JP2015040174A - Polymerizable compound and optical anisotropic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound which has high storage stability without inducing crystallization or the like when added to a polymerizable composition, to provide a polymerizable composition containing the polymerizable compound, which gives little haze or unevenness when a polymer is produced by polymerizing the polymerizable composition, and which hardly causes reduction in retardation when the polymer is heat treated, and further, to provide a polymer obtained by polymerizing the polymerizable composition, and an optical anisotropic material using the polymer.SOLUTION: A compound expressed by general formula (I) is provided; and also provided are a composition containing the above compound, a polymer obtained by polymerizing the composition, and an optical anisotropic material using the polymer.

Description

  The present invention relates to a compound having a polymerizable group, a polymerizable composition containing the compound, and an optical anisotropic body using the polymerizable composition.

  A compound having a polymerizable group (polymerizable compound) is used as a raw material for various films. For example, it is possible to prepare a film-like polymer having a uniform orientation by arranging a polymerizable composition containing a polymerizable compound in a liquid crystal state and then polymerizing it. Thus, the produced film can be used for a polarizing plate, a phase difference plate, etc. which are required for a display. In many cases, two or more types of polymerizability are required 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 polymerizable composition containing the compound is used. In that case, the polymerizable compound to be used is required to bring good physical properties to the polymerizable composition without adversely affecting other properties. In a retardation plate used for optical compensation such as a display, when a polymerizable composition before polymerization is prepared, the polymerizable compound in the component is precipitated from the polymerizable composition even if stored for a long time. It is particularly important that when the polymerizable composition is polymerized by electromagnetic waves to produce a film-like polymer, the haze is small and the unevenness is small. In addition, when post-baking (heat treatment) is performed in order to completely cure the obtained film-like polymer, it is required that the phase difference after post-baking does not decrease significantly compared to the phase difference before post-baking. It is done. In order to suppress a decrease in retardation due to post-baking, it is effective to irradiate a high-intensity electromagnetic wave or a long-time electromagnetic wave when polymerizing the polymerizable composition. Degradation of the polymerizable composition due to is accelerated. Therefore, in order to suppress a decrease in the retardation after post-baking without degrading the polymerizable composition, it is desirable that the polymerization proceeds with electromagnetic wave irradiation as low as possible and as short as possible. When a film with haze and unevenness or with a reduced phase difference is used, for example, for viewing angle expansion and polarization conversion of a display or the like, the brightness of the display is not uniform or the color of the image is unnatural. In some cases, light leakage may occur depending on the viewing angle due to the deviation of the polarization axis, or color deviation may occur, and the quality of the display product may be greatly degraded.

  Various polymerizable compounds have been reported in the field. However, when these polymerizable compounds are added to the polymerizable composition, crystals are precipitated, and the storage stability is insufficient. In addition, when a film-like polymer is produced using a polymerizable composition containing a polymerizable compound, there is a problem that haze increases or unevenness occurs. Alternatively, there has been a problem that the phase difference changes greatly when heat treatment is performed to completely cure the obtained film-like polymer (Patent Documents 1 to 3).

JP 2009-102245 A US2011-0178200A1 Publication WO2011-160765A1

  The problem to be solved by the present invention is to provide a polymerizable compound having a high storage stability without causing precipitation of crystals when added to the polymerizable composition, and a polymerizable compound containing the polymerizable compound An object of the present invention is to provide a polymerizable composition that has little haze and unevenness when producing a polymer obtained by polymerizing the composition, and that hardly causes a decrease in retardation when the polymer is heat-treated. Furthermore, it is providing the polymer obtained by polymerizing the said polymeric composition, and the optical anisotropic body using the said polymer.

  The present invention relates to the general formula (I)

(Wherein P represents a polymerizable group,
Sp represents a spacer group or a single bond, and when a plurality of Sp are present, they may be the same or different,
X represents —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 -, - (C (Y ¹ ) ₂ ) _n1 −, —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 -, - CY 1}} = CY 1 - ( wherein, ^{Y 1} are each independently hydrogen atom, 12 Al of from 1 carbon atoms Group, a fluorine atom, a chlorine atom or a cyano group, n1 represents an integer of 1 to 6, if Y ¹ there are a plurality thereof may be different even in the same.) Or a single bond In the case where a plurality of Xs are present, they may be the same or different,
A ¹ and A ⁴ are each independently 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, cyclohexane-1,4-diyl, 1,4-cyclohexenylene, bicyclo [ 2.2.2] Octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, thiophene-2,5-diyl or fluorene-2,7-diyl, these groups being unsubstituted or one or more And one or more ═CH— groups in these ring structures may be substituted with ═N—, or one or more non-consecutive —CH ₂ — groups in these groups may be Independent May be substituted with -O- or -S-, and when a plurality of A ¹ and A ⁴ are present, they may be the same or different,
A ² and A ³ are each independently 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, cyclohexane-1,4-diyl, 1,4-cyclohexenylene, bicyclo [ 2.2.2] Octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, thiophene-2,5-diyl or fluorene-2,7-diyl, these groups being unsubstituted or one or more And one or more ═CH— groups in these ring structures may be substituted with ═N—, or one or more non-consecutive —CH ₂ — groups in these groups may each be Independent May be substituted with -O- or -S-
At least one of A ² and A ³ represents naphthalene-2,6-diyl which may be unsubstituted or substituted by one or more Ls;
Z ¹ and Z ² are each independently a single bond, —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 —, — (C (Y ¹ ) ₂ ) _n1 —, —CH ₂ CF ₂ —, —CF ₂ CH 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 -, - CY 1 = C Y ¹ — or —C≡C— (wherein Y ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group; 6 represents an integer of 6; when a plurality of Y ¹ are present, they may be the same or different.) When a plurality of Z ¹ and Z ² are present, they are the same or different. Well,
n represents an integer of 0 to 10,
m1 and m2 represent integers from 0 to 5,
R represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 20 carbon atoms, and two or more non-adjacent —CH ₂ — in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O- may be substituted, and the alkyl group may be linear or branched. The hydrogen atom bonded to the carbon atom in the group may be replaced by a fluorine atom, but when R represents a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a methoxy group or a thiomethoxy group, m1 is from 1 Represents an integer of 5,
L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, —N (Y ³ ) ₂ , —Si (Y ³ ) ₃ , one —CH ₂ —. Or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O—. A linear or branched alkyl group having 1 to 20 atoms (wherein Y ³ is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, A cyano group, a hydroxyl group, a linear or branched alkyl group having 1 to 20 carbon atoms, and when there are a plurality of Y ^3, they may be the same or different), a hydroxyl group or Represents a mercapto group. And a composition containing the compound, a polymer obtained by polymerizing the composition, and an optical anisotropic body using the polymer.

  The compound of the present invention has high storage stability when constituting a polymerizable composition, and is useful as a constituent member of the polymerizable composition. Further, the optical anisotropic body using the polymer obtained by polymerizing the composition containing the compound of the present invention has a small haze and little unevenness, and it is difficult to cause a decrease in retardation even when heat-treated. Useful for applications such as optical films.

  The present invention provides a compound represented by the general formula (I), a composition containing the compound, a polymer obtained by polymerizing the composition, and an optical anisotropic body using the polymer. I will provide a.

  In the general formula (I), P represents the following formula (P-1) to formula (P-18)

Preferably, these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-7), formula (P-11) or formula (P-13) is more preferred, formula (P-1), formula (P-2) or formula (P-3) is more preferred, and formula (P- 1) or formula (P-2) is particularly preferred.

Sp represents a spacer group or a single bond, but when a plurality of Sp are present, they may be the same or different, and each is independently a —CH ₂ — or not adjacent to each other as a spacer group. Two or more —CH ₂ — each independently represents an alkylene group having 1 to 20 carbon atoms or a single bond which may be replaced by —O—, —COO—, —OCO— or —OCO—O—. From the viewpoint of availability of materials, liquid crystallinity, and compatibility with other components, Sp is independently composed of one —CH ₂ — or two or more non-adjacent —CH ₂ —. to -O -, - COO- or -OCO- preferably alkylene group having a carbon number of 1 to 12 be replaced with, Sp is the one -CH ₂ - or two or more nonadjacent -CH ₂ - are each independently -O- every More preferably an alkylene group having 12 from good 1 -C been gills, Sp is one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O- in An alkylene group having 1 to 8 carbon atoms which may be substituted is even more preferable, and Sp is particularly preferably an alkylene group having 1 to 8 carbon atoms.

