independently unsubstituted or independently can be by fluorine atom, methyl Or Isosorbide-5-Nitrae-phenylene of methoxy substitution or the situation of unsubstituted Isosorbide-5-Nitrae-cyclohexylene, Z is preferably each independently- O- ,-OCH2- ,-CH2O- ,-COO- ,-OCO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO- CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,- CH2CH2(in formula, it is former that Y each independently represents hydrogen atom, the alkyl of carbon number 1~12, fluorine by-OCO- ,-CY=CY- Son, chlorine atom or cyano.) ,-C ≡ C-, 1-CH2- or non-conterminous 2 or more-CH2- independently can be with By-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O-CO-O- ,-CO- NH- ,-NH-CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= (in formula, Y each independently represents hydrogen atom, the alkyl of carbon number 1~12, fluorine atom, chlorine atom by CH- ,-CY=CY- Or cyano.)-C ≡ C- substitution the alkylidene of carbon number 1~20 or the situation of singly-bound, more preferably each independently For-OCH2- ,-CH2O- ,-COO- ,-OCO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH =CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,-CH2CH2- COO- ,- CH2CH2(in formula, it is former that Y each independently represents hydrogen atom, the alkyl of carbon number 1~4 or fluorine by-OCO- ,-CY=CY- Son.) ,-C ≡ C-, 1-CH2- or non-conterminous 2 or more-CH2- independently can be by-O- ,-COO- Or the alkylidene of carbon number 1~20 or the situation of singly-bound of-OCO- substitutions, be even more preferably each independently- OCH2- ,-CH2O- ,-COO- ,-OCO-, 1-CH2- or non-conterminous 2 or more-CH2- independently may be used It is further more excellent with the alkylidene of carbon number 1~20 or the situation of singly-bound substituted by-O- ,-COO- or-OCO- Choosing is each independently-COO- ,-OCO-, 1-CH2- or non-conterminous 2 or more-CH2- independently can be with By-O- substitution the alkylidene of carbon number 1~20 or the situation of singly-bound, be particularly preferably each independently-COO- ,- The situation of OCO- or singly-bound, n are preferably the situation of 0~3 integer, the situation of more preferably 0~2 integer, further preferably For the situation of 0 or 1 situation, particularly preferably 0, m is preferably the situation of 1~4 integer, more preferably 1,2 or 4 situation, Particularly preferably 1 or 2 situation.
Further, when liquid-crystal composition is made in logical formula (VII) and logical formula (VIII) compound represented, from it is other into From the viewpoint of the compatibility divided, preferably Y1And Y2It is each independently the alkyl or carbon atom of hydrogen atom, carbon number 1~18 The situation of the alkoxy of number 1~18 is more preferably each independently hydrogen atom, the alkyl of carbon number 1~8 or carbon number 1 The situation of~8 alkoxy, further preferred Y1And Y2Among a side represent hydrogen atom, other party for hydrogen atom, carbon number 1~8 Alkyl or carbon number 1~8 alkoxy situation, particularly preferred Y1And Y2For the situation of tertiary butyl, Sp is preferably 1- CH2- or non-conterminous 2 or more-CH2- be each independently can by-O- ,-COO- or-OCO- substitute carbon The alkylidene of atomicity 1~20 or the situation of singly-bound, more preferably 1-CH2- or non-conterminous 2 or more-CH2- each It independently can be by-O- the alkylidenes of carbon number 1~20 substituted or the situation of singly-bound, further preferably carbon number 1~20 alkylidene or the situation of singly-bound are even more preferably the alkylidene of carbon number 1~10 or the situation of singly-bound, into One step is more preferably the alkylidene of carbon number 1~5 or the situation of singly-bound, is particularly preferably the alkylidene of carbon number 1~5 Situation, X are preferably each independently-O- ,-OCH2- ,-CH2O- ,-COO- ,-OCO- ,-CH=CH- COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO- CH2CH2- ,-CH2CH2- COO- ,-CH2CH2- OCO- ,-CY=CY- (in formula, Y each independently represent hydrogen atom, Alkyl, fluorine atom, chlorine atom or the cyano of carbon number 1~12.), the situation of-C ≡ C- or singly-bound, it is more preferably each independent Ground is the situation of-O- ,-COO- ,-OCO- or singly-bound, is even more preferably each independently the feelings of-O- or singly-bound Condition, the particularly preferably situation of singly-bound independently, A is preferably each independently unsubstituted or be each independently can be by Halogen can be substituted and 1-CH by 1 or more hydrogen atom by fluorine atom or chlorine atom independently2- or not 2 or more adjacent-CH2- the carbon number 1~10 that can be substituted independently by-O- ,-COO- or-OCO- Alkyl-substituted 1,4- phenylenes, naphthalene -2,6- diyls, 1,4- cyclohexylenes, 1,3- dioxane -2,5- diyls Situation, more preferably each independently to be unsubstituted or be each independently can be by fluorine atom or chlorine atom or each independent It ground can be by 1-CH2- or non-conterminous 2 or more-CH2- independently can by-O- ,-COO- or- The alkyl-substituted 1,4- phenylenes of carbon number 1~10 of OCO- substitutions, naphthalene -2,6- diyls, 1,4- cyclohexylenes, The situation of 1,3- dioxane -2,5- diyl is further preferably each independently unsubstituted or is each independently It can be by fluorine atom or independently can be by 1-CH2- or non-conterminous 2 or more-CH2- independently may be used With the alkyl-substituted Isosorbide-5-Nitrae-phenylene of carbon number 1~5 or the situation of Isosorbide-5-Nitrae-cyclohexylene substituted by-O-, into one Step is more preferably each independently to be unsubstituted or be each independently can be by fluorine atom, methyl, ethyl or methoxy substitution The situation of Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylene is particularly preferably each independently unsubstituted or be each independently can With the Isosorbide-5-Nitrae-phenylene or the situation of unsubstituted Isosorbide-5-Nitrae-cyclohexylene substituted by fluorine atom, methyl or methoxy, Z is preferably each From independently being-O- ,-OCH2- ,-CH2O- ,-COO- ,-OCO- ,-CH=CH-COO- ,-CH=CH- OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,- CH2CH2- COO- ,-CH2CH2(in formula, Y each independently represents hydrogen atom, carbon number 1 by-OCO- ,-CY=CY- ~12 alkyl, fluorine atom, chlorine atom or cyano.) ,-C ≡ C-, 1-CH2- or non-conterminous 2 or more-CH2- each From independently can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,-O- CO-O- ,-CO-NH- ,-NH-CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH= (in formula, Y each independently represents hydrogen atom, the alkane of carbon number 1~12 by CH- ,-OCO-CH=CH- ,-CY=CY- Base, fluorine atom, chlorine atom or cyano.)-C ≡ C- substitution the alkylidene of carbon number 1~20 or the situation of singly-bound, more It is preferred that it is each independently-OCH2- ,-CH2O- ,-COO- ,-OCO- ,-CH=CH-COO- ,-CH=CH- OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2- ,-OCO-CH2CH2- ,- CH2CH2- COO- ,-CH2CH2(in formula, Y each independently represents hydrogen atom, carbon number 1 by-OCO- ,-CY=CY- ~4 alkyl or fluorine atom.) ,-C ≡ C-, 1-CH2- or non-conterminous 2 or more-CH2- independently can be with It is further preferably each by-O- ,-COO- or the alkylidene of carbon number 1~20 or the situation of singly-bound of-OCO- substitutions From independently being-OCH2- ,-CH2O- ,-COO- ,-OCO-, 1-CH2- or non-conterminous 2 or more-CH2- It independently can be by-O- ,-COO- or-the OCO- alkylidene of carbon number 1~20 substituted or the feelings of singly-bound Condition is even more preferably each independently-COO- ,-OCO-, 1-CH2- or non-conterminous 2 or more-CH2- It independently can be by-O- the alkylidenes of carbon number 1~20 substituted or the situation of singly-bound, particularly preferably respective independence Ground is the situation of-COO- ,-OCO- or singly-bound, and n is preferably the situation of 0~3 integer, more preferably 0~2 integer The situation of the situation of situation, further preferably 0 or 1, particularly preferably 0, m is preferably the situation of 1~4 integer, more preferably For the situation of 1,2 or 4 situation, particularly preferably 1 or 2.
More specific embodiment is recorded below.
