JP7078089B2 - Polymerizable compounds and optical anisotropics - Google Patents

Description

The present invention relates to a compound having a polymerizable group, a polymerizable composition containing the compound, a polymerizable liquid crystal composition, and an optical variant using a polymer obtained by polymerizing the polymerizable liquid crystal composition.

Polymerizable compounds are used in various films. For example, it is possible to produce a film having a uniform orientation by arranging the polymerizable compounds in a liquid crystal state and then polymerizing them. The film thus produced can be used for a polarizing plate, a retardation plate, etc. required for a liquid crystal display. The polymerizable compound can also be used to prepare a film having a cholesteric structure. In particular, a polymerizable liquid crystal compound having a low refractive index anisotropy (Δn) is useful as a material for a film having a cholesteric phase having a narrow selective reflection wavelength width. In many cases, two or more types of polymerizable properties to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, film transparency, mechanical strength, surface hardness, heat resistance and light resistance. A composition consisting of a compound is used. At that time, the polymerizable compound used is required to bring good physical properties to the composition without adversely affecting other properties. In particular, when the purpose is to produce a film having a cholesteric structure, a polymerizable compound that can exist as a nematic phase or a cholesteric phase in a wide temperature range and has a high nematic phase or a cholesteric phase liquid crystal orientation is required.

When a polymerizable composition containing a polymerizable compound is used as an optical film material for a display or the like, when the polymerizable composition is applied to a substrate, liquid crystal phase orientation is induced in a short time and there are few orientation defects. Is preferable. Further, from the viewpoint of the process, it is preferable that the polymerizable composition has high storage stability without precipitating the polymerizable composition in the components even if the polymerizable composition is stored for a long period of time. However, conventionally known compounds have a problem that precipitation occurs when they are added to a polymerizable composition and stored for a long period of time, and from the time when the polymerizable composition is applied to a substrate until the liquid crystal phase orientation is induced. There was a problem that it took a long time and a problem that many alignment defects occurred (Patent Documents 1 to 4). When a film is produced using a polymerizable composition containing such a polymerizable compound, an additional step for redissolving the precipitate is required, or a step for inducing liquid crystal phase orientation. There is a problem that it is necessary to lengthen the time and that many orientation defects occur. Therefore, there has been a demand for the development of a polymerizable compound that can solve such a problem.

Publication No. KR10-2015-0037580 Japanese Unexamined Patent Publication No. 2005-035985 Japanese Unexamined Patent Publication No. 2011-246365 Japanese Unexamined Patent Publication No. 2010-270108

Recueil des Travaux Chemistries des Pays-Bas Magazine, 1996, Vol. 115, No. 6, pp. 321-328

The problem to be solved by the present invention is that it has high storage stability when added to a solution containing a polymerizable composition, and when the polymerizable composition is applied to a substrate, liquid crystal phase orientation is induced in a short time. It is an object of the present invention to provide a polymerizable composition having few orientation defects. Further, it is to provide a polymer obtained by polymerizing the polymerizable composition and an optically anisotropic substance using the polymer.

As a result of diligent research to solve the above problems, the present inventors have developed a polymerizable compound having a mesogen group containing a specific partial structure. That is, the present invention provides a compound represented by the general formula (I), a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, and an adhesive. Agents, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, mechanical parts, Provided are pesticides and foods, products using them, polymerizable liquid crystal compositions, polymers obtained by polymerizing the polymerizable liquid crystal compositions, and optically isomers using the polymers.

The compound of the present invention has high storage stability when added to a polymerizable composition containing other polymerizable compounds, and when the polymerizable composition is applied to a substrate, the liquid crystal phase orientation occurs in a short time. Since it is induced and has few orientation defects, it is useful as a constituent member of a polymerizable composition. Further, the polymerizable composition is useful for applications of optical materials such as retardation films and selective reflection films.

The present invention provides a compound having a specific structure, and a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, a pressure-sensitive adhesive, an oil, an ink, and the like. Pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, mechanical parts, pesticides and foods, and their products. Provided are a product used, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optical variant using the polymer.

The compound of the present invention is represented by the following general formula (I).

(In the formula, P ¹ represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization.
Sp ¹ represents a spacer group, but when there are a plurality of Sp ¹ , they may be the same or different.
X ¹ is -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -,- CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -,- CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH- , -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but if there are multiple X ¹ , they are the same but different. May be
k1 represents an integer from 0 to 10
A ¹ and A ² are independently expressed from the following equations (A-1) to (A-9).

Represents a group selected from (in the formula, these groups are unsubstituted or may be substituted with one or more substituents L).
L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyanogroup, or one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -O-, -S-,-, respectively. 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-, -CH = CH-, -CF = CF- or -C≡C- may be substituted carbon atoms. Representing a linear or branched alkyl group of number 1 to 20, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or ^{L is PL-(Sp L - XL} ). A group represented by _kL − may be represented, where PL represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, Sp ^L represents a spacer group or a single bond, but ^there are a plurality of Sp ^L. If so, they may be the same or different, and XL is -O-, -S-, ^-OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-,-. CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, When a plurality of ^XLs are present, they may be the same or different (however, ^{PL- (Sp L -} XL) ^kL- does not include an —O— bond), and _kL is Represents an integer from 0 to 10, and if there are multiple Ls in the compound, they are different even if they are the same. You may have.
B ¹ is from the following equation (B-1) to equation (B-15).

(In the formula, these groups may be unsubstituted or substituted with one or more of the above substituents L, where ^LB is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosul. Franyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, the above-mentioned substituents. A phenyl group optionally substituted with L, a benzyloxycarbonyl group substituted with at least one of the above substituents L, a 2-phenylethyloxycarbonyl group optionally substituted with the above substituent L, one -CH ₂ -Ga-S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR ^0- , -NR ⁰ -CO -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -N = N-, -CR ⁰ = N-, -N = It may be substituted with CR ^0- , -CH = CH-, -CF = CF- or -C≡C- (in the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). , An alkyl group having 2 carbon atoms in which any hydrogen atom in the group may be replaced with a fluorine atom, or one -CH _2- or two or more non-adjacent-CH ₂ -are independent of each other. -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR ⁰ -,- NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -N = N-, -CR ⁰ = N- , -N = CR ^0- , -CH = CH-, -CF = CF- or -C≡C- (in the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). Represents a linear, branched or cyclic alkyl group having 3 to 20 carbon atoms which may be used, although any hydrogen atom in the linear, branched or cyclic alkyl group having 3 to 20 carbon atoms may be used. It may be substituted with a fluorine atom, or ^LB may represent a group represented by P LB-(Sp ^LB -X ^LB ) _kLB ^- where P ^LB is radical polymerization, cationic polymerization or anion polymerization. Represents a group polymerized by, Sp ^LB represents a spacer group or a single bond, but S When there are multiple p ^LBs , they may be the same or different, and the X ^LBs are -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH- , -COO-CH ₂ CH _2- , -OCO-CH _{2 CH 2-, -CH 2 CH 2-COO-, -CH 2 CH 2 -- OCO- ,} -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C≡C- or simply It represents a bond, but if there are multiple X ^LBs , they may be the same or different, and kLB represents an integer from 0 to 10. ) Represents a group selected from
Z ¹ and Z ² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH- COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -OCO-CH _2- , -CH ₂ -COO-, -CH = CH-, -N = N-, -CH = N-, -N = CH- , -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond,
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one -CH _2- or adjacent to each other. Not two or more -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO Linear or linear with 1 to 20 carbon atoms which may be substituted by -O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- Representing a branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is a group represented by-(X2 ^- Sp2) _k2 ^- P2 ⁽ In the formula, P ² represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ² represents a spacer group, but when a plurality of Sp ² are present, they may be the same or different. X ² is -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -,- CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -,- CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH- , -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but if there are multiple X2s, ^they are the same but different. It may be, and k2 represents an integer from 0 to 10), but does not include an —O— bond in the general formula. ).

In the general formula (I), P ¹ and the existing P ² each independently represent a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and each of them independently represents a formula (P-1) from the following formula (P-1). P-20)

It is preferable to represent a group selected from. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), the formula (P-2), the formula (P-3), the formula (P-4), the formula (P-5), and the formula (P) are used. -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) is preferable, and formula (P-1), formula (P-2), formula (P-2). P-3), formula (P-8), formula (P-11) or formula (P-13) is more preferable, and formula (P-1), formula (P-2) or formula (P-3) is Further preferable, the formula (P-1) or the formula (P-2) is particularly preferable.