X represents —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 -, - (C (Y ¹ ) ₂ ) _n1 −, —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 -, - CY 1}} = CY 1 - ( wherein, ^{Y 1} are each independently hydrogen atom, 12 Al of from 1 carbon atoms Group, a fluorine atom, a chlorine atom or a cyano group, n1 represents an integer of 1 to 6, if Y ¹ there are a plurality thereof may be different even in the same.) Or a single bond In the case where a plurality of Xs are present, they may be the same or different,
X is a single bond, —O—, —S—, —COO—, —OCO—, —CO—S—, —S—CO— from the viewpoint of ease of synthesis, liquid crystallinity, and compatibility with other components. , —CO—NH—, —NH—CO—, —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—, or —CY ¹ ═CY ¹ — (wherein Y ¹ is each independently Preferably represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group, and n1 represents an integer of 1 to 6.)
X is a single bond, —O—, —S—, —COO—, —OCO—, —CO—S—, —S—CO—, —CO—NH—, —NH—CO—, —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 more preferably represents an ₂ -COO- or _-CH 2 _CH 2 -OCO-,
More preferably, X represents a single bond, —O—, —S—, —COO—, —OCO—, —CO—S—, —S—CO—,
More preferably, X represents a single bond, —O—, —COO—, —OCO—, and when a plurality of Xs appear, they may be the same or different from each other, and each independently represents —O—, —COO. -, -OCO- is even more preferred,
X particularly preferably represents -O-.

A ¹ and A ⁴ are each independently 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, cyclohexane-1,4-diyl, 1,4-cyclohexenylene, bicyclo [ 2.2.2] Octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, thiophene-2,5-diyl or fluorene-2,7-diyl,
1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, indan-2,5-diyl, thiophene- from the viewpoint of ease of synthesis, liquid crystallinity, and compatibility with other components More preferably it represents 2,5-diyl or fluorene-2,7-diyl,
Even more preferably, it represents 1,4-phenylene or naphthalene-2,6-diyl,
These groups may be unsubstituted or substituted by one or more L, and one or more ═CH— groups in these ring structures may be substituted by ═N—, or one of these groups The above non-continuous —CH ₂ — groups may each independently be substituted with —O— or —S—, and when a plurality of A ¹ and A ⁴ are present, they may be the same or different. Good but
It is particularly preferred that it represents 1,4-phenylene which is unsubstituted or substituted by 1 to 2 L or unsubstituted naphthalene-2,6-diyl,
A ² and A ³ are each independently 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, cyclohexane-1,4-diyl, 1,4-cyclohexenylene, bicyclo [ 2.2.2] Octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, thiophene-2,5-diyl or fluorene-2,7-diyl, these groups being unsubstituted or one or more And one or more ═CH— groups in these ring structures may be substituted with ═N—, or one or more non-consecutive —CH ₂ — groups in these groups may each be Independent Represents at least one of A ² and A ³ which is unsubstituted or optionally substituted by one or more Ls, and may be substituted with -O- or -S-,
From the viewpoints of ease of synthesis, compound stability, liquid crystallinity, and compatibility with other components, at least one represents naphthalene-2,6-diyl which may be unsubstituted or substituted with one or more Ls. More preferably, the other represents unsubstituted 1,4-phenylene or naphthalene-2,6-diyl, one represents naphthalene-2,6-diyl and the other represents 1,4-phenylene. The case is even more preferred, especially when A ² represents naphthalene-2,6-diyl and A ³ represents 1,4-phenylene.

Z ¹ and Z ² are each independently a single bond, —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 —, — (C (Y ¹ ) ₂ ) _n1 —, —CH ₂ CF ₂ —, —CF ₂ CH 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 -, - CY 1 = C Y ¹ — or —C≡C— (wherein Y ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group; 6 represents an integer of 6; when a plurality of Y ¹ are present, they may be the same or different.) When a plurality of Z ¹ and Z ² are present, they are the same or different. Well,
From the viewpoints of ease of synthesis, compound stability, liquid crystallinity, and compatibility with other components, each is independently a single bond, —COO—, —OCO—, —COO—CH ₂ CH ₂ —, —OCO. _{-CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - preferably may represent _CH 2 CH 2 -OCO-, wherein ^{if Z 1} and ^{Z 2} there are a plurality, even they are the same May be different,
Particularly preferably, each independently represents a single bond, -COO-, -OCO-,
Here, when a plurality of Z ¹ and Z ² are present, they may be the same or different.

  n represents an integer of 0 to 10, and is preferably an integer of 0 to 4 from the viewpoint of ease of synthesis, availability of raw materials, liquid crystallinity, and compatibility with other components. Is more preferable, the case of 1 or 2 is still more preferable, and the case of 1 is particularly preferable.

  m1 and m2 each represent an integer of 0 to 5, but are preferably an integer of 0 to 4 from the viewpoint of ease of synthesis, availability of raw materials, liquid crystallinity, and compatibility with other components. Is more preferably an integer from 0 to 3, even more preferably an integer from 0 to 2, even more preferably 0 or 1, particularly preferably m1 is 0 or 1 and m2 is 0. .

R represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 20 carbon atoms, and two or more non-adjacent —CH ₂ — in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O- may be substituted, and the alkyl group may be linear or branched. A hydrogen atom bonded to a carbon atom in the group may be replaced by a fluorine atom, but when R represents a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a methoxy group or a thiomethoxy group, When the compound is added to the composition, it is preferable not to significantly lower the nematic phase upper limit temperature of the composition. Therefore, m1 represents an integer of 1 to 5, and the ease of synthesis, liquid crystallinity, and other components Compatibility , Resulting difficulty of unevenness, from the viewpoint of retention of the phase difference, R represents a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group, a 1 -CH 2 _- or adjacent have not more than one - A straight chain of 1 to 20 carbon atoms in which CH ₂ — may be independently replaced with —O—, —S—, —CO—, —COO—, —OCO—, —OCO—O—, or still more preferred to a branched alkyl group, R represents a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group, one -CH 2 _- or nonadjacent two or more -CH 2 _- is A linear or branched alkyl group having 1 to 20 carbon atoms, each of which may be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -OCO-O- Even more preferably, R is from 1 to 12 carbon atoms. Chain alkyl group is particularly preferred.

L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, —N (Y ³ ) ₂ , —Si (Y ³ ) ₃ , one —CH ₂ —. Or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O—. A linear or branched alkyl group having 1 to 20 atoms (wherein Y ³ is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, A cyano group, a hydroxyl group, a linear or branched alkyl group having 1 to 20 carbon atoms, and when there are a plurality of Y ^3, they may be the same or different), a hydroxyl group or Preferably represents a mercapto group But fluorine atom, a chlorine atom, one -CH 2 _- or adjacent have not more than one -CH 2 _- are each independently -O- to replaced from a good 1 -C be 10 straight More preferably, it represents a chain alkyl group, and particularly preferably represents a fluorine atom, a chlorine atom, a methyl group, an ethyl group or a methoxy group.

  As the compound represented by the general formula (I), compounds represented by the following general formulas (i-1) to (i-9) are more preferable.

(In the formula, R, P, Sp, X, A ¹ , A ⁴ , Z ¹ , Z ² , m 1, m ² and L each independently represent the same as defined in formula (I). , R each independently represents an integer of 0 to 4, and s each independently represents an integer of 0 to 3, provided that R represents a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group or a thiomethoxy group. M1 represents an integer of 1 to 5.)
As the compound represented by the general formula (I), compounds represented by the following general formulas (ia-1) to (ia-3) are even more preferable.

(Wherein P, Sp, X, and L, r, and s each independently represent the same meaning as defined in formula (I), and have the same meaning as in claims 1 to 9, r independently represents an integer of 0 to 4, s independently represents an integer of 0 to 3, Z ^1a represents a single bond, —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—, wherein R ¹ represents one —CH ₂ — or A linear or branched alkyl group having 1 to 10 carbon atoms in which two or more non-adjacent —CH ₂ — may be independently replaced by —O—, —COO—, or —OCO—. Represents.)
The structure represented by the following formula (a-1) contained in the compounds represented by the general formulas (ia-1) to (ia-3) is represented by the following formulas (a-2) to (a-7). Some cases are preferred.

