CN103804158A - Preparing method of hindered phenol and manufacturing intermediate thereof - Google Patents

Abstract

The invention aims to provide a preparing method of hindered phenol, which does not easily cause voltage holding ratio reduction of liquid crystal material on condition that the hindered phenol is added in liquid crystal material, and a compound which is obtained through the preparing method. Besides, the invention provides a polymerization inhibitor which does not cause heat resistance reduction of the polymer and does not cause heat resistance of polymer and does not easily cause non-uniformity of the polymer when the polymer obtained through polymerizing polymerizable compound. Besides, the invention provides the polymer obtained through polymerizing the polymerizable compound and an optical anisotropy with the polymer. The method for settling the task of the invention is characterized in that: the invention provides the preparing method and the compound that is acquired through the preparing method; furthermore the invention provides the compound with the compound as the intermediate, and a composition with the compound; the manufacturing method is used for preparing acyl phenol (D) through phenol (A), carboxylic acid (B) and carboxylic anhydride (C); and organic solvent exists in reaction among the phenol (A), the carboxylic acid (B) and the carboxylic anhydride (C). Furthermore, the invention provides the compound represented by a general formula (IV) and a polymerizable composition with the compound, wherein in the general formula, Sp represents alkylene with 6-25 carbon atoms. Furthermore, the invention provides the preparing method for the compound (B) with at least one methylene and at least one hindered phenol through converting one or a plurality of carbonyls of the compound (A) with at least one carbonyl and at least one hindered phenol to methylene through contact hydrogenation reduction, a compound prepared through the preparing method, a compound with the former compound as the intermediate, and a composition with the former compound.

Description

The manufacture method of hindered phenol and manufacture intermediate thereof

Technical field

The present invention relates to the manufacture method of the compound with hindered phenol skeleton, compound, the composition that contains the compound obtaining by this manufacture method by the compound manufacture obtaining by this manufacture method and used resin, oil, purolator, grease, ink, medicine, makeup, lotion, liquid crystal material, agricultural chemicals, polymkeric substance, pigment, dyestuff, tackiness agent, caking agent, print, food, optically anisotropic body, display element or the electron device of said composition.

In addition, the present invention relates to the stopper of the structure with bisphenol derivative, using this stopper as intermediate and compound, the Polymerizable composition that contains this stopper of manufacturing and the optically anisotropic body that has used this Polymerizable composition.

Background technology

As the 1st background technology, as the problem of TFT liquid crystal display device, there is the problem of reliabilities such as " the image reservations " that occur in the situation that long-time continuous is carried out identical demonstration.Retain and can enumerate a variety of causes for image, one of them has the reduction due to the deteriorated voltage retention causing being caused by light, heat of liquid crystal material.Conventionally,, to suppress the deteriorated as object of such TFT liquid crystal material, in liquid crystal material, add antioxidant.

As the antioxidant of easy manufacture, the known hindered phenol that is connected with carbonyl.These antioxidants are to use 2,6-, bis--tert.-butyl phenol and carboxylic acid, under acid anhydrides exists, manufacture by paying gram (Friedel-Crafts) reaction.But, about the antioxidant of manufacturing by the reaction conditions of reporting in the past, making an addition to carry out panelization in liquid crystal material in the situation that, there is the problem (patent documentation 1, non-patent literature 1～2) that the voltage retention of panel reduced due to heat or light of being easy to.As its reason, can enumerate in the case of manufacturing antioxidant by reaction conditions in the past, produce the by product (patent documentation 1, non-patent literature 1～2) being difficult to by the common refining denier of removing.Consequently, can think in the TFT that requires special high-quality material used for liquid crystal display element, because the impact of this micro-impurity causes the reduction of voltage retention.

Because this reaction is intermolecular reaction, the Reaction time shorten in order to boost productivity, for this reason, the concentration of preferred reaction liquid is high.

In addition, although the reagent using in this reaction, the particularly carboxylic acid solvability in acid anhydrides is higher, being that solvability in inactive organic solvent is extremely low with respect to acid anhydrides.Therefore can think, compared with the situation of mixing with pure ground (neat), with an organic solvent in the situation that, make to dissolve the concentration that is present in the carboxylic acid in reaction system and significantly reduce, consider from the viewpoint of productivity, not preferred.Therefore be only knownly in this reaction, pure each reagent mixing to be made after paste mixture, in order making to stir and easily to add the methylene dichloride of minute quantity as the manufacture method (patent documentation 1) of lubricant, and in the manufacture method (non-patent literature 1～2) that pure each reagent mixing directly stirred after forming paste mixture.

Like this, because the antioxidant of manufacturing by known method for making has problem as described above, therefore in the situation that making an addition to TFT material used for liquid crystal display element, require method for making that exploitation only just can be manufactured by common refining step, that be difficult for the antioxidant of the voltage retention reduction that makes panel.

As the 2nd background technology, polymerizable liquid crystal compound is used in various films.For example, by carry out polymerization after said composition is arranged with mesomorphic state, thereby can make the film with even orientation.The film of making like this can be for liquid-crystal display required Polarizer, polarizer etc.In addition, polymerizable liquid crystal compound also can be for having the making of film of cholesteric structure.In most cases, in order to meet the transparency, physical strength, surface hardness, thermotolerance and the photostabilization of desired optical characteristics, polymerization velocity, solvability, fusing point, second-order transition temperature, film, and use the composition that comprises plural polymerizable compound and additive.

The known film with cholesteric structure optionally reflects the light of the wavelength corresponding with this cholesteric pitch.Attempt the reflection polarizing plate that this selection reflection characteristic is used for indicating meter.For this reason, be necessary in order to expand the research of selecting the wavelength region may of reflection and carry out.As a kind of method, the known stopper that adds in polymerizability cholesteric liquid crystal compositions is effective (patent documentation 2).

But, if normally used stopper is added in said composition, the problem that thermotolerance of rewarding film significantly reduces.In addition,, if the composition that is added with stopper is in the past coated to film, there is the inhomogeneous problem that mostly occurs (patent documentation 3～4).If such film is used in to indicating meter goods, can make the display quality of goods significantly reduce, therefore, in this purposes, require exploitation can not make the thermotolerance of film reduce, be difficult for film to cause inhomogeneous stopper.

As the 3rd background technology, the liquid crystalline cpd that TFT liquid crystal material uses and additive certainly preferably do not contain indicating meter are caused to the impurity that image retains, and, be preferably high purity as far as possible.

About PSA (the Polymer Sustained Alignment of one of kind as TFT liquid crystal display device, polymer stabilizing orientation) type liquid crystal display device, there is the polymer architecture for control tilt angle in unit, can carry out high-contrast demonstration and high-speed response.This element, by by being added with in the liquid-crystal composition injection unit of polymerizable compound, carries out UV irradiation under the state that has applied voltage, and polymerizable compound polymerization is made.Therefore, the liquid crystalline cpd using for this element and additive, special requirement do not contain due to UV irradiate and counter plate brings the dysgenic impurity such as image reservation.

Conventionally,, to prevent the deteriorated as object of TFT liquid crystal material, in liquid crystal material, add antioxidant.As this antioxidant, based on easy to manufacture, high to the consistency of liquid-crystal composition, the orientation of liquid crystal is not brought to the reasons such as detrimentally affect, therefore often utilize the phenol derivatives (patent documentation 5～6) with alkylidene group.

There is the manufacture method of the phenol derivatives of alkylidene group as this, known to the method (non-patent literature 3) that there is the carbonyl that exists in the phenol derivatives of corresponding carbonyl alkylen group and reduce by contact hydrogenation.But if use the method, the core that aromatic nucleus occurs in the reduction of carbonyl reduces and produces various core Reduction Bodies, is therefore difficult to obtain with high yield the target substance of high-quality.In order to address this problem, report the carbonyl pre-reduction existing in having the phenol derivatives of carbonyl alkylen group is become after hydroxyl the step synthesis (patent documentation 7) reducing by contact hydrogenation.According to the method, the pair that can significantly suppress the hexalin body among various core Reduction Bodies generates.But, carbonyl pre-reduction is being become after hydroxyl, need aftertreatment, refining step, therefore process number becomes many, not preferred.In addition, be applicable to have on phenol aromatic nucleus the hindered phenol of bulky group, although can suppress the generation of the core Reduction Body with hexalin structure among the secondary various core Reduction Bodies that generate, be difficult to suppress the generation of the core Reduction Body with pimelinketone structure.

Therefore, in the field of the highly purified compounds of special requirement such as TFT liquid crystal material, in the reduction operation of the carbonyl being connected with hindered phenol, can not use contact hydrogenation, and use Clemmensen reduction or hydride reduction (non-patent literature 4～6).If by the method for the manufacture of hindered phenol,, as the antioxidant in the TFT liquid crystal material purposes of type in the past, obtained the antioxidant effect of high-quality fully.On the other hand, as mentioned above, if use contact hydro-reduction, the aromatic nucleus that produces hindered phenol position is reduced by core and the by product that is difficult to remove that obtains, and the purity drop of the final compound obtaining, therefore can not be used in this purposes.

But, with respect to PSA type display element liquid crystal material, if add the hindered phenol of manufacturing by Clemmensen reduction or hydride reduction, there is the panel after manufacture to be easy to occur the problem that image retains.Infer that this is because the impurity of the contained denier of the hindered phenol manufactured by this method of reducing, in the UV irradiation process in the time that panel is manufactured, goes bad as reservation brings dysgenic material to image.

Except above reaction path, as the known manufacture method of hindered phenol with alkylidene group, the known phenol with alkylidene group that makes is under sulfuric acid or Lewis acid existence, with the method (patent documentation 5, non-patent literature 7) of tertiary butyl alcohol, tertiary butyl chloride or isobutene reaction.But with regard to these reaction paths, the time cost of responding is long-time or need the problem of specific installation for gas being blown in reaction solution.In addition, the known method (patent documentation 8) using benzoquinones as raw material, but have the problems such as the synthetic complexity of raw material.

Therefore, require exploitation not contain the manufacture method that image is retained to the hindered phenol with alkylidene group that brings the such impurity of detrimentally affect.

Prior art document

Patent documentation

Patent documentation 1:US5684204 communique

Patent documentation 2: TOHKEMY 2011-247934 communique

Patent documentation 3:DE1811322A1 communique

Patent documentation 4: Japanese kokai publication hei 05-301865 communique

Patent documentation 5: Japanese kokai publication hei 9-124529 communique

Patent documentation 6: TOHKEMY 2006-169472 communique

Patent documentation 7: TOHKEMY 2001-233811 communique

Patent documentation 8:US3660505 communique

Non-patent literature

Non-patent literature 1:The Journal of Organic Chemistry, nineteen eighty-two, 47 volumes, No. 12,2278-2285 page

Non-patent literature 2:Tetrahedron Letters, 1981,22 volumes, No. 52,5293-5296 page

Non-patent literature 3:Organic Reactions periodical, nineteen fifty-three, 17 volumes, 263-326 page

Non-patent literature 4:Synthetic Communications periodical, 2003,33 volumes, No. 2,199-205 page

Non-patent literature 5:Journal of Medicinal Chemistry periodical, 1989,32 volumes, 100-104 page

Non-patent literature 6:The Journal of Organic Chemistry periodical, 2005,70 volumes, 4338-4345 page

Non-patent literature 7:Chemische Berichte periodical, 1985,118 volumes, No. 5,1782-1797 page

Summary of the invention

Invent problem to be solved

The present application problem to be solved is, the manufacture method of hindered phenol of high-quality and the compound obtaining by this manufacture method are provided.

In addition, provide in the time making the polymkeric substance that Polymerizable composition polymerization is obtained, can not make the thermotolerance of polymkeric substance reduce, be difficult for making polymkeric substance to produce inhomogeneous stopper.In addition, provide the polymkeric substance by this Polymerizable composition polymerization is obtained, and used the optically anisotropic body of this polymkeric substance.

For solving the means of problem

The 1st; the compound that a kind of manufacture method is provided and obtains by this manufacture method; compound using this compound as intermediate is further provided and has used the composition of this compound; described making method is to use phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C) and the manufacture method of the Acylphenol (D) that carries out, has organic solvent in the time that phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C) react.

The 2nd, the compound shown in general formula (IV) and the Polymerizable composition that has used this compound are provided.

(in formula, Sp represents the alkylidene group of carbonatoms 6～25.)。

The 3rd, the manufacture method that one or more carbonyls with the compound (A) of at least one carbonyl with at least one phenolic group that is obstructed is converted into the compound (B) with at least one methylene radical and at least one phenolic group that is obstructed that methylene radical carries out by contacting hydro-reduction is provided, with the compound obtaining by this manufacture method, the compound using this compound as intermediate is further provided and has used the composition of this compound.

The effect of invention

About the compound with hindered phenol skeleton of manufacturing by the manufacture method of the present application, in the case of making an addition to the composition of liquid crystal material etc., the anti-metamorphic effect of composition is high, is therefore useful as the member of formation of various compositions.In addition the composition that, contains the compound of manufacturing by the manufacture method of the present application is useful in the purposes of resin, oil, purolator, grease, ink, medicine, makeup, lotion, liquid crystal material, agricultural chemicals, polymkeric substance, pigment, dyestuff, tackiness agent, caking agent, print, food, optically anisotropic body, display element or electron device.

In addition, the in the situation that the compound of the present application being made film making an addition to Polymerizable composition, thermotolerance is high, inhomogeneous few, is therefore useful as the member of formation of Polymerizable composition.In addition, use the Polymerizable composition of the compound that contains the present application and the optically anisotropic body made, thermotolerance is high, inhomogeneous few, in the purposes of blooming etc., is therefore useful.

Embodiment

A kind of manufacture method is provided; to use phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C) and the manufacture method of the Acylphenol (D) that carries out; wherein, in the time that reacting, phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C) there is organic solvent.

In these embodiments, preferably in the mixture (E) of 2 kinds and organic solvent that are selected from phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C), add a kind of the composition that does not become mixture (E) among phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C).When a kind of the composition that does not become mixture (E) among adding phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C), can under pure state, directly add, also can add with the solution that is dissolved in solvent, also can add with suspension.The solvent now using can be identical with the organic solvent using in order to mix with mixture (E), also can be different.

In these external these embodiments, preferably in the compound (F) of a kind and organic solvent as being selected from phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C), add 2 kinds except compound (F) among phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C).When among adding phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C) except compound (F) 2 kinds, can not make 2 kinds of compound and add successively, also can not make 2 kinds of compound and add simultaneously, also 2 kinds of compound can be added.In addition, 2 kinds of compounds directly can be added under pure state, also can add with the solution that is dissolved in solvent, also can add with suspension.The solvent now using can be identical with the organic solvent using in order to mix with compound (F), also can be different.

In these external these embodiments, from operation easiness viewpoint consider, preferably add carboxylic acid anhydride (C) for phenol (A), carboxylic acid (B) and organic solvent, add carboxylic acid (B) for phenol (A), carboxylic acid anhydride (C) and organic solvent, or add phenol (A) for carboxylic acid (B), carboxylic acid anhydride (C) and organic solvent, more preferably add carboxylic acid anhydride (C) for phenol (A), carboxylic acid (B) and organic solvent.

Further, phenol (A) is preferably the compound shown in following general formula (I).

(in formula, Y ¹, Y ², Y ³, Y ⁴and Y ⁵represent independently of one another alkyl, the alkenyl of carbonatoms 1～18 or the alkynyl of carbonatoms 1～18 of hydrogen atom, carbonatoms 1～18, the hydrogen atom in these groups independently of one another can be by 1-CH in fluorine atom, chlorine atom, bromine atoms, iodine atom, cyano group, nitro, hydroxyl replacement and/or these groups ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-S-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-replace, Y ¹, Y ², Y ³, Y ⁴and Y ⁵in at least 1 group represent hydrogen atom.)

In addition, carboxylic acid (B) is preferably the compound shown in following general formula (II).