As the catalyst for being used in contact hydrogen reduction, homogeneous series catalysts or heterogeneous series catalysts are preferred, but From the viewpoint of from the easiness and refined easiness of synthesis, heterogeneous series catalysts are more preferably.As preferred metal Species can enumerate palladium, platinum, iridium, ruthenium, rhodium, gold, silver, nickel, they can be simple substance or oxide, hydroxide, salt, Alloy, carrying metal.As concrete example, Pd carbon, Pd aluminium oxide, Pd barium sulfate, Pd black, Pd calcium carbonate, palladium oxide, hydrogen can be enumerated Palladium oxide, Pt carbon, sulfurous acid Pt carbon, Pt aluminium oxide, Pt are black, platinum oxide, nickel, Raney nickel, Ru carbon, Ru aluminium oxide, Ru are black, oxidation Ruthenium, Ru titanium dioxide, Rh carbon, Rh aluminium oxide, Rh are black, rhodium oxide, palladium bichloride (II), palladium nitrate (II), palladium sulfate (II), acetic acid Double (acetonitrile) palladiums (II) of palladium (II), palladium propionate (II), dinitro diamino palladium (II), palladium bromide (II), palladium iodide (II), dichloro, Dichloro double (benzonitrile) palladium (II), dichloro (η -1,5- cyclo-octadiene) palladium (II), dichloro (η -2,5- norbornadienes) palladiums (II), two-μ-chlorine double [(η-pi-allyl) palladiums (II)], double (acetylacetone,2,4-pentanedione) palladiums (II), double (triphenylphosphine) palladiums of dichloro (II), four ammonia palladium (II) chloride hydrates, tetrachloro palladium (II) acid, the sour sodium of tetrachloro palladium (II), the sour potassium of tetrachloro palladium (II), tetrachloro palladium (II) the sour potassium of sour ammonium, chlordene palladium (IV), the sour ammonium of chlordene palladium (IV), tetrabromo palladium (II) acid, the sour lithium of tetrabromo palladium (II), tetrabromo palladium (II) The sour potassium of sour sodium, tetrabromo palladium (II), the sour ammonium of tetrabromo palladium (II), the sour cetyltrimethyl ammonium of tetrabromo palladium (II), palladium sulfate (II) water Close the sour potassium hydrate of object, cyaniding palladium (II), four cyano palladium (II), the sour potassium hydrate of tetranitro palladium (II), four ammonia palladium (II) chlorinations Object, four ammonia palladium (II) acetates, four ammonia palladium (II) nitrate, four ammonia palladium (II) sulfate hydrates, four ammonia palladium (II) amino sulphurs Hydrochlorate, four ammonia palladium (II) mesylates, trans-dichloro diamino palladium (II), trans-dibromo diamino palladium (II), double (ethylenediamines) Palladium (II) chloride, dichloro (ethylenediamine) palladium (II), tetrakis triphenylphosphine palladium (0), double (dibenzalacetone) palladiums (0), double (two Methyl ketoxime) palladium (II), four ammonia palladium (II) carbonate, four ammonia palladium (II) acetates, dichloro be double (N, N '-dimethyl formamide) The sour sodium of palladium (II), four hydroxyl palladiums (II), three (dibenzalacetone) two palladium (0), [1,1 '-bis- (diphenylphosphino) ferrocene] palladium (II) chloride, [1,1 '-bis- (diphenylphosphino) ferrocene] palladium (II) chloride dichloromethane adduct, chlordene platinum (IV) The sour potassium of acid hydrate, chlordene platinum (IV), the sour ammonium of chlordene platinum (IV), cis-dichlorodiamine platinum (II), cis-dinitro diamino Double (triphenylphosphine) platinum (II) of platinum (II), cis-dichloro, four (triphenylphosphine) platinum (0), four ammonia platinum (II) chloride hydrates, The sour sodium of platinum chloride (II), platinum diiodide (II), chlordene platinum (IV), chlordene platinum (IV) acid hydrate, the sour potassium of chlordene platinum (IV), chlordene platinum (IV) sour ammonium, tetrachloro platinum (II) acid, the sour potassium of tetrachloro platinum (II), the sour ammonium of tetrachloro platinum (II), the sour potassium of tetrabromo platinum (II), tetranitro platinum (II) the sour potassium hydrate of sour potassium, four cyano platinum (II), the sour potassium of four (thiocyano) platinum (II), six hydroxyl platinum (IV) acid, six hydroxyl platinum (IV) Sour potassium hydrate, four ammonia platinum (II) acetates, four ammonia platinum (II) acetate hydrates, four ammonia platinum (II) nitrate, four ammonia platinum (II) sour four ammonia of sulfate, chlorine five ammonia platinum (IV) chloride hydrates, hydroxyl five ammonia platinum (IV) chloride hydrates, tetrachloro platinum (II) Platinum (II), trans-dichloro diamino platinum (II), cis-bis- (thiocyano) diamino platinum (II), cis-diiodo diamino platinum (II), Double (isopropylamine) platinum (II) of double (isopropylamine) platinum (II) of cis-dichloro, trans-dichloro, double (acetylacetone,2,4-pentanedione) platinum (II), Double (dibenzalacetone) platinum (0), dichloro (η -1,5- cyclo-octadiene) platinum (II), the sour lithium of chlordene platinum (IV), four cyano platinum (II) sour barium hydrate, four ammonia platinum (II) sulfamates, four ammonia platinum (II) carbonate, the sour sodium of six hydroxyl platinum (IV), the double (acetyl of chlorine Acetone) the sour potassium hydrate of platinum (II), four ammonia platinum (II) bicarbonates, Pt-VTS-IPA, Pt-VTS- dimethylbenzene, Pt-VTS- Toluene, Pt-CTS-IPA, Pt-CTS- dimethylbenzene, Pt-CTS- toluene, ruthenium chloride hydrate, tri acetylacetonato ruthenium (III), ten dicarbapentaborane, three ruthenium (0), chlorine five ammonia ruthenium (III) chloride, six ammonia ruthenium (III) chlorides, dichloro-benzenes ruthenium (II) dimerization Body, the double tricyclohexyl phosphine rutheniums (II) of dichloro (tertiary butyl ethenylidene), dichloro (p-cymene) ruthenium (II) dimer, diiodo- are (right Cymene) ruthenium (II) dimer, ruthenium bromide hydrate, iodate ruthenium (III), the sour ammonium of pentachloro- hydration ruthenium (III), pentachloro- hydration ruthenium (III) the sour ammonium of sour potassium, chlordene ruthenium (IV), the sour potassium of chlordene ruthenium (IV), pentachloro- nitrosyl ruthenic acid (II) potassium, nitric acid Ru nitrosyl are water-soluble The sour sodium of liquid (three nitrato nitrosyl two be hydrated ruthenium solution), ruthenium (VI), six ammonia ruthenium (II) chlorides, six ammonia ruthenium (II) bromides, Six ammonia ruthenium (III) bromides, six ammonia ruthenium (III) iodide, six ammonia ruthenium (III) sulfate hydrates, six ammonia ruthenium (III) nitric acid Salt, two-mu-oxo, 14 ammonia three ruthenium (III-IV) chloride hydrates, bromine five ammonia ruthenium (III) bromide, five ammonia of nitrosyl Ruthenium (III) chloride, hydroxyl nitrosyl four ammonia ruthenium (II) nitrate, formate dicarbapentaborane ruthenium (I) ,-six-μ acetic acid of μ 3- oxos Root three is hydrated three rutheniums (I) acetate hydrate, dichloro (η -1,5- cyclo-octadiene) ruthenium (II), dichloro four (triphenylphosphine) ruthenium (II), dichloro three (triphenylphosphine) ruthenium (II), chlorine hydrogenate three (triphenylphosphine) ruthenium (II) toluene addition products, four (triphen of dihydro Base phosphine) ruthenium (II), the sour potassium hydrate of six cyano rutheniums (II), hydroxyl nitrosyl four ammonia ruthenium (II) nitrate, tetranitro hydroxyl nitrosyl ruthenium (II) sour potassium, chlorine hydrogenized carbonyl three (triphenylphosphine) ruthenium (II), dihydro carbonyl three (triphenylphosphine) ruthenium (II), ten chloro- μ- Two ruthenium of oxo (IV) acid potassium hydrate, radium chloride (III) hydrate, iodate rhodium (III), rhodium nitrate (III), rhodium sulfate (III), Rhodium acetate (II), chlorine three (triphenylphosphine) rhodium (I), chlorocarbonyl double (triphenylphosphine) rhodium (I), trans-three (triphens of hydrogenized carbonyl Base phosphine) rhodium (I), two-μ-chlorine, four carbonyl, two rhodium (I), ten dicarbapentaborane, four rhodium (0), 16 carbonyl, six rhodium (0), (acetylacetone,2,4-pentanedione) Dicarbonyl rhodium (I), tri acetylacetonato rhodium (III), two-μ-chlorine double [(η -1,5- cyclo-octadiene) rhodium (I)], diacetoxyls Double (cyclo-octadiene) two rhodiums (I), bromination rhodium (III) hydrate, chlordene rhodium (III) acid, hexabromo rhodium (III) acid, rhodium hydroxide (III) the sour potassium of hydrate, phosphoric acid rhodium (III), hexanitro rhodium (III), chlorine five ammonia rhodium (III) chloride, five ammonium hydroxide close rhodium (III) Nitrate hydrate, six ammonia rhodium (III) chlorides, six ammonia rhodium (III) acidic nitric salt, (acetylacetone,2,4-pentanedione) carbonyl (triphenylphosphine) Rhodium (I), two-μ-chlorine dicarbapentaborane double (triphenylphosphine) two rhodium (I), benzoic acid rhodium (II), rhodium caprylate (II), rhodium acetate (II) water Close the sour ammonium hydrate of object, chlordene rhodium (III), the sour ammonium of pentachloro- hydration rhodium (III), five ammonium hydroxide close rhodium (III) chloride, five ammonium hydroxide close The sour sodium of rhodium (III) nitrate solution, hexanitro rhodium (III), the sour potassium of six cyano rhodiums (III), [(η -1,5- rings are pungent for acetylacetone,2,4-pentanedione Diene) rhodium (I)], dichloro double [(norbornadiene) rhodium (I)], gold cyanide (I), the sour potassium of dicyan fund (I), tetrachloro golden (III) acid The sour potassium of hydrate, four cyano golden (III), the sour sodium of curing golden (I), golden (I) ammonium of curing, the sour sodium of tetrachloro golden (III), tetrachloro gold (III) sour potassium hydrate, chlorine (triethyl phosphine) golden (I), chlorine (triphenylphosphine) golden (I), the sour ammonium of dicyan fund (I), dicyan fund (I) sour barium hydrate, iridium chloride hydrate, chlordene iridium (IV) acid, the sour ammonium of chlordene iridium (IV), the sour potassium of chlordene iridium (IV), chlordene iridium (IV) the sour sodium hydrate of sour sodium hydrate, chlordene iridium (III), the sour potassium hydrate of chlordene iridium (III), bromination iridium (III) hydrate, The sour potassium hydrate of hexabromo iridium (III) acid, yttrium oxide (IV), three (oxalate) iridium (III), the hydration of chlorine five ammonia iridium (III) chloride Double (triphenylphosphine) iridium (I) of object, chlorocarbonyl, two-μ-chlorine double (η -1,5- cyclo-octadiene) two iridium (I), hexanitro iridium (III) The sour potassium of sodium, hexabromo iridium (IV), the sour potassium of pentachloro- hydration iridium (III), gold cyanide (I), the sour potassium of dicyan fund (I), tetrachloro golden (III) acid The sour potassium of hydrate, four cyano golden (III), the sour sodium of curing golden (I), the sour ammonium of curing golden (I), the sour sodium of tetrachloro golden (III), tetrachloro Golden (III) sour potassium hydrate, chlorine (triethyl phosphine) golden (I), chlorine (triphenylphosphine) golden (I), the sour ammonium of dicyan fund (I), dicyano Golden (I) sour barium hydrate, iridium chloride hydrate, chlordene iridium (IV) acid, the