  Moreover, as a structure represented by the following formula (b-1) contained in the compound represented by the general formula (ia-1) or (ia-2), the following formulas (b-2) to (b-5) Is preferred.

  Specifically, compounds represented by the following formulas (I-1) to (I-42) are preferable as the compounds represented by the general formula (I).

The compound of this invention can be manufactured with the following manufacturing methods.
(Production method 1) Production of a compound represented by the following formula (S-10)

(In the formula, P, Sp and L each independently represent the same as defined in the general formula (I), and R ¹ is the same as R defined in the general formula (I). And r independently represents an integer from 0 to 4, s independently represents an integer from 0 to 3. Halogen represents a halogen atom or a halogen equivalent, and PG represents a protecting group.)
A compound represented by the general formula (S-2) is obtained by reacting the compound represented by the general formula (S-1) with, for example, trifluoromethanesulfonic anhydride (Tf ₂ O).

  A compound represented by the general formula (S-3) is obtained by, for example, Sonogashira cross-coupling of the compound represented by the general formula (S-2) with trimethylsilylacetylene. Reaction conditions include, for example, Metal-Catalyzed Cross-Coupling Reactions (co-authored by Armin de Meijere, Francois Diedrich, Wiley-VCH), Palladium Reagents and Catalysts: New Perspective. , Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry) (SL Buchwald, K. Fugami, T. Hiyama, M. Kosur, M. Miura, M. Miura, M. Miura, M. Miura, M. , M.Nomura, E.Shirakawa, K.Tamao al, a method described in literature Springer) or the like. Palladium catalysts include allyl palladium (II) chloride, benzyl bis (triphenylphosphine) palladium (II) chloride, bis (acetonitrile) palladium (II) dichloride, bis (benzonitrile) palladium (II) dichloride, bis [1,2- Bis (diphenylphosphino) ethane] palladium (0), bis (dibenzylideneacetone) palladium (0), [1,1′-bis (di-tert-butylphosphino) ferrocene] palladium (II) dichloride, [1 , 4-Bis (diphenylphosphino) butane] palladium (II) dichloride, [1,2-bis (diphenylphosphino) ethane] palladium (II) dichloride, [1,1′-bis (diphenylphosphino) ferrocene] Palladium (II) dichloride Dichloromethane adduct, [1,3-bis (diphenylphosphino) propane] palladium (II) dichloride, bis (methyldiphenylphosphine) palladium (II) dichloride, bis (2,4-pentanedionato) palladium (II), 1,2-bis (phenylsulfinyl) ethanepalladium (II) diacetate, bis (tri-tert-butylphosphine) palladium (0), bis (tricyclohexylphosphine) palladium (II) dichloride, bis (triphenylphosphine) palladium ( II) Diacetate, bis (triphenylphosphine) palladium (II) dichloride, bis (tri-o-tolylphosphine) palladium (II) dichloride, bromo [[1,3-bis [(4S, 5S) -1-benzoyl- 4,5-di Phenyl-2-imidazolin-2-yl] benzene] palladium (II)], chloro [[1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] (acetanilide) palladium (II)], chloro [[1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] (N, N-dimethylbenzylamine) palladium (II)], chloro [[1,3-bis (2,6-diisopropyl Phenyl) imidazol-2-ylidene] (N, N-dimethyl-3,5-dimethoxybenzylamine) palladium (II)], chloro [[1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene ] (4′-methoxyacetanilide) palladium (II)], di-μ-chlorobis [5-chloro-2] [(4-Chlorophenyl) (hydroxyimino) methyl] phenyl] palladium (II) dimer, di-μ-chlorobis [2-[(dimethylamino) methyl] phenyl-C, N] dipalladium (II), di-μ -Chlorobis [5-hydroxy-2- [1- (hydroxyimino) ethyl] phenyl] palladium (II) dimer, dichloro (1,5-cyclooctadiene) palladium (II), palladium (II) acetate, palladium bromide (II), palladium (II) chloride, palladium (II) trifluoroacetate, sodium tetrachloropalladium (II), tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), Palladium / carbon, palladium / barium carbonate, palladium / Barium, palladium / calcium carbonate, palladium hydroxide / carbon, palladium / silica gel, palladium / SH silica gel and the like. Examples of the copper catalyst include copper (I) iodide. Examples of the base include N, N-diethylhexadecylamine, N, N-dimethyl-2-ethylhexylamine, N, N-dimethyldocosylamine, N-hexadecyl-N-methylhexadecylamine, N, N, 3, 3-tetramethylbutylamine, N-methyl-N-octyloctylamine, N-dodecyl-N-methyldodecylamine, N, N-dimethyl-2-propenylamine, N, N-dimethylbutylamine, N-ethyl-N- Methylethylamine, N, N-dimethylethylamine, N, N-dimethyloctadecylamine, triethylamine, N, N-dimethyldodecylamine, tridodecylamine, tributylamine, tripropenylamine, tripropylamine, trimethylamine, N-butylhexadecyl Amine, N-methylpenta Silamine, N-ethylpropylamine, N-isopropyl-6-methyl-2-heptylamine, N-ethylbutylamine, N-methyldodecylamine, didodecylamine, diheptylamine, dipentylamine, dinonylamine, didecylamine, dioctylamine, N- (3-methylbutyl) -6-methyl-2-heptylamine, dihexylamine, dipropylamine, dimethylamine, di-2-propenylamine, dibutylamine, diisobutylamine, N-methylbutylamine, diethylamine, diisopropylamine, 2,2,3,3-tetramethyl-1-butylamine, 2-tridecin-1-amine, 3-methyl-2,2-diisopropyl-1-butylamine, 2,2-dimethyl-3-pentylamine, 2- Pentylamine, 0-undecen-1-amine, 5-decyn-1-amine, ethanamine, 9-hexadecene-1-amine, 7-tridecylamine, 1-docosylamine, 1-nonadecylamine, 2-butylamine, 1-eicosylamine, 1-undecylamine, 2,2-dimethyl-1-propylamine, 1-heptadecylamine, 3,3-dimethyl-2-butylamine, 2-methyl-3-butynyl-2-amine, 1-pentadecylamine 1-decylamine, 1-tetradecylamine, 2-methyl-3,5-hexadiynyl-2-amine, 2-octylamine, 2-ethyl-1-butylamine, 3-methyl-2-butylamine, 2-methyl- 2-butylamine, 6-methyl-2-heptylamine, 1-hexadecylamine, 1-octadecylamine, 1- Dodecylamine, 1-nonanylamine, 1-octylamine, 1-heptylamine, 1-hexylamine, 1-pentylamine, 1-butylamine, 3-methyl-1-butylamine, 2-propenyl-1-amine, 1-propyl Amine, 2-methyl-1-propylamine, 2-methyl-2-propylamine, 2-propylamine, ethylamine, methylamine, pyridine, N-methylpyridine, 2-chloropyridine, 2-bromopyridine, piperidine, pyrimidine Quinoline, acridine, N, N-dimethyl-4-aminopyridine, picoline, bipyridine, 2,6-lutidine, pyridinium chlorochromate, pyridinium p-toluenesulfonate, triethanolamine, trimethanolamine, piperazine, hydroxyethylpiperazine 2-methylpiperazine, trans-2,5-piperazine, cis-2,6-dimethylpiperazine, morpholine, N-methylmorpholine, N-ethylmorpholine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane, Ethylenediamine, tetramethylethylenediamine, hexamethylenediamine, aniline, catecholamine, phenethylamine, toluidine, benzidine, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N- (β-aminoethyl) ethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, N-butylethanolamine, N-propylethanolamine, N -Propyldiethanolamine, N-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, N- (β-aminoethyl) isopropanolamine, N, N-diethylisopropanolamine, diethanolamine and the like.

  A compound represented by the general formula (S-4) is obtained by reacting the compound represented by the general formula (S-3) with, for example, potassium carbonate. As a method for introducing an ethynyl group, 2-methyl-3-butyn-2-ol, ethynyl (phenyl) iodonium tetrafluoroborate, dimethyl (1-diazo-2-oxopropyl) phosphonate, acetylene gas instead of trimethylsilylacetylene Etc. may be used. Moreover, after introducing an ethenyl group, it may be derived into an ethynyl group by halogenation and treatment with a base.