(in formula, G represents the organic group of 4 valencys, and R represents the group shown in following general formula (III), and m represents 1～4 integer, and R can be the same or different existing multiple in the situation that,

(in formula, Sp represents 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-or-alkylidene group or the singly-bound of the carbonatoms 1～20 that S-replaces, represent-O-of X ,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ¹¹=CY ¹¹-(in formula, Y ¹¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.),-C ≡ C-or singly-bound, A represents 1, 4-phenylene, naphthalene-2, 6-bis-bases, 1, 4-cyclohexylene, 1, 4-cycloethylene thiazolinyl, 1, it is octylene that 4-bis-encircles ［ 2.2.2 ］, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-naphthane-2, 6-bis-bases, pyridine-2, 6-bis-bases, pyrimidine-2, 5-bis-bases, 1, 3-dioxane-2, 5-bis-bases, these groups are without replacing, or independently of one another can be by halogen, cyano group, nitro, the alkyl of Pentafluorosulfanyl or carbonatoms 1～10 replaces, in this alkyl, more than 1 hydrogen atom can be replaced by fluorine atom or chlorine atom independently of one another, 1-CH on this alkyl ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY ²¹=CY ²¹-(in formula, Y ²¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.) or-C ≡ C-replacement, represent-O-of Z ,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ³¹=CY ³¹-(in formula, Y ³¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.) ,-C ≡ C-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY ⁴¹=CY ⁴¹-(in formula, Y ⁴¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.) or-alkylidene group or the singly-bound of carbonatoms 1～20 that C ≡ C-replaces, n represents 0～5 integer, and they can be the same or different A existing multiple in the situation that, and they can be the same or different Z existing multiple in the situation that.)。)

Further, about the compound shown in general formula (I), from synthetic easiness, reaction efficiency be used in the situation of liquid crystal material with the viewpoint of the consistency of liquid crystal material and consider, preferably Y ¹for the situation of the alkyl of carbonatoms 1～8, more preferably Y ¹and Y ⁵for the situation of the alkyl of carbonatoms 1～8, further preferred Y ¹for sec.-propyl or the tertiary butyl, Y ⁵for the situation of the alkyl of carbonatoms 1～8, further more preferably Y ¹for sec.-propyl or the tertiary butyl, Y ⁵for alkyl, the Y of carbonatoms 1～8 ³represent the situation of hydrogen atom, further preferred Y ¹and Y ⁵for sec.-propyl or the tertiary butyl, Y ³represent the situation of hydrogen atom, further more preferably Y ¹and Y ⁵for sec.-propyl or the tertiary butyl, Y ², Y ³and Y ⁴represent the situation of hydrogen atom, particularly preferably Y ¹and Y ⁵for the tertiary butyl, Y ², Y ³and Y ⁴represent the situation of hydrogen atom.

In addition, about the compound shown in general formula (II), from synthetic easiness, reaction efficiency be used in the situation of liquid crystal material with the viewpoint of the consistency of liquid crystal material and consider, about G, the situation that preferably represents carbon atom, about Sp, preferably represents 1-CH ₂-or non-conterminous 2 above-CH ₂-the alkylidene group of carbonatoms 1～20 or the situation of singly-bound that can be replaced by-O-independently of one another, more preferably represents 1-CH ₂-or non-conterminous 2 above-CH ₂the situation of the alkylidene group of-carbonatoms 1～20 that can be replaced by-O-independently of one another, further preferably represent the situation of the alkylidene group of carbonatoms 1～20, further more preferably represent the situation of the alkylidene group of carbonatoms 1～12, further more preferably represent the situation of the alkylidene group of carbonatoms 1～7, particularly preferably represent the situation of the alkylidene group of carbonatoms 1～3, about X, preferably expression-O-,-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂the situation of-OCO-or singly-bound, more preferably expression-O-,-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂the situation of-OCO-or singly-bound, the further preferred situation of expression-O-,-COO-,-OCO-or singly-bound independently of one another, about A, preferably represent independently of one another without replacing or independently of one another can by halogen, cyano group, nitro, Pentafluorosulfanyl or more than 1 hydrogen atom can be by fluorine atom or the replacement of chlorine atom and 1-CH independently of one another ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-, (in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 to-CY=CY-independently of one another.) or-C ≡ C-replace carbonatoms 1～10 alkyl replace, 1, 4-phenylene, naphthalene-2, 6-bis-bases, 1, 4-cyclohexylene, 1, 4-cycloethylene thiazolinyl, 1, it is octylene that 4-bis-encircles ［ 2.2.2 ］, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-naphthane-2, 6-bis-bases, pyridine-2, 6-bis-bases, pyrimidine-2, 5-bis-bases, 1, 3-dioxane-2, the situation of 5-bis-bases, more preferably represent independently of one another without replacing, or independently of one another can be by fluorine atom, chlorine atom or independently of one another more than 1 hydrogen atom can be replaced by fluorine atom and 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can be by-O-,-COO-, the alkyl of the carbonatoms 1～10 that-OCO-replaces replaces, 1, 4-phenylene, naphthalene-2, 6-bis-bases, 1, 4-cyclohexylene, 1, 4-cycloethylene thiazolinyl, 1, it is octylene that 4-bis-encircles ［ 2.2.2 ］, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-naphthane-2, 6-bis-bases, pyridine-2, 6-bis-bases, pyrimidine-2, 5-bis-bases, 1, 3-dioxane-2, the situation of 5-bis-bases, further preferably represent independently of one another without replacing, independently of one another can by fluorine atom or independently of one another more than 1 hydrogen atom can be replaced by fluorine atom and 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can be by-O-,-COO-, the alkyl of the carbonatoms 1～10 that-OCO-replaces replaces, 1, 4-phenylene, 1, the situation of 4-cyclohexylene, further more preferably represent independently of one another without replacing, or can be by the alkyl of carbonatoms 1～5, alkoxyl group or alkyloyl replace, 1, 4-phenylene, 1, the situation of 4-cyclohexylene, particularly preferably represent independently of one another without replacing, or can be by methyl, methoxy substitution, 1, 4-phenylene or without replace 1, the situation of 4-cyclohexylene, about Z, preferably expression-O-independently of one another,-OCH ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂(in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 independently of one another for-OCO-,-CY=CY-.) ,-C ≡ C-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-alkylidene group of carbonatoms 1～20 or the situation of singly-bound that O-,-COO-,-OCO-replace, more preferably expression-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-alkylidene group of carbonatoms 1～20 or the situation of singly-bound that O-,-COO-,-OCO-replace, further preferred expression-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-, the alkylidene group of carbonatoms 1～20 or the situation of singly-bound, further more preferably expression-COO-independently of one another,-OCO-, the alkylidene group of carbonatoms 1～10 or the situation of singly-bound, further more preferably expression-COO-independently of one another,-OCO-, the alkylidene group of carbonatoms 2～8 or the situation of singly-bound, further more preferably expression-COO-independently of one another,-OCO-, the alkylidene group of the even number of carbonatoms 2～6 or the situation of singly-bound, further more preferably expression-COO-independently of one another, the situation of-OCO-or singly-bound, particularly preferably represent independently of one another the situation of singly-bound, about n, the preferably situation of the integer of expression 0～3, more preferably represent the situation of 0～2 integer, further preferably represent 0 or 1 situation, further more preferably represent 0 situation, about m, the preferably situation of the integer of expression 1～3, more preferably represent 1 or 2 situation.

Carboxylic acid anhydride (C) is preferably the alkyl carboxylic acid acid anhydride that can be replaced by halogen atom, more preferably fluoro-alkyl carboxylic acid anhydride, more preferably trifluoroacetic anhydride.

Below record embodiment more specifically.

Temperature of reaction is preferably-100 ℃～200 ℃, consider from the viewpoint of yield and speed of response, more preferably-20 ℃～100 ℃, more preferably 0 ℃～60 ℃, further more preferably 0 ℃～40 ℃, be particularly preferably 0 ℃～below room temperature.

As reaction solvent, be preferably organic solvent, more preferably the organic solvent of non-proton property.As concrete reaction solvent, for example, can enumerate chloroform, tetracol phenixin, methylene dichloride, 1,2-ethylene dichloride, 1,2-dichloroethene, sym.-tetrachloroethane, trieline, 1-chlorobutane, dithiocarbonic anhydride, acetone, acetonitrile, cyanobenzene, N,N-dimethylacetamide, methyl-sulphoxide, Anaesthetie Ether, ethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, orthodichlorobenzene, dimethylbenzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, Isoamyl Acetate FCC, ethyl acetate, butylacetate, propyl acetate, pentyl acetate, methyl acetate, 2-Methoxyethyl acetate, HMPA, three (dimethylamino) phosphine, pimelinketone, Isosorbide-5-Nitrae-dioxane, zellon, tetrahydrofuran (THF), pyridine, 1-Methyl-2-Pyrrolidone, 1，1，1-trichloroethane, toluene, hexane, pentane, hexanaphthene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), t-butyl methyl ether, methyl ethyl ketone, methylcyclohexanone, methyl butyl ketone, metacetone, gasoline, coal-tar naphtha, sherwood oil, petroleum naphtha, low-density oil, turps, mineral spirits, but from yield, the viewpoint of the easiness of aftertreatment and acquisition is considered, is preferably chloroform, tetracol phenixin, methylene dichloride, 1,2-ethylene dichloride, 1,2-dichloroethene, sym.-tetrachloroethane, trieline, 1-chlorobutane, Anaesthetie Ether, diethylene glycol diethyl ether, Isosorbide-5-Nitrae-dioxane, zellon, tetrahydrofuran (THF), 1，1，1-trichloroethane, hexane, pentane, hexanaphthene, pentamethylene, heptane, t-butyl methyl ether, gasoline, coal-tar naphtha, sherwood oil, petroleum naphtha, low-density oil, turps, mineral spirits, more preferably chloroform, tetracol phenixin, methylene dichloride, 1,2-ethylene dichloride, 1,2-dichloroethene, sym.-tetrachloroethane, 1-chlorobutane, Anaesthetie Ether, diethylene glycol diethyl ether, Isosorbide-5-Nitrae-dioxane, zellon, tetrahydrofuran (THF), 1，1，1-trichloroethane, hexane, pentane, hexanaphthene, pentamethylene, heptane, t-butyl methyl ether, more preferably chloroform, tetracol phenixin, methylene dichloride, 1,2-ethylene dichloride, 1,2-dichloroethene, sym.-tetrachloroethane, 1-chlorobutane, zellon, 1，1，1-trichloroethane, hexane, pentane, hexanaphthene, pentamethylene, heptane.In addition, reaction solvent can be that single solvent also can use two or more mixing of above-mentioned solvent.

About the amount of reaction solvent, as long as the amount that can make fully to escape by reacting the reaction heat that produces, be not particularly limited, if but the amount of solvent is very few, and reaction heat is accumulated in and in reaction system, is easy to produce by product.Particularly, if thereby due to further superfluous reaction of the reaction heat reaction product of accumulating, the secondary impurity that generates high molecular.Due to extremely trace of these macromolecule impurities, be therefore difficult to direct quantitative by common analytical procedure.In addition, due to molecular structure and target substance similar, be therefore difficult to remove by common purification operations.But, even trace extremely, in the situation that making an addition to liquid crystal material, also can significantly reduce voltage retention due to heat or light, be therefore preferably the reaction conditions of not secondary generation high molecular impurity as far as possible.In addition, can think that before reaction reagent is all mixed, adding in advance solvent is effective for the inhibition of high molecular impurity.On the other hand, if the amount of solvent is too much, the concentration of reactant reduces, and speed of response reduces significantly.Consider from above viewpoint, be suitably for respect to 1 gram of phenol (A), the amount of solvent is 0.01 milliliter～100 liters, be more suitable for as with respect to 1 gram of phenol (A), solvent is 0.1 milliliter～10 liters, further be suitably for respect to 1 gram of phenol (A), solvent is 0.15 milliliter～1 liter, be preferably with respect to 1 gram of phenol (A), solvent is 0.2 milliliter～500 milliliters, more preferably with respect to 1 gram of phenol (A), solvent is 0.4 milliliter～100 milliliters, more preferably with respect to 1 gram of phenol (A), solvent is 0.5 milliliter～50 milliliters, further more preferably with respect to 1 gram of phenol (A), solvent is 1 milliliter～20 milliliters, further more preferably with respect to 1 gram of phenol (A), solvent is 2 milliliters～15 milliliters, further more preferably with respect to 1 gram of phenol (A), solvent is 2.5 milliliters～10 milliliters, be particularly preferably with respect to 1 gram of phenol (A), solvent is 3 milliliters～8 milliliters.

As the mode for implementing the 2nd invention, the present application provide the compound shown in general formula (IV), in the lump contain this compound Polymerizable composition, by making the polymkeric substance that this Polymerizable composition polymerization obtains and the optically anisotropic body that has used this polymkeric substance.

In general formula (IV), Sp represents the alkylidene group of carbonatoms 6～25, but consider from the viewpoint that obtains easiness of raw material, be preferably the straight-chain alkyl-sub-of carbonatoms 6～25, the more preferably straight-chain alkyl-sub-of carbonatoms 6～18, consider from the inhomogeneous few viewpoint making an addition to Polymerizable composition and making film, more preferably carbonatoms is the straight-chain alkyl-sub-of the even number among 6～18, be the straight-chain alkyl-sub-of the even number among 6～10 from considering with the viewpoint of the consistency of other composition, being particularly preferably carbonatoms.

As the compound shown in general formula (I), particularly, be preferably the compound shown in following formula (IV-1)～formula (IV-12).

The compound of the present application can be manufactured by following method for making.

The manufacture of the compound shown in (method for making 1) following formula (S-3)

By making the compound shown in formula (S-1) under acid exists, react with the compound shown in formula (S-2), can obtain the compound shown in formula (S-3).As acid, as long as obtain the acid of the compound shown in formula (S-3) in reaction process, be not particularly limited, but can enumerate for example aluminum chloride, aluminum isopropylate, aluminum ethylate, aluminum chloride hydrate, aluminum bromide, boron trifluoride, dibutyl boron trifluoromethanesulfonic acid, trifluoromethanesulfonic acid dicyclohexyl boron, boron trichloride, boron trichloride methyl sulfide coordination compound, boron trifluoride tetrahydrofuran (THF) coordination compound, boron trifluoride t-butyl methyl ether coordination compound, boron trifluoride methanol coordination compound, boron trifluoride dihydrate, boron trifluoride Anaesthetie Ether compound, boron trifluoride dibutyl ether compound, boron trifluoride phenol coordination compound, boron trifluoride propyl alcohol coordination compound, boron trifluoride methyl ether compound, boron trifluoride Anaesthetie Ether compound, boron trifluoride methyl sulfide coordination compound, boron trifluoride acetic acid coordination compound, metal trifluoroacetate mesylate, trifluoroacetic anhydride, silicon compound etc.Compound shown in formula (S-1) can be directly used in reaction, is used further to reaction after also hydroxyl can being protected.As protecting group; be preferably for example GREENE ' S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((the 4th edition); PETER G.M.WUTS; THEODORA W.GREENE is outstanding altogether; A John Wiley & Sons; Inc., Publication) in the group enumerated.Compound shown in formula (S-2) can be directly used in reaction, also can be derivatized to acetyl halide compound, ester, aldehyde or mixed acid anhydride and re-use.As this reaction conditions, for example be preferably, (Japanization association compiles in experimental chemistry lecture, 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), Fiesers ' Reagents for Organic Synthesis (John Wiley & Sons, etc. Inc.) condition of enumerating in the database such as document or SciFinder or Reaxys.In addition, can use as required reaction solvent.As reaction solvent, as long as obtain the reaction solvent of the compound shown in formula (S-3) in reaction process, be not particularly limited, but as preferred reaction solvent, for example can enumerate chloroform, tetracol phenixin, methylene dichloride, 1,2-ethylene dichloride, 1,2-dichloroethene, sym.-tetrachloroethane, trieline, 1-chlorobutane, dithiocarbonic anhydride, acetone, acetonitrile, cyanobenzene, DMF, N,N-dimethylacetamide, methyl-sulphoxide, Anaesthetie Ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, orthodichlorobenzene, dimethylbenzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, Isoamyl Acetate FCC, ethyl acetate, butylacetate, propyl acetate, pentyl acetate, methyl acetate, 2-Methoxyethyl acetate, HMPA, three (dimethylamino) phosphine, pimelinketone, Isosorbide-5-Nitrae-dioxane, methylene dichloride, vinylbenzene, zellon, tetrahydrofuran (THF), pyridine, 1-Methyl-2-Pyrrolidone, 1，1，1-trichloroethane, toluene, hexane, pentane, hexanaphthene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), t-butyl methyl ether, methyl ethyl ketone, methylcyclohexanone, methyl butyl ketone, metacetone, gasoline, coal-tar naphtha, sherwood oil, petroleum naphtha, low-density oil, turps, mineral spirits.

The compound of the present application is preferably used in nematic liquid-crystal composition, smectic liquid crystal composition, chiral smectic liquid crystal composition and cholesteric liquid crystal compositions.Use in the liquid-crystal composition of reactive compounds of the present application, also can add the present application compound in addition.

Other reactive compounds using as mixing with the reactive compounds of the present application, particularly, is preferably the compound shown in general formula (2II), is particularly preferably the P of general formula (2II) ¹and P ²for the situation of acryl or methacryloyl.