sour ammonium of chlordene iridium (IV), the sour potassium of chlordene iridium (IV), chlordene Iridium (IV) acid sodium hydrate, the sour sodium hydrate of chlordene iridium (III), the sour potassium hydrate of chlordene iridium (III), bromination iridium (III) hydration The sour potassium hydrate of object, hexabromo iridium (III) acid, yttrium oxide (IV), three (oxalate) iridium (III), chlorine five ammonia iridium (III) chloride water Close double (triphenylphosphine) iridium (I) of object, chlorocarbonyl, two-μ-chlorine double (η -1,5- cyclo-octadiene) two iridium (I), hexanitro iridium (III) the sour potassium of sodium, hexabromo iridium (IV), the sour potassium of pentachloro- hydration iridium (III), as heterogeneous series catalysts, more preferably Pd carbon, Pd Aluminium oxide, Pd barium sulfate, Pd are black, Pd calcium carbonate, palladium oxide, palladium dydroxide, Pt carbon, sulfurous acid Pt carbon, Pt aluminium oxide, Pt are black, Platinum oxide, nickel, Raney nickel, Ru carbon, Ru aluminium oxide, Ru are black, ruthenium-oxide, Ru titanium dioxide, Rh carbon, Rh aluminium oxide, Rh are black, oxidation Rhodium, from the viewpoint of cost and the easiness that obtains, further preferably Pd carbon, Pd aluminium oxide, Pd barium sulfate, Pd be black, Pd Calcium carbonate, palladium oxide, palladium dydroxide, Pt carbon, sulfurous acid Pt carbon, Pt aluminium oxide, Pt are black, platinum oxide, nickel, Raney nickel, further More preferably Pd carbon, Pd aluminium oxide, Pd barium sulfate, Pd be black, Pd calcium carbonate, palladium oxide, palladium dydroxide, nickel, Raney nickel, further More preferably Pd carbon, Raney nickel, particularly preferably Pd carbon.In addition catalyst can be aqueous product or dry product.
Pressure when contacting the reaction of hydrogen reduction is preferably, and using atmospheric pressure as 0MPa, hydrogen pressure is 0MPa~10MPa, from From the viewpoint of the viewpoint and security of equipment, more preferably using atmospheric pressure as 0MPa, hydrogen pressure is 0MPa~1MPa, especially excellent It elects as using atmospheric pressure as 0MPa, hydrogen pressure is more than 0MPa until 0.5MPa.
The reaction temperature for contacting hydrogen reduction is preferably -100 DEG C~200 DEG C, and the viewpoint of slave device and the viewpoint of yield are examined Consider, more preferably -20 DEG C~100 DEG C, further preferably 0 DEG C~60 DEG C, more preferably 0 DEG C~40 DEG C, particularly preferably 0 DEG C~room temperature below.
As contact hydrogen reduction used in reaction dissolvent, can enumerate for example, tertiary butyl alcohol, isobutyl alcohol, isopropyl alcohol, Isoamyl alcohol, cyclohexanol, n-butyl alcohol, 2- butanol, 1- octanols, 2-methyl cellosolve, ethylene glycol, diethylene glycol, methanol, first Cyclohexanol, ethyl alcohol, propyl alcohol, chloroform, carbon tetrachloride, dichloromethane, 1,2- dichloroethanes, 1,2- dichloroethylene, 1,1,2, 2- tetrachloroethanes, trichloro ethylene, 1-chlorobutane, carbon disulfide, acetone, acetonitrile, benzonitrile, DMAC N,N' dimethyl acetamide, two First sulfoxide, Anaesthetie Ether, ethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, o-dichlorohenzene, dimethylbenzene, adjacent diformazan Benzene, paraxylene, meta-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, Propyl acetate, pentyl acetate, methyl acetate, 2-Methoxyethyl acetate, hexamethylphosphoramide, three (dimethylamino) phosphines, Cyclohexanone, 1,4- dioxane, styrene, tetrachloro-ethylene, tetrahydrofuran, pyridine, 1-Methyl-2-Pyrrolidone, 1,1, 1- trichloroethanes, toluene, hexane, pentane, hexamethylene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), t-butyl methyl ether, first Base ethyl ketone, methyl cyclohexanone, methyl butyl ketone, metacetone, gasoline, coal tar naphtha, petroleum ether, naphtha, lightweight Oil, turpentine oil, mineral spirits, water, from the viewpoint of yield, the easiness for post-processing and obtaining, be preferably tertiary butyl alcohol, Isobutyl alcohol, isopropyl alcohol, isoamyl alcohol, cyclohexanol, n-butyl alcohol, 2- butanol, 1- octanols, 2-methyl cellosolve, second two Alcohol, diethylene glycol, methanol, methyl cyclohexanol, ethyl alcohol, propyl alcohol, Anaesthetie Ether, diethylene glycol diethyl ether, o-dichlorohenzene, diformazan Benzene, ortho-xylene, paraxylene, meta-xylene, 1,4- dioxane, tetrahydrofuran, 1-Methyl-2-Pyrrolidone, first Benzene, hexane, pentane, hexamethylene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), t-butyl methyl ether, methyl ethyl ketone, oil Ether, water, more preferably isopropyl alcohol, methanol, ethyl alcohol, propyl alcohol, Anaesthetie Ether, dimethylbenzene, ortho-xylene, paraxylene, two Toluene, 1,4- dioxane, tetrahydrofuran, toluene, hexane, pentane, hexamethylene, pentamethylene, heptane, benzene, tertbutyl methyl Ether, petroleum ether, water, further preferably isopropyl alcohol, methanol, ethyl alcohol, propyl alcohol, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran, toluene, Hexane, pentane, hexamethylene, pentamethylene, heptane, t-butyl methyl ether, water are even more preferably isopropyl alcohol, methanol, second Alcohol, propyl alcohol, 1,4- dioxane, tetrahydrofuran, t-butyl methyl ether, water.In addition, reaction dissolvent can be single solvent, Can also above-mentioned solvent be mixed and used two or more.
It is further possible to acid is used in part or all of solvent or acid is used as additive.As acid, Can be organic acid, or inorganic acid, but the preferably situation of Bronsted (Br φ nsted) acid.As concrete example, Can enumerate hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, orthophosphoric acid, pyrophosphoric acid, alkyl sulfonic acid, aryl sulfonic acid, phosphonic acids, carboxylic acid, perchloric acid, Phosphomolybdic acid, silico-tungstic acid, vanadium molybdic acid, heteropoly acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, naphthalene sulfonic acids, Loprazolam, ethane sulfonic acid, propane sulphur Acid, tertiary butyl sulfonic acid, 2- hydroxypropanesulfonic acids, trifluoromethanesulfonic acid, trichloromethanesulfonic, phenyl-phosphonic acid, monoxone, dichloroacetic acid, three Monoxone, trifluoroacetic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, neopentanoic acid, valeric acid, caproic acid, octanoic acid, capric acid, lauric acid, Myristic acid, palmitic acid, stearic acid, oxalic acid, cyclohexane-carboxylic acid, benzoic acid, phthalic acid, M-phthalic acid, terephthaldehyde Acid, acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid, aspartic acid, Glutamic acid, polyphosphoric acid, solid acid etc., but from the viewpoint of the refined easiness of target substance, it is more preferably hydrochloric acid, hydrogen bromine Acid, sulfuric acid, nitric acid, alkyl sulfonic acid, aryl sulfonic acid, carboxylic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, ethane sulfonic acid, propane sulphur Acid, tertiary butyl sulfonic acid, 2- hydroxypropanesulfonic acids, trifluoromethanesulfonic acid, trichloromethanesulfonic, monoxone, dichloroacetic acid, trichloroacetic acid, Trifluoroacetic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, neopentanoic acid, valeric acid, caproic acid, octanoic acid, capric acid, lauric acid, nutmeg Acid, palmitic acid, stearic acid, oxalic acid, cyclohexane-carboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid, aspartic acid, paddy Propylhomoserin, solid acid, further preferably hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, alkyl sulfonic acid, carboxylic acid, benzene sulfonic acid, to toluene sulphur Acid, methanesulfonic acid, ethane sulfonic acid, propane sulfonic acid, tertiary butyl sulfonic acid, 2- hydroxypropanesulfonic acids, trifluoromethanesulfonic acid, trichloromethanesulfonic, Monoxone, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, neopentanoic acid, oxalic acid, Malaysia Acid, fumaric acid, solid acid are even more preferably hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, carboxylic acid, methanesulfonic acid, ethane sulfonic acid, third Alkyl sulfonic acid, tertiary butyl sulfonic acid, 2- hydroxypropanesulfonic acids, trifluoromethanesulfonic acid, trichloromethanesulfonic, monoxone, dichloroacetic acid, trichlorine Acetic acid, trifluoroacetic acid, formic acid, acetic acid, propionic acid are even more preferably hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, first Acid, acetic acid, particularly preferably hydrochloric acid, sulfuric acid, formic acid, acetic acid.Acid or conduct can be used in part or all of solvent Additive and use acid, but from the viewpoint of reaction speed and yield, acid is preferably added in arbitrary ratio in a solvent, Or the situation of acid is used only as solvent, from the viewpoint of the easiness of post processing, using the situation of the strong acid such as sulfuric acid Under, more preferably in a solvent with arbitrary ratio add in acid situation, further preferably compared with 100 parts by volume of solvent with The ratio of the parts by volume of 0.0001 parts by volume~100 adds in the situation of acid, even more preferably for compared with 100 parts by volume of solvent with The ratio of the parts by volume of 0.001 parts by volume~50 adds in the situation of acid, even more preferably for compared with 100 parts by volume of solvent with The ratio of the parts by volume of 0.01 parts by volume~10 adds in the situation of acid, particularly preferably compared with 100 parts by volume of solvent with 0.1 volume Part~10 parts by volume ratio add in acid situation, in the case where using the weak acid such as acetic acid, be preferably solvent with acid volume Than for solvent：Acid=100：0.1~0：100 use situation of the acid as solvent, and the volume ratio of more preferably solvent and acid is Solvent：Acid=100：1~0：100 are used only situation of the acid as solvent, and the volume ratio of further preferably solvent and acid is Solvent：Acid=10：1~0：100 are used only situation of the acid as solvent, and the even more preferably volume ratio for solvent and acid is Solvent：Acid=5：1~0：100 are used only situation of the acid as solvent, and the volume ratio of particularly preferably solvent and acid is 0：100 Situation of the acid as solvent is used only.Further, specifically, preferably compared with solvent with the body of 0.01 volume %~10 Product % adds in sulfuric acid or hydrochloric acid or using the formic acid of more than the 10 volume % compared with solvent or acetic acid as solvent or only with formic acid Or situation of the acetic acid as solvent, more preferably compared with solvent add in the volume % of 0.1 volume %~5 sulfuric acid or hydrochloric acid or Using the formic acid of more than the 50 volume % compared with solvent or acetic acid as solvent or only using formic acid or acetic acid as the situation of solvent.