In the general formula (I), Sp ¹ and existing Sp ² each independently represent a spacer group, but when a plurality of Sp ^1s are present, they may be the same or different, and there are a plurality of Sp ^2s . If so, they may be the same or different. From the viewpoint of liquidity, availability of raw materials, and ease of synthesis, Sp ¹ and existing Sp ² may be the same or different when there are a plurality of them, and each of them is independently one-. CH ₂ -or two or more non-adjacent-CH ₂ -s are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO. -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O- , -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-,- COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH ₂ -,- Replaced by CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF- or -C≡C- It is preferable to represent an alkylene group having 1 to 20 carbon atoms, and Sp ¹ and Sp ² existing may be the same or different when a plurality of Sp 1 are present, and each of them is independently one-. CH ₂ -or two or more non-adjacent-CH ₂ -s are independently -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO- It is more preferable to represent an alkylene group having 1 to 20 carbon atoms which may be replaced with -CH = CH- or -C≡C-, and Sp ¹ and Sp ² existing are the same when there are a plurality of them. They may be present or different, and each independently has one -CH _2- or two or more non-adjacent-CH ₂ -s independently of -O-, -COO-, -OCO- or. It is more preferable to represent a linear alkylene group having 1 to 20 carbon atoms which may be replaced with —OCO—O—, and Sp ¹ and Sp 2 existing may be the same or different when a plurality of Sp ² are present. 1 to 12 carbon atoms, each of which may be independently replaced by one -CH _2- or two or more non-adjacent-CH _2- , each of which may be independently replaced by -O-. It is even more preferable to represent a linear alkylene group, and Sp ¹ and Sp ² existing may be the same when a plurality of Sp 1 are present. It may be different, and it is particularly preferable that each of them independently represents a linear alkylene group having 1 to 12 carbon atoms.

In the general formula (I), X ¹ and the existing X ² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, respectively. -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-,- OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO- CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond. , When there are a plurality of X ¹ , they may be the same or different, and when there are a plurality of X ² , they may be the same or different. From the viewpoint of availability of raw materials and ease of synthesis, X ¹ that directly binds to A ¹ among X ¹ and X ² that directly binds to A ² among existing X ² are independent of each other. OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or single bond is preferable, and each independently represents -OCH. _2- , -CH ₂ O-, -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO- or -CH ₂ CH _2- It is more preferable to represent OCO-, and it is more preferable to represent -OCH _2- , -CH ₂ O-, -COO- or -OCO-, respectively, and each independently represents -COO- or -OCO-. It is particularly preferable to represent it.

Further, from the viewpoint of easy availability of raw materials and ease of synthesis, X ^{1 of X 1 which} is not directly bonded to A ¹ and X ² of existing X ² which is not directly bonded to A ² are , If there are multiple, they may be the same or different, and they are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -COO-, -OCO-,-. CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -,- CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or single bond is preferred, and each independently represents -O-, -OCH _2- , -CH ₂ O-, -COO-, -OCO. -, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO- or a single bond is more preferable, and each of them is independent. It is even more preferable to represent -O-, -COO-, -OCO- or a single bond, even more preferably to represent -O- or a single bond independently, and particularly preferably to represent -O-.

In the general formula (I), k1 and existing k2 each independently represent an integer of 0 to 10, but from the viewpoint of ease of synthesis and liquid crystallinity, each of them may independently represent an integer of 0 to 5. It is more preferable to represent an integer of 0 to 2 independently, and it is further preferable to represent 0 or 1 independently, respectively, and each represents 1 from the viewpoint of low curing shrinkage when formed into a film. Is particularly preferred.
However, in the general formula (I), P1- (Sp ¹ -X ¹ ) _k1- and existing- (X2 ^{-Sp 2 )} _k2 ^{-P 2 do} not include an -O-O- bond.

In the general formula (I), A ¹ and A ² are independently unsubstituted or may be substituted with one or more substituents L from the following formula (A-1) to formula (A-9). )

Represents a group selected from. From the viewpoint of availability of raw materials, ease of synthesis, liquidity, storage stability, liquid crystal phase orientation and orientation defects, the above may be unsubstituted or substituted with one or more substituents L. The above formula (A-1) preferably represents a group selected from the formula (A-1) to the formula (A-7) and may be unsubstituted or substituted with one or more substituents L. It is more preferable to represent a group selected from the formula (A-6) from the above formula (A-1) or the above formula (A-) which is unsubstituted or may be substituted with one or more substituents L. It is more preferable to represent a group selected from 2), and further to represent a group represented by the above formula (A-1) which is unsubstituted or may be substituted with one or more substituents L. More preferably (here, the preferred group of the substituent L is the same as the preferred group adopted by the following substituent L), and in particular, it represents an unsubstituted group represented by the above formula (A-1). preferable.

In the general formula (I), the substituent L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group and a methylamino group. A group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyanogroup, or one -CH _2- or two or more non-adjacent-CH ₂ -independently. -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-, -CH = CH-, -CF = CF- or -C≡C Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with −, but any hydrogen atom in the alkyl group may be substituted with a fluorine atom or a substituent L. May represent a group represented by P ^L- (Sp ^L -XL) _kL- , but if a plurality of substituents ^L are present in the compound, they may be the same or different. From the viewpoint of liquidity and ease of synthesis, the substituent L is a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or any arbitrary group. The hydrogen atom may be replaced with a fluorine atom, and one -CH _2- or two or more non-adjacent-CH ₂ -s are independently -O-, -S-, -CO-,-, respectively. COO-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- may be substituted with a group having 1 to 20 carbon atoms. It preferably represents a linear or branched alkyl group, where the substituent L may be substituted with a fluorine atom, a chlorine atom, or any hydrogen atom with a fluorine atom, and one -CH _2- or adjacent to it. Two or more -CH _2- that are not present may be independently substituted with a group selected from -O-, -COO- or -OCO- in a linear or branched form having 1 to 12 carbon atoms. It is more preferable to represent an alkyl group, in which the substituent L is a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted with a fluorine atom. It is more preferable to represent an alkoxy group, and it is particularly preferable that the substituent L represents a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms. Further, the substituent ^L may represent a group represented by PL- (Sp ^L -XL) _kL- , but the preferred structures of ^{P L} , Sp ^L , ^XL and kL are P ¹ , Sp, respectively. ¹ , ^X1 and k1 are similar to the preferred structures.

In the general formula (I), B ¹ may be unsubstituted or substituted with one or more of the above substituents L from the following formulas (B-1) to formulas (B-15).

Represents a group selected from. Unsubstituted or by one or more of the above substituents L in terms of availability of raw materials, ease of synthesis, liquidity, refractive index anisotropy, storage stability, liquid crystal phase orientation and orientation defects. May be substituted It is preferable to represent a group selected from the above formula (B-1) to the above formula (B-12), and it may be unsubstituted or substituted with one or more of the above substituents L. It is more preferable to represent a group selected from the above formula (B-1) to the above formula (B-5), and the above formula (which may be unsubstituted or substituted by one or more of the above substituents L). It is more preferable to represent a group selected from the formula (B-3) or the formula (B-5) from B-1), and the above may be unsubstituted or substituted with one or more of the above substituents L. It is even more preferable to represent a group selected from the above formula (B-1) or formula (B-2) of the above, and to represent an unsubstituted group selected from the above formula (B-1) or formula (B-2). Is particularly preferred.