(in formula, P ¹and P ²represent to be independently of one another selected from the group in following formula (P-1)～formula (P-17),

S ¹and S ²represent independently of one another the alkylidene group of 1～18 of singly-bound or carbonatoms, 1-CH ₂-or non-conterminous 2 above-CH ₂-can be replaced by Sauerstoffatom ,-COO-,-OCO-,-OCOO-X ³and X ⁴represent independently of one another singly-bound ,-O-,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-OCOOCH ₂-,-CH ₂oCOO-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CH=N-,-SCH ₂-,-CH ₂s-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CF ₂-,-CF ₂o-,-OCF ₂-,-CH ₂cH ₂-,-CF ₂cH ₂-,-CH ₂cF ₂-,-CF ₂cF ₂-,-CY=CY-or-(in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 to C ≡ C-independently of one another.), Z ¹represent independently of one another singly-bound ,-O-,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-OCOOCH ₂-,-CH ₂oCOO-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CH=N-,-SCH ₂-,-CH ₂s-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CF ₂-,-CF ₂o-,-OCF ₂-,-CH ₂cH ₂-,-CF ₂cH ₂-,-CH ₂cF ₂-,-CF ₂cF ₂-,-CY=CY-or-(in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 to C ≡ C-independently of one another.), A ¹and A ²represent independently of one another Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylene, pyridine-2,5-bis-bases, pyrimidine-2,5-bis-bases, naphthalene-2,6-bis-bases, naphthane-2,6-bis-bases or 1,3-dioxane-2,5-bis-bases, A ¹and A ²for nothing replaces or can be replaced by alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogeno-group, cyano group or nitro, m1 represents 0,1,2 or 3 independently of one another, in the situation that m1 represents 2 or 3, and 2 or 3 A of existence ¹and/or Z ¹can be the same or different.)。

Particularly, be preferably the compound shown in general formula (2III), be particularly preferably the compound shown in following formula (2III-1)～formula (2III-8).

(in formula, S ³and S ⁴represent independently of one another alkylidene group, the X of carbonatoms 2～18 ³and X ⁴expression-O-,-COO-,-OCO-or singly-bound independently of one another, Z ³and Z ⁴independently of one another expression-COO-or-OCO-, A ³, A ⁴and A ⁵indicate independently of one another without replacement or by the Isosorbide-5-Nitrae-phenylene of the alkyl of fluorine atom, chlorine atom or carbonatoms 1～4 or alkoxyl group replacement.)。

(in formula, S ³s in expression and general formula (2III) ³identical implication, S ⁴s in expression and general formula (2III) ⁴identical implication.) in above-mentioned formula (2III-1)～formula (2III-8), more preferably S ³and S ⁴be the compound of the alkylidene group of carbonatoms 2～8 independently of one another.

In addition, be preferably the compound shown in general formula (2IV), be particularly preferably the compound shown in following formula (2IV-1)～formula (2IV-8).

(in formula, S ⁵and S ⁶represent independently of one another the alkylidene group of carbonatoms 2～18, X ⁵and X ⁶expression-O-,-COO-,-OCO-or singly-bound independently of one another, Z ⁵expression-COO-or-OCO-, A ⁶, A ⁷and A ⁸indicate independently of one another without the Isosorbide-5-Nitrae-phenylene that replaces or replaced by the alkyl of fluorine atom, chlorine atom or carbonatoms 1～4 or alkoxyl group.)。

(in formula, S ⁵s in expression and general formula (2IV) ⁵identical implication, S ⁶s in expression and general formula (2IV) ⁶identical implication.) in above-mentioned formula (2IV-1)～formula (2IV-8), consider from the viewpoint of thermotolerance and weather resistance, be preferably the compound shown in formula (2IV-2), formula (2IV-5), formula (2IV-6), formula (2IV-7) and formula (2IV-8), more preferably the compound shown in formula (2IV-2), is particularly preferably S ⁵and S ⁶be the compound of the alkylidene group of carbonatoms 2～8 independently of one another.

In addition,, as preferred 2 officials' energy polymerizable compounds, can enumerate the compound shown in following general formula (2V-1)～formula (2V-5).

(in formula, S ⁷and S ⁸represent independently of one another the alkylidene group of carbonatoms 2～18.) in above-mentioned formula (2V-1)～formula (2V-5), be preferably the compound shown in formula (2V-2), formula (2V-3) and formula (2V-5), be particularly preferably S ⁷and S ⁸be the compound of the alkylidene group of carbonatoms 2～8 independently of one another.

In the polymerizable liquid crystal compound of the compound that contains the present application, also can, damaging not significantly the degree of the liquid crystal liquid crystal property of said composition, add the polymerizable compound that does not show liquid crystal liquid crystal property.Particularly, as long as be considered to the compound of polymer formative monomer or polymer formative oligopolymer in this technical field, be not particularly limited, can use.

In addition, make an addition to the concentration of the Photoepolymerizationinitiater initiater in the polymerizable liquid crystal compound of the compound that contains the present application, be preferably 0.1～10 quality %, more preferably 0.2～5 quality %.As Photoepolymerizationinitiater initiater, can use benzoin ethers, benzophenone, acetophenones, benzil ketals class, acylphosphine oxide etc.

In addition,, for the polymerizable liquid crystal compound of the compound that contains the present application, in order to improve this storage stability, also can add stablizer.As stablizer, for example can enumerate quinhydrones, quinhydrones monoalkyl ethers, tert-butyl catechol class, pyrogallol class, thiophenol class, nitro-compound class, beta-naphthylamine class, 2-Naphthol class, nitroso compound etc.Addition in the situation that using stablizer is with respect to liquid-crystal composition, to be preferably 0.005～1 quality %, more preferably 0.02～0.5 quality %.

In addition, in the case of the polymerizable liquid crystal compound of the compound that contains the present application is used in the purposes such as film class, optical element class, functional pigment class, drug class, toiletries, coating agent class, synthetic resin, also can add according to its object the metal oxides such as metal, metal complex, dyestuff, pigment, pigment, fluorescent material, phosphor material, tensio-active agent, flow agent, thixotropic agent, gelating agent, polyose, UV light absorber, infrared absorbent, antioxidant, ion exchange resin, titanium oxide etc.

Can in various uses, utilize by the polymerizable liquid crystal compound of the compound that contains the present application being carried out to the polymkeric substance that polymerization obtains.For example, thereby carry out by the polymerizable liquid crystal compound of the compound that contains the present application is not orientated the polymkeric substance that polymerization obtains, can prevent plate (モ ア レ Onyx prevents plate) and utilize as light diffuser plate, polarisation elimination plate, Moire fringe.In addition, by carrying out the polymkeric substance that polymerization obtains after orientation, having optical anisotropy, is useful.Such optically anisotropic body can be manufactured as follows, for example, makes the polymerizable liquid crystal compound of the compound that contains the present application, supports in the substrate that has carried out friction treatment with cloth etc., is formed with the substrate of organic film or has inclination evaporation and have SiO ₂the substrate of alignment films, or after being held between substrate, this polymerizable liquid crystal compound is carried out to polymerization, thereby manufactures.

Method when making polymerizable liquid crystal compound support on substrate, can enumerate rotary coating, die coating, extrusion coated, roller coat cloth, the coating of silk bar type, intaglio plate coating, spray coating, dipping, print process etc.In addition, while coating, can in polymerizable liquid crystal compound, add organic solvent.As organic solvent, can use hydrocarbon system solvent, halohydrocarbon series solvent, ether series solvent, alcohol series solvent, ketone series solvent, ester series solvent, non-protonic solvent etc., for example can enumerate toluene or hexane as hydrocarbon system solvent, can enumerate methylene dichloride as halohydrocarbon series solvent, can enumerate tetrahydrofuran (THF) as ether series solvent, acetoxyl group-2-Ethoxyethane or propylene glycol monomethyl ether, can enumerate methyl alcohol as alcohol series solvent, ethanol or Virahol, can enumerate acetone as ketone series solvent, methyl ethyl ketone, pimelinketone, gamma-butyrolactone or N-Methyl pyrrolidone class, can enumerate ethyl acetate or cellosolve as ester series solvent, can enumerate dimethyl formamide or acetonitrile as non-protonic solvent.They may be used alone, can also be used in combination, and carry out suitable selection as long as consider the solvability of its vapour pressure and polymerizable liquid crystal compound.As the method for the organic solvent volatilization that makes to add, can use seasoning, heat drying, drying under reduced pressure, decompression heat drying.For the coating that makes polymerizable liquid crystal material further improves, it is also effective the middle layers such as Kapton being set on substrate, in polymerizable liquid crystal material, adding flow agent.It is effective that the method that the middle layers such as Kapton are set on substrate makes by polymerizable liquid crystal material being carried out to polymkeric substance that polymerization obtains and the adaptation of substrate for raising.

As the orientation process beyond above-mentioned, can enumerate the utilization in utilization, electric field or the magnetic field of the flow orientation of liquid crystal material.These orientation means can be used separately, also can combine in addition and use.Further, instead the method for orientation treatment of friction, also can use optical alignment method.As the shape of substrate, except flat board, can there is curved surface as component part.No matter the material that forms substrate is that organic materials or inorganic materials can be used.As the organic materials of material that becomes substrate, for example can enumerate, polyethylene terephthalate, polycarbonate, polyimide, polymeric amide, polymethylmethacrylate, polystyrene, polyvinyl chloride, tetrafluoroethylene, polychlorotrifluoroethylene, polyarylester, polysulfones, triacetyl cellulose, Mierocrystalline cellulose, polyether-ether-ketone etc., in addition, as inorganic materials, can enumerate such as silicon, glass, calcite etc.

In the time of the polymerizable liquid crystal compound polymerization that makes the compound that contains the present application, expect that promptly polymerization carries out, it is preferred therefore making the method for its polymerization by irradiation ultraviolet radiation or electron rays isoreactivity energy-ray.Using in ultraviolet situation, can use polarization light source, also can use non-polarization light source.In addition, carry out polymerization in the case of liquid-crystal composition is held under 2 states between substrate, at least the substrate of shadow surface side must have the suitable transparency with respect to active energy beam.In addition, can use following method: in the time of rayed, use mask and only make specific partially polymerized after, by the condition such as electric field, magnetic field or temperature is changed, and the not state of orientation of polymeric part is changed, further irradiate active energy beam and carry out polymerization.In addition, temperature when irradiation is preferably in the temperature range of mesomorphic state that keeps polymerizable liquid crystal compound of the present invention.Particularly, in the situation that will manufacturing optically anisotropic body by photopolymerization, consider from the meaning of bringing out of avoiding unintentional thermopolymerization, be also preferably the temperature close to room temperature as far as possible, that is, typically carry out polymerization with the temperature of 25 ℃.The intensity of active energy beam is preferably 0.1mW/cm ²～2W/cm ².Be 0.1mW/cm in intensity ²in following situation, photopolymerization is completed needs a large amount of time, and productivity worsens, at 2W/cm ²in above situation, there is the deteriorated danger of polymerizable liquid crystal compound or polymerizable liquid crystal compound.

About this optically anisotropic body obtaining by polymerization, using the characteristic variations at the initial stage of alleviating, realize stable characteristic and show as object, also can implement thermal treatment.Heat treated temperature is preferably the scope of 50～250 ℃, and heat treatment time is preferably 30 seconds～scope of 12 hours.

This optically anisotropic body of manufacturing by such method, can use as independent body from strippable substrate, also can not peel off and uses.In addition, the optically anisotropic body of gained can be carried out stackedly, also can fit in other substrate and use.

Providing a kind of will have one or more carbonyls of compound (3A) of at least one carbonyl and at least one hindered phenol skeleton, is converted into the manufacture method of the compound (3B) of methylene radical by contact hydro-reduction.Wherein, so-called hindered phenol, is the compound that represents that hydrogen atom on phenol aromatic nucleus has been replaced by the substituting group of large volume.In addition be hindered phenol skeleton by such representation.

In these embodiments, compound (3A) preferably has at least one carbonyl with the direct combination of hindered phenol skeleton, as catalyzer, preferably uses homogeneous phase series catalysts or heterogeneous series catalysts, preferably hydrogen pressure is below 10MPa, and preferable reaction temperature is-100 ℃～200 ℃.

In addition, compound (3A) is preferably the compound shown in following logical formula V.

(in formula, G represents the organic group of 4 valencys, and R represents following general formula (VI), and m represents 1～4 integer, and they can be the same or different R existing multiple in the situation that.

(in formula, Y ¹and Y ²the alkyl, the alkoxyl group of carbonatoms 1～18 or the alkyloyl of carbonatoms 1～18 that represent independently of one another hydrogen atom, carbonatoms 1～18, Sp represents 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-, (in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 to-CY=CY-independently of one another.) or-alkylidene group or the singly-bound of carbonatoms 1～20 that C ≡ C-replaces, represent independently of one another-O-of X ,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ¹¹=CY ¹¹-(in formula, Y ¹¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.),-C ≡ C-or singly-bound, A represents 1 independently of one another, 4-phenylene, naphthalene-2, 6-bis-bases, 1, 4-cyclohexylene, 1, 4-cycloethylene thiazolinyl, 1, it is octylene that 4-bis-encircles ［ 2.2.2 ］, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-naphthane-2, 6-bis-bases, pyridine-2, 6-bis-bases, pyrimidine-2, 5-bis-bases, 1, 3-dioxane-2, 5-bis-bases, these groups are without replacing, or independently of one another can be by halogen, cyano group, nitro, the alkyl of Pentafluorosulfanyl or carbonatoms 1～10 replaces, in this alkyl, more than 1 hydrogen atom can be replaced by fluorine atom or chlorine atom independently of one another, 1-CH on this alkyl ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-, (in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 to-CY=CY-independently of one another.) or-C ≡ C-replacement, represent independently of one another-O-of Z ,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ¹²=CY ¹²-(in formula, Y ¹²represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.) ,-C ≡ C-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY ¹³=CY ¹³-(in formula, Y ¹³represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.) or-alkylidene group or the singly-bound of carbonatoms 1～20 that C ≡ C-replaces, n represents 0～5 integer, and they can be the same or different A existing multiple in the situation that, and they can be the same or different Z existing multiple in the situation that.)。)。

In addition, compound (3B) is preferably the compound shown in following general formula (VII).

(in formula, G and m represent the implication same with leading to formula V, and R ' represents following general formula (VIII).

(in formula, Y ¹, Y ², Sp, X, A, Z and n represent the implication identical with general formula (VI), as these groups expression-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-CY=CY-,-CY in general formula (VI) ¹¹=CY ¹¹-,-CY ¹²=CY ¹²-,-CY ¹³=CY ¹³-(in formula, Y, Y ¹¹, Y ¹², Y ¹³represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12.) or-situation of C ≡ C-under, expression-CH separately in general formula (IV) ₂-CH ₂-COO-,-CH ₂-CH ₂-OCO-,-COO-CH ₂-CH ₂-,-OCO-CH ₂-CH ₂-,-CHY-CHY-,-CHY ¹¹-CHY ¹¹-,-CHY ¹²-CHY ¹²-,-CHY ¹³-CHY ¹³-or-CH ₂-CH ₂-.)。)