Embodiment
Hereinafter, enumerate embodiment and further describe the present invention, but the present invention is not limited to these embodiments.Following reality " % " in the composition of example and comparative example is applied to mean " quality % ".Hereinafter, in order to easily distinguish, will be sent out by the application Bright manufacturing method and the compound that manufactures are stated in a manner of " I-1 ", are had what is manufactured by well known manufacturing method Mutually isostructural compound encloses " C " to state in a manner of " I-1C " at end.The purity of compound by GC or UPLC into Row analysis.Analysis condition is as described below.
(GC analysis conditions)
Column：Agilent Technologies (Agilent Technologies), J＆W Column DB-1HT, 15m × 0.25mm × 0.10μm
Temperature program(me)：- 250 DEG C of 100 DEG C (1 minutes)-(20 DEG C/min)--380 DEG C of (10 DEG C/min)-(7 DEG C/ Minute) -400 DEG C (2.64 minutes)
Inlet temperature：350℃
Detector temperature：400℃
(UPLC analysis conditions)
Column：Water generation (Waters) ACQUITY UPLC BEH C18, 2.1 × 100mm, 1.7 μm
Eluting solvent：Acetonitrile/water (90：10)
Flow velocity：0.5mL/min
Detector：UV, 210nm
Column oven：40℃
The manufacture of (embodiment 1) formula (I-1) compound represented
In possessing the flask of agitating device and dropping funel, add in shown in 60.00g (0.291 mole) formulas (I-1-1) Compound, 25.83g (0.148 mole) formula (I-1-2) compound represented, 180mL dichloromethane.While it carries out ice-cold But while 67.19g (0.32 mole) trifluoroacetic anhydride is added dropwise below 15 DEG C.Be stirred at room temperature 20 it is small when after, be injected into 500mL In water.100mL dichloromethane is added in, carries out liquid separation processing.By organic layer brine It 5 times.By column chromatography (silica gel, Aluminium oxide) it is refined, solvent is distilled off to become 217g until concentrate.400mL hexanes are added in, in -20 DEG C of standings Afterwards, it is filtered.After adding in 180mL acetone and heating and it is made to suspend, ice cooling is carried out, 180mL hexanes are added in, at -20 DEG C It after standing, is filtered, so as to obtain the formula of purpose (I-1) compound represented 63.03g.
1H NMR(CDCl3) δ 1.45 (m, 40H), 1.75 (quin, 4H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H)ppm.
13C NMR(CDCl3) δ 24.6,29.4,30.1,34.3,38.0,125.7,128.9,135.6,158.2, 199.9ppm.
172 DEG C of fusing point
LRMS(EI)m/z 550
The manufacture of (comparative example 1) formula (I-1C) compound represented
In possessing the flask of agitating device and dropping funel, add in shown in 6.00g (0.029 mole) formulas (I-1-1) Compound, 2.58g (0.015 mole) formula (I-1-2) compound represented.Ice cooling is carried out while adding in 6.72g (0.032 mole) trifluoroacetic anhydride.Be stirred at room temperature 5 it is small when after, with 50mL dichloromethane dilute, be injected into 50mL water.It will Organic layer brine It 5 times.It is refined by column chromatography (silica gel, aluminium oxide), with same operation suspend and wash It washs, obtains formula (I-1C) the compound represented 6.30g of purpose.
1H NMR(CDCl3) δ 1.45 (m, 40H), 1.75 (quin, 4H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H)ppm.
13C NMR(CDCl3) δ 24.6,29.4,30.1,34.3,38.0,125.7,128.9,135.6,158.2, 199.9ppm.
172 DEG C of fusing point
LRMS(EI)m/z 550
The manufacture of (embodiment 2) formula (I-2) compound represented
In the reaction vessel for possessing agitating device, the chemical combination shown in 1.43g (12.1 mMs) formulas (I-2-1) is added in Object and 20mL 1,2- dichloroethanes.Add in 5.00g (24.2 mMs) formula (I-1-1) compounds represented and 5.09g (24.2 mMs) trifluoroacetic anhydride.Be stirred at room temperature 18 it is small when after, be injected into 100mL water.100mL dichloromethane is added in, Carry out liquid separation processing.By organic layer brine It 5 times.Refined by column chromatography (silica gel, aluminium oxide), with hexane into Row dispensing laundry, so as to obtain the formula of purpose (I-2) compound represented 4.91g.
1H NMR(CDCl3) δ 1.47 (s, 36H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H) ppm.
13C NMR(CDCl3) δ 30.1,38.0,125.7,128.9,135.6,158.2,199.9ppm.
LRMS(EI)m/z 494
The manufacture of (comparative example 2) formula (I-2C) compound represented
In the reaction vessel for possessing agitating device, the chemical combination shown in 5.00g (24.2 mMs) formulas (I-1-1) is added in Object, 1.43g (12.1 mMs) formula (I-2-1) compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride.Then, Add 0.5mL dichloromethane, be stirred at room temperature 6 it is small when.50mL dichloromethane, 50mL water are added in, carries out liquid separation processing.It will be organic Layer uses brine It 5 times.It is refined by column chromatography (silica gel, aluminium oxide), dispensing laundry is carried out with hexane, so as to obtain The formula of purpose (I-2C) compound represented 5.02g.
1H NMR(CDCl3) δ 1.47 (s, 36H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H) ppm.
13C NMR(CDCl3) δ 30.1,38.0,125.7,128.9,135.6,158.2,199.9ppm.
LRMS(EI)m/z 494
The manufacture of (embodiment 3) formula (I-3) compound represented
In possessing the reaction vessel of agitating device and dropping funel, 3.15g (24.2 mMs) formula (I-3-1) is added in Compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride, 30mL hexanes.Ice cooling is carried out while being added dropwise makes 5.00g (24.2 mMs) formula (I-1-1) compound represented is dissolved in the solution of 15mL dichloromethane.It is stirred at room temperature 2 After it, it is injected into 100mL water.100mL toluene is added in, carries out liquid separation carrying out washing treatment.By column chromatography (silica gel, aluminium oxide) into Row is refined, so as to obtain the formula of purpose (I-3) compound represented 6.01g.
1H NMR(CDCl3) δ 0.89 (t, 3H), 1.38 (m, 8H), 1.47 (s, 18H), 2.92 (t, 2H), 5.70 (s, 1H), 7.85 (s, 2H) ppm.
13C NMR(CDCl3) δ 14.1,22.7,29.4,29.6,30.1,34.3,38.0,125.7,128.9,135.6, 158.2,199.9ppm.
LRMS(EI)m/z 318
The manufacture of (comparative example 3) formula (I-3C) compound represented
In the reaction vessel for possessing agitating device, the chemical combination shown in 5.00g (24.2 mMs) formulas (I-1-1) is added in Object, 3.15g (24.2 mMs) formula (I-3-1) compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride.In room After when temperature stirring 6 is small, 50mL water is added in.50mL toluene is added in, carries out liquid separation carrying out washing treatment.Pass through column chromatography (silica gel, oxidation Aluminium) it is refined, so as to obtain the formula of purpose (I-3C) compound represented 6.21g.
1H NMR(CDCl3) δ 0.89 (t, 3H), 1.38 (m, 8H), 1.47 (s, 18H), 2.92 (t, 2H), 5.70 (s, 1H), 7.85 (s, 2H) ppm.