In the above formulas (B-1) and ( ^B -2), LB is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group and an isocyano group. , Amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, phenyl group which may be substituted with the above-mentioned substituent L, at least 1 A benzyloxycarbonyl group substituted with the above substituent L, a 2-phenylethyloxycarbonyl group optionally substituted with the above substituent L, and one -CH _2- is -S-, -CO-, -COO. -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR ^0- , -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ^0- , -CH = CH-, -CF = CF- or -C≡C- (in the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) may be substituted, and any hydrogen atom in the group becomes a fluorine atom. Alkyl groups having 2 carbon atoms which may be substituted, or one -CH _2- or two or more non-adjacent -CH _2- are independently -O-, -S-, -CO. -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR ^0- , -NR ⁰ -CO-, -CH = CH-COO -, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ^0- , -CH = CH -, -CF = CF- or -C≡C- (in the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) may be substituted with 3 to 20 carbon atoms. Representing a chain, branched or cyclic alkyl group, any hydrogen atom in the linear, branched or cyclic alkyl group having 3 to 20 carbon atoms may be substituted with a fluorine atom or L. ^B represents a group represented by P _LB- (Sp ^LB -X ^LB ) ^kLB- . From the viewpoints of availability of raw materials, ease of synthesis, liquidity, refractive index anisotropy, storage stability, liquid crystal phase orientation and orientation defects, ^LB is a fluorine atom, chlorine atom, bromine atom, iodine atom, Pentafluorosulfuranyl group, nitro group, cyano group, dimethylamino group, diethylamino group, diisopropylamino group, phenyl group which may be substituted with the above-mentioned substituent L, or 2-phenyl which may be substituted with the above-mentioned substituent L. Ethyloxycarbonyl group, one -CH _2- is -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-,- CO-NR ^0- , -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -N = N- , -CR ⁰ = N-, -N = CR ^0- , -CH = CH-, -CF = CF- or -C≡C- (In the formula, R ⁰ is a hydrogen atom or an alkyl having 1 to 8 carbon atoms. It may be substituted with (representing a group), and any hydrogen atom in the group may be substituted with a fluorine atom. An alkyl group having 2 carbon atoms, or one -CH _2- or not adjacent to each other. Two or more -CH _2- are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO- O-, -CO-NR ^0- , -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-,- N = N-, -CR ⁰ = N-, -N = CR ^0- , -CH = CH-, -CF = CF- or -C≡C- (In the formula, R ⁰ is a hydrogen atom or 1 carbon atom. A linear, branched or cyclic alkyl group having 3 to 20 carbon atoms which may be substituted with (representing an alkyl group of 8 to 8) and any hydrogen atom in the group may be substituted with a fluorine atom. It is preferable to represent LB as a fluorine atom, a chlorine atom, a nitro group, a cyano group, a phenyl group which may be substituted with the above ^- mentioned substituent L, and one -CH _2- is -CO-, -COO-,-. OCO-, -O-CO-O-, -CO-NR ^0- , -NR ⁰ -CO-, -CH = CH-COO-, -OCO-CH = CH-, -CR ⁰ = N-, -N = CR ^0- , -CH = CH-, -CF = CF- or -C≡C- (in the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). Well, any hydrogen atom in the group Alkyl groups with 2 carbon atoms that may be substituted with fluorine atoms, or one -CH _2- or two or more non-adjacent -CH _2- are independently -O-, -CO-, respectively. , -COO-, -OCO-, -O-CO-O-, -CO-NR ^0- , -NR ⁰ -CO-, -CH = CH-COO-, -OCO-CH = CH-, -CR ⁰ = N-, -N = CR ^0- , -CH = CH-, -CF = CF- or -C≡C- (in the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) May be substituted, and any hydrogen atom in the group may be substituted with a fluorine atom. It is more preferable to represent a linear, branched or cyclic alkyl group alkyl group having 3 to 20 carbon atoms. LB is a fluorine atom, a chlorine atom, a nitro group, a cyano group, a phenyl group which may be substituted with the above ^- mentioned substituent L, a linear or branched alkyl group having 13 to 20 carbon atoms, and 6 to 19 carbon atoms. Linear or branched alkoxy group, one -CH _2- is -CO-, -COO-, -OCO-, -O-CO-O-, -CO-NR ^0- , -NR ⁰ -CO -, -CH = CH-COO-, -OCO-CH = CH-, -CR ⁰ = N-, -N = CR ^0- , -CH = CH-, -CF = CF- or -C≡C- ( In the formula, ^R0 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and in addition, one non-adjacent to _—CH2- substituted by the group. -CH ₂ -or two or more non-adjacent -CH _2- may be substituted with -O-, and any hydrogen atom in the group may be substituted with a fluorine atom, starting from 2 carbon atoms. It is more preferable to represent 20 linear or branched alkyl groups, wherein LB is a fluorine atom, a chlorine atom, a nitro group, a cyano group, a phenyl group which may be substituted with the above ^- mentioned substituent L, and 13 carbon atoms. 20 linear or branched alkyl groups, linear or branched alkoxy groups with 6 to 19 carbon atoms, one -CH _2- is -CO-, -COO-, -OCO-, -CO- Substituted by NR ^0- , -NR ⁰ -CO-, -CR ⁰ = N- or -N = CR ^0- (in the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). In addition, one -CH _2- or two or more non-adjacent -CH _2- may be substituted with -O-, and any hydrogen atom in the group is substituted with a fluorine atom. It is even more preferable to represent a linear or branched alkyl group having 2 to 20 carbon atoms, in which ^LB is a fluorine atom, a cyano group, a phenyl group, and one -CH _2- is -CO-. , -COO-, -OCO-, -CO-NR ^0- , -NR ⁰ -CO-, -CR ⁰ = N- or -N = CR ^0- (In the formula, R ⁰ is a hydrogen atom or 1 carbon atom. Represents an alkyl group from 8 to 8), plus one -CH _2- or adjacent. It is particularly preferred to represent a linear or branched alkyl group having 2 to 10 carbon atoms, wherein no two or more -CH _2- may be substituted with -O-.

Among the groups represented by B ¹ in the general formula (I), the groups represented by the above formula (B-1) are more specifically represented by the following formulas (B-1-1) to the formulas (B-1-1). B-1-11)

(In the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³¹ is represented by one -CH _2- or two or more non-adjacent-CH _2- by -O-. It represents a linear or branched alkyl group having 1 to 20 carbon atoms, which may be substituted or any hydrogen atom in the group may be substituted with a fluorine atom, where R ³² is a hydrogen atom and one. -CH ₂ -or two or more non-adjacent -CH _2- may be substituted with -O-, and any hydrogen atom in the group may be substituted with a fluorine atom, starting from 1 carbon atom. It is preferable to represent a group selected from 20 linear or branched alkyl groups), and among the groups represented by B1 in the general formula ( ^I ), the above formula (B-2) is used. More specifically, the following formulas (B-2-1) to formulas (B-2-9) are used as the bases.

(In the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³¹ is represented by one -CH _2- or two or more non-adjacent-CH _2- by -O-. It represents a linear or branched alkyl group having 1 to 20 carbon atoms, which may be substituted or any hydrogen atom in the group may be substituted with a fluorine atom, where R ³² is a hydrogen atom and one. -CH ₂ -or two or more non-adjacent -CH _2- may be substituted with -O-, and any hydrogen atom in the group may be substituted with a fluorine atom, starting from 1 carbon atom. It is preferable to represent a group selected from 20 linear or branched alkyl groups).

In the general formula (I), Z ¹ and Z ² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, respectively. , -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-,- NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -OCO-CH _2- , -CH ₂ -COO-, -CH = CH-, -N = N-, -CH = N -, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond. From the viewpoint of liquidity, availability of raw materials, and ease of synthesis, Z ¹ and Z ² are independently -OCH _2- , -CH ₂ O-, -COO-, -OCO-, and -CF ₂ O, respectively. -, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -CH = CH-, -CF = CF- , -C≡C- or a single bond, preferably -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH ₂ -, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ --OCO-, -CH = CH-, -C≡C- or It is more preferred to represent a single bond, more preferably -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- or -OCH. _2- , -CH ₂ O-, -COO-, -OCO- or a single bond is even more preferred, and -COO- or -OCO- is particularly preferred.

In the general formula (I), R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one-. CH ₂ -or two or more non-adjacent-CH ₂ -are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S- Number of carbon atoms 1 which may be substituted by CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- Represents a linear or branched alkyl group from 20 to 20, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is-(X2-Sp ² ) _k2 ^- P. Represents a group represented by ² . When emphasizing the flexibility of a film, R ² preferably represents a group other ^than the group represented by-(X2 ^- Sp2) _k2 ^- P2, and the mechanical strength of the film is determined. When emphasizing, it is preferable that R ² represents a group represented by − (X2 ^- Sp ² ) _k2 -P ² .

When R ² represents a group other than the group represented by-(X ² -Sp ² ) _k2 -P ² , R ² is a hydrogen atom, a fluorine atom, a chlorine atom, from the viewpoint of liquidity and ease of synthesis. A cyano group, or one -CH _2- or two or more non-adjacent -CH _2- , respectively, independently -O-, -CO-, -COO-, -OCO-, -O-CO. Linear or branched with 1 to 12 carbon atoms which may be substituted by -O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- It is preferable to represent an alkyl group, in which R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or one -CH _2- or two or more non-adjacent-CH ₂ -independently -O-. , -CO-, -COO-, -OCO- or -O-CO-O- may be substituted to represent a linear or branched alkyl group having 1 to 12 carbon atoms, where R ² is hydrogen. It is more preferable to represent an atom, a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 12 carbon atoms, and ^R2 is a linear alkyl group or a linear group having 1 to 12 carbon atoms. It is particularly preferred to represent an alkoxy group.
Further, when R ² represents a group represented by-(X ² -Sp ² ) _k2 -P ² , the preferable structures of P ² , Sp ² , X ² and k 2 are P ¹ , Sp ¹ , X, respectively. It is the same as the preferable structure adopted by ¹ and k1.

Examples of the compound represented by the general formula (I) include the following general formula (Ii).