Further, when the compound shown in logical formula V and general formula (VI) is made liquid-crystal composition, from considering with the viewpoint of the consistency of other composition, preferably Y ¹and Y ²being the situation of the alkyl of hydrogen atom, carbonatoms 1～18 or the alkoxyl group of carbonatoms 1～18 independently of one another, is more preferably the situation of the alkyl of hydrogen atom, carbonatoms 1～8 or the alkoxyl group of carbonatoms 1～8 independently of one another, further preferred Y ¹and Y ²among a side represent the situation that hydrogen atom, the opposing party are hydrogen atom, the alkyl of carbonatoms 1～8 or the alkoxyl group of carbonatoms 1～8, particularly preferably Y ¹and Y ²for the situation of the tertiary butyl, Sp is preferably 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-OCO-replace the alkylidene group of carbonatoms 1～20 or the situation of singly-bound, more preferably 1-CH ₂-or non-conterminous 2 above-CH ₂-the alkylidene group of carbonatoms 1～20 or the situation of singly-bound that can be replaced by-O-independently of one another, the more preferably alkylidene group of carbonatoms 1～20 or the situation of singly-bound, the further more preferably alkylidene group of carbonatoms 1～10 or the situation of singly-bound, the further more preferably alkylidene group of carbonatoms 1～5 or the situation of singly-bound, be particularly preferably the situation of the alkylidene group of carbonatoms 1～5, X is preferably-O-,-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂(in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 independently of one another for-OCO-,-CY=CY-.), the situation of-C ≡ C-or singly-bound, more preferably be independently of one another-O-, the situation of-COO-,-OCO-or singly-bound, be independently of one another more preferably further-situation of O-or singly-bound, the particularly preferably situation of singly-bound independently of one another, A is preferably without replacing or can can being replaced and 1-CH by fluorine atom or chlorine atom by more than 1 hydrogen atom by halogen or independently of one another independently of one another independently of one another ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-OCO-replace carbonatoms 1～10 alkyl replace 1,4-phenylene, naphthalene-2,6-bis-bases, 1,4-cyclohexylene, 1,3-dioxane-2, the situation of 5-bis-bases is more preferably without replacing or independently of one another can be by fluorine atom or chlorine atom or independently of one another can be by 1-CH independently of one another ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-OCO-replace carbonatoms 1～10 alkyl replace 1,4-phenylene, naphthalene-2,6-bis-bases, 1,4-cyclohexylene, 1,3-dioxane-2, the situation of 5-bis-bases, further preferably independently of one another without replacing or independently of one another for being replaced by fluorine atom or independently of one another can be by 1-CH ₂-or non-conterminous 2 above-CH ₂the alkyl of-the carbonatoms 1～5 that can be replaced by-O-independently of one another replace 1,4-phenylene or 1, the situation of 4-cyclohexylene, be independently of one another more preferably further without replace or independently of one another can be by 1 of fluorine atom, methyl, ethyl or methoxy substitution, 4-phenylene or 1, the situation of 4-cyclohexylene, be independently of one another particularly preferably without replace or can be replaced by fluorine atom, methyl or methoxy independently of one another 1,4-phenylene or without replace 1, the situation of 4-cyclohexylene, Z is preferably-O-,-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂(in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 independently of one another for-OCO-,-CY=CY-.) ,-C ≡ C-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-, (in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 to-CY=CY-independently of one another.) or-C ≡ C-replace the alkylidene group of carbonatoms 1～20 or the situation of singly-bound, be independently of one another more preferably-OCH ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂(in formula, Y represents alkyl or the fluorine atom of hydrogen atom, carbonatoms 1～4 independently of one another for-OCO-,-CY=CY-.) ,-C ≡ C-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-OCO-replace the alkylidene group of carbonatoms 1～20 or the situation of singly-bound, be independently of one another more preferably further-OCH ₂-,-CH ₂o-,-COO-,-OCO-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-alkylidene group of carbonatoms 1～20 or the situation of singly-bound that OCO-replaces, be independently of one another more preferably further-COO-,-OCO-, 1-CH ₂-or non-conterminous 2 above-CH ₂-the alkylidene group of carbonatoms 1～20 or the situation of singly-bound that can be replaced by-O-independently of one another, be independently of one another particularly preferably-COO-, the situation of-OCO-or singly-bound, n is preferably the situation of 0～3 integer, the more preferably situation of 0～2 integer, more preferably 0 or 1 situation, is particularly preferably 0 situation, and m is preferably the situation of 1～4 integer, more preferably 1,2 or 4 situation, is particularly preferably 1 or 2 situation.

Further, in the time that the compound shown in general formula (VII) and general formula (VIII) is made liquid-crystal composition, from considering with the viewpoint of the consistency of other composition, preferably Y ¹and Y ²being the situation of the alkyl of hydrogen atom, carbonatoms 1～18 or the alkoxyl group of carbonatoms 1～18 independently of one another, is more preferably the situation of the alkyl of hydrogen atom, carbonatoms 1～8 or the alkoxyl group of carbonatoms 1～8 independently of one another, further preferred Y ¹and Y ²among a side represent hydrogen atom, other party is the situation of the alkyl of hydrogen atom, carbonatoms 1～8 or the alkoxyl group of carbonatoms 1～8, particularly preferably Y ¹and Y ²for the situation of the tertiary butyl, Sp is preferably 1-CH ₂-or non-conterminous 2 above-CH ₂-be independently of one another can by-O-,-COO-or-OCO-replace the alkylidene group of carbonatoms 1～20 or the situation of singly-bound, more preferably 1-CH ₂-or non-conterminous 2 above-CH ₂-the alkylidene group of carbonatoms 1～20 or the situation of singly-bound that can be replaced by-O-independently of one another, the more preferably alkylidene group of carbonatoms 1～20 or the situation of singly-bound, the further more preferably alkylidene group of carbonatoms 1～10 or the situation of singly-bound, the further more preferably alkylidene group of carbonatoms 1～5 or the situation of singly-bound, be particularly preferably the situation of the alkylidene group of carbonatoms 1～5, X is preferably-O-,-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂(in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 independently of one another for-OCO-,-CY=CY-.), the situation of-C ≡ C-or singly-bound, more preferably be independently of one another-O-, the situation of-COO-,-OCO-or singly-bound, be independently of one another more preferably further-situation of O-or singly-bound, the particularly preferably situation of singly-bound independently of one another, A is preferably without replacing or independently of one another for can being replaced and 1-CH by fluorine atom or chlorine atom by more than 1 hydrogen atom by halogen or independently of one another independently of one another ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-OCO-replace carbonatoms 1～10 alkyl replace 1,4-phenylene, naphthalene-2,6-bis-bases, 1,4-cyclohexylene, 1,3-dioxane-2, the situation of 5-bis-bases is more preferably without replacing or independently of one another for can be by fluorine atom or chlorine atom or independently of one another can be by 1-CH independently of one another ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-OCO-replace carbonatoms 1～10 alkyl replace 1,4-phenylene, naphthalene-2,6-bis-bases, 1,4-cyclohexylene, 1,3-dioxane-2, the situation of 5-bis-bases is more preferably without replacing or independently of one another for can be by fluorine atom or independently of one another can be by 1-CH independently of one another ₂-or non-conterminous 2 above-CH ₂the alkyl of-the carbonatoms 1～5 that can be replaced by-O-independently of one another replace 1, 4-phenylene or 1, the situation of 4-cyclohexylene, be more preferably further without replacing independently of one another, or be can be by fluorine atom independently of one another, methyl, 1 of ethyl or methoxy substitution, 4-phenylene or 1, the situation of 4-cyclohexylene, be particularly preferably without replacing independently of one another, or be can be by fluorine atom independently of one another, 1 of methyl or methoxy replacement, 4-phenylene or without replace 1, the situation of 4-cyclohexylene, Z is preferably-O-independently of one another,-OCH ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂(in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 independently of one another for-OCO-,-CY=CY-.) ,-C ≡ C-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-, (in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12 to-CY=CY-independently of one another.) or-C ≡ C-replace the alkylidene group of carbonatoms 1～20 or the situation of singly-bound, be independently of one another more preferably-OCH ₂-,-CH ₂o-,-COO-,-OCO-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂(in formula, Y represents alkyl or the fluorine atom of hydrogen atom, carbonatoms 1～4 independently of one another for-OCO-,-CY=CY-.) ,-C ≡ C-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-OCO-replace the alkylidene group of carbonatoms 1～20 or the situation of singly-bound, be independently of one another preferably further-OCH ₂-,-CH ₂o-,-COO-,-OCO-, 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-alkylidene group of carbonatoms 1～20 or the situation of singly-bound that OCO-replaces, be independently of one another more preferably further-COO-,-OCO-, 1-CH ₂-or non-conterminous 2 above-CH ₂-the alkylidene group of carbonatoms 1～20 or the situation of singly-bound that can be replaced by-O-independently of one another, be independently of one another particularly preferably-COO-, the situation of-OCO-or singly-bound, n is preferably the situation of 0～3 integer, the more preferably situation of 0～2 integer, more preferably 0 or 1 situation, is particularly preferably 0 situation, and m is preferably the situation of 1～4 integer, more preferably 1,2 or 4 situation, is particularly preferably 1 or 2 situation.

Below record embodiment more specifically.

As the catalyzer that is used in contact hydrogen reduction, homogeneous phase series catalysts or heterogeneous series catalysts are preferred, but consider more preferably heterogeneous series catalysts from the viewpoint of synthetic easiness and refining easiness.As preferred metal species, can enumerate palladium, platinum, iridium, ruthenium, rhodium, gold and silver, nickel, they can be simple substance, can be also oxide compound, oxyhydroxide, salt, alloy, carrying metal.As concrete example, can enumerate Pd carbon, Pd aluminum oxide, Pd barium sulfate, Pd is black, Pd calcium carbonate, palladous oxide, palladium hydroxide, Pt carbon, sulfurous acid Pt carbon, Pt aluminum oxide, Pt is black, platinum oxide, nickel, draw Buddhist nun's nickel, Ru carbon, Ru aluminum oxide, Ru is black, ruthenium oxide, Ru titanium dioxide, Rh carbon, Rh aluminum oxide, Rh is black, rhodium oxide, Palladous chloride (II), Palladous nitrate (II), palladous sulfate (II), acid chloride (II), propionic acid palladium (II), dinitrobenzene diamino palladium (II), palladium bromide (II), palladium iodide (II), two (acetonitrile) palladiums (II) of dichloro, two (cyanobenzene) palladiums (II) of dichloro, dichloro (η-1,5-cyclooctadiene) palladium (II), dichloro (η-2,5-norbornadiene) palladium (II), two-μ-chlorine two ［ (η-allyl group) palladium (II) ］, two (methyl ethyl diketone) palladium (II), two (triphenylphosphine) palladiums (II) of dichloro, four ammonia palladium (II) muriate hydrates, tetrachloro palladium (II) acid, the sour sodium of tetrachloro palladium (II), the sour potassium of tetrachloro palladium (II), the sour ammonium of tetrachloro palladium (II), the sour potassium of chlordene palladium (IV), the sour ammonium of chlordene palladium (IV), tetrabromo palladium (II) acid, the sour lithium of tetrabromo palladium (II), the sour sodium of tetrabromo palladium (II), the sour potassium of tetrabromo palladium (II), the sour ammonium of tetrabromo palladium (II), the sour cetyltrimethyl ammonium of tetrabromo palladium (II), palladous sulfate (II) hydrate, cyaniding palladium (II), the sour potassium hydrate of four cyano palladium (II), the sour potassium hydrate of tetranitro palladium (II), four ammonia palladium (II) muriates, four ammonia palladium (II) acetates, four ammonia palladium (II) nitrate, four ammonia palladium (II) sulfate hydrates, four ammonia palladium (II) sulfamates, four ammonia palladium (II) mesylates, trans-dichloro diamino palladium (II), trans-dibromo diamino palladium (II), two (quadrol) palladium (II) muriate, dichloro (quadrol) palladium (II), tetrakis triphenylphosphine palladium (0), two (dibenzalacetone) palladium (0), two (DMKO) palladium (II), four ammonia palladium (II) carbonate, four ammonia palladium (II) acetates, two (N, the N '-dimethyl formamide) palladiums (II) of dichloro, the sour sodium of four hydroxyl palladiums (II), three (dibenzalacetone) two palladiums (0), ［ 1,1 '-bis-(diphenylphosphino) ferrocene ］ palladium (II) muriate, ［ 1,1 '-bis-(diphenylphosphino) ferrocene ］ palladium (II) muriate methylene dichloride affixture, chlordene platinum (IV) acid hydrate, the sour potassium of chlordene platinum (IV), the sour ammonium of chlordene platinum (IV), CDDP (II), cis-dinitrobenzene diamino platinum (II), two (triphenylphosphine) platinum (II) of cis-dichloro, four (triphenylphosphine) platinum (0), four ammonia platinum (II) muriate hydrates, platinum chloride (II), platinic iodide (II), the sour sodium of chlordene platinum (IV), chlordene platinum (IV) acid hydrate, the sour potassium of chlordene platinum (IV), the sour ammonium of chlordene platinum (IV), 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), the sour potassium of tetranitro platinum (II), the sour potassium hydrate of four cyano platinum (II), the sour potassium of four (thiocyano) platinum (II), six hydroxyl platinum (IV) acid, the sour potassium hydrate of six hydroxyl platinum (IV), four ammonia platinum (II) acetates, four ammonia platinum (II) acetate hydrates, four ammonia platinum (II) nitrate, four ammonia platinum (II) vitriol, chlorine five ammonia platinum (IV) muriate hydrates, hydroxyl five ammonia platinum (IV) muriate hydrates, the sour four ammonia platinum (II) of tetrachloro platinum (II), trans-platinum diamminodichloride (II), cis-bis-(thiocyano) diamino platinum (II), cis-diiodo-diamino platinum (II), two (isopropylamine) platinum (II) of cis-dichloro, two (isopropylamine) platinum (II) of trans-dichloro, two (methyl ethyl diketone) platinum (II), two (dibenzalacetone) platinum (0), dichloro (η-1,5-cyclooctadiene) platinum (II), the sour lithium of chlordene platinum (IV), the sour barium hydrate of four cyano platinum (II), four ammonia platinum (II) sulfamates, four ammonia platinum (II) carbonate, the sour sodium of six hydroxyl platinum (IV), the two sour potassium hydrates of (methyl ethyl diketone) platinum (II) of chlorine, four ammonia platinum (II) hydrogen-carbonates, 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 rutheniums (0), chlorine five ammonia ruthenium (III) muriates, six ammonia ruthenium (III) muriates, dichlorobenzene ruthenium (II) dimer, dichloro (tertiary butyl vinylidene) two tricyclohexyl phosphine rutheniums (II), dichloro (Paracymene) ruthenium (II) dimer, diiodo-(Paracymene) ruthenium (II) dimer, ruthenium bromide hydrate, iodate ruthenium (III), the sour ammonium of pentachloro-hydration ruthenium (III), the sour potassium of pentachloro-hydration ruthenium (III), the sour ammonium of chlordene ruthenium (IV), the sour potassium of chlordene ruthenium (IV), pentachloro-nitrosyl ruthenic acid (II) potassium, the nitric acid Ru nitrosyl aqueous solution (three nitroxyl nitrosyl two hydration ruthenium solutions), the sour sodium of ruthenium (VI), six ammonia ruthenium (II) muriates, 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) nitrate, two-mu-oxo, 14 ammonia three rutheniums (III-IV) muriate hydrates, bromine five ammonia ruthenium (III) bromides, nitrosyl five ammonia ruthenium (III) muriates, hydroxyl nitrosyl four ammonia ruthenium (II) nitrate, formate dicarbapentaborane ruthenium (I), μ 3-oxo-six-μ acetate moiety three hydration three rutheniums (I) acetate hydrates, dichloro (η-1,5-cyclooctadiene) ruthenium (II), dichloro four (triphenylphosphine) ruthenium (II), dichloro three (triphenylphosphine) ruthenium (II), chlorine hydrogenation three (triphenylphosphine) ruthenium (II) toluene affixture, dihydro four (triphenylphosphine) ruthenium (II), the sour potassium hydrate of six cyano group rutheniums (II), hydroxyl nitrosyl four ammonia ruthenium (II) nitrate, the sour potassium of tetranitro hydroxyl nitrosyl ruthenium (II), chlorine hydrogenized carbonyl three (triphenylphosphine) ruthenium (II), dihydro carbonyl three (triphenylphosphine) ruthenium (II), the sour potassium hydrate of ten chloro-mu-oxo two rutheniums (IV), rhodium chloride (III) hydrate, iodate rhodium (III), rhodium nitrate (III), rhodium sulfate (III), rhodium acetate (II), chlorine three (triphenylphosphine) rhodium (I), chloroformyl two (triphenylphosphine) rhodium (I), trans-hydrogenized carbonyl three (triphenylphosphine) rhodium (I), two-μ-chlorine, four carbonyl diurethane rhodiums (I), ten dicarbapentaborane four rhodiums (0), 16 carbonyl six rhodiums (0), (methyl ethyl diketone) dicarbonyl rhodium (I), tri acetylacetonato rhodium (III), two-μ-chlorine two ［ (η-1,5-cyclooctadiene) rhodium (I) ］, two (cyclooctadiene) two rhodiums (I) of diacetoxyl, bromination rhodium (III) hydrate, chlordene rhodium (III) acid, hexabromo rhodium (III) acid, rhodium hydroxide (III) hydrate, phosphoric acid rhodium (III), the sour potassium of hexanitro-rhodium (III), chlorine five ammonia rhodium (III) muriates, five ammoniacal liquor close rhodium (III) nitrate hydrate, six ammonia rhodium (III) muriates, the acid nitrate of six ammonia rhodiums (III), (methyl ethyl diketone) carbonyl (triphenylphosphine) rhodium (I), two (triphenylphosphine) two rhodiums (I) of two-μ-chlorine dicarbapentaborane, phenylformic acid rhodium (II), sad rhodium (II), rhodium acetate (II) hydrate, the sour ammonium hydrate of chlordene rhodium (III), the sour ammonium of pentachloro-hydration rhodium (III), five ammoniacal liquor close rhodium (III) muriate, five ammoniacal liquor close rhodium (III) nitrate solution, the sour sodium of hexanitro-rhodium (III), the sour potassium of six cyano group rhodiums (III), methyl ethyl diketone ［ (η-1,5-cyclooctadiene) rhodium (I) ］, dichloro two ［ (norbornadiene) rhodium (I) ］, gold tricyanide (I), the sour potassium of dicyan fund (I), tetrachloro gold (III) acid hydrate, the sour potassium of four cyano gold (III), the sour sodium of curing gold (I), curing gold (I) ammonium, the sour sodium of tetrachloro gold (III), the sour potassium hydrate of tetrachloro gold (III), chlorine (triethyl phosphine) gold (I), chlorine (triphenylphosphine) gold (I), the sour ammonium of dicyan fund (I), the sour barium hydrate of dicyan fund (I), iridium chloride hydrate, chlordene iridium (IV) acid, the sour ammonium of chlordene iridium (IV), the sour potassium of chlordene iridium (IV), the sour sodium hydrate of chlordene iridium (IV), the sour sodium hydrate of chlordene iridium (III), the sour potassium hydrate of chlordene iridium (III), bromination iridium (III) hydrate, hexabromo iridium (III) acid, iridium oxide (IV), the sour potassium hydrate of three (oxalate) iridium (III), chlorine five ammonia iridium (III) muriate hydrates, chloroformyl two (triphenylphosphine) iridium (I), two (η-1,5-cyclooctadiene) two iridium (I) of two-μ-chlorine, hexanitro-iridium (III) sodium, the sour potassium of hexabromo iridium (IV), the sour potassium of pentachloro-hydration iridium (III), gold tricyanide (I), the sour potassium of dicyan fund (I), tetrachloro gold (III) acid hydrate, the sour potassium of four cyano gold (III), the sour sodium of curing gold (I), the sour ammonium of curing gold (I), the sour sodium of tetrachloro gold (III), the sour potassium hydrate of tetrachloro gold (III), chlorine (triethyl phosphine) gold (I), chlorine (triphenylphosphine) gold (I), the sour ammonium of dicyan fund (I), the sour barium hydrate of dicyan fund (I), iridium chloride hydrate, chlordene iridium (IV) acid, the sour ammonium of chlordene iridium (IV), the sour potassium of chlordene iridium (IV), the sour sodium hydrate of chlordene iridium (IV), the sour sodium hydrate of chlordene iridium (III), the sour potassium hydrate of chlordene iridium (III), bromination iridium (III) hydrate, hexabromo iridium (III) acid, iridium oxide (IV), the sour potassium hydrate of three (oxalate) iridium (III), chlorine five ammonia iridium (III) muriate hydrates, chloroformyl two (triphenylphosphine) iridium (I), two (η-1,5-cyclooctadiene) two iridium (I) of two-μ-chlorine, hexanitro-iridium (III) sodium, the sour potassium of hexabromo iridium (IV), the sour potassium of pentachloro-hydration iridium (III), as heterogeneous series catalysts, more preferably Pd carbon, Pd aluminum oxide, Pd barium sulfate, Pd is black, Pd calcium carbonate, palladous oxide, palladium hydroxide, Pt carbon, sulfurous acid Pt carbon, Pt aluminum oxide, Pt is black, platinum oxide, nickel, draw Buddhist nun's nickel, Ru carbon, Ru aluminum oxide, Ru is black, ruthenium oxide, Ru titanium dioxide, Rh carbon, Rh aluminum oxide, Rh is black, rhodium oxide, considers more preferably Pd carbon from the viewpoint of cost and the easiness obtaining, Pd aluminum oxide, Pd barium sulfate, Pd is black, Pd calcium carbonate, palladous oxide, palladium hydroxide, Pt carbon, sulfurous acid Pt carbon, Pt aluminum oxide, Pt is black, platinum oxide, nickel, draw Buddhist nun's nickel, further Pd carbon more preferably, Pd aluminum oxide, Pd barium sulfate, Pd is black, Pd calcium carbonate, palladous oxide, palladium hydroxide, nickel, draw Buddhist nun's nickel, further Pd carbon more preferably, draw Buddhist nun's nickel, be particularly preferably Pd carbon.In addition catalyzer can be that moisture product can be also dry product.