13C NMR(CDCl3) δ 14.1,22.7,29.4,29.6,30.1,34.3,38.0,125.7,128.9,135.6, 158.2,199.9ppm.
LRMS(EI)m/z 318
The manufacture of (embodiment 4) formula (I-4) compound represented
In the reaction vessel for possessing agitating device, the chemical combination shown in 5.00g (24.2 mMs) formulas (I-1-1) is added in Object, 5.09g (24.2 mMs) trifluoroacetic anhydride, 15mL dichloromethane.5.15g (24.2 mMs) formula (I-4-1) of addition Compound represented.After being stirred at room temperature 2 days, it is injected into 100mL water.100mL dichloromethane is added in, carries out liquid separation washup Reason.It is refined by column chromatography (silica gel, aluminium oxide), so as to obtain the formula of purpose (I-4) compound represented 7.75g.
LRMS(EI)m/z 400
The manufacture of (comparative example 4) formula (I-4C) compound represented
In the reaction vessel for possessing agitating device, the chemical combination shown in 5.00g (24.2 mMs) formulas (I-1-1) is added in Object, 5.15g (24.2 mMs) formula (I-4-1) compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride.Stirring 5 After minute, 0.5mL hexanes are added in.Be stirred at room temperature 6 it is small when after, add in 50mL water.50mL dichloromethane is added in, liquid separation is carried out and washes Wash processing.It is refined by column chromatography (silica gel, aluminium oxide), so as to obtain the formula of purpose (I-4C) compound represented 7.80g。
LRMS(EI)m/z 400
The manufacture of (embodiment 5) formula (I-5) compound represented
In the manufacturing method described in embodiment 4, formula (I-1-1) is replaced using formula (I-5-1) compound represented Compound represented replaces formula (I-4-1) compound represented using formula (I-5-2) compound represented, in addition, It similarly operates, obtains formula (I-5) compound represented.
LRMS(EI)m/z 298
The manufacture of (comparative example 5) formula (I-5C) compound represented
By with 4 same method of comparative example, obtain formula (I-5C) compound represented.
LRMS(EI)m/z 298
The manufacture of (embodiment 6) formula (I-6) compound represented
In the manufacturing method described in embodiment 4, formula (I-1-1) is replaced using formula (I-6-1) compound represented Compound represented replaces formula (I-4-1) compound represented using formula (I-6-2) compound represented, in addition, It similarly operates, obtains formula (I-6) compound represented.
LRMS(EI)m/z 230
The manufacture of (comparative example 6) formula (I-6C) compound represented
By with 4 same method of comparative example, obtain formula (I-6C) compound represented.
LRMS(EI)m/z 230
(embodiment 7~12 and comparative example 7~12)
The liquid-crystal composition being made of following compounds is modulated, parent liquid crystal (X) is made.
In the parent liquid crystal (X), the change as evaluation object manufactured in Examples 1 to 6 and comparative example 1~6 is added It closes object 0.1% and makes its dissolving.The liquid-crystal composition of the evaluation object by vacuum impregnation is injected into and is coated with 3.5 μm Unit interval induce in the unit with ITO of vertical orientated alignment film of polyimide, so as to make as evaluation object Vertical orientated property liquid crystal display element (XI-1)~(XI-12).Following table shows the compound and liquid crystal as evaluation object The relation of display element.
[table 1]
[assay method of voltage retention (VHR)]
Measurement device has used the multichannel liquid crystal display device " Model 6254 " of Dongyang scientific ＆ technical corporation.Measuring temperature For 25 DEG C, it will cut off, measured 16.67m seconds after liquid crystal device 64 microseconds of application from the source voltage that the rectangular wave of ± 1V is formed In voltage attenuation, in the case where 100% will be set to without situation about decaying completely, calculate area ratio on the other hand Rate is respectively as voltage retention (VHR (initial stage) (%)).In addition, by display element when 80 DEG C of heating 2 are small after the electricity that measures Pressure conservation rate is set to VHR (heating) (%), will irradiate 30 minutes UV with USHIO motors society extra-high-pressure mercury vapour lamp USH-500D The voltage retention measured afterwards is set to VHR (UV) (%).It shows the result in following table.
[table 2]
It follows that on first and the liquid crystal display of the compound manufactured containing the manufacturing method by the present application Part, the voltage retention at initial stage is with comparative example on an equal basis or more than it, and the impurity content for causing conservation rate reduction is few.In addition may be used Know, on the liquid crystal display element of compound manufactured containing the manufacturing method by the present application, due to after heating and Voltage retention after light irradiation is higher than comparative example, therefore the compound manufactured by the manufacturing method of the present application is opposite It is high in the durability of heat or light.The compound manufactured by comparing the manufacturing method of example is all difficult to accurately quantify, but It is suggested by detailed analysis containing high-boiling-point impurity.On the other hand, manufactured by the manufacturing method of the present application Compound be also all similarly difficult to accurately quantitative, but be entirely free of or almost by detailed analysis to suggest High-boiling-point impurity is not contained.As can be known from the above results, the compound manufactured containing the manufacturing method by the present application Display element be not easy the reduction for causing voltage retention, therefore be useful as material used for liquid crystal display element.
The manufacture of (embodiment 13) formula (IV-1) compound represented
In the flask for possessing agitating device, addition 5.00g (24.2 mMs) formula (IV-1-1) compound represented, 2.11g (12.1 mMs) formula (IV-1-2) compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride are simultaneously mixed It closes.Stir 5 it is small when after, diluted with dichloromethane, carry out liquid separation processing, by column chromatography (silica gel) and dispensing laundry (hexane) into Row is refined, so as to obtain the formula of purpose (I-1) compound represented 5.31g.
The physics value of formula (IV-1) compound represented
1H NMR(CDCl3) δ 1.45 (m, 40H), 1.75 (quin, 4H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H)ppm.
13C NMR(CDCl3) δ 24.6,29.4,30.1,34.3,38.0,125.7,128.9,135.6,158.2, 199.9ppm.
172 DEG C of fusing point
LRMS(EI)m/z 550
The manufacture of (embodiment 14) formula (IV-2) compound represented
Formula (IV-1-2) compound represented described in embodiment 13 is replaced into the change shown in an accepted way of doing sth (IV-2-1) Object is closed, in addition, formula (IV-2) compound represented is manufactured by method similarly to Example 13.
The physics value of formula (IV-2) compound represented
1H NMR(CDCl3) δ 1.45 (m, 42H), 1.75 (quin, 4H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H)ppm.
13C NMR(CDCl3) δ 24.6,24.6,29.4,30.1,34.3,38.0,125.7,128.9,135.6,158.2, 199.9ppm.
LRMS(EI)m/z 564
The manufacture of (embodiment 15) formula (IV-3) compound represented
Formula (IV-1-2) compound represented described in embodiment 13 is replaced into the change shown in an accepted way of doing sth (IV-3-1) Object is closed, in addition, formula (IV-3) compound represented is manufactured by method similarly to Example 13.
The physics value of formula (IV-3) compound represented
1H NMR(CDCl3) δ 1.45 (m, 44H), 1.75 (quin, 4H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H)ppm.
13C NMR(CDCl3) δ 24.6,24.6,29.4,30.1,34.3,38.0,125.7,128.9,135.6,158.2, 199.9ppm.
LRMS(EI)m/z 578
The manufacture of (embodiment 16) formula (IV-4) compound represented
Formula (IV-1-2) compound represented described in embodiment 13 is replaced into the change shown in an accepted way of doing sth (IV-4-1) Object is closed, in addition, formula (IV-4) compound represented is manufactured by method similarly to Example 13.
The physics value of formula (IV-4) compound represented
1H NMR(CDCl3) δ 1.45 (m, 60H), 1.75 (quin, 4H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H)ppm.
13C NMR(CDCl3) δ 24.6,24.6,24.6,24.6,29.4,30.1,34.3,38.0,125.7,128.9, 135.6,158.2,199.9ppm.
LRMS(EI)m/z 690
The manufacture of (embodiment 17) formula (IV-5) compound represented
Formula (IV-1-2) compound represented described in embodiment 13 is replaced into the change shown in an accepted way of doing sth (IV-5-1) Object is closed, in addition, formula (IV-5) compound represented is manufactured by method similarly to Example 13.
The physics value of formula (IV-5) compound represented
1H NMR(CDCl3) δ 1.45 (m, 64H), 1.75 (quin, 4H), 2.92 (t, 4H), 5.70 (s, 2H), 7.85 (s, 4H)ppm.
13C NMR(CDCl3) δ 24.6,24.6,24.6,24.6,29.4,30.1,34.3,38.0,125.7,128.9, 135.6,158.2,199.9ppm.
LRMS(EI)m/z 718
(embodiment 18~27 and comparative example 13~20)
By the change shown in the formula (IV-1) of the present application described in 13~embodiment of embodiment 17~formula (IV-5) It closes object and is typically used as formula (C-1) compound represented of the polymerization inhibitor, (Japanese Unexamined Patent Publication 05-301865 of patent document 4 Publication) record formula (C-2) compound represented, patent document 3 (DE1811322A1 publications) record formula (C-3) and Formula (C-4) compound represented is respectively added in liquid-crystal composition and carries out membranization, is evaluated.
It is shown formula (X-1) compound represented 20%, formula (X-2) compound represented 32%, formula (X-3) will to be included Compound 40%, the liquid-crystal composition of formula (X-4) compound represented 8% is as parent liquid crystal (X).