  The hydroxyl group of the compound represented by formula (S-5) is protected with a protecting group (PG). The kind of the protective group (PG) is not particularly limited as long as it gives the compound represented by the general formula (S-6) in the reaction process, and can stably protect the hydroxyl group in the subsequent steps. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODARA W. GREENE co-authored, A John Wiley & Son, Inc.). Groups are preferred.

  The compound represented by the general formula (S-7) is obtained by subjecting the compound represented by the general formula (S-6) to Sonogashira cross coupling with the acetylene compound represented by the general formula (S-4). Reaction conditions include, for example, Metal-Catalyzed Cross-Coupling Reactions (co-authored by Armin de Meijere, Francois Diedrich, Wiley-VCH), Palladium Reagents and Catalysts: New Perspective. , Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry) (SL Buchwald, K. Fugami, T. Hiyama, M. Kosur, M. Miura, M. Miura, M. Miura, M. Miura, M. , M.Nomura, E.Shirakawa, K.Tamao al, a method described in literature Springer) or the like. Examples of the catalyst and the base include those described above.

  The protecting group (PG) of the compound represented by formula (S-7) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-8) in the reaction process. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition) , PETER G.M.WUTS, THEODARA W.GREENE, A John Wiley & Sons, Inc., Publication).

  A compound represented by the formula (S-10) is obtained by reacting the compound represented by the general formula (S-8) with a compound represented by the general formula (S-9). As reaction conditions, for example, Mitsunobu reaction or a compound represented by general formula (S-9) is reacted with sulfonic acid or the like to form a sulfonic acid ester, and then a compound represented by general formula (S-8) and a base. The method of making it react in presence is mentioned. When Mitsunobu reaction is used, examples of the azodicarboxylic acid include diethyl azodicarboxylate, dibenzyl azodicarboxylate, dimethyl azodicarboxylate, 1,1 ′-(azodicarbonyl) dipiperidine, diisopropyl azodicarboxylate, and bis (2) azodicarboxylate. , 2,2-trichloroethyl), 1,1′-azobis (N, N-dimethylformamide), bis (2-methoxyethyl) azodicarboxylate, di-tert-butyl azodicarboxylate, and the like. Examples of phosphine include diethylphenylphosphine, dicyclohexylphenylphosphine, diphenyl-2-pyridylphosphine, 4- (dimethylamino) phenyldiphenylphosphine, 4-diphenylphosphinomethylpolystyrene resin, isopropyldiphenylphosphine, phenoxydiphenylphosphine, tributylphosphine, Examples include octyl phosphine, triphenyl phosphine, trihexyl phosphine, tricyclohexyl phosphine, and tri-tert-butyl phosphine. A Kakuda reagent such as cyanomethylenetributylphosphorane may also be used. When passing through a sulfonic acid ester, examples of the sulfonic acid include fluorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. As the base, in addition to the above, for example, aluminum hydroxide, aqueous ammonia, barium hydrate, caustic barite, barium hydroxide, bismuth hydroxide, cadmium hydroxide, cesium hydroxide, calcium hydroxide, lime, cerium hydroxide, Chromium hydroxide, cobalt hydroxide, copper hydroxide, ferric hydrate, iron hydroxide, lithium hydroxide, magnesium hydroxide, manganese hydroxide, nickel hydroxide, potassium hydroxide, sodium hydroxide, hypochlorite Sodium sulfate, sodium sesquicarbonate, strontium hydroxide, thallium hydroxide, thorium hydroxide, sodium acetate, sodium aluminum sulfate, sodium ammonium phosphate, sodium bicarbonate, sodium carbonate, calcium acetate, calcium carbonate, calcium formate, calcium phosphate, acetic acid Thallium, potash acetate , Potassium carbonate, potassium bicarbonate, potassium formate, potassium oxalate, ammonium bicarbonate, ammonium carbonate, cesium carbonate, ammonium formate, ammonium sulfate and the like.