Contact hydrogen reduction reaction time pressure be preferably, using normal atmosphere as 0MPa, hydrogen pressure is 0MPa～10MPa, the viewpoint of slave unit and the viewpoint of security are considered, more preferably using normal atmosphere as 0MPa, hydrogen pressure is 0MPa～1MPa, is particularly preferably using normal atmosphere as 0MPa, and hydrogen pressure is greater than 0MPa until 0.5MPa.

The temperature of reaction of contact hydrogen reduction is preferably-100 ℃～200 ℃, and the viewpoint of slave unit and the viewpoint of yield consider, more preferably-20 ℃～100 ℃, more preferably 0 ℃～60 ℃, more preferably 0 ℃～40 ℃, be particularly preferably 0 ℃～below room temperature.

The reaction solvent using as contact hydrogen reduction, for example can enumerate tertiary butyl alcohol, isobutyl alcohol, isopropyl alcohol, isoamyl alcohol, hexalin, n-butyl alcohol, 2-butanols, 1-octanol, 2-methyl cellosolve, ethylene glycol, Diethylene Glycol, methyl alcohol, methyl-cyclohexanol, ethanol, propyl alcohol, chloroform, tetracol phenixin, methylene dichloride, 1,2-ethylene dichloride, 1,2-dichloroethene, sym.-tetrachloroethane, trieline, 1-chlorobutane, dithiocarbonic anhydride, acetone, acetonitrile, cyanobenzene, N,N-dimethylacetamide, methyl-sulphoxide, Anaesthetie Ether, ethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, orthodichlorobenzene, dimethylbenzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, Isoamyl Acetate FCC, ethyl acetate, butylacetate, propyl acetate, pentyl acetate, methyl acetate, 2-Methoxyethyl acetate, HMPA, three (dimethylamino) phosphine, pimelinketone, Isosorbide-5-Nitrae-dioxane, vinylbenzene, zellon, tetrahydrofuran (THF), pyridine, 1-Methyl-2-Pyrrolidone, 1，1，1-trichloroethane, toluene, hexane, pentane, hexanaphthene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), t-butyl methyl ether, methyl ethyl ketone, methylcyclohexanone, methyl butyl ketone, metacetone, gasoline, coal-tar naphtha, sherwood oil, petroleum naphtha, low-density oil, turps, mineral spirits, water, from yield, the viewpoint of the easiness of aftertreatment and acquisition is considered, is preferably tertiary butyl alcohol, isobutyl alcohol, isopropyl alcohol, isoamyl alcohol, hexalin, n-butyl alcohol, 2-butanols, 1-octanol, 2-methyl cellosolve, ethylene glycol, Diethylene Glycol, methyl alcohol, methyl-cyclohexanol, ethanol, propyl alcohol, Anaesthetie Ether, diethylene glycol diethyl ether, orthodichlorobenzene, dimethylbenzene, o-Xylol, p-Xylol, m-xylene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), 1-Methyl-2-Pyrrolidone, toluene, hexane, pentane, hexanaphthene, pentamethylene, heptane, benzene, methyl iso-butyl ketone (MIBK), t-butyl methyl ether, methyl ethyl ketone, sherwood oil, water, more preferably isopropyl alcohol, methyl alcohol, ethanol, propyl alcohol, Anaesthetie Ether, dimethylbenzene, o-Xylol, p-Xylol, m-xylene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), toluene, hexane, pentane, hexanaphthene, pentamethylene, heptane, benzene, t-butyl methyl ether, sherwood oil, water, more preferably isopropyl alcohol, methyl alcohol, ethanol, propyl alcohol, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), toluene, hexane, pentane, hexanaphthene, pentamethylene, heptane, t-butyl methyl ether, water, further isopropyl alcohol more preferably, methyl alcohol, ethanol, propyl alcohol, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), t-butyl methyl ether, water.In addition, reaction solvent can be single solvent, also two or more mixing of above-mentioned solvent can be used.

In addition, also can in part or all of solvent, use acid or use acid as additive.As acid, can be organic acid, can be also mineral acid, but be preferably Bronsted (

) sour situation.As concrete example, can enumerate hydrochloric acid, Hydrogen bromide, sulfuric acid, nitric acid, ortho-phosphoric acid, tetra-sodium, alkylsulphonic acid, aryl sulfonic acid, phosphonic acids, carboxylic acid, perchloric acid, phospho-molybdic acid, silicotungstic acid, vanadium molybdic acid, heteropolyacid, Phenylsulfonic acid, tosic acid, naphthene sulfonic acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, tertiary butyl sulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, phosphenylic acid, Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, acetic acid, propionic acid, butyric acid, isopropylformic acid, PIVALIC ACID CRUDE (25), valeric acid, caproic acid, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oxalic acid, hexahydrobenzoic acid, phenylformic acid, phthalic acid, m-phthalic acid, terephthalic acid, vinylformic acid, methacrylic acid, propynoic acid, β-crotonic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, oleic acid, aspartic acid, L-glutamic acid, Tripyrophosphoric acid, solid acid etc., but consider more preferably hydrochloric acid from the viewpoint of the refining easiness of target substance, Hydrogen bromide, sulfuric acid, nitric acid, alkylsulphonic acid, aryl sulfonic acid, carboxylic acid, Phenylsulfonic acid, tosic acid, methylsulfonic acid, ethane sulfonic acid, propane sulfonic acid, tertiary butyl sulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, acetic acid, propionic acid, butyric acid, isopropylformic acid, PIVALIC ACID CRUDE (25), valeric acid, caproic acid, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oxalic acid, hexahydrobenzoic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, oleic acid, aspartic acid, L-glutamic acid, solid acid, more preferably hydrochloric acid, Hydrogen bromide, sulfuric acid, nitric acid, alkylsulphonic acid, carboxylic acid, Phenylsulfonic acid, tosic acid, methylsulfonic acid, ethane sulfonic acid, propane sulfonic acid, tertiary butyl sulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, acetic acid, propionic acid, butyric acid, isopropylformic acid, PIVALIC ACID CRUDE (25), oxalic acid, toxilic acid, fumaric acid, solid acid, further hydrochloric acid more preferably, Hydrogen bromide, sulfuric acid, nitric acid, carboxylic acid, methylsulfonic acid, ethane sulfonic acid, propane sulfonic acid, tertiary butyl sulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, acetic acid, propionic acid, further hydrochloric acid more preferably, sulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, formic acid, acetic acid, is particularly preferably hydrochloric acid, sulfuric acid, formic acid, acetic acid.Can in part or all of solvent, use acid, or use acid as additive, but consider from the viewpoint of speed of response and yield, be preferably in solvent with ratio arbitrarily and add acid, or only use sour situation as solvent, consider from the viewpoint of the easiness of aftertreatment, in the situation that using the strong acid such as sulfuric acid, more preferably in solvent, add sour situation with ratio arbitrarily, more preferably add sour situation with respect to solvent 100 parts by volume with the ratio of 0.0001 parts by volume～100 parts by volume, further more preferably add sour situation with respect to solvent 100 parts by volume with the ratio of 0.001 parts by volume～50 parts by volume, further more preferably add sour situation with respect to solvent 100 parts by volume with the ratio of 0.01 parts by volume～10 parts by volume, be particularly preferably with respect to solvent 100 parts by volume and add sour situation with the ratio of 0.1 parts by volume～10 parts by volume, in the situation that using the weak acid such as acetic acid, being preferably solvent and sour volume ratio is that solvent: acid=100:0.1～0:100 uses the situation of acid as solvent, more preferably solvent and sour volume ratio are that solvent: acid=100:1～0:100 only uses the situation of acid as solvent, more preferably solvent and sour volume ratio are that solvent: acid=10:1～0:100 only uses the situation of acid as solvent, further more preferably solvent and sour volume ratio are that solvent: acid=5:1～0:100 only uses the situation of acid as solvent, being particularly preferably solvent and sour volume ratio is that 0:100 only uses the situation of acid as solvent.Further, particularly, be preferably with respect to solvent and add sulfuric acid or hydrochloric acid with 0.01 volume %～10 volume %, or the situation using formic acid or acetic acid as solvent using the formic acid more than 10 volume % with respect to solvent or acetic acid as solvent or only, more preferably add sulfuric acid or the hydrochloric acid of 0.1 volume %～5 volume % with respect to solvent, or the situation using formic acid or acetic acid as solvent using the formic acid more than 50 volume % with respect to solvent or acetic acid as solvent or only.

Embodiment

Below, enumerate embodiment and further describe the present invention, but the present invention is not limited to these embodiment.The meaning of " % " in following embodiment and the composition of comparative example is " quality % ".Below, for easy difference, the compound of manufacturing by the manufacture method of the present application is explained in the mode of " I-1 ", the compound with same structure of manufacturing is enclosed to " C " in the mode of " I-1C " explain by known manufacture method at end.The purity of compound is analyzed by GC or UPLC.Analysis condition is as described below.

(GC analysis condition)

Post: Agilent science and technology (Agilent Technologies), J & W Column DB-1HT, 15m × 0.25mm × 0.10 μ m

Temperature program(me) :-250 ℃ of 100 ℃ (1 minute)-(20 ℃/min)-(10 ℃/min)-380 ℃-(7 ℃/min)-400 ℃ (2.64 minutes)

Inlet temperature: 350 ℃

Detector temperature: 400 ℃

(UPLC analysis condition)

Post: water generation (Waters) ACQUITY UPLC BEH C ₁₈, 2.1 × 100mm, 1.7 μ m

Eluting solvent: acetonitrile/water (90:10)

Flow velocity: 0.5mL/min

Detector: UV, 210nm

Column oven: 40 ℃

The manufacture of the compound shown in (embodiment 1) formula (I-1)

Possessing in the flask of whipping appts and dropping funnel, add compound, the 180mL methylene dichloride shown in the compound shown in 60.00g (0.291 mole) formula (I-1-1), 25.83g (0.148 mole) formula (I-1-2).Carry out ice-cooled while at the 15 ℃ of following 67.19g (0.32 mole) of dropping trifluoroacetic anhydrides., after 20 hours, be injected in 500mL water in stirring at room temperature.Add 100mL methylene dichloride, carry out separatory processing.By salt solution washing 5 times for organic layer.Refine by column chromatography (silica gel, aluminum oxide), solvent distillation is removed until concentrated solution becomes 217g.Add 400mL hexane ,-20 ℃ leave standstill after, filter.After adding 180mL acetone and heating and it is suspended, carry out ice-cooledly, add 180mL hexane ,-20 ℃ leave standstill after, filter, thereby obtained the compound 63.03g shown in the formula (I-1) of object.

¹H?NMR(CDCl ₃)δ1.45(m，40H)，1.75(quin，4H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ24.6，29.4，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

172 ℃ of fusing points

LRMS(EI)m/z550

The manufacture of the compound shown in (comparative example 1) formula (I-1C)

Possessing in the flask of whipping appts and dropping funnel, add the compound shown in the compound shown in 6.00g (0.029 mole) formula (I-1-1), 2.58g (0.015 mole) formula (I-1-2).Carry out ice-cooled while add 6.72g (0.032 mole) trifluoroacetic anhydride., after 5 hours, with the dilution of 50mL methylene dichloride, be injected in 50mL water in stirring at room temperature.By salt solution washing 5 times for organic layer.Refine by column chromatography (silica gel, aluminum oxide), with the same operation washing that suspends, obtained the compound 6.30g shown in the formula (I-1C) of object.

¹H?NMR(CDCl ₃)δ1.45(m，40H)，1.75(quin，4H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ24.6，29.4，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

172 ℃ of fusing points

LRMS(EI)m/z550

The manufacture of the compound shown in (embodiment 2) formula (I-2)

In the reaction vessel that possesses whipping appts, add compound and the 20mL1 shown in 1.43g (12.1 mmole) formula (I-2-1), 2-ethylene dichloride.Add the compound shown in 5.00g (24.2 mmole) formula (I-1-1) and 5.09g (24.2 mmole) trifluoroacetic anhydride., after 18 hours, be injected in 100mL water in stirring at room temperature.Add 100mL methylene dichloride, carry out separatory processing.By salt solution washing 5 times for organic layer.Refine by column chromatography (silica gel, aluminum oxide), disperse washing with hexane, thereby obtained the compound 4.91g shown in the formula (I-2) of object.

¹H?NMR(CDCl ₃)δ1.47(s，36H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ30.1,38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z494

The manufacture of the compound shown in (comparative example 2) formula (I-2C)

In the reaction vessel that possesses whipping appts, add the compound shown in the compound shown in 5.00g (24.2 mmole) formula (I-1-1), 1.43g (12.1 mmole) formula (I-2-1), 5.09g (24.2 mmole) trifluoroacetic anhydride.Then, add 0.5mL methylene dichloride, stirring at room temperature 6 hours.Add 50mL methylene dichloride, 50mL water, carry out separatory processing.By salt solution washing 5 times for organic layer.Refine by column chromatography (silica gel, aluminum oxide), disperse washing with hexane, thereby obtained the compound 5.02g shown in the formula (I-2C) of object.