(In the formula, P ¹ , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k1, k2, A ¹ , A ² , B ¹ , Z ¹ and Z ² are P ¹ in the general formula (I), respectively. , P ² , Sp ¹ , Sp ² , X ¹ , X ² , k1, k2, A ¹ , A ² , B ¹ , Z ¹ and Z ² ) are preferable. General formula (I-i-i)

(In the formula, P ¹ , P ² , Sp ¹ , Sp ² , A ¹ , A ² , B ¹ , Z ¹ and Z ² are P ¹ , P ² , Sp ¹ , Sp ² and Sp 2 in the general formula (I), respectively. Compounds represented by A ¹ , A ² , B ¹ , Z ¹ and Z ² ) are more preferable, and the following general formula (I-i-i) is used.

(In the formula, P ¹ , P ² , Sp ¹ and Sp ² have the same meanings as P ¹ , P ² , Sp ¹ and Sp ² in the general formula (I), respectively, and B ¹¹ is unsubstituted or 1 Representing a group selected from the above formula (B-1) to the formula (B-5) which may be substituted by one or more substituents L, Z ¹¹ and Z ²¹ are independently -OCH ₂ -,-, respectively. A compound represented by CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- or a single bond) is more preferable, and the following general formula (I-i-i-) is more preferable. i-i) or general formula (I-i-i-ii)

(In the formula, P ¹ , P ² , Sp ¹ and Sp ² have the same meanings as P ¹ , P ² , Sp ¹ and Sp ² in the general formula (I), respectively, and B ¹¹ is unsubstituted or 1 The compound represented by the above formula (B-1) to the group selected from the formula (B-5) which may be substituted by one or more substituents L is further preferable, and the following general formula (representing a group) is further preferable. From I-i-i-i-i) to the general formula (I-i-i-i-ix)

(In the formula, P ¹ , P ² , Sp ¹ , Sp ² and L have the same meanings as P ¹ , P ² , Sp 1, ^{Sp 2} and L in the general formula (I), respectively, and LB ¹ is a fluorine atom. A chlorine atom, a nitro group, a cyano group, a phenyl group which may be substituted by the above-mentioned substituent L, a linear or branched alkyl group having 13 to 20 carbon atoms, and a linear or branched group having 6 to 19 carbon atoms. Alkoxy group, one -CH _2- is -CO-, -COO-, -OCO-, -CO-NR ^0- , -NR ⁰ -CO-, -CR ⁰ = N- or -N = CR ⁰ -(In the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and in addition, one -CH _2- or two or more non-adjacent- CH _2- represents a linear or branched alkyl group having 2 to 20 carbon atoms, wherein —O— may be substituted and any hydrogen atom in the group may be substituted with a fluorine atom.) The compound represented by is even more preferable.

The compounds represented by the general formulas (I-i-i-i-i) to the general formula (I-i-i-i-iv) are described in the following general formula (I-i-i). -I-i-i-1) to the general formula (I-i-i-i-iv-2)

(In the formula, P ¹ , P ² , Sp ¹ , Sp ² and L have the same meanings as P ¹ , P ² , Sp ¹ , Sp ² and L in the general formula (I), respectively, and R ⁰ is a hydrogen atom or Representing an alkyl group having 1 to 8 carbon atoms, R ³¹ may be substituted with one -CH _2- or two or more non-adjacent -CH _2- by -O-, and is arbitrary in the group. Represents a linear or branched alkyl group with 1 to 20 carbon atoms in which the hydrogen atom of is optionally substituted with a fluorine atom, where R ³² is a hydrogen atom, one -CH _2- or non-adjacent 2 A linear or branched alkyl group having 1 to 20 carbon atoms, in which more than one -CH _2- may be substituted with -O-- and any hydrogen atom in the group may be substituted with a fluorine atom. The compound represented by the above-mentioned general formula (Ii-i-i-i-vi), general formula (I-i-i-i-vii), general formula (I-). The compound represented by i-i-i-viii) or the general formula (I-i-i-i-ix) is particularly preferable.

In the compound represented by the general formula (I-i-i-i-ix) from the general formula (I-i-i-i-i-1), the general formula (I-i-i) is used. The compounds represented by the general formulas (I-i-i-i-iv-2) from -i-i-i-1) are more preferable, and the compounds represented by the general formula (I-i-i-i-i) are more preferable. The compounds represented by the general formulas (I-i-i-i-i-9) from -1) are more preferable, and the general formulas (I-i-i-i-i-5) and general formulas are more preferable. Compounds represented by (I-i-i-i-i-6) and the general formula (I-i-i-i-i-9) are even more preferable, and the general formula (I-i-) is even more preferable. The compounds represented by i-i-i-5) and the general formula (I-i-i-i-i-6) are particularly preferable.

From the viewpoint of liquid crystallinity, 1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl contained in the compound represented by the general formula (I). The group, tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group may be either only one of the cis form and the trans form, or a mixture of both, but liquid crystallinity. From the viewpoint of the above, it is preferable that the trans form is the main component, and it is particularly preferable that the trans form is the only component.

Specifically, as the compound represented by the general formula (I), the compounds represented by the following formulas (I-1) to (I-80) are preferable.

The compound of the present invention can be produced by the following production method.
(Manufacturing method 1) Production of a compound represented by the following formula (S-10)

(In the formula, P ¹ , P ² , Sp ¹ , Sp ² and LB have the same meanings as ^{P 1} , ^{P 2} , Sp ¹ , Sp ² and LB in the general formula (I), respectively, and PG is a protecting group. And hallogen represents a halogen atom or a halogen equivalent.)
The carboxyl group of the compound represented by the formula (S-1) is protected by a protecting group (PG). The protecting group (PG) is not particularly limited as long as it can stably protect up to the deprotection step. Protecting groups (PGs) listed in WUTS, THEODORA W. GREENE, John Wiley & Sons, Inc., Publication) and the like are preferred. Specific examples of the protecting group include a tetrahydropyranyl group, a tert-butyl group, a methoxymethyl group, an ethoxymethyl group, a methyl group, an ethyl group, a benzyl group and the like.

The protecting group (PG) of the compound represented by the formula (S-2) is deprotected. The deprotection reaction conditions are not particularly limited as long as they give the compound represented by the formula (S-3), but those listed in the above-mentioned documents are preferable. It is also possible to obtain the compound represented by the formula (S-3) by protecting only one carboxyl group of the compound represented by the formula (S-1) with a protecting group (PG).

By reacting the compound represented by the formula (S-3) with the compound represented by the formula (S-4) in the presence of a base, the compound represented by the formula (S-5) can be obtained. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

The protecting group (PG) of the compound represented by the formula (S-5) is deprotected. The deprotection reaction conditions are not particularly limited as long as they give a compound represented by the formula (S-6), but those listed in the above-mentioned documents are preferable.

By reacting the compound represented by the formula (S-6) with the compound represented by the formula (S-7), the compound represented by the formula (S-8) can be obtained. As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-6) is represented by an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride, and then represented by the general formula (S-7). Examples thereof include a method of reacting with a compound in the presence of a base. When a condensing agent is used, examples of the condensing agent include N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the base include triethylamine, diisopropylethylamine and the like.

A compound represented by the formula (S-10) by reacting the compound represented by the formula (S-8) with the compound represented by the formula (S-9) by the same method as the method of the previous step. Can be obtained.
(Manufacturing method 2) Production of a compound represented by the following formula (S-17)

The carboxyl group of the compound represented by the formula (S-11) is reduced. The conditions for the reduction reaction are not particularly limited as long as they give the compound represented by the formula (S-12), and examples thereof include a borane-tetrahydrofuran complex.

By reacting the compound represented by the formula (S-12) with the compound represented by the formula (S-13), the compound represented by the formula (S-14) can be obtained. Examples of the reaction conditions include the Mitsunobu reaction. Alternatively, the hydroxyl group of the compound represented by the formula (S-12) is changed to a methane sulfoxy group, a p-toluene sulfoxy group, or the like, and then reacted with the compound represented by the formula (S-13) in the presence of a base. It is also possible to make it. Examples of the base include potassium carbonate, cesium carbonate, potassium phosphate and the like.

The protecting group (PG) of the compound represented by the formula (S-14) is deprotected. The deprotection reaction conditions are not particularly limited as long as they give a compound represented by the formula (S-15), but those listed in the above-mentioned documents are preferable.

By reacting the compound represented by the formula (S-15) with the compound represented by the formula (S-16) in the presence of a base, the compound represented by the formula (S-17) can be obtained. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

Reaction conditions other than those described in each step of manufacturing method 1 and manufacturing method 2 include, for example, an experimental chemistry course (edited by the Japan Chemistry Society, published by Maruzen Co., Ltd.), Organic Synthesis (John Wiley & Sons, Inc., Publication), Belstein 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，Ｉｎｃ．）等の文献に記載の条件又はＳｃｉＦｉｎｄｅｒ（ Conditions provided by an online search service such as Chemical Abstracts Service, American Chemical Society) or Reagents (Elsevier Ltd.) can be mentioned.