A reaction solvent can be appropriately used in each step. The solvent is not particularly limited as long as it gives the target compound. For example, tert-butyl alcohol, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, cyclohexanol, 1-butanol, 2-butanol, 1-octanol, 2- Methoxyethanol, ethylene glycol, diethylene glycol, methanol, methylcyclohexanol, ethanol, propanol, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethylene 1-chlorobutane, carbon disulfide, acetone, acetonitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, di Chill ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, o-dichlorobenzene, xylene, o-xylene, p-xylene, m-xylene, chlorobenzene, Isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl acetate, 2-methoxyethyl acetate, hexamethylphosphate triamide, tris (dimethylamino) phosphine, cyclohexanone, 1,4-dioxane , Dichloromethane, styrene, tetrachloroethylene, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, 1,1,1 Trichloroethane, toluene, hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, methyl isobutyl ketone, tert-butyl methyl ether, methyl ethyl ketone, methyl cyclohexanone, methyl butyl ketone, diethyl ketone, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha , Petroleum benzine, turpentine oil, mineral spirit and the like. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Examples of the phase transfer catalyst include tetrabutylammonium fluoride, tetraethylammonium fluoride, acetylcholine chloride, (3-acrylamidopropyl) trimethylammonium chloride, benzalkonium chloride, benzoylcholine chloride, benzylcetyldimethylammonium chloride, N-benzyl. Cinchonidium chloride, benzyldimethylphenylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethyltetradecylammonium chloride, N-benzylquinidium chloride, N-benzylquininium chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethyl Ammonium chloride, 1-butyl-1-methyl Rhodium chloride, carbamylcholine chloride, carnitine hydrochloride, chlorocholine chloride, (3-chloro-2-hydroxypropyl) trimethylammonium chloride, choline chloride, decyltrimethylammonium chloride, diallyldimethylammonium chloride, dimethyldistearylammonium chloride, Dodecyltrimethylammonium chloride, (hydrazinocarbonylmethyl) trimethylammonium chloride, hexadecyltrimethylammonium chloride, hexamethylenebis (trimethylammonium chloride), lauroylcholine chloride, methacholine chloride, methacryloylcholine chloride, (2-methoxyethoxymethyl) triethylammonium Chloride, β-methylcholine chloride, methyltrio Cutylammonium chloride, octyltrimethylammonium chloride, phenyltriethylammonium chloride, phosphocholine chloride calcium, stachydrine hydrochloride, succinylcholine chloride, tetraamylammonium chloride, tetrabutylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, tetrapropylammonium chloride , Triethylmethylammonium chloride, trimethyl [2,3- (dioleyloxy) propyl] ammonium chloride, trimethylphenylammonium chloride, trimethylstearylammonium chloride, trimethyltetradecylammonium chloride, trimethyl [3- (triethoxysilyl) propyl] ammonium Chloride, G Octylmethylammonium chloride, acetylcholine bromide, benzoylcholine bromide, benzyltributylammonium bromide, benzyltriethylammonium bromide, benzyltrimethylammonium bromide, bromocholine bromide, 1,1 ′-(butane-1,4-diyl) bis [4-aza -1-azoniabicyclo [2.2.2] octane] dibromide, 1-butyl-1-methylpiperidinium bromide, chlorin bromide, decamethonium bromide, 1,1 ′-(decane-1,10-diyl) bis [ 4-aza-1-azoniabicyclo [2.2.2] octane] dibromide, decyltrimethylammonium bromide, didecyldimethylammonium bromide, dilauryldimethylammonium bromide, dimethyldimyristate Ruammonium bromide, dimethyldioctadecylammonium bromide, dimethyldioctylammonium bromide, dimethyldipalmitylammonium bromide, dodecyltrimethylammonium bromide, ethylhexadecyldimethylammonium bromide, (ferrocenylmethyl) dodecyldimethylammonium bromide, (ferrocenylmethyl) ) Trimethylammonium bromide, hexadecyltrimethylammonium bromide, hexamethonium bromide, hexyldimethyloctylammonium bromide, hexyltrimethylammonium bromide, methylformatropin bromide, methacholine bromide, neostigmine bromide, octyltrimethylammonium bromide, phenyltrimethylammonium bromide, scopolami Methyl bromide, tetraamylammonium bromide, tetrabutylammonium bromide, tetra (decyl) ammonium bromide, tetradecyltrimethylammonium bromide, tetraethylammonium bromide, tetraheptylammonium bromide, tetramethylammonium bromide, tetraoctylammonium bromide, tetrapropylammonium bromide, 3- (trifluoromethyl) phenyltrimethylammonium bromide, trimethylpropylammonium bromide, trimethylstearylammonium bromide, trimethylvinylammonium bromide, baletamate bromide, acetylcholine iodide, acetylthiocholine iodide, benzoylcholine iodide, benzoylthiocholine iodide De Benji Triethylammonium iodide, butyrylcholine iodide, butyrylthiocholine iodide, decamethonium iodide, 1,1-dimethyl-4-phenylpiperazinium iodide, ethyltrimethylammonium iodide, ethyltripropylammonium iodide, ( Ferrocenylmethyl) trimethylammonium iodide, (2-hydroxyethyl) triethylammonium iodide, β-methylcholine iodide, O-β-naphthyloxycarbonylcholine iodide, tetraamylammonium iodide, tetrabutylammonium iodide Tetraethylammonium iodide, tetraheptylammonium iodide, tetrahexylammonium iodide, tetramethylammonium iodide, tetraoctylammonium iodide Tetrapropylammonium iodide, triethylphenylammonium iodide, 3- (trifluoromethyl) phenyltrimethylammonium iodide, trimethylphenylammonium iodide, trimethyl [2-[(trimethylsilyl) methyl] benzyl] ammonium iodide, benzyltriethylammonium Hydroxide, benzyltrimethylammonium hydroxide, choline, hexadecyltrimethylammonium hydroxide, sphingomyelin, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetrahexylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, 3- (Trifluoromethyl) phenyltrimethylan Monium hydroxide, trimethylphenylammonium hydroxide, tris (2-hydroxyethyl) methylammonium hydroxide, acetylcholine perchlorate, amyltriethylammonium bis (trifluoromethanesulfonyl) imide, benzyltriethylammonium borohydride, benzyltrimethylammonium dichloroiodate , Benzyltrimethylammonium tetrachloroiodate, benzyltrimethylammonium tribromide, anhydrous betaine, betaine hydrochloride, bis (tetrabutylammonium dichromate), bis (tetrabutylammonium) tetracyanodiphenoquinodimethanide, 1-butyl -1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, L-carnitine, 3-[(3-co Midopropyl) dimethylammonio] -1-propanesulfonate, choline bitartrate, 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimidometh-p-toluenesulfonate, cyclohexyltrimethylammonium bis (trifluoromethanesulfonyl) imide, benzoate Denatonium acid [vitrex], dodecyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, N-fluoro-N ′-(chloromethyl) triethylenediaminebis (tetrafluoroborate), palmitylsulfobetaine, hexadecyl Trimethylammonium hexafluorophosphate, hexadecyltrimethylammonium perchlorate, hexadecyltrimethylammonium tetrafluoroborate, 2- (methacryloyl phosphate) Xyl) ethyl 2- (trimethylammonio) ethyl, methyl N- (triethylammoniosulfonyl) carbamate, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, methyltrioctylammonium bis (trifluoromethane) Sulfonyl) imide, methyltrioctylammonium hydrogen sulfate, neostigmine methylsulfate, octadecyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, propionylcholine p-toluenesulfonate, methylscopolamine nitrate, tetrabutylammonium acetate, tetra Butylammonium azide, tetrabutylammonium bifluoride, tetrabutylammonium borohydride, tetrabutylammonium bromodiiodide, teto Butylammonium dibromoaurate, tetrabutylammonium dibromochloride, tetrabutylammonium dibromoiodide, tetrabutylammonium dichloroaurate, tetrabutylammonium dichlorobromide, tetrabutylammonium difluorotriphenylsilicate, tetrabutylammonium difluorotriphenyltin, tetra Butylammonium dihydrogen trifluoride, tetrabutylammonium diiodoaurate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, tetrabutylammonium perrhenate, tetrabutylammonium phosphate , Tetrabutylammonium p-nitrophenoxide, tetrabutylammonium Nium salicylate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium tetraphenylborate, tetrabutylammonium thiocyanate, tetrabutylammonium tribromide, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium triiodide, 3 -(Tetradecyldimethylammonio) propanesulfonate, tetraethylammonium borohydride, tetraethylammonium perchlorate,
Tetraethylammonium p-toluenesulfonate, tetraethylammonium tetrafluoroborate, tetraethylammonium trifluoromethanesulfonate, tetramethylammonium acetate, tetramethylammonium borohydride, tetramethylammonium hexafluorophosphate, tetramethylammonium hydrogensulfate, persulfate Tetramethylammonium chlorate, tetramethylammonium p-toluenesulfonate, tetramethylammonium sulfate, tetramethylammonium tetrafluoroborate, tetramethylammonium triacetoxyborohydride, tetrapropylammonium perruthenate, triethylmethylammonium tetrafluoroborate Rat, trimethylphenylammonium tri Romid, N, N-bis (3-D-gluconamidopropyl) colamide [BIGCHAP], N, N-bis (3-D-gluconamidopropyl) deoxycoramide [Deoxy-BIGCHAP], NIKKOL BL-9EX [poly Oxyethylene (9) lauryl ether], octanoyl-N-methylglucamide [MEGA-8], nonanoyl-N-methylglucamide [MEGA-9], decanoyl-N-methylglucamide [MEGA-10], polyoxy Ethylene (8) octyl phenyl ether [Triton X-114], polyoxyethylene (9) octyl phenyl ether [NP-40], polyoxyethylene (10) octyl phenyl ether [Triton X-100], polyoxyethylene (20 ) Sorbitan Mono Urate [Tween 20], polyoxyethylene (20) sorbitan monopalmitate [Tween 40], polyoxyethylene (20) sorbitan monostearate [Tween 60], polyoxyethylene (20) sorbitan monooleate [Tween 80] , Polyoxyethylene sorbitan trioleate [Tween 85], polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (23) lauryl ether [Brij35], polyoxyethylene (20) cetyl ether [Brij58], dodecyl-β- D-maltopyranoside, heptyl-β-D-thioglucopyranicid, octyl-β-D-thioglucopyranicid, nonyl-β-D-thiomaltoside, IGELPAL CA-630, Digiton n, Saponin, from Soybeans, 3-[(3-Colamidopropyl) dimethylammonio] -2-hydroxy-1-propanesulfonate [CHAPSO], 3-[(3-Colamidopropyl) dimethylammonio]- 1-propanesulfonate [CHAPS], ammonium heptadecafluoro-1-octanesulfonate, ammonium pentadecafluorooctanoate, heptadecafluorooctanesulfonate, lithium hepadecafluoro-1-octanesulfonate, pentadecafluorooctanoate , Potassium heptadecafluoro-1-octanesulfonate, 3- (hexadecyldimethylammonio) propanesulfonate, sodium cholate, sodium laurate, sodium myristate, N-lauroylsarco Sodium oleate, sodium palmitate, sodium stearate, sodium bis (2-ethylhexyl) sulfosuccinate, dodecene-1LAS, dimethyl sodium 5-sulfoisophthalate, sodium 1-dodecanesulfonate, sodium dodecylbenzenesulfonate, Sodium 1-hexadecanesulfonate, sodium 1-octadecanesulfonate, sodium 1-pentadecanesulfonate, sodium 1-tetradecanesulfonate, sodium 1-tridecanesulfonate, monododecyl sodium phosphate, monododecyl sodium phosphate (mono, Disodium mixture), sodium dodecyl sulfate, sodium hexadecyl sulfate, benzethonium chloride, hexadecylpyridinium chloride, 1-dode Rupyridinium chloride, hexadecylpyridinium bromide, hexadecylpyridinium chloride, monomyristin, monopalmitin, monostearin, polyethylene glycol monostearate, polyethylene glycol monostearate (palmitate, stearate mixture), sorbitan monolaurate [Span 20] Sorbitan monopalmitate [Span 40], sorbitan monostearate [Span 60], sorbitan monooleate [Span 80], sorbitan sesquioleate [Span 83], sorbitan trioleate [Span 85], diethylene glycol monododecyl ether, Ethylene glycol monododecyl ether, polyethylene glycol monocetyl ether, polyethylene glycol Examples include nododecyl ether, polyethylene glycol mono-4-octylphenyl ether, tetraethyl glycol monododecyl ether, and triethylene glycol monododecyl ether.