Each group modulated with respect to the compound 0.5% that evaluation object is added in parent liquid crystal (X) Object is closed, cyclopentanone is dissolved in after 907 (BASF societies systems) 3% of addition Photoepolymerizationinitiater initiater Irgacure and 25% solution is made. The solution is coated on by method of spin coating on the glass with polyimides for having carried out friction treatment, at 65 DEG C dry 3 Minute.The film of gained is placed on 60 DEG C of electric hot plate, using bandpass filter with 15mW/cm2Intensity illumination 365nm Ultraviolet light 10 seconds.Then bandpass filter is removed and with 70mW/cm2Intensity illumination 20 seconds.On the film of gained, into Row is on non-uniform evaluation.◎ is set to if not having uneven and entirety by visual observation and on film uniformly, in visible unevenness Be set in the case of even according to non-uniform degree zero, △ or ×.It the results are shown in following table.
[table 3]
Evaluate compound It is uneven
Embodiment 18 The compound (I-1) of the present application ◎
Embodiment 19 The compound (I-2) of the present application ○
Embodiment 20 The compound (I-3) of the present application ◎
Embodiment 21 The compound (I-4) of the present application ◎
Embodiment 22 The compound (I-5) of the present application ◎
Comparative example 13 Comparative compound (C-1) ○
Comparative example 14 Comparative compound (C-2) ×
Comparative example 15 Comparative compound (C-3) △
Comparative example 16 Comparative compound (C-4) ×
※ if do not have by visual observation and on film it is uneven and it is whole uniformly if be set to ◎, at 1~2 smallly it is visible not Be set to zero in the case of uniformly, it is visible at 5~10 non-uniform to be set to △, it is seen that it is countless it is non-uniform in the case of be set to ×。
It follows that it is made on the polymerizable liquid crystal compound for using the compound for being with the addition of the present application Film is all that uneven few or non-uniform degree is same compared with the film of the comparative example 13 added with comparative compound (C-1) Etc. degree, therefore be the equal or uniformity more than it.In addition understand, on using the compound added with the present application Polymerizable liquid crystal compound and the film made, with the comparative example added with comparative compound (C-2)~comparative compound (C-4) The film of 14~comparative example 16 is compared, and is all uneven few.
It is anti-that the selection of the cholesteric films of gained is measured using Hitachi Co., Ltd spectrophotometer U-4100 Ejected wave is long.In order to carry out Evaluation of Heat Tolerance, the film of gained is toasted 60 minutes after 200 DEG C.After being toasted after similarly measuring Film selection reflection wavelength.The results are shown in following table.
[table 4]
In this way, on the film for using the polymerizable liquid crystal compound added with comparative compound (C-1) and making, rear Selection reflection wavelength band domain is greatly reduced after baking.In addition, it is added with comparative compound (C-2) and comparison on using The film for closing the polymerizable liquid crystal compound of object (C-3) and making selects reflection wavelength band domain slightly to reduce after rear baking. It understands on the other hand, the film made on the polymerizable liquid crystal compound for using the compound added with the present application, After rear baking reflection wavelength band domain is selected also all hardly to reduce, there is high heat resistance.
As can be known from the above results, on use added with the present application compound polymerizable liquid crystal compound and The film of making, it is uneven less and heat resistance is high.Therefore, member of formation of the compound of the present application as polymerizable composition, polymerizable composition It is useful.In addition, the optically anisotropic body of the composition of the compound containing the present application has been used in optical film etc. Purposes in be useful.
Hydrogen pressure refer to using atmospheric pressure as 0MPa in the case of pressure.Below to the preparation method by the present application and ratio The compound manufactured compared with the preparation method of example is described, but for ease of understanding, will be manufactured by the preparation method of the present application Compound be only attached number at end as (V-1), will by comparing the preparation method of example the compound picture (V- that manufactures 1a) so letter is attached at end.
The purity of compound is analyzed by GC or UPLC.Analysis condition is as described below.
(GC analysis conditions)
Column：Agilent Technologies (Agilent Technologies), J＆W Column DB-1HT, 15m × 0.25mm × 0.10μm
Temperature program(me)：- 250 DEG C of 100 DEG C (1 minutes)-(20 DEG C/min)--380 DEG C of (10 DEG C/min)-(7 DEG C/ Minute) -400 DEG C (2.64 minutes)
Inlet temperature：350℃
Detector temperature：400℃
(UPLC analysis conditions)
Column：Water generation (Waters) ACQUITY UPLC BEH C18, 2.1 × 100mm, 1.7 μm
Eluting solvent：Acetonitrile/water (90：10)
Flow velocity：0.5mL/min
Detector：UV, 210nm
Column oven：40℃
The manufacture of (embodiment 28) formula (V-1) compound represented
In the flask for possessing agitating device, addition 5.00g (24.2 mMs) formula (V-1-1) compound represented, 2.11g (12.1 mMs) formula (V-1-2) compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride simultaneously mix.It stirs Mix 5 it is small when after, diluted with dichloromethane, carry out liquid separation processing, pass through column chromatography (silica gel) and dispensing laundry (hexane) carry out it is smart System, so as to obtain formula (V-1-3) compound represented 5.31g (9.64 mMs).
5.31g (9.64 mMs) formula (V-1-3) compound represented, 50mL tetra- are added in the autoclave of 200mL Hydrogen furans, the 0.25mL concentrated sulfuric acids and 0.27g 5%Pd carbon (50% is aqueous), hydrogen press 0.1MPa, be stirred at room temperature 3 it is small when.It uses After diatomite removes catalyst, solvent is distilled off.The crude product of gained is made to be dissolved in toluene, uses brine It.It will be organic Layer is carried out by column chromatography (silica gel) after refining, and (acetone) is recrystallized, so as to obtain shown in the formula of purpose (V-1) Compound 4.28g.Purity is 99.78%.As impurity, contain the core with cyclohexanone skeleton shown in following formula (V-1i) Reduction Body 0.03%.
1H NMR(CDCl3) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13C NMR(CDCl3) δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5, 151.6ppm
LRMS(EI)m/z 522(100)
The manufacture of (comparative example 21) formula (V-1a) compound represented
30mL water, 30g zinc powders and 1g mercury chloride (II) are added in the flask for possessing agitating device, is stirred 30 minutes. Water is decanted, zinc amalgam is washed with water.It is added in reaction vessel shown in 8.26g (15.0 mMs) formulas (V-1-3) Compound, 120mL ethyl alcohol, zinc amalgam.While stirring, while 30mL concentrated hydrochloric acids, the mixed aqueous solution of 30mL water is added dropwise.It heats back Flow 12 it is small when, add in toluene 100mL.Stirring after five minutes, crosses filter solid.Organic layer is washed with water 3 times, is dried with sodium sulphate. Column chromatography (silica gel) and recrystallization (acetone) are carried out, so as to obtain the formula of purpose (V-1a) compound represented 3.20g.It is pure It spends for 99.75%.As impurity, the core Reduction Body with cyclohexanone skeleton shown in formula (V-1i) is not detected.
1H NMR(CDCl3) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13C NMR(CDCl3) δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5, 151.6ppm
LRMS(EI)m/z 522(100)
The manufacture of (comparative example 22) formula (V-1b) compound represented
The chemical combination shown in 9.68g (17.6 mMs) formulas (V-1-3) is added in the reaction vessel for possessing agitating device Object and 500mL 2- propyl alcohol.Add in 2.0g (53 mMs) sodium borohydride, be stirred at room temperature 22 it is small when.Additional 0.8g (21 mmoles You) sodium borohydride, futher stir 1 it is small when.In 2N hydrochloric acid and ice, reaction solution is injected.Filter the solid being precipitated.Carry out column layer (silica gel) and recrystallization (acetone) are analysed, so as to obtain the formula of purpose (V-1b) compound represented 2.23g.Purity is 99.73%.As impurity, the core Reduction Body with cyclohexanone skeleton shown in formula (V-1i) is not detected.
1H NMR(CDCl3) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13C NMR(CDCl3) δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5, 151.6ppm
LRMS(EI)m/z 522(100)
The manufacture of (embodiment 29) formula (V-2) compound represented
In the flask for possessing agitating device, addition 5.00g (24.2 mMs) formula (V-1-1) compound represented, 3.15g (24.2 mMs) formula (V-2-1) compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride simultaneously mix.It stirs Mix 5 it is small when after, diluted with dichloromethane, carry out liquid separation processing, refined by column chromatography (silica gel), so as to obtain formula (V-2-2) compound represented 6.46g (20.3 mMs).
6.46g (20.3 mMs) formula (V-2-2) compound represented, 30mL tetra- are added in the autoclave of 200mL Hydrogen furans, 60mL acetic acid and 0.32g 5%Pd carbon (50% is aqueous), hydrogen press 0.5MPa, be stirred at room temperature 3 it is small when.Use diatom After catalyst is removed in earth removal, tetrahydrofuran is distilled off.The crude product of gained is made to be dissolved in toluene, uses brine It.To have Machine layer is refined with column chromatography (silica gel), so as to obtain the formula of purpose (V-2) compound represented 5.06g.Purity is 99.58%.As impurity, contain the core Reduction Body 0.32% with cyclohexanone skeleton shown in following formula (V-2i).
1H NMR(CDCl3) δ 0.89 (t, 3H), 1.31 (m, 8H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13C NMR(CDCl3) δ 14.1,22.6,29.2,29.6,30.3,31.8,32.0,34.2,36.0,124.8, 133.5,135.5,151.6ppm
LRMS(EI)m/z 304(100)
The manufacture of (comparative example 23) formula (V-2a) compound represented
By being manufactured with 21 same method of comparative example, refined by column chromatography (silica gel), synthesized formula (V-2a) compound represented.Purity is 99.83%.As impurity, being not detected shown in formula (V-2i) has cyclohexanone The core Reduction Body of skeleton.