Further, a reaction solvent can be appropriately used in each step. The solvent is not limited as long as it gives the desired compound, but for example, isopropyl alcohol, ethylene glycol, methanol, ethanol, chloroform, dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N, N-dimethylformamide, N. , N-dimethylacetamide, dimethylsulfoxide, diethyl ether, ethylene glycol monoethyl ether, xylene, ethyl acetate, 1,4-dioxane, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, toluene, hexane, cyclohexane, heptane, methyl Examples thereof include isobutyl ketone, tert-butyl methyl ether and methyl ethyl ketone. When the reaction is carried out in a two-phase system of an organic solvent and water, it is also possible to add a phase transfer catalyst. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, polyoxyethylene (20) sorbitan monolaurate [Tween 20], sorbitan monooleate [Span 80] and the like.

In addition, purification can be performed as needed in each step. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purifying agent, silica gel, alumina, activated charcoal, activated clay, cellite, zeolite, mesoporous silica, carbon nanotubes, carbon nanohorn, Bicho charcoal, charcoal, graphene, ion exchange resin, acidic clay, silicon dioxide, diatomaceous earth, Examples include pearlite, cellulose, organic polymers, porous gels and the like.

The compound of the present invention is preferably used in a nematic liquid crystal composition, a smectic liquid crystal composition, a chiral smectic liquid crystal composition and a cholesteric liquid crystal composition, and particularly preferably used in a chiral smectic liquid crystal composition and a cholesteric liquid crystal composition. .. A compound other than the present invention may be added to the liquid crystal composition using the reactive compound of the present invention.

Specific examples of the other polymerizable compound used in combination with the polymerizable compound of the present invention include the general formula (X-11).

And / or general formula (X-12)

(In the formula, P ¹¹ , P ¹² and P ¹³ each independently represent a group polymerized by radical polymerization, cationic polymerization or anion polymerization, and Sp ¹¹ , Sp ¹² and Sp ¹³ are independent single bonds or carbon atoms, respectively. Represents the number 1 to 20 alkylene groups, but replaces one -CH _2- or two or more non-adjacent -CH _2- with -O-, -COO-, -OCO-, -OCOO- X ¹¹ , X ¹² and X ¹³ are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-,-, respectively. CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH ₂ -OCO-, -CH = CH-, -CF = CF-, -C≡C- or single bond, Z ¹¹ and Z ¹² are independently -O-, -S-, respectively. , -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH ₂ CH _2- , -CH ₂ CF _2- , -CF ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-,- COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH ₂ -,- Represents CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond, and A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are independent of each other. Then, 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group As represented, A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are each independently unsubstituted or an alkyl group, an alkyl halide group, an alkoxy group, an alkoxy halide group, a halogen atom, a cyano group or a nitro group. It may be substituted, and R ¹¹ may be a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one-. CH ₂ -or two or more non-adjacent-CH ₂ -s are independently -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- Represents a linear or branched alkyl group with 1 to 20 carbon atoms which may be substituted by CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, where m11 and m12 are 0, Represents 1, 2 or ³ , but if m11 and / or ^m12 represents ² or ³ , the two or three A11, A13, Z11 and / or Z12 are different even if they are the same. May be. ) Is preferable, and the case where P ¹¹ , P ¹² and P ¹³ are an acrylic group or a methacrylic group is particularly preferable. Specifically, as the compound represented by the general formula (X-11), the general formula (X-11a)

(In the formula, W ¹¹ and W ¹² each independently represent a hydrogen atom or a methyl group, Sp ¹⁴ and Sp ¹⁵ are independent alkylene groups having 2 to 18 carbon atoms, and X ¹⁴ and X ¹⁵ are independent, respectively. Then -O-, -COO-, -OCO- or a single bond, Z ¹³ and Z ¹⁴ independently represent -COO- or -OCO-, and A ¹⁵ , A ¹⁶ and A ¹⁷ are independent, respectively. It may be substituted with an unsubstituted or fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched alkoxy group having 1 to 4 carbon atoms1. , 4-Representing a phenylene group) is preferable, and the following formulas (X-11a-1) to (X-11a-4) are preferable.

(In the formula, W ¹¹ , W ¹² , Sp ¹⁴ and Sp ¹⁵ have the same meanings as those in the general formula (X-11a)), and the compound represented by the general formula (X-11a) is particularly preferable. In the above formulas (X-11a-1) to (X-11a-4), compounds in which Sp ¹⁴ and Sp ¹⁵ are independently alkylene groups having 2 to 8 carbon atoms are particularly preferable.

In addition, preferred bifunctional polymerizable compounds include the following general formulas (X-11b-1) to formulas (X-11b-3).

(In the formula, W ¹³ and W ¹⁴ each independently represent a hydrogen atom or a methyl group, and Sp ¹⁶ and Sp ¹⁷ each independently represent an alkylene group having 2 to 18 carbon atoms). Can be mentioned. In the above formulas (X-11b-1) to (X-11b-3), compounds in which Sp ¹⁶ and Sp ¹⁷ are independently alkylene groups having 2 to 8 carbon atoms are particularly preferable.

Further, specifically, as the compound represented by the general formula (X-12), the following general formulas (X-12-1) to formulas (X-12-7) are specifically used.

(In the formula, P ¹⁴ represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ¹⁸ represents a single bond or an alkylene group having 1 to 20 carbon atoms, but one -CH _2- or Two or more non-adjacent -CH _2- may be replaced with -O-, -COO-, -OCO-, -O-CO-O-, and X ¹⁶ is a single bond, -O-,-. COO- or -OCO-, Z ¹⁵ represents a single bond, -COO- or -OCO-, L ¹¹ represents a fluorine atom, a chlorine atom, one -CH _2- or two or more non-adjacent ones. _-CH2- represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be independently replaced with -O-, -COO-, and -OCO-, respectively, and s11 represents 0 to 4. R ¹² represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, and one -CH _2- or two or more non-adjacent -CH ₂ --independently -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-, -CH = CH-, -CF = CF- or -C≡C- Examples thereof include compounds represented by linear or branched alkyl groups having 1 to 20 carbon atoms which may be replaced.

It is also possible to add a polymerizable compound that does not exhibit liquid crystallinity to the polymerizable liquid crystal composition containing the compound of the present invention to the extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples include those described in "Photocuring Technology Data Book, Material Edition (Monomer, Oligomer, Photopolymerization Initiator)" (Kunihiro Ichimura, supervised by Kiyomi Kato, Technonet Co., Ltd.).

Further, the compound of the present invention can be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added depending on the purpose. In that case, the concentration of the photopolymerization initiator is preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, and 0.4% by mass to 8% by mass with respect to the compound of the present invention. % Is more preferable. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like. Specific examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (IRGACURE 907) and benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene]. Amino (IRGACURE OXE 01) and the like can be mentioned. Examples of the thermal polymerization initiator include azo compounds and peroxides. Specific examples of the thermal polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile) and the like. Further, one kind of polymerization initiator may be used, or two or more kinds of polymerization initiators may be used in combination.

Further, a stabilizer may be added to the liquid crystal composition of the present invention in order to improve the storage stability thereof. Examples of the stabilizers that can be used include hydroquinones, hydroquinone monoalkyl ethers, tertiary butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like. Be done. When a stabilizer is used, the amount added is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. From 0.5% by mass is more preferable. Further, one kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specific examples of the stabilizer include formulas (X-13-1) to formulas (X-13-35).

(In the formula, n represents an integer from 0 to 20.) The compound represented by is preferable.

Further, when the polymerizable liquid crystal composition containing the compound of the present invention is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins and the like, Metals, metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixo agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, depending on the purpose. , Ion exchange resin, metal oxides such as titanium oxide, etc. can also be added.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used for various purposes. For example, a polymer obtained by polymerizing a polymerizable liquid crystal composition containing the compound of the present invention without orientation can be used as a light scattering plate, a depolarizing plate, and a moire fringe prevention plate. Further, the polymer obtained by polymerizing after orientation has optical anisotropy and is useful. Such an optical variant is, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth or the like, a substrate on which an organic thin film is formed, or an alignment film obtained by obliquely vapor-depositing SiO ₂ . It can be produced by carrying it on a substrate having it or sandwiching it between the substrates and then polymerizing the polymerizable liquid crystal composition.

Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, printing method and the like. .. Further, at the time of coating, an organic solvent may be added to the polymerizable liquid crystal composition. As the organic solvent, a hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an alcohol solvent, a ketone solvent, an ester solvent, an aprotonic solvent and the like can be used, and for example, a hydrocarbon solvent can be used. The solvent is toluene or hexane, the halogenated hydrocarbon solvent is methylene chloride, the ether solvent is tetrahydrofuran, acetoxy-2-ethoxyethane or propylene glycol monomethyl ether acetate, and the alcohol solvent is methanol, ethanol or Examples of isopropanol include acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone or N-methylpyrrolidinone as the ketone solvent, ethyl acetate or cellosolve as the ester solvent, and dimethylformamide or acetonitrile as the aprotonic solvent. Can be done. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, vacuum drying, and vacuum heating drying can be used. In order to further improve the coatability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide thin film on the substrate is effective for improving the adhesion between the polymer obtained by polymerizing the polymerizable liquid crystal material and the substrate.

Examples of the orientation treatment other than the above include the use of the flow orientation of the liquid crystal material and the use of an electric field or a magnetic field. These alignment means may be used alone or in combination. Further, a photo-alignment method can be used as an orientation treatment method instead of rubbing. As the shape of the substrate, a curved surface may be provided as a constituent portion in addition to the flat plate. The material constituting the substrate can be used regardless of whether it is an organic material or an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyallylate, polysulfone, and triacetyl. Examples thereof include cellulose, cellulose, polyether ether ketone and the like, and examples of the inorganic material include silicon, glass, polystyrene and the like.

When polymerizing a polymerizable liquid crystal composition containing the compound of the present invention, it is desirable that the polymerization proceeds rapidly. Therefore, a method of polymerizing by irradiating with an active energy ray such as ultraviolet rays or an electron beam is preferable. When ultraviolet rays are used, a polarized light source may be used, or a non-polarized light source may be used. Further, when the liquid crystal composition is sandwiched between two substrates for polymerization, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy rays. In addition, after polymerizing only a specific part using a mask during light irradiation, the orientation of the unpolymerized part is changed by changing conditions such as electric field, magnetic field, or temperature, and further irradiation with active energy rays. You may use the means of polymerizing. Further, the temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention is maintained. In particular, when an optical variant is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible, that is, typically at a temperature of 25 ° C. in order to avoid inducing unintended thermal polymerization. It is preferable to let it. The intensity of the active energy ray is preferably 0.1 mW / cm ² to 2 W / cm ² . When the intensity is 0.1 mW / cm ² or less, a large amount of time is required to complete the photopolymerization and the productivity deteriorates, and when the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal There is a risk that the composition will deteriorate.

The optically anisotropic substance obtained by polymerization can also be heat-treated for the purpose of reducing initial characteristic changes and achieving stable characteristic development. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

The optically anisotropic substance produced by such a method may be peeled off from the substrate and used alone, or may be used without peeling. Further, the obtained optically anisotropic bodies may be laminated or bonded to another substrate for use.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Further, "%" in the compositions of the following Examples and Comparative Examples means "mass%". When handling substances that are unstable to oxygen and / or moisture in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. In addition to the operations specifically described below, operations such as quenching, liquid separation / extraction, neutralization, washing, separation, purification, drying, and concentration, which are usually performed among those skilled in the art, are performed as necessary. May be done.
(Example 1) Production of a compound represented by the formula (I-1)

Under a nitrogen atmosphere, 20.0 g of the compound represented by the formula (I-1-1), 8.8 g of tert-butyl alcohol, 1.3 g of N, N-dimethylaminopyridine and 100 mL of dichloromethane were added to the reaction vessel. 16.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 8 hours. The precipitate was removed by filtration and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 20.8 g of the compound represented by the formula (I-1-2).

20.8 g of the compound represented by the formula (I-1-2), 200 mL of methanol and 30 mL of a 25% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was heated and stirred at 60 ° C. After cooling, chloroform was added. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, and the liquid was separated. The organic layer was washed with saline and dried over sodium sulfate. The insoluble material was filtered through cerite, and then the solvent was distilled off and dried to obtain 17.7 g of the compound represented by the formula (I-1-3).

5.0 g of the compound represented by the formula (I-1-3), 4.2 g of the compound represented by the formula (I-1-4), 4.5 g of potassium carbonate, 20 mL of N, N-dimethylformamide in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 8 hours. Diluted with dichloromethane and washed with water. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 6.7 g of the compound represented by the formula (I-1-5).

6.7 g of the compound represented by the formula (I-1-5), 25 mL of dichloromethane and 15 mL of formic acid were added to the reaction vessel, and the mixture was heated at 40 ° C. for 8 hours. After distilling off the solvent, it was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 4.6 g of the compound represented by the formula (I-1-6).

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-1-6), 0.7 g of the compound represented by the formula (I-1-7), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 1.4 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.5 g of the compound represented by the formula (I-1). ..
LCMS: 769 [M + 1]
(Example 2) Production of the compound represented by the formula (I-2)

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-2-1), 0.8 g of the compound represented by the formula (I-2-2), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 1.4 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.9 g of the compound represented by the formula (I-2). ..
LCMS: 785 [M + 1]
(Example 3) Production of the compound represented by the formula (I-3)

5.0 g of the compound represented by the formula (I-3-1), 3.9 g of the compound represented by the formula (I-3-2), 0.1 g of dibutyltin oxide, and toluene in a reaction vessel equipped with a Dean-Stark apparatus. 90 mL was added, and the mixture was heated under reflux for 8 hours while replacing toluene. After distilling off toluene, purification was performed by column chromatography (silica gel, ethyl acetate / hexane) to obtain 6.9 g of the compound represented by the formula (I-3-3).

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-3-4), 1.2 g of the compound represented by the formula (I-3-3), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 1.4 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.8 g of the compound represented by the formula (I-3). ..
LCMS: 873 [M + 1]
(Example 4) Production of the compound represented by the formula (I-4)

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-4-1), 0.5 g of the compound represented by the formula (I-4-2), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 1.4 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 1.7 g of the compound represented by the formula (I-4). ..
LCMS: 733 [M + 1]
(Example 5) Production of the compound represented by the formula (I-5)

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-5-1), 0.9 g of the compound represented by the formula (I-5-2), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 1.4 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.9 g of the compound represented by the formula (I-5). ..
LCMS: 803 [M + 1]
(Example 6) Production of the compound represented by the formula (I-6)

To a reaction vessel equipped with a Dean-Stark apparatus, 15.0 g of the compound represented by the formula (I-6-1), 7.1 g of acrylic acid, 0.8 g of p-toluenesulfonic acid monohydrate, and 150 mL of toluene were added. It was heated to reflux for 8 hours while removing water. After washing with saturated aqueous sodium hydrogen carbonate solution and brine, the solvent was distilled off to obtain 17.8 g of the compound represented by the formula (I-6-2).

3.0 g of the compound represented by the formula (I-6-2), 3.1 g of the compound represented by the formula (I-6-3), 2.8 g of potassium carbonate, 20 mL of N, N-dimethylformamide in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 10 hours. It was diluted with dichloromethane and washed with water and saline. Purification was performed by column chromatography (alumina, dichloromethane / hexane) to obtain 4.5 g of the compound represented by the formula (I-6-4).

4.5 g of the compound represented by the formula (I-6-4), 20 mL of tetrahydrofuran, 20 mL of methanol and 1 mL of concentrated hydrochloric acid were added to the reaction vessel, and the mixture was stirred at room temperature for 7 hours. It was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 3.5 g of the compound represented by the formula (I-6-5).

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-6-5), 1.0 g of the compound represented by the formula (I-6-6), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 1.8 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 1.5 g of the compound represented by the formula (I-6-7).

15.0 g of the compound represented by the formula (I-6-8), 11.9 g of 2-fluoroacrylic acid, 0.8 g of p-toluenesulfonic acid monohydrate, 150 mL of toluene in a reaction vessel equipped with a Dean-Stark apparatus. Was added, and the mixture was heated under reflux for 8 hours while removing water. After washing with saturated aqueous sodium hydrogen carbonate solution and brine, the solvent was distilled off to obtain 18.9 g of the compound represented by the formula (I-6-9).

3.0 g of the compound represented by the formula (I-6-9), 3.5 g of the compound represented by the formula (I-6-10), 3.2 g of potassium carbonate, 20 mL of N, N-dimethylformamide in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 10 hours. It was diluted with dichloromethane and washed with water and saline. Purification was performed by column chromatography (alumina, dichloromethane / hexane) to obtain 5.0 g of the compound represented by the formula (I-6-11).

5.0 g of the compound represented by the formula (I-6-11), 20 mL of tetrahydrofuran, 20 mL of methanol and 1 mL of concentrated hydrochloric acid were added to the reaction vessel, and the mixture was stirred at room temperature for 7 hours. It was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 3.8 g of the compound represented by the formula (I-6-12).