  Other reaction conditions include, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic Chemistry (Industry Chemistry Bank) der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co. K), Fiesers' Reagents for Organic Synthesis, Rebirth of Science, etc. (John Wiley & S. et al., John Wiley & S. et al.) Conditions that are recorded, and the like.

In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, perlite, cellulose , Organic polymers, porous gels and the like.
(Production method 2) Production of a compound represented by the following formula (S-14)

(In the formula, P, Sp and L each independently represent the same as defined in the general formula (I), and R ¹ is the same as R defined in the general formula (I). Each represents independently an integer from 0 to 4, and each s independently represents an integer from 0 to 3.)
The compound represented by the general formula (S-12) is obtained by reacting the compound represented by the general formula (S-11) with the compound represented by the general formula (S-9). Examples of the reaction method include the method described in the step of obtaining general formula (S-10) of production method 1.

  The compound represented by the general formula (S-13) is obtained by oxidizing the compound represented by the general formula (S-12). Examples of the oxidizing agent include hydrogen peroxide water and sodium hypochlorite.

  The compound represented by the general formula (S-14) is obtained by reacting the compound represented by the general formula (S-13) with the compound represented by the general formula (S-8). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the general formula (S-13) is converted into an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride, and then the general formula (S-8) is used. The method of making it react with the compound represented by base presence is mentioned. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- [3- (dimethyl Amino) propyl] -N'-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N'-ethylcarbodiimide methiodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'- (2-morpholinoethyl) carbodiimide meth-p-toluenesulfonate, N, N′-di-tert-butylcarbodiimide, N, N′-di-p-tolylcarbodiimide, 4- (4,6-dimethoxy-1, 3,5-triazin-2-yl) -4-methylmorpholinium chloride, etc. It is below. As in production method 1, a reaction solvent, reaction conditions, and purification method can be appropriately selected.

  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. In the liquid crystal composition using the reactive compound of the present invention, a compound other than the present invention may be added.

  Specific examples of other reactive compounds used in combination with the reactive compound of the present invention include those represented by the general formula (II)

(Wherein P ¹ and P ² each independently represent the same meaning as P in formula (I), and S ¹ and S ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms) represents a one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced by a, ^{X 1} and X ² is each independently a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S. _{-CO -, - O-CO-} O -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CH = N _{-, - SCH 2 -, -} CH 2 S -, - 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 -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CF 2 CH _2- , —CH ₂ CF ₂ —, —CF ₂ CF ₂ —, —CY ¹ ═CY ¹ — (wherein Y ¹ is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom Represents a chlorine atom or a cyano group) or —C≡C—, and each Z ³ independently represents a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, — CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-,- _{COOCH 2 -, - CH 2 OCOO} -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CH = N -, - SCH 2 -, - CH 2 S-, -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 -, - CF 2 - , —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ —, —CY ² = CY ² — , Y ² is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, fluoride Atom, a chlorine atom or a cyano group. ) Or -C≡C-, and A ⁵ and A ⁶ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5 - diyl group, naphthalene-2,6-diyl group, represents a tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, ^{a 5} and ^{a 6} are each independently unsubstituted May be substituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen atom, a cyano group, or a nitro group, m3 represents 0, 1, 2, or 3; Represents 2 or 3, the two or three A ⁵ and / or Z ³ may be the same or different. It is preferably a compound represented by), when P ¹ and P ² of the general formula (II) is an acrylic group or methacrylic group are particularly preferable. Specifically, the general formula (III)

(Wherein S ³ and S ⁴ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ³ and X ⁴ each independently represent —O—, —COO—, —OCO— or a single bond). , Z ⁴ and Z ⁵ each independently represent —COO— or —OCO—, and A ⁷ , A ⁸ and A ⁹ each independently represents an unsubstituted or fluorine atom, chlorine atom or carbon atom having 1 to 4 carbon atoms. Represents a 1,4-phenylene group substituted by an alkyl group or an alkoxy group.), And compounds represented by the following formulas (III-1) to (III-8) are particularly preferable.

(Wherein, ^{S 3} has the same meaning as ^{S 3} in the general formula (III), ^{S 4} represents the same meaning as ^{S 4} in the general formula (III).) The above formula (III-1) from the formula (III In −8), a compound in which S ³ and S ⁴ are each independently an alkylene group having 2 to 8 carbon atoms is further preferred.

  Moreover, general formula (IV)

(In the formula, S ⁵ and S ⁶ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ⁵ and X ⁶ each independently represent —O—, —COO—, —OCO— or a single bond. , Z ⁶ represents —COO— or —OCO—, and A ¹⁰ , A ¹¹ and A ¹² are each independently unsubstituted or substituted by a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. And a compound represented by the following formula (IV-1) to formula (IV-8) is particularly preferable.

(Wherein, ^{S 5} has the same meaning as ^{S 5} in the general formula (IV), ^{S 6} in the general formula (IV) represents the same meaning as ^{S 6.)} The formula (IV-1) from the formula (IV -8), from the viewpoint of heat resistance and durability, the formula (IV-2), formula (IV-5), formula (IV-6), formula (IV-7) and formula (IV-8) are used. The compound represented by formula (IV-2) is more preferable, and the compound in which S ⁵ and S ⁶ are each independently an alkylene group having 2 to 8 carbon atoms is particularly preferable.

  In addition, preferable bifunctional polymerizable compounds include compounds represented by the following general formulas (V-1) to (V-7).

(In the formula, S ⁷ and S ⁸ each independently represents an alkylene group having 2 to 18 carbon atoms.) In the above formulas (V-1) to (V-7), the formula (V-2), Compounds represented by formula (V-3), formula (V-5), formula (V-6) and formula (V-7) are preferred, and S ⁷ and S ⁸ are each independently from 2 carbon atoms. A compound that is an alkylene group of 8 is particularly preferred.

  Preferable monofunctional polymerizable compounds include compounds represented by the following general formulas (VI-1) to (VI-9).

(Wherein P ³ represents the same meaning as P in formula (I), S ⁹ represents a single bond or an alkylene group having 1 to 20 carbon atoms, but one —CH ₂ — or adjacent one is Two or more —CH ₂ — not present may be replaced by —O—, —COO—, —OCO—, —OCOO—, and X ³ represents a single bond, —O—, —COO—, —OCO—. Z ⁷ is a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —CY ³ = CY ³ — (wherein Y ³ is independently Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group.) Or —C≡C—, and A ¹³ represents a 1,4-phenylene group or naphthalene-2,6. - represents a diyl group, a ¹³ is or an alkyl group is unsubstituted, halogenated alkyl , Alkoxy group, halogenated alkoxy group, a halogen atom, may be substituted with a cyano group or a nitro group, L ¹ is fluorine atom, chlorine atom, the one -CH 2 _- or two or more nonadjacent -CH ₂ - are each independently -O -, - COO -, - OCO- the replaced represents a linear or branched alkyl group which may having 1 to 10 carbon atoms also, r is 0 to 4 R ¹ represents an integer, and R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O—, —COO—, — (It represents a linear or branched alkyl group having 1 to 20 carbon atoms that may be replaced by OCO- or -OCO-O-.)
A polymerizable compound that does not exhibit liquid crystallinity can be added to the polymerizable liquid crystal composition containing the compound of the present invention to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound that is recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation.

  The concentration of the photopolymerization initiator added to the polymerizable liquid crystal composition containing the compound of the present invention is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass. preferable. As the photopolymerization initiator, benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like can be used.

  In addition, a stabilizer may be added to the polymerizable liquid crystal composition containing the compound of the present invention in order to improve its storage stability. Examples of the stabilizer include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like. When the stabilizer is used, the addition amount is preferably 0.005 to 1% by mass and more preferably 0.02 to 0.5% by mass with respect to the liquid crystal composition.

  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, Depending on the purpose, metals, metal complexes, dyes, pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants Further, metal oxides such as ion exchange resin and titanium oxide can be added.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used for various applications. 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. Moreover, the polymer obtained by superposing | polymerizing after orientating has optical anisotropy, and is useful. Such an optical anisotropic body includes, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth, a substrate on which an organic thin film is formed, or an alignment film on which SiO ₂ is obliquely deposited. It can be produced by polymerizing the polymerizable liquid crystal composition after it is supported on a substrate having it or sandwiched between substrates.