1H NMR(CDCl3) δ 0.89 (t, 3H), 1.31 (m, 8H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13C NMR(CDCl3) δ 14.1,22.6,29.2,29.6,30.3,31.8,32.0,34.2,36.0,124.8, 133.5,135.5,151.6ppm
LRMS(EI)m/z 304(100)
The manufacture of (comparative example 24) formula (V-2b) compound represented
3.10g (9.74 mMs) formula (V-2-2) institute is added in possessing the reaction vessel of agitating device and thermometer The compound shown, 30mL trifluoroacetic acids.Ice cooling is carried out while adding in 2.06g (39.0 mMs) cyano sodium borohydride. Stir 3 it is small when after, be injected into hydrochloric acid.Toluene is added in, is washed with sodium bicarbonate solution and saline solution.It is carried out with magnesium sulfate After drying, solvent is distilled off.It is refined with column chromatography (silica gel), so as to obtain the change shown in the formula of purpose (V-2b) Close object 2.02g.Purity is 99.79%.As impurity, the core with cyclohexanone skeleton shown in formula (V-2i) is not detected also Substance.
1H NMR(CDCl3) δ 0.89 (t, 3H), 1.31 (m, 8H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13C NMR(CDCl3) δ 14.1,22.6,29.2,29.6,30.3,31.8,32.0,34.2,36.0,124.8, 133.5,135.5,151.6ppm
LRMS(EI)m/z 304(100)
The manufacture of (embodiment 30) formula (V-3) compound represented
In the flask for possessing agitating device, addition 5.00g (24.2 mMs) formula (V-1-1) compound represented, 6.46g (24.2 mMs) formula (V-3-1) compound represented, 5.09g (24.2 mMs) trifluoroacetic anhydride simultaneously mix.It stirs Mix 5 it is small when after, diluted with dichloromethane, carry out liquid separation processing, refined by column chromatography (silica gel), so as to obtain formula (V-3-2) compound represented 8.93g (19.6 mMs).
8.93g (19.6 mMs) formula (V-3-2) compound represented, 89mL tetra- are added in the autoclave of 200mL Hydrogen furans, the 0.89mL concentrated sulfuric acids and 0.45g 5%Pd carbon (50% is aqueous), hydrogen press 0.2MPa, be stirred at room temperature 2 it is small when.It uses After diatomite removes catalyst, solvent is distilled off.The crude product of gained is made to be dissolved in toluene, is washed with saline solution. Organic layer is refined with column chromatography (silica gel), so as to obtain the formula of purpose (V-3) compound represented 6.92g.Purity is 99.45%.As impurity, contain the core Reduction Body 0.32% with cyclohexanone skeleton shown in following formula (V-3i).
1H NMR(CDCl3) δ 0.95~1.59 (m, 29H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13C NMR(CDCl3) δ 14.4,20.5,26.8,26.8,29.3,29.4,30.9,30.9,31.6,34.7,37.1, 37.3,38.3,41.6,41.6,124.7,133.5,135.5,151.6ppm
LRMS(EI)m/z 440(100)
The manufacture of (embodiment 31) formula (V-4) compound represented
By method similarly to Example 28, formula (V-4) compound represented has been synthesized.Purity is 99.65%.Make For impurity, contain the core Reduction Body 0.21% with cyclohexanone skeleton shown in following formula (V-4i).
1H NMR(CDCl3) δ 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13C NMR(CDCl3) δ 30.3,32.0,34.2,36.0,124.7,133.5,135.5,151.6ppm
LRMS(EI)m/z 466(100)
The manufacture of (embodiment 32) formula (V-5) compound represented
In the reaction vessel for possessing dropping funel, thermometer and agitating device add in 0.54g (22.2 mMs) magnesium, 2mL tetrahydrofurans and being slowly added dropwise makes 3.10g (20.5 mMs) formula (V-5-2) compound represented be dissolved in 6mL tetrahydrochysenes Solution obtained from furans and modulate Grignard Reagent.Add in the reaction vessel for possessing dropping funel, thermometer and agitating device Enter 5.00g (17.1 mMs) formula (V-5-1) compound represented, 10mL tetrahydrofurans and dissolve.Grignard examination is slowly added dropwise Agent.Stir 3 it is small when after, add in hydrochloric acid and toluene and carry out liquid separation processing.Organic layer by column chromatography (silica gel) is refined, is obtained Obtained formula (V-5-3) compound represented 3.64g (10.9 mMs).
3.64g (10.9 mMs) formula (V-5-3) compound represented, 36mL second are added in the autoclave of 200mL Alcohol, 36mL acetic acid and 0.18g 5%Pd carbon (50% is aqueous), when hydrogen presses 0.5MPa, 40 DEG C of stirrings 2 are small.Use diatom earth removal After removing catalyst, add in toluene and use brine It.Organic layer is refined with column chromatography (silica gel), so as to obtain purpose Formula (V-5) compound represented 2.77g.Purity is 99.58%.As impurity, contain having shown in following formula (V-5i) The core Reduction Body 0.37% of cyclohexanone skeleton.
1H NMR(CDCl3) δ 0.89 (t, 3H), 1.31 (m, 10H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13C NMR(CDCl3) δ 14.1,22.6,29.2,29.6,29.6,30.3,31.8,32.0,34.2,36.0, 124.8,133.5,135.5,151.6ppm
LRMS(EI)m/z 318(100)
The manufacture of (comparative example 25) formula (V-5a) compound represented
By with 22 same method of comparative example, synthesized formula (V-5a) compound represented.Purity is 99.81%.Make For impurity, the core Reduction Body with cyclohexanone skeleton shown in formula (V-5i) is not detected.
1H NMR(CDCl3) δ 0.89 (t, 3H), 1.31 (m, 10H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13C NMR(CDCl3) δ 14.1,22.6,29.2,29.6,29.6,30.3,31.8,32.0,34.2,36.0, 124.8,133.5,135.5,151.6ppm
LRMS(EI)m/z 318(100)
The manufacture of (comparative example 26) formula (V-1c) compound represented
In the reaction vessel for possessing agitating device, Dean and Stark apparatus, cooler and thermometer, 3.00g is added in (5.45 mMs) formula (V-1-3) compound represented, 2.18g (43.5 mMs) hydrazine monohydrate, 1.09g (27.3 millis Mole) sodium hydroxide, 15mL ethylene glycol, remove water at 200 DEG C while be heated to reflux 8 it is small when.It is analyzed by GC, but Non- production (V-1c) compound represented.
The manufacture of (comparative example 27) formula (V-1d) compound represented
In the reaction vessel for possessing agitating device, thermometer and dropping funel, 100.00g (0.455 mole) formula is added in (V-1d-1) compound represented, 1.73g (9.08 mMs) cupric iodide (I), 300mL tetrahydrofurans, 100mL 2- amino Ethyl alcohol, 150mL water., with after nitrogen displacement, 5.25g (4.54 mMs) tetrakis triphenylphosphine palladium (0) will be added in reaction vessel And it is heated to reflux.Being added dropwise with 30 minutes makes 24.13g (0.227g) formula (V-1d-2) compound represented be dissolved in 48mL Solution obtained from tetrahydrofuran.Then, be heated to reflux 3 it is small when.It adds in 400mL ethyl acetate and 10% hydrochloric acid of 600mL carries out After liquid separation processing, by organic layer 400mL brine Its 5 times.It is refined by column chromatography (aluminium oxide), makes its concentration dry Dry curing, so as to obtain the brown solid 68.41g for including formula (V-1d-3) compound represented.
In the autoclave for the 2L for possessing agitating device, formula (V-1d-3) compound represented comprising gained is added in 68.41g brown solids, 5% palladium carbons of 6.84g (50% is aqueous), 342mL ethyl alcohol.It is reacted 3 days in hydrogen pressure 0.5MPa, 50 DEG C.It is logical It filters and removes catalyst, solvent is distilled off, so as to obtain the brown for including formula (V-1d-4) compound represented Solid 69.81g.
In the reaction vessel for possessing agitating device, thermometer and dropping funel, add in comprising shown in formula (V-1d-4) 5.00g (16.75 mMs) brown solid of compound, 4.97g (67.05 mMs) tertiary butyl alcohol, 10mL acetic acid.On one side Ice cooling is carried out while 6.57g (66.99 mMs) concentrated sulfuric acid is added dropwise.It is stirred at room temperature 1 week, but only generates the formula (V- of purpose 1d) compound represented 55% (GC).Reaction solution is injected into ice water, is extracted with ethyl acetate, uses brine It.Dense After contracting dry solidification, refined by column chromatography (silica gel, hexane) and recrystallization (acetone), obtain the formula (V- of purpose 1d) compound represented 2.31g.
1H NMR(CDCl3) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13C NMR(CDCl3) δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5, 151.6ppm
LRMS(EI)m/z 522(100)
The manufacture of (comparative example 28) formula (V-1e) compound represented
In the reaction vessel for possessing agitating device, thermometer and gas leading-in device, add in comprising formula (V-1d-4) 5.00g (16.75 mMs) brown solid of compound represented, 30mL toluene, 0.49g (5.00 mMs) concentrated sulfuric acid. 65 DEG C while stir, while being continuously introduced into isobutene.Reaction 1 week, but only generate formula (V-1e) compound represented of purpose 75% (GC).Reaction solution is injected into ice water, is extracted with ethyl acetate, uses brine It.After curing is concentrated and dried, lead to It crosses column chromatography (silica gel, hexane) and recrystallization (acetone) is refined, obtain formula (I-1e) compound represented of purpose 3.20g。
1H NMR(CDCl3) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13C NMR(CDCl3) δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5, 151.6ppm
LRMS(EI)m/z 522(100)
The manufacture of (comparative example 29) formula (V-1f) compound represented
5.00g (9.08 mMs) formula (V-1-3) compound represented is made to be suspended in the in the mixed solvent of second alcohol and water, Add in 0.69g (18.2 mMs) sodium borohydride.Be stirred at room temperature 5 it is small when after, be slowly added to hydrochloric acid.It is extracted with ethyl acetate, After brine It, solvent is distilled off, so as to obtain formula (V-1-4) compound represented.Make the compound of gained Isopropyl alcohol is dissolved in, adds in 10%Pd carbon and concentrated hydrochloric acid, when hydrogen presses 0.29MPa, 80 DEG C of stirrings 2 are small.Filtration catalytic agent is simultaneously Solvent is distilled off, adds hexane and toluene, in -5 DEG C of crystallizations, filtering, drying, obtains the chemical combination shown in formula (V-1f) Object.Purity is 96.98%.As impurity, contain the core Reduction Body 2.15% with cyclohexanone skeleton shown in formula (V-1i).