Under a nitrogen atmosphere, 1.5 g of the compound represented by the formula (I-6-7), 1.0 g of the compound represented by the formula (I-6-12), N, N-dimethylaminopyridine 0. 1 g and 20 mL of dichloromethane were added. 0.4 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 1.7 g of the compound represented by the formula (I-6).
LCMS: 821 [M + 1]
(Example 7) Production of the compound represented by the formula (I-7)

10.0 g of the compound represented by the formula (I-7-1), 9.4 g of the compound represented by the formula (I-7-2), 24.1 g of potassium carbonate, 100 mL of N, N-dimethylformamide in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 20 hours. The reaction was cooled and poured into 5% hydrochloric acid. It was extracted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (silica gel, ethyl acetate / hexane) to obtain 6.9 g of the compound represented by the formula (I-7-3).

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-7-3), 3.6 g of the compound represented by the formula (I-7-4), N, N-dimethylaminopyridine 0. 1 g and 20 mL of dichloromethane were added. 1.5 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 3.2 g of the compound represented by the formula (I-7-5).

Under a nitrogen atmosphere, 3.2 g of the compound represented by the formula (I-7-5), 1.1 g of the compound represented by the formula (I-7-6), N, N-dimethylaminopyridine 0. 1 g and 20 mL of dichloromethane were added. 0.8 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 3.4 g of the compound represented by the formula (I-7-7).

3.4 g of the compound represented by the formula (I-7-7), 15 mL of dichloromethane and 10 mL of formic acid were added to the reaction vessel, and the mixture was heated at 40 ° C. for 8 hours. After distilling off the solvent, the obtained solid was washed with water and dried to obtain 2.9 g of the compound represented by the formula (I-7-8).

Under a nitrogen atmosphere, 2.9 g of the compound represented by the formula (I-7-8), 0.5 g of the mixture represented by the formula (I-7-9), N, N-dimethylaminopyridine 0. 1 g and 20 mL of dichloromethane were added. 0.6 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.6 g of the compound represented by the formula (I-7).
LCMS: 909 [M + 1]
(Example 8) Production of the compound represented by the formula (I-8)

To a reaction vessel equipped with a Dean-Stark apparatus, 5.0 g of the compound represented by the formula (I-8-1), 3.9 g of propanol, 0.3 g of p-toluenesulfonic acid monohydrate, and 50 mL of toluene were added, and water was added. Was heated to reflux for 8 hours while removing. Purification was performed by column chromatography (silica gel, ethyl acetate / hexane) to obtain 5.1 g of the compound represented by the formula (I-8-2).

Under a nitrogen atmosphere, 17.7 g of the compound represented by the formula (I-8-3) and 100 mL of tetrahydrofuran were added to the reaction vessel. 103 mL of 0.9 mol / L borane-tetrahydrofuran complex was added dropwise while cooling with ice, and the mixture was stirred for 1 hour. After dropping 5% hydrochloric acid, the mixture was extracted with ethyl acetate and washed with brine. After drying over sodium sulfate and distilling off the solvent, 14.9 g of the compound represented by the formula (I-8-4) was obtained.

Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (I-8-4), 10.1 g of the compound represented by the formula (I-8-5), N, N-dimethylaminopyridine 0. 3 g and 80 mL of dichloromethane were added. 7.1 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 15.4 g of the compound represented by the formula (I-8-6).

15.4 g of the compound represented by the formula (I-8-6), 40 mL of dichloromethane and 40 mL of formic acid were added to the reaction vessel, and the mixture was heated at 40 ° C. for 8 hours. It was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 12.0 g of the compound represented by the formula (I-8-7).

Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-8-2), 5.4 g of the compound represented by the formula (I-8-7), N, N-dimethylaminopyridine 0. 2 g and 50 mL of dichloromethane were added. 2.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 4.1 g of the compound represented by the formula (I-8-8).

Under a nitrogen atmosphere, 4.1 g of the compound represented by the formula (I-8-8), 1.8 g of the compound represented by the formula (I-8-9), N, N-dimethylaminopyridine 0. 1 g and 50 mL of dichloromethane were added. 1.2 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (alumina, dichloromethane) to obtain 4.6 g of the compound represented by the formula (I-8-10).

4.6 g of the compound represented by the formula (I-8-10), 20 mL of tetrahydrofuran, 20 mL of methanol and 1 mL of concentrated hydrochloric acid were added to the reaction vessel, and the mixture was stirred at room temperature for 7 hours. It was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 3.8 g of the compound represented by the formula (I-8-11).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-8-12), 0.2 g of pyridinium p-toluenesulfonate and 30 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 3.8 g of 3,4-dihydro-2H-pyran was added and stirred. After washing with saturated aqueous sodium hydrogen carbonate solution and brine, purification was performed by column chromatography (alumina, dichloromethane) to obtain 7.6 g of the compound represented by the formula (I-8-13).

4.1 g of the compound represented by the formula (I-8-14), 20 mL of tetrahydrofuran and 1.1 g of sodium hydride were added to the reaction vessel, and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 7.6 g of the compound represented by the formula (I-8-13) in 20 mL of tetrahydrofuran was added dropwise, and the mixture was heated and stirred at 50 ° C. for 8 hours. The reaction was poured into ice water and extracted with dichloromethane. Purification was performed by column chromatography (alumina, hexane) to obtain 7.3 g of the compound represented by the formula (I-8-15).

30 mL of formic acid and 30 mL of dichloromethane were added to the reaction vessel, and 15 mL of 35% hydrogen peroxide solution was added dropwise and stirred. A solution prepared by dissolving 7.3 g of the compound represented by the formula (I-8-15) in 20 mL of dichloromethane was added dropwise, and the mixture was heated and stirred at 40 ° C. for 6 hours. After washing with water and brine, purification was performed by column chromatography (alumina, hexane) to obtain 6.1 g of the compound represented by the formula (I-8-16).

6.1 g of the compound represented by the formula (I-8-16), 30 mL of methanol, 30 mL of tetrahydrofuran and 1 mL of concentrated hydrochloric acid were added to the reaction vessel, and the mixture was stirred at room temperature for 5 hours. After diluting with dichloromethane, it was washed with water and saline. Purification was performed by column chromatography (silica gel, dichloromethane / hexane) to obtain 4.0 g of the compound represented by the formula (I-8-17).

Under a nitrogen atmosphere, 3.8 g of the compound represented by the formula (I-8-11), 1.2 g of the compound represented by the formula (I-8-17), N, N-dimethylaminopyridine 0. 1 g and 50 mL of dichloromethane were added. 0.8 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.9 g of the compound represented by the formula (I-8).
LCMS: 885 [M + 1]
(Example 9) Production of the compound represented by the formula (I-9)

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-9-1), 3.3 g of the compound represented by the formula (I-9-2), N, N-dimethylaminopyridine 0. 1 g and 50 mL of dichloromethane were added. 3.5 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 6.3 g of the compound represented by the formula (I-9-3).

6.3 g of the compound represented by the formula (I-9-3), 15 mL of dichloromethane and 10 mL of formic acid were added to the reaction vessel, and the mixture was heated at 40 ° C. for 8 hours. After diluting with ethyl acetate, it was washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 4.7 g of the compound represented by the formula (I-9-4).

Under a nitrogen atmosphere, 4.7 g of the compound represented by the formula (I-9-4), 2.7 g of the compound represented by the formula (I-9-5), N, N-dimethylaminopyridine 0. 1 g and 50 mL of dichloromethane were added. 2.5 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 3.5 g of the compound represented by the formula (I-9-6).

Under a nitrogen atmosphere, 3.5 g of the compound represented by the formula (I-9-6), 1.9 g of the compound represented by the formula (I-9-7), N, N-dimethylaminopyridine 0. 1 g and 50 mL of dichloromethane were added. 1.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 4.3 g of the compound represented by the formula (I-9-8).

4.3 g of the compound represented by the formula (I-9-8), 15 mL of dichloromethane and 10 mL of formic acid were added to the reaction vessel, and the mixture was heated at 40 ° C. for 8 hours. After diluting with ethyl acetate, it was washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) and recrystallization (ethyl acetate / hexane) to obtain 3.5 g of the compound represented by the formula (I-9-9).

Under a nitrogen atmosphere, 3.5 g of the compound represented by the formula (I-9-9), 1.3 g of the compound represented by the formula (I-9-10), N, N-dimethylaminopyridine 0. 1 g and 50 mL of dichloromethane were added. 0.9 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.3 g of the compound represented by the formula (I-9).
LCMS: 775 [M + 1]
(Example 10) Production of the compound represented by the formula (I-10)

Under a nitrogen atmosphere, 14.9 g of the compound represented by the formula (I-10-1), 7.2 g of pyridine, and 150 mL of dichloromethane were added to the reaction vessel. 8.8 g of methanesulfonyl chloride was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 3 hours. It was poured into water and washed sequentially with 5% hydrochloric acid and saline. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) and recrystallization (acetone / hexane) to obtain 16.3 g of the compound represented by the formula (I-10-2).