  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, and printing. . Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. As the organic solvent, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, aprotic solvents and the like 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 Isopropanol, acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone or N-methylpyrrolidinone as the ketone solvent, ethyl acetate or cellosolve as the ester solvent, dimethyl as the aprotic solvent It can be mentioned formamide or acetonitrile. 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, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability 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 a substrate is effective for improving the adhesion between a polymer obtained by polymerizing a polymerizable liquid crystal material and the substrate.

  Examples of the alignment treatment other than the above include use of fluid alignment of a liquid crystal material, use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and 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, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

When the polymerizable liquid crystal composition containing the compound of the present invention is polymerized, it is desirable that the polymerization proceeds rapidly. Therefore, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation exists in the temperature range by which the liquid crystal state of the polymeric liquid crystal composition of this invention is hold | maintained. In particular, when an optical anisotropic body is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. It is preferable to make 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 great amount of time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

  The optical anisotropic body obtained by polymerization can be subjected to a heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. 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 optical anisotropic body manufactured by such a method may be peeled off from the substrate and used alone or without being peeled off. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
Example 1 Production of Compound Represented by Formula (I-1)

  To a reaction vessel equipped with a dropping funnel and a thermometer, 20.0 g (0.090 mol) of a compound represented by the formula (I-1-1), 10.6 g (0.13 mol) of pyridine, and 120 mL of dichloromethane were added. . While cooling with ice, 9.15 g (0.12 mol) of acetyl chloride was added dropwise. After the reaction, the mixture was washed successively with 5% hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate and brine, purified by column chromatography (silica gel) and recrystallization, and 23.3 g of the compound represented by the formula (I-1-2). (0.088 mol) was obtained.

  In a reaction vessel equipped with a thermometer and purged with nitrogen, 23.3 g (0.088 mol) of the compound represented by the formula (I-1-2) and 16.7 g of the compound represented by the formula (I-1-3) ( 0.097 mol), tetrakis (triphenylphosphine) palladium (0) 1.02 g (0.88 mmol), copper (I) iodide 0.33 g (1.8 mmol), triethylamine 30 mL, N, N-dimethyl 90 mL of formamide was added and heated at 90 ° C. After the reaction, the mixture was diluted with toluene, washed with 5% hydrochloric acid, water and brine, purified by column chromatography (silica gel) and recrystallization, and 21.9 g of the compound represented by the formula (I-1-4) ( 0.062 mol) was obtained.

  To a reaction vessel equipped with a cooler and a thermometer, 21.9 g (0.062 mol) of the compound represented by the formula (I-1-4), 19.7 g of 25% aqueous sodium hydroxide and 100 mL of methanol were added and heated to reflux. I let you. After the reaction, water and 10% hydrochloric acid were added dropwise for neutralization, and the precipitate was filtered. The solid was sufficiently washed with water and dried to obtain 19.3 g (0.062 mol) of a compound represented by the formula (I-1-5).

In a reaction vessel equipped with a thermometer, 19.3 g (0.062 mol) of the compound represented by the formula (I-1-5) and 11.9 g (0. 1 mol) of the compound represented by the formula (I-1-6). 080 mol), 12.8 g (0.092 mol) of potassium carbonate and 120 mL of N, N-dimethylformamide were added and heated at 90 ° C. After the reaction, dichloromethane was added and the mixture was washed with 5% hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 20.9 g of a compound represented by the formula (I-1).
Phase transition temperature: C 85 N 104 I
¹ H NMR (CDCl ₃ ) δ 0.90 (t, 6.6 Hz, 3H), 1.32 (m, 4H), 1.62 (quin, 6.8 Hz, 2H), 2.24 (quin, 6 .3 Hz, 2 H), 2.62 (t, 7.9 Hz, 2 H), 4.19 (t, 6.1 Hz, 2 H), 4.41 (t, 6.2 Hz, 2 H), 5.85 (dd , 10.4, 1.4 Hz, 1H), 6.14 (dd, 17.3, 10.4 Hz, 1H), 6.43 (dd, 17.3, 1.4 Hz, 1H), 7.11- 7.18 (m, 4H), 7.47 (d, 7.8 Hz, 2H), 7.53 (dd, 8.5, 1.2 Hz, 1H), 7.69 (dd, 14.5, 8 .8 Hz, 2H), 7.97 (s, 1H) ppm.
¹³ C NMR (CDCl ₃ ) δ 14.0, 22.5, 28.5, 30.9, 31.4, 35.8, 61.3, 64.3, 89.2, 89.3, 106. 4, 118.4, 119.5, 120.4, 126.7, 128.3, 128.4, 128.5, 129.0, 129.3, 131.0, 131.1, 131.4, 133.9, 143.3, 157.3, 166.2 ppm.
Example 2 Production of Compound Represented by Formula (I-2)

It is represented by the formula (I-2) in the same manner as in Example 1 except that the compound represented by the formula (I-1-3) is replaced with the compound represented by the formula (I-2-2). A compound was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
¹ H NMR (CDCl ₃ ) δ 0.90 (t, 6.6 Hz, 3H), 1.33 (m, 2H), 1.62 (quin, 6.8 Hz, 2H), 2.24 (quin, 6 .3 Hz, 2 H), 2.62 (t, 7.9 Hz, 2 H), 4.19 (t, 6.1 Hz, 2 H), 4.41 (t, 6.2 Hz, 2 H), 5.85 (dd , 10.4, 1.4 Hz, 1H), 6.14 (dd, 17.3, 10.4 Hz, 1H), 6.43 (dd, 17.3, 1.4 Hz, 1H), 7.11- 7.18 (m, 4H), 7.47 (d, 7.8 Hz, 2H), 7.53 (dd, 8.5, 1.2 Hz, 1H), 7.69 (dd, 14.5, 8 .8 Hz, 2H), 7.97 (s, 1H) ppm.
¹³ C NMR (CDCl ₃ ) δ 14.0, 22.1, 28.5, 33.4, 35.5, 61.3, 64.3, 89.2, 89.3, 106.4, 118. 4, 119.5, 120.4, 126.7, 128.3, 128.4, 128.5, 129.0, 129.3, 131.0, 131.1, 131.4, 133.9, 143.3, 157.3, 166.2 ppm.
LRMS: 412
HRMS: 412.20
Example 3 Production of Compound Represented by Formula (I-3)

  In a reaction vessel equipped with a thermometer and a condenser, 50.00 g (0.224 mol) of a compound represented by the formula (I-3-1), 27.55 g (0.291 mol) of 3-chloropropanol, carbonic acid 109.55 g (0.366 mol) of cesium and 300 mL of dimethyl sulfoxide were added. The mixture was stirred with heating at 75 ° C. for 5 hours, diluted with ethyl acetate, and washed with hydrochloric acid and brine. Purification was performed by column chromatography (alumina) and recrystallization to obtain 40.01 g of a compound represented by the formula (I-3-2).

  In a reaction vessel equipped with a thermometer and a cooler, 16.09 g (0.0572 mol) of the compound represented by formula (I-3-2) and compound 15.15 represented by formula (I-3-3) 00 g (0.0629 mol), copper (I) iodide 0.22 g (1.16 mmol), N, N-dimethylformamide 97 mL, and triethylamine 32 mL were added. After substituting with nitrogen, 0.66 g (0.571 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 86 ° C. for 5 hours. The reaction solution was poured into water, and the precipitated solid was filtered and washed. By dissolving in dichloromethane and performing column chromatography (alumina) and recrystallization, 15.8 g of a compound represented by the formula (I-3-4) was obtained.