(embodiment 33~37 and comparative example 30~34)
Hereinafter, describe by the compound manufactured in embodiment 28~32 and comparative example 21~25 be added in parent liquid crystal into Result obtained from row evaluation.
The liquid-crystal composition being made of following compounds is modulated, as parent liquid crystal (X).
In the parent liquid crystal (X), the compound 0.1% as evaluation object and following polymerizable compounds are added 0.3% makes it dissolve and modulate polymerizable liquid crystal compound, the polymerizable liquid crystal compound as evaluation object.
This as the polymerizable liquid crystal compound of evaluation object by vacuum impregnation is injected into and is coated with 3.5 μm Unit interval induces the unit with ITO of vertical orientated alignment film of polyimide.While apply 1.8V's with frequency 1kHz Rectangular wave is while using high-pressure mercury-vapor lamp with 10mW/cm2It irradiates the UV of more than 320nm 600 seconds, makes as evaluation object Vertical orientated property liquid crystal display element (XI).The pre-tilt angle of liquid crystal is fixed as 87.3 degree.Following table shows the change as evaluation object Close the relation of object and liquid crystal display element.
[table 5]
Liquid crystal display element as evaluation object Compound as evaluation object
Embodiment 33 Display element (XI-1) Compound (V-1)
Embodiment 34 Display element (XI-2) Compound (V-2)
Embodiment 35 Display element (XI-3) Compound (V-3)
Embodiment 36 Display element (XI-4) Compound (V-4)
Embodiment 37 Display element (XI-5) Compound (V-5)
Comparative example 30 Compare display element (XI-6) Comparative compound (V-1a)
Comparative example 31 Compare display element (XI-7) Comparative compound (V-1b)
Comparative example 32 Compare display element (XI-8) Comparative compound (V-2a)
Comparative example 33 Compare display element (XI-9) Comparative compound (V-2b)
Comparative example 34 Compare display element (XI-10) Comparative compound (V-5a)
Voltage is applied to the display element of embodiment 33~37 and comparative example 30~34, it is thus identified that every section of elapsed time it is outer It sees.◎ is being denoted as in the case of having no that image retains completely in the case where visual picture retains according to the degree of image reservation And be denoted as zero (image retains pole and slightly occurs), △ (image reservation slightly occurs by force), × (image reservation is very strongly sent out It is raw).It shows the result in following table.
[table 6]
On the display element of the comparative compound containing comparative example 30~34, after the display 1000 it is small when within slightly Occur by force image reservation, when 10000 is small within almost entire surface it is visible display it is bad.In contrast, containing passing through this The display element of compound applied for the manufacturing method of invention and manufactured after the display 10000 it is small when after also maintain high-quality~good Good dispaly state.
As can be known from the above results, the compound manufactured on the manufacturing method by the present application, and by special Preparation method that sharp document 3 is recorded and situation about manufacturing is compared, the content with the impurity of cyclohexanone structure is few.Pass through in addition, containing The manufacturing method of the present application and the display element of compound that manufactures triggers image to retain due to being not easy, pass through this Shen The manufacturing method that please be invent and the compound that the manufactures material used for liquid crystal display element as PSA type is useful.In addition, with public affairs The manufacturing method known is compared, and the reaction time is the short time, therefore the productivity of the manufacturing method of the present application is excellent.

Claims (22)

1. a kind of manufacturing method, which is characterized in that be using phenol (A), carboxylic acid (B) and the carboxylic acid anhydrides shown in the following general formula (I) (C) and carry out Acylphenol (D) manufacturing method, when phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C) are reacted there are Solvent,
In formula, Y1And Y5Represent tertiary butyl, Y2、Y3And Y4Represent hydrogen atom,
Carboxylic acid (B) represents with the following general formula (II),
In formula, G represents carbon atom, and R is the group shown in the following general formula (III), and m represents that 2, R can be the same or different,
In formula, Sp represents the alkylidene of carbon number 1~7, and X represents singly-bound, and n represents 0,
Acylphenol (D) by the following general formula (IV) represent,
In formula, Sp represents the alkylidene of carbon number 6~18,
In 2 kinds of the mixture (E) and organic solvent in phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C), phenol is added in (A), a kind of the ingredient for not becoming mixture (E) among carboxylic acid (B) and carboxylic acid anhydrides (C), alternatively, as selected from phenol (A), in a kind of compound (F) and organic solvent in carboxylic acid (B) and carboxylic acid anhydrides (C), phenol (A), carboxylic acid (B) and carboxylic are added in 2 kinds among acid anhydrides (C) in addition to compound (F), reacted phenol (A), carboxylic acid (B) and carboxylic acid anhydrides (C), wherein, carboxylic Acid anhydrides (C) is fluoroalkyl carboxylic acids' acid anhydride, organic solvent be selected from chloroform, carbon tetrachloride, dichloromethane, 1,2- dichloroethanes, 1, 2- dichloroethylene, 1,1,2,2- tetrachloroethanes, 1-chlorobutane, tetrachloro-ethylene, 1,1,1- trichloroethanes, hexane, pentane, ring One kind or two or more organic solvent in hexane, pentamethylene, heptane.
2. manufacturing method according to claim 1, which is characterized in that by for phenol (A), carboxylic acid (B) and organic molten Agent adds in carboxylic acid anhydrides (C) and carries out.
3. manufacturing method according to claim 1, which is characterized in that by for phenol (A), carboxylic acid anhydrides (C) and organic Solvent adds in carboxylic acid (B) and carries out.
4. manufacturing method according to claim 1, which is characterized in that by for carboxylic acid (B), carboxylic acid anhydrides (C) and organic Solvent adds in phenol (A) and carries out.
5. manufacturing method according to any one of claims 1 to 4, which is characterized in that carboxylic acid anhydrides (C) is trifluoroacetic acid Acid anhydride.
6. manufacturing method according to any one of claims 1 to 4, which is characterized in that reaction temperature for -100 DEG C~ 200℃。
7. manufacturing method according to any one of claims 1 to 4, which is characterized in that reaction temperature is -20 DEG C~100 ℃。
8. manufacturing method according to any one of claims 1 to 4, which is characterized in that reaction temperature is 0 DEG C~60 DEG C.
9. a kind of compound, which is characterized in that it is represented by logical formula (IV),
In formula, Sp represents the alkylidene of carbon number 6~18.
10. compound according to claim 9, which is characterized in that in logical formula (IV), Sp is the carbon atom comprising even number The alkylidene of several straight chains.
11. a kind of composition, which is characterized in that contain the compound described in claim 9 or 10.
12. a kind of polymer, which is characterized in that be by the way that the composition described in claim 11 is made to polymerize to obtain.
13. a kind of optically anisotropic body, which is characterized in that used the polymer described in claim 12.
14. a kind of resin, oil, oil filter, grease, ink, drug, cosmetics, lotion, liquid crystal material, pesticide, polymer, face Material, dyestuff, sticker, bonding agent, printed article, food, optically anisotropic body, display element or electronic device, feature exist In containing the compound described in claim 9 or 10.
15. a kind of drug, pesticide, liquid crystal material, polymer, resin, pigment, dyestuff, cosmetics, food, ink, sticker, Bonding agent, printed article, optically anisotropic body, display element or electronic device, which is characterized in that contain claim 9~13 Any one of compound, composition, polymer or optically anisotropic body or with any one of claim 9~13 Compound, composition, polymer or the optically anisotropic body is as member of formation.
16. a kind of manufacturing method of compound (3B), which is characterized in that system according to any one of claims 1 to 8 will be passed through The one or more carbonyls for the compound (3A) represented by leading to formula (IV) made method and obtained, are turned by contacting hydro-reduction Turn to methylene,
In formula, Sp represents the alkylidene of carbon number 6~18.
17. manufacturing method according to claim 16, which is characterized in that use homogeneous series catalysts or heterogeneous system's catalysis Agent.
18. manufacturing method according to claim 16, which is characterized in that hydrogen pressure during contact reduction is below 10MPa.
19. manufacturing method according to claim 16, which is characterized in that reaction temperature during contact reduction is -100 DEG C ~200 DEG C.
20. manufacturing method according to claim 16, which is characterized in that compound (3B) is shown in the following general formula (VII) Compound,
In formula, G represents carbon atom, and m represents that 2, R ' represent the following general formula (VIII),
In formula, Y1And Y2Represent hydrogen atom, Sp represents the alkylidene of carbon number 1~7, and X represents singly-bound, and n represents 0.
21. manufacturing method according to claim 16, which is characterized in that in part or all of solvent using acid, Or acid is used as additive.
22. the manufacturing method according to claim 16 or 17, which is characterized in that carry out contact hydrogenation also using carrying metal It is former.
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