¹H?NMR(CDCl ₃)δ1.47(s，36H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ30.1,38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z494

The manufacture of the compound shown in (embodiment 3) formula (I-3)

Possessing in the reaction vessel of whipping appts and dropping funnel, add the compound shown in 3.15g (24.2 mmole) formula (I-3-1), 5.09g (24.2 mmole) trifluoroacetic anhydride, 30mL hexane.Carry out ice-cooled while drip and make the compound dissolution shown in 5.00g (24.2 mmole) formula (I-1-1) in the solution of 15mL methylene dichloride., after 2 days, be injected in 100mL water in stirring at room temperature.Add 100mL toluene, carry out separatory carrying out washing treatment.Refine by column chromatography (silica gel, aluminum oxide), thereby obtained the compound 6.01g shown in the formula (I-3) of object.

¹H?NMR(CDCl ₃)δ0.89(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(CDCl ₃)δ14.1,22.7，29.4，29.6，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z318

The manufacture of the compound shown in (comparative example 3) formula (I-3C)

In the reaction vessel that possesses whipping appts, add the compound shown in the compound shown in 5.00g (24.2 mmole) formula (I-1-1), 3.15g (24.2 mmole) formula (I-3-1), 5.09g (24.2 mmole) trifluoroacetic anhydride.After 6 hours, add 50mL water in stirring at room temperature.Add 50mL toluene, carry out separatory carrying out washing treatment.Refine by column chromatography (silica gel, aluminum oxide), thereby obtained the compound 6.21g shown in the formula (I-3C) of object.

¹H?NMR(CDCl ₃)δ0.89(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(CDCl ₃)δ14.1,22.7，29.4，29.6，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z318

The manufacture of the compound shown in (embodiment 4) formula (I-4)

In the reaction vessel that possesses whipping appts, add the compound shown in 5.00g (24.2 mmole) formula (I-1-1), 5.09g (24.2 mmole) trifluoroacetic anhydride, 15mL methylene dichloride.Add the compound shown in 5.15g (24.2 mmole) formula (I-4-1)., after 2 days, be injected in 100mL water in stirring at room temperature.Add 100mL methylene dichloride, carry out separatory carrying out washing treatment.Refine by column chromatography (silica gel, aluminum oxide), thereby obtained the compound 7.75g shown in the formula (I-4) of object.

LRMS(EI)m/z400

The manufacture of the compound shown in (comparative example 4) formula (I-4C)

In the reaction vessel that possesses whipping appts, add the compound shown in the compound shown in 5.00g (24.2 mmole) formula (I-1-1), 5.15g (24.2 mmole) formula (I-4-1), 5.09g (24.2 mmole) trifluoroacetic anhydride.Stir after 5 minutes, add 0.5mL hexane.After 6 hours, add 50mL water in stirring at room temperature.Add 50mL methylene dichloride, carry out separatory carrying out washing treatment.Refine by column chromatography (silica gel, aluminum oxide), thereby obtained the compound 7.80g shown in the formula (I-4C) of object.

LRMS(EI)m/z400

The manufacture of the compound shown in (embodiment 5) formula (I-5)

In the manufacture method described in embodiment 4, compound shown in use formula (I-5-1) replaces the compound shown in formula (I-1-1), compound shown in use formula (I-5-2) replaces the compound shown in formula (I-4-1), in addition, similarly operation, has obtained the compound shown in formula (I-5).

LRMS(EI)m/z298

The manufacture of the compound shown in (comparative example 5) formula (I-5C)

By the method same with comparative example 4, obtain the compound shown in formula (I-5C).

LRMS(EI)m/z298

The manufacture of the compound shown in (embodiment 6) formula (I-6)

In the manufacture method described in embodiment 4, compound shown in use formula (I-6-1) replaces the compound shown in formula (I-1-1), compound shown in use formula (I-6-2) replaces the compound shown in formula (I-4-1), in addition, similarly operation, has obtained the compound shown in formula (I-6).

LRMS(EI)m/z230

The manufacture of the compound shown in (comparative example 6) formula (I-6C)

By the method same with comparative example 4, obtain the compound shown in formula (I-6C).

LRMS(EI)m/z230

(embodiment 7～12 and comparative example 7～12)

The liquid-crystal composition that modulation is made up of following compound, makes parent liquid crystal (X).

In this parent liquid crystal (X), add the compound 0.1% as evaluation object of manufacturing in embodiment 1～6 and comparative example 1～6 and make its dissolving.The liquid-crystal composition of this evaluation object is injected into be coated with the unit interval of 3.5 μ m by vacuum impregnation and brings out in the unit with ITO of vertical orientated alignment film of polyimide, thereby make as the vertical orientated property liquid crystal display device (XI-1) of evaluation object～(XI-12).Following table shows the relation as compound and the liquid crystal display device of evaluation object.

[table 1]

?	As the liquid crystal display device of evaluation object	As the compound of evaluation object
			Embodiment 7	Display element (XI-1)	Compound (I-1)
Embodiment 8	Display element (XI-2)	Compound (I-2)

Embodiment 9	Display element (XI-3)	Compound (I-3)
			Embodiment 10	Display element (XI-4)	Compound (I-4)
Embodiment 11	Display element (XI-5)	Compound (I-5)
			Embodiment 12	Display element (XI-6)	Compound (I-6)
Comparative example 7	Relatively display element (XI-7)	Comparative compound (I-1C)
			Comparative example 8	Relatively display element (XI-8)	Comparative compound (I-2C)
Comparative example 9	Relatively display element (XI-9)	Comparative compound (I-3C)
			Comparative example 10	Relatively display element (XI-10)	Comparative compound (I-4C)
Comparative example 11	Relatively display element (XI-11)	Comparative compound (I-5C)
			Comparative example 12	Relatively display element (XI-12)	Comparative compound (I-6C)

［ measuring method of voltage retention (VHR) ］

Determinator has used the hyperchannel liquid crystal indicator " Model6254 " of Dongyang scientific & technical corporation system.Measuring temperature is 25 ℃, after applying 64 microseconds to liquid crystal device, the source voltage that the square wave by ± 1V is formed cuts off, measure the decrement of the voltage in 16.67m second, in the case of situation about not decaying is completely made as 100%, calculate on the other hand area ratio respectively as voltage retention (VHR (initial stage) (%)).In addition, the voltage retention that display element is measured after 2 hours 80 ℃ of heating is made as VHR (heating) (%), is made as VHR (UV) (%) by irradiating with the extra-high-pressure mercury vapour lamp USH-500D processed of USHIO motor society the voltage retention of measuring after UV for 30 minutes.Show the result in following table.

[table 2]

?	VHR (initial stage) (%)	VHR (heating) (%)	VHR(UV)(%)
				Embodiment 7	98.2	97.6	97.4
Embodiment 8	97.8	97.3	97.2
				Embodiment 9	98.5	98.1	97.9
Embodiment 10	97.7	97.2	97.0
				Embodiment 11	97.5	97.0	96.5
Embodiment 12	98.3	97.1	96.3
				Comparative example 7	97.2	90.1	89.3
Comparative example 8	97.2	87.3	85.3

Comparative example 9	98.6	82.3	80.1
				Comparative example 10	97.7	83.1	79.8
Comparative example 11	97.1	84.3	78.9
				Comparative example 12	98.5	88.7	75.5

Hence one can see that, and about the liquid crystal display device that contains the compound of manufacturing by the manufacture method of the present application, the voltage retention at initial stage is equal or more than it with comparative example, causes that the foreign matter content that conservation rate reduces is few.In addition known, about the liquid crystal display device that contains the compound of manufacturing by the manufacture method of the present application, because the voltage retention after heating and after rayed is higher than comparative example, the Compound Phase of therefore manufacturing by the manufacture method of the present application is high for the weather resistance of heat or light.The compound of manufacturing by the manufacture method of comparative example is all difficult to carry out quantitative accurately, but has been enlightened and contained high-boiling-point impurity by detailed analysis.On the other hand, the compound of manufacturing by the manufacture method of the present application is also all similarly difficult to carry out quantitative accurately, but has been enlightened and do not contained or contain hardly high-boiling-point impurity completely by detailed analysis.As can be known from the above results, the display element that contains the compound of manufacturing by the manufacture method of the present application is difficult for causing the reduction of voltage retention, is therefore useful as material used for liquid crystal display element.

The manufacture of the compound shown in (embodiment 13) formula (IV-1)

In the flask that possesses whipping appts, add the compound shown in the compound shown in 5.00g (24.2 mmole) formula (IV-1-1), 2.11g (12.1 mmole) formula (IV-1-2), 5.09g (24.2 mmole) trifluoroacetic anhydride and mix.Stir after 5 hours, with methylene dichloride dilution, carry out separatory processing, by column chromatography (silica gel) with disperse to wash (hexane) and refine, thereby obtained the compound 5.31g shown in the formula (I-1) of object.

The physics value of the compound shown in formula (IV-1)

¹H?NMR(CDCl ₃)δ1.45(m，40H)，1.75(quin，4H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ24.6，29.4，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

172 ℃ of fusing points

LRMS(EI)m/z550

The manufacture of the compound shown in (embodiment 14) formula (IV-2)

Compound shown in the formula (IV-1-2) of recording in embodiment 13 is replaced to the compound shown in an accepted way of doing sth (IV-2-1), in addition, the method by similarly to Example 13 and the compound shown in manufacture formula (IV-2).

The physics value of the compound shown in formula (IV-2)

¹H?NMR(CDCl ₃)δ1.45(m，42H)，1.75(quin，4H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ24.6，24.6，29.4，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z564

The manufacture of the compound shown in (embodiment 15) formula (IV-3)

Compound shown in the formula (IV-1-2) of recording in embodiment 13 is replaced to the compound shown in an accepted way of doing sth (IV-3-1), in addition, manufacture the compound shown in formula (IV-3) by method similarly to Example 13.

The physics value of the compound shown in formula (IV-3)

¹H?NMR(CDCl ₃)δ1.45(m，44H)，1.75(quin，4H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ24.6，24.6，29.4，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z578

The manufacture of the compound shown in (embodiment 16) formula (IV-4)

Compound shown in the formula (IV-1-2) of recording in embodiment 13 is replaced to the compound shown in an accepted way of doing sth (IV-4-1), in addition, manufacture the compound shown in formula (IV-4) by method similarly to Example 13.

The physics value of the compound shown in formula (IV-4)

¹H?NMR(CDCl ₃)δ1.45(m，60H)，1.75(quin，4H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ24.6，24.6，24.6，24.6，29.4，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z690

The manufacture of the compound shown in (embodiment 17) formula (IV-5)

Compound shown in the formula (IV-1-2) of recording in embodiment 13 is replaced to the compound shown in an accepted way of doing sth (IV-5-1), in addition, manufacture the compound shown in formula (IV-5) by method similarly to Example 13.

The physics value of the compound shown in formula (IV-5)

¹H?NMR(CDCl ₃)δ1.45(m，64H)，1.75(quin，4H)，2.92(t，4H)，5.70(s，2H)，7.85(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ24.6，24.6，24.6，24.6，29.4，30.1,34.3，38.0，125.7，128.9，135.6，158.2，199.9ppm.

LRMS(EI)m/z718

(embodiment 18～27 and comparative example 13～20)

By the compound shown in formula (the IV-1)～formula (IV-5) of the present application of recording in embodiment 13～embodiment 17 and be typically used as the compound shown in the compound shown in the compound shown in the formula (C-1) of stopper, formula (C-2) that patent documentation 4 (Japanese kokai publication hei 05-301865 communique) is recorded, formula (C-3) and formula (C-4) that patent documentation 3 (DE1811322A1 communique) is recorded and add to respectively in liquid-crystal composition and carry out membranization, evaluate.

Using the liquid-crystal composition of the compound 8% shown in the compound 32% shown in the compound 20% shown in contained (X-1), formula (X-2), the compound 40% shown in formula (X-3), formula (X-4) as parent liquid crystal (X).

With respect to each composition of modulating by the compound 0.5% that is added to evaluation object in parent liquid crystal (X), add being dissolved in cyclopentanone after Photoepolymerizationinitiater initiater Irgacure907 (BASF society system) 3% and making 25% solution.This solution is coated on on glass with polyimide that has carried out friction treatment by method of spin coating, 65 ℃ dry 3 minutes.The film of gained is placed on the hot plate of 60 ℃, uses bandpass filter with 15mW/cm ²intensity irradiate 10 seconds of ultraviolet ray of 365nm.Then remove bandpass filter and with 70mW/cm ²intensity irradiated for 20 seconds.About the film of gained, carry out about inhomogeneous evaluation.If there is no an inhomogeneous and overall ◎ that is evenly made as by visual on film, visible inhomogeneous in the situation that according to inhomogeneous degree be made as zero, △ or ×.The results are shown in following table.

[table 3]

?	Assessing compound	Inhomogeneous
			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 ※ does not have an inhomogeneous and overall ◎ that is evenly made as by visual on film, in the inhomogeneous situation of 1～2 little ground, place visible, be made as zero, be made as △ inhomogeneous in the situation that 5～10 places are visible, in visible countless inhomogeneous situations, be made as ×.

Hence one can see that, add the polymerizable liquid crystal compound of compound of the present application about use and the film made, compared with being added with the film of comparative example 13 of comparative compound (C-1), all inhomogeneous few, or inhomogeneous degree is equal extent, it is therefore equal or its above homogeneity.In addition known, be added with the polymerizable liquid crystal compound of compound of the present application about use and the film made, compared with being added with the film of comparative example 14～comparative example 16 of comparative compound (C-2)～comparative compound (C-4), be all inhomogeneous few.

Measure the selection reflection wavelength of the cholesteric films of gained with the spectrophotometer U-4100 processed of Hitachi Co., Ltd.In order to carry out Evaluation of Heat Tolerance, the film of gained is toasted 60 minutes after 200 ℃.The selection reflection wavelength of the film after similarly measuring after baking.The results are shown in following table.

[table 4]

Like this, be added with the polymerizable liquid crystal compound of comparative compound (C-1) and the film made about use, after rear baking, select reflection wavelength band territory significantly to reduce.In addition, be added with the polymerizable liquid crystal compound of comparative compound (C-2) and comparative compound (C-3) and the film made about use, after rear baking, select reflection wavelength band territory slightly to reduce.Known on the other hand, be added with about use the present application compound polymerizable liquid crystal compound and the film made selects reflection wavelength band territory also all to reduce hardly after rear baking, there is high thermotolerance.

As can be known from the above results, be added with the polymerizable liquid crystal compound of compound of the present application about use and the film made, less inhomogeneous and thermotolerance is high.Therefore, the compound of the present application is useful as the member of formation of Polymerizable composition.In addition, used the optically anisotropic body of the composition of the compound that contains the present application is useful in the purposes of blooming etc.

Hydrogen pressure refers to the pressure in the situation using normal atmosphere as 0MPa.The compound of below method for making of the method for making by the present application and comparative example being manufactured is described, but for ease of understanding, by the compound of manufacturing by the method for making of the present application as (V-1) at end remarks numeral only, by the compound of manufacturing by the method for making of comparative example as (V-1a) at end remarks letter.

The purity of compound is analyzed by GC or UPLC.Analysis condition is as described below.

(GC analysis condition)

Post: Agilent science and technology (Agilent Technologies), J & W Column DB-1HT, 15m × 0.25mm × 0.10 μ m

Temperature program(me) :-250 ℃ of 100 ℃ (1 minute)-(20 ℃/min)-(10 ℃/min)-380 ℃-(7 ℃/min)-400 ℃ (2.64 minutes)

Inlet temperature: 350 ℃

Detector temperature: 400 ℃

(UPLC analysis condition)

Post: water generation (Waters) ACQUITY UPLC BEH C ₁₈, 2.1 × 100mm, 1.7 μ m

Eluting solvent: acetonitrile/water (90:10)

Flow velocity: 0.5mL/min

Detector: UV, 210nm

Column oven: 40 ℃

The manufacture of the compound shown in (embodiment 28) formula (V-1)

In the flask that possesses whipping appts, add the compound shown in the compound shown in 5.00g (24.2 mmole) formula (V-1-1), 2.11g (12.1 mmole) formula (V-1-2), 5.09g (24.2 mmole) trifluoroacetic anhydride and mix.Stir after 5 hours, dilute with methylene dichloride, carry out separatory processing, refine by column chromatography (silica gel) and dispersion washing (hexane), thereby obtained the compound 5.31g (9.64 mmole) shown in formula (V-1-3).