5.0 g of the compound represented by the formula (I-10-2), 2.5 g of the compound represented by the formula (I-10-3), 7.1 g of potassium carbonate, 70 mL of N, N-dimethylformamide in the reaction vessel. Was added, and the mixture was heated and stirred at 90 ° C. for 15 hours. The reaction was cooled and poured into 5% hydrochloric acid. It was extracted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) and recrystallization (hexane / ethyl acetate) to obtain 2.9 g of the compound represented by the formula (I-10-4).

Under a nitrogen atmosphere, 2.9 g of the compound represented by the formula (I-10-4), 1.7 g of the compound represented by the formula (I-10-5), N, N-dimethylaminopyridine 0. 1 g and 50 mL of dichloromethane were added. 1.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.6 g of the compound represented by the formula (I-10-6).

3.6 g of the compound represented by the formula (I-10-6), 20 mL of dichloromethane and 20 mL of formic acid were added to the reaction vessel, and the mixture was heated at 40 ° C. for 8 hours. After diluting with ethyl acetate, it was washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) and recrystallization (ethyl acetate / hexane) to obtain 2.9 g of the compound represented by the formula (I-10-7).

Under a nitrogen atmosphere, 2.9 g of the compound represented by the formula (I-10-7), 0.9 g of the compound represented by the formula (I-10-8), N, N-dimethylaminopyridine 0. 1 g and 40 mL of dichloromethane were added. 0.9 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. After removing the precipitate by filtration, the filtrate was washed successively with 1% hydrochloric acid, water and saline. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 2.9 g of the compound represented by the formula (I-10).
LCMS: 597 [M + 1]
By combining the same method as described above and a known method, a compound represented by the formula (I-11) to the formula (I-80) was produced.
(Examples 11 to 30, Comparative Examples 1 to 8)
The compounds represented by the formulas (I-1) to (I-10) described in Examples 1 to 10, the compound (R-1) described in Patent Document 1, and the compound (R-) described in Patent Document 2. 2), the compound described in Patent Document 3 (R-3), and the compound described in Patent Document 4 (R-4) were used as the compounds to be evaluated.

Further, the compound (X-1) described in JP-A-2004-175728, the compound (X-2) described in JP-A-2004-231638: 20%, and the compound described in JP-A-2005-179557 A liquid crystal composition composed of (X-3): 45% and compound (X-4): 5% described in JP-A-2004-175728 was designated as a parent liquid crystal display (X).

In order to evaluate the storage stability, a polymerizable liquid crystal composition was prepared by adding the compound to be evaluated to the parent liquid crystal display (X) in 5% increments from 10% to 60% and dissolving by heating at 70 ° C. .. After storing the prepared polymerizable liquid crystal composition at 25 ° C. for 5 weeks, the maximum addition concentration of the compound to be evaluated that does not cause crystal precipitation is shown in the table below.

From the above results, all the compounds represented by the formulas (I-1) to (I-10) of the present invention are compared with the compounds represented by the comparative compounds (R-1) to (R-4). It can be seen that the storage stability is equal to or higher than that.

A polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm by a spin coating method, dried at 100 ° C. for 10 minutes, and then fired at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to a rubbing treatment. The rubbing treatment was performed using a commercially available rubbing device.

11.87% of the parent liquid crystal (X), 7.91% of the compound to be evaluated (40% with respect to the total content of the mother liquid crystal (X) and the compound), photopolymerization initiator Irgacure907 (manufactured by BASF). , 0.20%, 4-methoxyphenol 0.02% and cyclohexanone 80.00% were mixed to prepare a coating liquid. This coating liquid was applied to the rubbed glass substrate using a bar coater (No. 9), and then placed on a hot plate at 100 ° C. to evaporate the solvent. A cholesteric liquid crystal phase was induced with evaporation of the solvent. The orientation rates until the cholesteric liquid crystal phase was induced at that time were compared. When the cholesteric liquid crystal phase was induced almost simultaneously with the evaporation of the solvent, it was marked with ○, when the cholesteric liquid crystal phase was induced with a slight delay, it was marked with Δ, and when the cholesteric liquid crystal phase was induced with a further delay, it was marked with ×. .. In addition, the obtained cholesteric liquid crystal phase was evaluated for orientation defects by observation with a polarizing microscope. The coating film was divided into areas of 10 squares in length × 10 squares in width, for a total of 100 squares, and the number of squares in which orientation defects occurred was counted. The smaller the value, the less the orientation defect. The results are shown in the table below.

In Comparative Example 7, the cholesteric liquid crystal phase was not induced. From the above results, all the compounds represented by the formulas (I-1) to (I-10) of the present invention are compared with the compounds represented by the comparative compounds (R-1) to (R-4). Therefore, it can be seen that the time required to induce the cholesteric liquid crystal phase is short, and the obtained cholesteric liquid crystal phase has few orientation defects.

From the above results, all the compounds represented by the formulas (I-1) to (I-10) of the present invention are more polymerizable than the comparative compound (R-1) to the comparative compound (R-4). It can be seen that it has high storage stability when added to a solution containing the composition, induces liquid crystal phase orientation in a short time when the polymerizable composition is applied to a substrate, and has few orientation defects. Therefore, the compound of the present invention is useful as a constituent member of the polymerizable composition. Further, an optically anisotropic substance using a polymerizable liquid crystal composition containing the compound of the present invention is useful for applications such as optical films.

Claims (8)

The following general formula (I)

(During the ceremony,
X ¹ is -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -,- CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -,- CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH- , -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but if there are multiple X ¹ , they are the same but different. May be
k1 represents an integer from 0 to 10
A ¹ and A ² are independently expressed from the following equations (A-1) to (A-9).

Represents a group selected from (in the formula, these groups are unsubstituted or may be substituted with one or more substituents L).
L is a fluorine atom, a chlorine atom, or one -CH _2- or two or more non-adjacent-CH _2- independently of -O- , -CH = CH-, -CF = CF- Alternatively, it represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by −C≡C—, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom . If there are multiple L's in the compound, they may be the same or different.
B ¹ is from the following equation (B-1) to equation (B-15).

(In the formula, these groups may be unsubstituted or substituted with one or more of the above substituents L, where ^LB is a hydrogen atom, a fluorine atom, a chlorine atom , and one -CH _2- is-. An alkyl group having 2 carbon atoms, which may be substituted by CH = CH-, -CF = CF- or -C≡C- , and any hydrogen atom in the group may be substituted with a fluorine atom, or 1 Two -CH _2- or two or more non-adjacent -CH _2- are independently formed by -O-, -S-, -CH = CH-, -CF = CF- or -C≡C- . Represents a linear, branched or cyclic alkyl group having 3 to 20 carbon atoms which may be substituted, but any hydrogen atom in the linear, branched or cyclic alkyl group having 3 to 20 carbon atoms. May be replaced with a fluorine atom ,
Z ¹ and Z ² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH- COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -OCO-CH _2- , -CH ₂ -COO-, -CH = CH-, -N = N-, -CH = N-, -N = CH- , -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond, where at least one of Z ¹ and Z ² is -OCH _2- or -CH ₂ O. -Represents
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one -CH _2- or two or more non-adjacent-CHs. ₂ -Independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO- Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C-. , Any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is a group represented by-(X ² -Sp ² ) _k2 -P ² (in the formula, X ² is-). O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH- COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = Represents N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but if there are multiple X2s, ^they may be the same or different. , K2 represents an integer from 0 to 10), but does not include -O-O- coupling in the general formula.
P ¹ and existing P ² are independently derived from the following equations (P-1) to (P-3) and equations (P-7) to (P-20).

Represents a group selected from
Sp ¹ and existing Sp ² each have one -CH _2- or two or more non-adjacent -CH _2- independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- , -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO -, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-N = CH -Represents an alkylene group having 1 to 20 carbon atoms which may be replaced by -CF = CF- or -C≡C-. )
The compound represented by. The compound according to claim 1, wherein in the general formula (I), B ¹ represents a group selected from the formulas (B-1) to (B-2) and (B-6) to the formula (B-15). The compound according to claim 1 or 2, wherein at least one of A ¹ and A ² is represented by the formula (A-1) in the general formula (I). A polymerizable composition containing the compound according to any one of claims 1 to 3. A polymerizable liquid crystal composition containing the compound according to any one of claims 1 to 3. A polymer obtained by polymerizing the composition according to claim 4 or 5. An optically anisotropic substance using the polymer according to claim 6. Resins, resin additives, oils, filters, adhesives, adhesives, fats and oils, inks, cosmetics, detergents, building materials, packaging materials, liquid crystals using the compound according to any one of claims 1 to 3. Materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, mechanical parts, pesticides and foods, and products using them.