In the autoclave of 200mL, add the compound shown in 5.31g (9.64 mmole) formula (V-1-3), 50mL tetrahydrofuran (THF), the 0.25mL vitriol oil and 0.27g5%Pd carbon (50% is moisture), hydrogen pressure 0.1MPa, stirring at room temperature 3 hours.Use diatomite to remove after catalyzer, distillation is except desolventizing.Make the crude product of gained be dissolved in toluene, wash with salt solution.After organic layer is refined by column chromatography (silica gel), carry out recrystallization (acetone), thereby obtained the compound 4.28g shown in the formula (V-1) of object.Purity is 99.78%.As impurity, contain the core Reduction Body 0.03% with pimelinketone skeleton shown in following formula (V-1i).

¹H?NMR(CDCl ₃)δ1.34(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(CDCl ₃)δ29.5，29.6，30.3，32.0，34.2,36.0，124.7，133.5，135.5，151.6ppm

LRMS(EI)m/z522(100)

The manufacture of the compound shown in (comparative example 21) formula (V-1a)

In the flask that possesses whipping appts, add 30mL water, 30g zinc powder and 1g mercury chloride (II), stir 30 minutes.By water decant, zinc amalgam is washed with water.In reaction vessel, add the compound shown in 8.26g (15.0 mmole) formula (V-1-3), 120mL ethanol, zinc amalgam.Stir on one side, drip the mixed aqueous solution of 30mL concentrated hydrochloric acid, 30mL water on one side.Reflux 12 hours, adds toluene 100mL.Stir after 5 minutes, cross filter solid.Organic layer is washed with water 3 times, use dried over sodium sulfate.Carry out column chromatography (silica gel) and recrystallization (acetone), thereby obtained the compound 3.20g shown in the formula (V-1a) of object.Purity is 99.75%.As impurity, the core Reduction Body with pimelinketone skeleton shown in formula (V-1i) do not detected.

¹H?NMR(CDCl ₃)δ1.34(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(CDCl ₃)δ29.5，29.6，30.3，32.0，34.2,36.0，124.7，133.5，135.5，151.6ppm

LRMS(EI)m/z522(100)

The manufacture of the compound shown in (comparative example 22) formula (V-1b)

In the reaction vessel that possesses whipping appts, add the compound shown in 9.68g (17.6 mmole) formula (V-1-3) and 500mL2-propyl alcohol.Add 2.0g (53 mmole) sodium borohydride, stirring at room temperature 22 hours.Append 0.8g (21 mmole) sodium borohydride, further stir 1 hour.In 2N hydrochloric acid and ice, inject reaction solution.The solid that filtration is separated out.Carry out column chromatography (silica gel) and recrystallization (acetone), thereby obtained the compound 2.23g shown in the formula (V-1b) of object.Purity is 99.73%.As impurity, the core Reduction Body with pimelinketone skeleton shown in formula (V-1i) do not detected.

¹H?NMR(CDCl ₃)δ1.34(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(CDCl ₃)δ29.5，29.6，30.3，32.0，34.2,36.0，124.7，133.5，135.5，151.6ppm

LRMS(EI)m/z522(100)

The manufacture of the compound shown in (embodiment 29) formula (V-2)

In the flask that possesses whipping appts, add the compound shown in the compound shown in 5.00g (24.2 mmole) formula (V-1-1), 3.15g (24.2 mmole) formula (V-2-1), 5.09g (24.2 mmole) trifluoroacetic anhydride and mix.Stir after 5 hours, with methylene dichloride dilution, carry out separatory processing, refine by column chromatography (silica gel), thereby obtained the compound 6.46g (20.3 mmole) shown in formula (V-2-2).

In the autoclave of 200mL, add the compound shown in 6.46g (20.3 mmole) formula (V-2-2), 30mL tetrahydrofuran (THF), 60mL acetic acid and 0.32g5%Pd carbon (50% is moisture), hydrogen pressure 0.5MPa, stirring at room temperature 3 hours.Use diatomite to remove after catalyzer, tetrahydrofuran (THF) is removed in distillation.The crude product of gained is dissolved in toluene, washs with salt solution.By refining column chromatography for organic layer (silica gel), thereby obtain the compound 5.06g shown in the formula (V-2) of object.Purity is 99.58%.As impurity, contain the core Reduction Body 0.32% with pimelinketone skeleton shown in following formula (V-2i).

¹H?NMR(CDCl ₃)δ0.89(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(CDCl ₃)δ14.1,22.6，29.2,29.6，30.3，31.8，32.0，34.2,36.0，124.8，133.5，135.5，151.6ppm

LRMS(EI)m/z304(100)

The manufacture of the compound shown in (comparative example 23) formula (V-2a)

Manufacture by the method same with comparative example 21, refine by column chromatography (silica gel), synthesized the compound shown in formula (V-2a).Purity is 99.83%.As impurity, the core Reduction Body with pimelinketone skeleton shown in formula (V-2i) do not detected.

¹H?NMR(CDCl ₃)δ0.89(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(CDCl ₃)δ14.1,22.6，29.2,29.6，30.3，31.8，32.0，34.2,36.0，124.8，133.5，135.5，151.6ppm

LRMS(EI)m/z304(100)

The manufacture of the compound shown in (comparative example 24) formula (V-2b)

In the reaction vessel that possesses whipping appts and thermometer, add the compound shown in 3.10g (9.74 mmole) formula (V-2-2), 30mL trifluoroacetic acid.Carry out ice-cooled while add 2.06g (39.0 mmole) cyano group sodium borohydride.Stir after 3 hours, be injected in hydrochloric acid.Add toluene, wash with sodium hydrogen carbonate solution and salt solution.After being dried with magnesium sulfate, distillation is except desolventizing.Refine with column chromatography (silica gel), thereby obtained the compound 2.02g shown in the formula (V-2b) of object.Purity is 99.79%.As impurity, the core Reduction Body with pimelinketone skeleton shown in formula (V-2i) do not detected.

¹H?NMR(CDCl ₃)δ0.89(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(CDCl ₃)δ14.1,22.6，29.2,29.6，30.3，31.8，32.0，34.2,36.0，124.8，133.5，135.5，151.6ppm

LRMS(EI)m/z304(100)

The manufacture of the compound shown in (embodiment 30) formula (V-3)

In the flask that possesses whipping appts, add the compound shown in the compound shown in 5.00g (24.2 mmole) formula (V-1-1), 6.46g (24.2 mmole) formula (V-3-1), 5.09g (24.2 mmole) trifluoroacetic anhydride and mix.Stir after 5 hours, with methylene dichloride dilution, carry out separatory processing, refine by column chromatography (silica gel), thereby obtained the compound 8.93g (19.6 mmole) shown in formula (V-3-2).

In the autoclave of 200mL, add the compound shown in 8.93g (19.6 mmole) formula (V-3-2), 89mL tetrahydrofuran (THF), the 0.89mL vitriol oil and 0.45g5%Pd carbon (50% is moisture), hydrogen pressure 0.2MPa, stirring at room temperature 2 hours.Use diatomite to remove after catalyzer, distillation is except desolventizing.The crude product of gained is dissolved in toluene, washs with salt solution.By refining column chromatography for organic layer (silica gel), thereby obtain the compound 6.92g shown in the formula (V-3) of object.Purity is 99.45%.As impurity, contain the core Reduction Body 0.32% with pimelinketone skeleton shown in following formula (V-3i).

¹H?NMR(CDCl ₃)δ0.95～1.59(m，29H)，2.50(t，4H)，5.00(s，2H)，6.97(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ14.4，20.5，26.8，26.8，29.3，29.4，30.9，30.9，31.6，34.7，37.1,37.3，38.3,41.6，41.6，124.7，133.5，135.5，151.6ppm

LRMS(EI)m/z440(100)

The manufacture of the compound shown in (embodiment 31) formula (V-4)

By method similarly to Example 28, synthesize the compound shown in formula (V-4).Purity is 99.65%.As impurity, contain the core Reduction Body 0.21% with pimelinketone skeleton shown in following formula (V-4i).

¹H?NMR(CDCl ₃)δ1.43(s，36H)，1.59(m，4H)，2.50(t，4H)，5.00(s，2H)，6.97(s，4H)ppm.

¹³C?NMR(CDCl ₃)δ30.3，32.0，34.2,36.0，124.7，133.5，135.5，151.6ppm

LRMS(EI)m/z466(100)

The manufacture of the compound shown in (embodiment 32) formula (V-5)

In the reaction vessel that possesses dropping funnel, thermometer and whipping appts, add 0.54g (22.2 mmole) magnesium, 2mL tetrahydrofuran (THF) and slowly drip and make the solution that the compound dissolution shown in 3.10g (20.5 mmole) formula (V-5-2) obtains in 6mL tetrahydrofuran (THF) and modulate Grignard reagent.In the reaction vessel that possesses dropping funnel, thermometer and whipping appts, add the compound shown in 5.00g (17.1 mmole) formula (V-5-1), 10mL tetrahydrofuran (THF) and dissolve.Slowly drip Grignard reagent.Stir after 3 hours, add hydrochloric acid and toluene to carry out separatory processing.Organic layer is refined by column chromatography (silica gel), obtained the compound 3.64g (10.9 mmole) shown in formula (V-5-3).

In the autoclave of 200mL, add the compound shown in 3.64g (10.9 mmole) formula (V-5-3), 36mL ethanol, 36mL acetic acid and 0.18g5%Pd carbon (50% is moisture), stir 2 hours hydrogen pressure 0.5MPa, 40 ℃.Use diatomite to remove after catalyzer, add toluene and wash with salt solution.By refining column chromatography for organic layer (silica gel), thereby obtain the compound 2.77g shown in the formula (V-5) of object.Purity is 99.58%.As impurity, contain the core Reduction Body 0.37% with pimelinketone skeleton shown in following formula (V-5i).

¹H?NMR(CDCl ₃)δ0.89(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(CDCl ₃)δ14.1,22.6，29.2,29.6，29.6，30.3，31.8，32.0，34.2,36.0，124.8，133.5，135.5，151.6ppm

LRMS(EI)m/z318(100)

The manufacture of the compound shown in (comparative example 25) formula (V-5a)

By the method same with comparative example 22, synthesize the compound shown in formula (V-5a).Purity is 99.81%.As impurity, the core Reduction Body with pimelinketone skeleton shown in formula (V-5i) do not detected.

¹H?NMR(CDCl ₃)δ0.89(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(CDCl ₃)δ14.1,22.6，29.2,29.6，29.6，30.3，31.8，32.0，34.2,36.0，124.8，133.5，135.5，151.6ppm

LRMS(EI)m/z318(100)

The manufacture of the compound shown in (comparative example 26) formula (V-1c)

Possessing in the reaction vessel of whipping appts, Dean and Stark apparatus, water cooler and thermometer, add the compound shown in 3.00g (5.45 mmole) formula (V-1-3), 2.18g (43.5 mmole) hydrazine monohydrate, 1.09g (27.3 mmole) sodium hydroxide, 15mL ethylene glycol, remove and anhydrate while reflux 8 hours at 200 ℃.Analyze by GC, but the compound shown in production (V-1c) not.

The manufacture of the compound shown in (comparative example 27) formula (V-1d)

Possessing in the reaction vessel of whipping appts, thermometer and dropping funnel, add the compound shown in 100.00g (0.455 mole) formula (V-1d-1), 1.73g (9.08 mmole) cupric iodide (I), 300mL tetrahydrofuran (THF), 100mL2-monoethanolamine, 150mL water.By in reaction vessel with after nitrogen replacement, add 5.25g (4.54 mmole) tetrakis triphenylphosphine palladium (0) and carry out reflux.The solution that compound dissolution shown in 24.13g (0.227g) formula (V-1d-2) is obtained with dropping in 30 minutes in 48mL tetrahydrofuran (THF).Then, reflux 3 hours.Add 400mL ethyl acetate and 600mL10% hydrochloric acid to carry out after separatory processing, by 400mL salt solution washing 5 times for organic layer.Refine by column chromatography (aluminum oxide), its concentrate drying is solidified, thereby obtained the brown solid 68.41g of the compound shown in contained (V-1d-3).

In the autoclave of 2L that possesses whipping appts, add 68.41g brown solid, 6.84g5% palladium carbon (50% is moisture), the 342mL ethanol of the compound shown in the formula (V-1d-3) that comprises gained.Hydrogen pressure 0.5MPa, 50 ℃ reaction 3 days.Remove catalyzer by filtering, distillation removes desolventizing, thereby has obtained the brown solid 69.81g of the compound shown in contained (V-1d-4).

Possessing in the reaction vessel of whipping appts, thermometer and dropping funnel, add 5.00g (16.75 mmole) brown solid, 4.97g (67.05 mmole) tertiary butyl alcohol, the 10mL acetic acid of the compound shown in contained (V-1d-4).Carry out ice-cooled while drip 6.57g (66.99 mmole) vitriol oil.Stirring at room temperature 1 week, but only generate the compound 55% (GC) shown in the formula (V-1d) of object.Reaction solution is injected in frozen water, extracts by ethyl acetate, wash with salt solution.After concentrate drying solidifies, refine by column chromatography (silica gel, hexane) and recrystallization (acetone), obtain the compound 2.31g shown in the formula (V-1d) of object.

¹H?NMR(CDCl ₃)δ1.34(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(CDCl ₃)δ29.5，29.6，30.3，32.0，34.2,36.0，124.7，133.5，135.5，151.6ppm

LRMS(EI)m/z522(100)

The manufacture of the compound shown in (comparative example 28) formula (V-1e)

Possessing in the reaction vessel of whipping appts, thermometer and gas leading-in device, add 5.00g (16.75 mmole) brown solid, 30mL toluene, 0.49g (5.00 mmole) vitriol oil of the compound shown in contained (V-1d-4).Stir on one side at 65 ℃, import continuously iso-butylene on one side.React 1 week, but only generate the compound 75% (GC) shown in the formula (V-1e) of object.Reaction solution is injected in frozen water, extracts by ethyl acetate, wash with salt solution.After concentrate drying solidifies, refine by column chromatography (silica gel, hexane) and recrystallization (acetone), obtain the compound 3.20g shown in the formula (I-1e) of object.

¹H?NMR(CDCl ₃)δ1.34(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(CDCl ₃)δ29.5，29.6，30.3，32.0，34.2,36.0，124.7，133.5，135.5，151.6ppm

LRMS(EI)m/z522(100)

The manufacture of the compound shown in (comparative example 29) formula (V-1f)

Compound shown in 5.00g (9.08 mmole) formula (V-1-3) is suspended in the mixed solvent of second alcohol and water, adds 0.69g (18.2 mmole) sodium borohydride.After 5 hours, slowly add hydrochloric acid in stirring at room temperature.Extract by ethyl acetate, with after salt solution washing, distillation removes desolventizing, thereby has obtained the compound shown in formula (V-1-4).Make the compound dissolution of gained in isopropyl alcohol, add 10%Pd carbon and concentrated hydrochloric acid, stir 2 hours hydrogen pressure 0.29MPa, 80 ℃.Filtering catalyst distillation, except desolventizing, are added hexane and toluene, in-5 ℃ of crystallizatioies, filtration, dry, have obtained the compound shown in formula (V-1f).Purity is 96.98%.As impurity, contain the core Reduction Body 2.15% with pimelinketone skeleton shown in formula (V-1i).

(embodiment 33～37 and comparative example 30～34)

Below, describe and add the compound of manufacturing in embodiment 28～32 and comparative example 21～25 to evaluate in parent liquid crystal and obtain result.

The liquid-crystal composition that modulation is made up of following compound, as parent liquid crystal (X).

In this parent liquid crystal (X), add and make its dissolving and modulate polymerizable liquid crystal compound as compound 0.1% and the following polymerizable compound 0.3% of evaluation object, as the polymerizable liquid crystal compound of evaluation object.

Polymerizable liquid crystal compound using this as evaluation object is injected into and is coated with the unit with ITO that brings out vertical orientated alignment film of polyimide with the unit interval of 3.5 μ m by vacuum impregnation.The square wave that one side applies 1.8V with frequency 1kHz uses high pressure mercury vapour lamp with 10mW/cm on one side ²irradiate UV600 second more than 320nm, make the vertical orientated property liquid crystal display device (XI) as evaluation object.The tilt angle of liquid crystal is fixed as 87.3 degree.Following table shows the relation as compound and the liquid crystal display device of evaluation object.

[table 5]

?	As the liquid crystal display device of evaluation object	As the compound of evaluation object
			Embodiment 33	Display element (XI-1)	Compound (I-1)
Embodiment 34	Display element (XI-2)	Compound (I-2)
			Embodiment 35	Display element (XI-3)	Compound (I-3)
Embodiment 36	Display element (XI-4)	Compound (I-4)
			Embodiment 37	Display element (XI-5)	Compound (I-5)
Comparative example 30	Relatively display element (XI-6)	Comparative compound (I-1a)
			Comparative example 31	Relatively display element (XI-7)	Comparative compound (I-1b)
Comparative example 32	Relatively display element (XI-8)	Comparative compound (I-2a)
			Comparative example 33	Relatively display element (XI-9)	Comparative compound (I-2b)
Comparative example 34	Relatively display element (XI-10)	Comparative compound (I-5a)

Display element to embodiment 33～37 and comparative example 30～34 applies voltage, has confirmed the outward appearance in every period of elapsed time.Be designated as ◎ having no completely the in the situation that image retaining, the degree retaining according to image in the situation that visual picture retains is designated as zero (image retains the utmost point and slightly occurs), △ (image retain a little doughtily occur), × (image retains generation very doughtily).Show the result in following table.

[table 6]

?	After 100 hours	After 1000 hours	After 10000 hours
				Embodiment 33	◎	◎	◎
Embodiment 34	◎	◎	◎
				Embodiment 35	◎	◎	○
Embodiment 36	◎	◎	◎
				Embodiment 37	◎	◎	○

Comparative example 30	○	×	×
				Comparative example 31	◎	△	×
Comparative example 32	○	×	×
				Comparative example 33	◎	△	×
Comparative example 34	◎	△	×

About the display element of the comparative compound that contains comparative example 30～34, all there is a little doughtily image in demonstration in latter 1000 hours and retain, in 10000 hours almost whole visible show bad.On the other hand, the display element that contains the compound of manufacturing by the manufacture method of the present application also maintains high-quality～good show state after latter 10000 hours in demonstration.

As can be known from the above results, about the compound of manufacturing by the manufacture method of the present application, compared with situation about manufacturing with the method for making of recording by patent documentation 3, the content of impurity with pimelinketone structure is few.In addition, the display element that contains the compound of manufacturing by the manufacture method of the present application retains owing to being difficult for causing image, and the compound of therefore manufacturing by the manufacture method of the present application is useful as PSA type material used for liquid crystal display element.In addition, compared with known manufacture method, the reaction times is the short period of time, therefore the productivity excellence of the manufacture method of the present application.

Claims (46)

1. a manufacture method; it is characterized in that; to use phenol (A), carboxylic acid (B) and the carboxylic acid anhydride (C) shown in following general formula (I) and the manufacture method of the Acylphenol (D) that carries out; in the time that reacting, phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C) there is organic solvent

In formula, Y ¹, Y ², Y ³, Y ⁴and Y ⁵represent independently of one another alkyl, the alkenyl of carbonatoms 1～18 or the alkynyl of carbonatoms 1～18 of hydrogen atom, carbonatoms 1～18, hydrogen atom in these groups can be replaced by fluorine atom, chlorine atom, bromine atoms, iodine atom, cyano group, nitro, hydroxyl independently of one another, and/or 1-CH in these groups ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-S-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-replace, Y ¹, Y ², Y ³, Y ⁴and Y ⁵among at least 1 group represent hydrogen atom.

2. manufacture method according to claim 1, it is characterized in that, in the mixture (E) of 2 kinds and organic solvent that are selected from phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C), add a kind of the composition that does not become mixture (E) among phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C).

3. manufacture method according to claim 1, it is characterized in that, in the compound (F) of a kind and organic solvent as being selected from phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C), add 2 kinds except compound (F) among phenol (A), carboxylic acid (B) and carboxylic acid anhydride (C).

4. manufacture method according to claim 2, is characterized in that, by adding carboxylic acid anhydride (C) to carry out for phenol (A), carboxylic acid (B) and organic solvent.

5. manufacture method according to claim 2, is characterized in that, by adding carboxylic acid (B) to carry out for phenol (A), carboxylic acid anhydride (C) and organic solvent.

6. manufacture method according to claim 2, is characterized in that, by adding phenol (A) to carry out for carboxylic acid (B), carboxylic acid anhydride (C) and organic solvent.

7. according to the manufacture method described in any one in claim 1～6, it is characterized in that, carboxylic acid (B) represents with following general formula (II),

In formula, G represents the organic group of 4 valencys, and R is the group shown in following general formula (III), and m represents 1～4 integer, and they can be the same or different R existing multiple in the situation that,

In formula, Sp represents 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-or-alkylidene group or the singly-bound of the carbonatoms 1～20 that S-replaces, represent-O-of X ,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ¹¹=CY ¹¹-,-C ≡ C-or singly-bound, in formula, Y ¹¹represent independently of one another hydrogen atom, the alkyl of carbonatoms 1～12, fluorine atom, chlorine atom or cyano group, A represents 1, 4-phenylene, naphthalene-2, 6-bis-bases, 1, 4-cyclohexylene, 1, 4-cycloethylene thiazolinyl, 1, it is octylene that 4-bis-encircles ［ 2.2.2 ］, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-naphthane-2, 6-bis-bases, pyridine-2, 6-bis-bases, pyrimidine-2, 5-bis-bases, 1, 3-dioxane-2, 5-bis-bases, these groups are without replacing, or independently of one another can be by halogen, cyano group, nitro, the alkyl of Pentafluorosulfanyl or carbonatoms 1～10 replaces, in this alkyl, more than 1 hydrogen atom can be replaced by fluorine atom or chlorine atom independently of one another, 1-CH on this alkyl ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY ²¹=CY ²¹-or-C ≡ C-replacement, in formula, Y ²¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12, represent-O-of Z ,-S-,-OCH ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ³¹=CY ³¹-, alkylidene group or the singly-bound of-C ≡ C-, carbonatoms 1～20, in formula, Y ³¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12,1-CH in the alkylidene group of carbonatoms 1～20 or singly-bound ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY ⁴¹=CY ⁴¹-or-C ≡ C-replacement, in formula, Y ⁴¹represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12, n represents 0～5 integer, they can be the same or different A existing multiple in the situation that, and they can be the same or different Z existing multiple in the situation that.

8. according to the manufacture method described in any one in claim 1～6, it is characterized in that, carboxylic acid anhydride (C) is fluoro-alkyl carboxylic acid anhydride.

9. according to the manufacture method described in any one in claim 1～6, it is characterized in that Y ¹and Y ⁵represent the tertiary butyl, Y ², Y ³and Y ⁴represent hydrogen atom.

10. manufacture method according to claim 7, it is characterized in that, G represents carbon atom, and Sp represents the alkylidene group of carbonatoms 1～20, represent-O-of X ,-COO-,-OCO-or singly-bound, A indicates without replacement or independently of one another by fluorine atom, chlorine atom or 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another can by-O-,-COO-or-alkyl of the carbonatoms 1～10 that OCO-replaces replace, Isosorbide-5-Nitrae-phenylene, naphthalene-2,6-bis-bases or Isosorbide-5-Nitrae-cyclohexylene, represent independently of one another-OCH of Z ₂-,-CH ₂alkylidene group or the singly-bound of O-,-COO-,-OCO-, carbonatoms 1～20, n represents 0～3 integer, m represents 1 or 2.

11. according to the manufacture method described in any one in claim 1～6, it is characterized in that, carboxylic acid anhydride (C) is trifluoroacetic anhydride.

12. manufacture method according to claim 7, it is characterized in that, G represents carbon atom, Sp represents the alkylidene group of carbonatoms 1～12, and X represents singly-bound, A indicate without replace or independently of one another can by the alkoxyl group of the alkyl of fluorine atom, carbonatoms 1～5 or carbonatoms 1～3 replace 1,4-phenylene or 1,4-cyclohexylene, alkylidene group or the singly-bound of represent-COO-of Z ,-OCO-, carbonatoms 1～8, n represents 0～3 integer.

13. according to the manufacture method described in any one in claim 1～12, it is characterized in that, temperature of reaction is-100 ℃～200 ℃.

14. according to the manufacture method described in any one in claim 1～12, it is characterized in that, temperature of reaction is-20 ℃～100 ℃.

15. according to the manufacture method described in any one in claim 1～14, it is characterized in that, solvent is the organic solvent of non-proton property.

16. according to the manufacture method described in any one in claim 1～13, it is characterized in that, temperature of reaction is 0 ℃～60 ℃.

17. 1 kinds of compounds, is characterized in that, are to manufacture by the manufacture method described in any one in claim 1～17.

18. 1 kinds of compounds, is characterized in that, manufacture as intermediate using the compound described in claim 17.

19. 1 kinds of compositions, is characterized in that, contain the compound described in claim 17 or 18.

20. 1 kinds of resins, oil, purolator, grease, ink, medicine, makeup, lotion, liquid crystal material, agricultural chemicals, polymkeric substance, pigment, dyestuff, tackiness agent, caking agent, print, food, optically anisotropic body, display element or electron devices, it is characterized in that, contain the compound described in claim 17 or 18.

21. compounds according to claim 17, is characterized in that, the compound of manufacture by general formula (IV) represent,

In formula, Sp represents the alkylidene group of carbonatoms 6～25.

22. compounds according to claim 21, is characterized in that, in general formula (IV), Sp is the alkylidene group of carbonatoms 6～18.

23. according to the compound described in claim 21 or 22, it is characterized in that, in general formula (IV), Sp is the alkylidene group of the straight chain of the carbonatoms that comprises even number.

24. 1 kinds of compounds, is characterized in that, manufacture as intermediate using the compound described in any one in claim 21～23.

25. 1 kinds of compositions, is characterized in that, contain the compound described in any one in claim 21～24.

26. 1 kinds of polymkeric substance, is characterized in that, are by the composition polymerization described in claim 25 is obtained.

27. 1 kinds of optically anisotropic bodies, is characterized in that, have used the polymkeric substance described in claim 26.

28. 1 kinds of medicines, agricultural chemicals, liquid crystal material, polymkeric substance, resin, pigment, dyestuff, makeup, food, ink, tackiness agent, caking agent, print, optically anisotropic body, display element or electron devices, it is characterized in that, contain the compound described in any one, composition, polymkeric substance or optically anisotropic body in claim 21～27 or using compound, composition, polymkeric substance or optically anisotropic body described in any one in claim 21～27 as member of formation.

The manufacture method of 29. 1 kinds of compounds (3B), it is characterized in that, by one or more carbonyls of the compound (3A) with at least one carbonyl and at least one hindered phenol skeleton obtaining by the manufacture method described in any one in claim 1～16, be converted into methylene radical by contact hydro-reduction.

30. manufacture method according to claim 29, is characterized in that, compound (3A) has at least one carbonyl with the direct combination of hindered phenol skeleton.

31. manufacture method according to claim 29, is characterized in that, use homogeneous phase series catalysts or heterogeneous series catalysts.

32. manufacture method according to claim 29, is characterized in that, hydrogen pressure when contact reduction is below 10MPa.

33. manufacture method according to claim 29, is characterized in that, temperature of reaction when contact reduction is-100 ℃～200 ℃.

34. manufacture method according to claim 29, is characterized in that, compound (3A) is the compound shown in following logical formula V,

In formula, G represents the organic group of 4 valencys, and R represents following general formula (VI), and m represents 1～4 integer, and they can be the same or different R existing multiple in the situation that,

In formula, Y ¹and Y ²the alkyl, the alkoxyl group of carbonatoms 1～18 or the alkyloyl of carbonatoms 1～18 that represent independently of one another hydrogen atom, carbonatoms 1～18, Sp represents 1-CH ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY=CY-or-alkylidene group or the singly-bound of the carbonatoms 1～20 that C ≡ C-replaces, in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12, represent independently of one another-O-of X ,-S-,-OCH independently of one another ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ¹¹=CY ¹¹-,-C ≡ C-or singly-bound, in formula, Y ¹¹represent independently of one another hydrogen atom, the alkyl of carbonatoms 1～12, fluorine atom, chlorine atom or cyano group, A represents 1 independently of one another, 4-phenylene, naphthalene-2, 6-bis-bases, 1, 4-cyclohexylene, 1, 4-cycloethylene thiazolinyl, 1, it is octylene that 4-bis-encircles ［ 2.2.2 ］, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-naphthane-2, 6-bis-bases, pyridine-2, 6-bis-bases, pyrimidine-2, 5-bis-bases, 1, 3-dioxane-2, 5-bis-bases, these groups are without replacing, or independently of one another can be by halogen, cyano group, nitro, the alkyl of Pentafluorosulfanyl or carbonatoms 1～10 replaces, in this alkyl, more than 1 hydrogen atom can be replaced by fluorine atom or chlorine atom independently of one another, 1-CH on this alkyl ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY=CY-or-C ≡ C-replaces, in formula, Y represents alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12, represent independently of one another-O-of Z ,-S-,-OCH independently of one another ₂-,-CH ₂o-,-CO-,-COO-,-OCO-,-CO-S-,-S-CO-,-O-CO-O-,-CO-NH-,-NH-CO-,-SCH ₂-,-CH ₂s-,-CF ₂o-,-OCF ₂-,-CF ₂s-,-SCF ₂-,-CH ₂cF ₂-,-CF ₂cH ₂-,-CF ₂cF ₂-,-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-COO-CH ₂cH ₂-,-OCO-CH ₂cH ₂-,-CH ₂cH ₂-COO-,-CH ₂cH ₂-OCO-,-COO-CH ₂-,-OCO-CH ₂-,-CH ₂-COO-,-CH ₂-OCO-,-CY ¹²=CY ¹²-, alkylidene group or the singly-bound of-C ≡ C-, carbonatoms 1～20, in formula, Y ¹²represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12, wherein, 1-CH in the alkylidene group of carbonatoms 1～20 or singly-bound ₂-or non-conterminous 2 above-CH ₂-independently of one another 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-,-CY ¹³=CY ¹³-or-C ≡ C-replacement, in formula, Y ¹³represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12, n represents 0～5 integer, they can be the same or different A existing multiple in the situation that, and they can be the same or different Z existing multiple in the situation that.

35. manufacture method according to claim 29, is characterized in that, compound (3B) is the compound shown in following general formula (VII),

In formula, G and m represent the implication same with leading to formula V, and R ' represents following general formula (VIII),

In formula, Y ¹, Y ², Sp, X, A, Z and n represent the implication identical with general formula (VI), as these groups expression-CH=CH-COO-,-CH=CH-OCO-,-COO-CH=CH-,-OCO-CH=CH-,-CY=CY-,-CY in general formula (VI) ¹¹=CY ¹¹-,-CY ¹²=CY ¹²-,-CY ¹³=CY ¹³-or-C ≡ C-, in formula, Y, Y ¹¹, Y ¹², Y ¹³represent independently of one another alkyl, fluorine atom, chlorine atom or the cyano group of hydrogen atom, carbonatoms 1～12, in this case, expression-CH separately in general formula (VIII) ₂-CH ₂-COO-,-CH ₂-CH ₂-OCO-,-COO-CH ₂-CH ₂-,-OCO-CH ₂-CH ₂-,-CHY-CHY-,-CHY ¹¹-CHY ¹¹-,-CHY ¹²-CHY ¹²-,-CHY ¹³-CHY ¹³-or-CH ₂-CH ₂-.

36. manufacture method according to claim 29, is characterized in that, use acid or use acid as additive in part or all of solvent.

37. manufacture method according to claim 35, is characterized in that, in logical formula V and general formula (VII), G represents carbon atom, 1,2,4,5-benzene four bases, 1,2,3,5-benzene four bases, 1,2,4,5-hexanaphthene, four bases or 1,2,3,5-hexanaphthene, four bases.

38. manufacture method according to claim 35, is characterized in that, in logical formula V and general formula (VII), m represents 1 or 2.

39. manufacture method according to claim 35, is characterized in that, in general formula (VI) and general formula (VIII), Y ¹and Y ²represent hydrogen atom.

40. manufacture method according to claim 35, is characterized in that, in general formula (VI) and general formula (VIII), Sp represents the alkylidene group of carbonatoms 1～20.

41. manufacture method according to claim 35, is characterized in that, in general formula (VI) and general formula (VIII), X represents singly-bound.

42. manufacture method according to claim 35, is characterized in that, in general formula (VI) and general formula (VIII), n represents 0.

43. 1 kinds of compounds, is characterized in that, are to manufacture by the manufacture method described in any one in claim 29～42.

44. 1 kinds of compounds, is characterized in that, manufacture as intermediate using the compound described in claim 43.

45. 1 kinds of compositions, is characterized in that, contain the compound described in claim 43 or 44.

46. 1 kinds of resins, oil, purolator, grease, ink, medicine, makeup, lotion, liquid crystal material, agricultural chemicals, polymkeric substance, pigment, dyestuff, tackiness agent, caking agent, print, food, optically anisotropic body, display element or electron devices, it is characterized in that, contain the compound described in claim 43 or 44.