In a reaction vessel equipped with a thermometer and a dropping funnel, 15.77 g (0.0360 mol) of the compound represented by the formula (I-3-4), 6.97 g (0.0539 mol) of diisopropylethylamine, and 200 mL of dichloromethane were added. added. While cooling with ice, 4.23 g (0.0467 mol) of acryloyl chloride was added dropwise. After stirring at room temperature for 5 hours, the mixture was washed with hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 6.1 g of a compound represented by the formula (I-3).
Phase transition temperature: C 120 N> 200 I
¹ H NMR (CDCl ₃ ) δ 0.98 (t, 3H), 1.68 (m, 2H), 2.24 (quin, 2H), 2.62 (t, 2H), 4.20 (t, 2H), 4.41 (t, 2H), 5.84 (dd, 1H), 6.14 (dd, 1H), 6.43 (dd, 1H), 7.01 (m, 2H), 7. 15 (m, 2H), 7.36 (t, 1H), 7.55 (d, 3H), 7.62 (d, 2H), 7.70 (dd, 2H), 7.99 (s, 1H) ) Ppm.
¹³ C NMR (CDCl ₃ ) δ 13.7, 24.2, 28.6, 37.4, 61.3, 64.4, 89.0, 90.5, 106.6, 115.9, 116. 1,118.2,119.5,122.4,124.5,124.6,125.4,125.5,126.8,128.3,128.5,128.8,128.8, 129.0, 129.4, 130.1, 130.1, 130.9, 131.3, 131.6, 134.1, 135.7, 144.7, 144.8, 157.4, 158. 4, 160.9, 166.2 ppm.
Example 4 Production of Compound Represented by Formula (I-4)

A compound represented by the formula (I-4) was obtained in the same manner as in Example 3 except that the formula 3-chloropropanol was replaced with 6-chlorohexanol.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 534
HRMS: 534.26
Example 5 Production of Compound Represented by Formula (I-5)

  To a reaction vessel equipped with a thermometer and a dropping funnel, 50.0 g (0.224 mol) of the compound represented by the formula (I-1-1) and 150 mL of dichloroethane were added. 33.3 g (0.247 mol) of sulfuryl chloride was added dropwise. After stirring at 30 ° C. for 5 hours, ethyl acetate was added and washed with brine. Purification was performed by column chromatography (alumina) and dispersion washing to obtain 52.7 g of a compound represented by the formula (I-5-1).

It is represented by the formula (I-5) by the same method except that the compound represented by the formula (I-1-1) in Example 1 is replaced with the compound represented by the formula (I-5-1). A compound was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 460
HRMS: 460.18
Example 6 Production of Compound Represented by Formula (I-6)

In a reaction vessel equipped with a thermometer and a dropping funnel, 12.0 g (0.0372 mol) of the compound represented by the formula (I-6-1) and the compound represented by the formula (I-1-5) 11. 7 g (0.0372 mol), 0.23 g (1.86 mmol) of N, N-dimethylaminopyridine and 100 mL of dichloromethane were added. While cooling with ice, 5.64 g (0.0447 mol) of diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 5 hours, the mixture was washed with hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 16.1 g of a compound represented by the formula (I-6).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 618
HRMS: 618.33
Example 7 Production of Compound Represented by Formula (I-7)

  In a reaction vessel equipped with a thermometer, 30.0 g (0.118 mol) of the compound represented by the formula (I-7-1), 12.8 g (0.13 mol) of trimethylsilylacetylene, copper (I) iodide 0.45 g (2.36 mmol), N, N-dimethylformamide 150 mL, and triethylamine 50 mL were added. After nitrogen substitution, 1.37 g (1.18 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was stirred with heating at 90 ° C. for 8 hours. Purification was performed by column chromatography (silica gel) to obtain 25.6 g (0.0945 mol) of a compound represented by the formula (I-7-2).

  In a reaction vessel equipped with a thermometer, 25.6 g (0.0945 mol) of the compound represented by formula (I-7-2) and 15.5 g (0 of compound represented by formula (I-7-3)) 0.0945 mol), 19.6 g (0.142 mol) of potassium carbonate, and 200 mL of tetrahydrofuran were added. After nitrogen substitution, 1.09 g (0.945 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 8 hours. Purification was performed by column chromatography (silica gel) to obtain 23.5 g (0.0756 mol) of a compound represented by the formula (I-7-4).

  To the reaction vessel, 23.5 g (0.0756 mol) of the compound represented by the formula (I-7-4), 200 mL of methanol, and 20.9 g (0.151 mol) of potassium carbonate were added and stirred at room temperature for 10 hours. . Hexane was added and the mixture was washed with brine, and purified by column chromatography (silica gel) and recrystallization to obtain 17.5 g (0.0734 mol) of the compound represented by the formula (I-7-5).

  In a reaction vessel equipped with a thermometer, 17.5 g (0.0734 mol) of the compound represented by the formula (I-7-5) and 16.4 g of the compound represented by the formula (I-3-1) (0. 0734 mol), 0.28 g (1.47 mmol) of copper (I) iodide, 200 mL of N, N-dimethylformamide, and 70 mL of triethylamine were added. After substituting with nitrogen, 0.85 g (0.73 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and stirred at 90 ° C. for 8 hours. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 19.5 g (0.0513 mol) of a compound represented by the formula (I-7-6).

In a reaction vessel equipped with a thermometer, 19.5 g (0.0513 mol) of the compound represented by the formula (I-7-6), 13.7 g (0.0668 mol) of 6-chlorohexyl methacrylate, potassium carbonate 10 .6 g (0.0770 mol) and 200 mL of N, N-dimethylformamide were added. The mixture was heated and stirred at 80 ° C. for 10 hours. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 19.6 g of a compound represented by the formula (I-7).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 548
HRMS: 548.27
Example 8 Production of Compound Represented by Formula (I-8)

  In a reaction vessel equipped with a thermometer, 30.0 g (0.162 mol) of the compound represented by the formula (I-8-1), 23.9 g (0.243 mol) of trimethylsilylacetylene, copper (I) iodide 0.62 g (3.24 mmol), N, N-dimethylformamide 150 mL, and triethylamine 50 mL were added. After replacing with nitrogen, 1.87 g (1.62 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 90 ° C. for 8 hours. Purification was performed by column chromatography (silica gel) to obtain 26.2 g (0.130 mol) of a compound represented by the formula (I-8-2).

  To the reaction vessel, 26.2 g (0.130 mol) of the compound represented by the formula (I-8-2), 200 mL of methanol, and 35.8 g (0.259 mol) of potassium carbonate were added and stirred at room temperature for 10 hours. . Hexane was added and the mixture was washed with brine, and then purified by column chromatography (silica gel) and recrystallization to obtain 16.0 g (0.123 mol) of a compound represented by the formula (I-8-3).

  In a reaction vessel equipped with a thermometer, 30.0 g (0.134 mol) of the compound represented by the formula (I-3-1) and 23.9 g (0. 3 mol) of the compound represented by the formula (I-8-4). 175 mol), 27.9 g (0.202 mol) of potassium carbonate, and 300 mL of N, N-dimethylformamide were added. The mixture was heated and stirred at 80 ° C. for 60 hours. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 34.8 g (0.108 mol) of a compound represented by the formula (I-8-5).

  In a reaction vessel equipped with a thermometer, 15.0 g (0.0464 mol) of a compound represented by formula (I-8-5) and 6.04 g (0 of compound represented by formula (I-8-3)) 0.064 mol), 0.18 g (0.93 mmol) of copper (I) iodide, 150 mL of N, N-dimethylformamide, and 50 mL of triethylamine were added. After substituting with nitrogen, 0.54 g (0.46 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 90 ° C. for 8 hours. Purification was performed by column chromatography (silica gel) to obtain 12.1 g (0.0325 mol) of a compound represented by the formula (I-8-6).

In a reaction vessel equipped with a thermometer and a dropping funnel, 12.1 g (0.0325 mol) of the compound represented by the formula (I-8-6) and 3.43 g of the compound represented by the formula (I-8-7) (0.0390 mol), 10.2 g (0.0390 mol) of triphenylphosphine, and 100 mL of tetrahydrofuran were added. While cooling with ice, 7.88 g (0.0390 mol) of diisopropyl azodicarboxylate was added dropwise. After stirring at room temperature for 4 hours, purification was performed by column chromatography (silica gel) and recrystallization to obtain 8.62 g of a compound represented by the formula (I-8).
LRMS: 442
HRMS: 442.25
Example 9 Production of Compound Represented by Formula (I-9)

  In a reaction vessel equipped with a thermometer, 30.0 g (0.100 mol) of the compound represented by the formula (I-5-2) and 13.2 g (0) of the compound represented by the formula (I-9-1) 100 mol), 0.38 g (2.00 mmol) of copper (I) iodide, 150 mL of N, N-dimethylformamide, and 50 mL of triethylamine were added. After nitrogen substitution, 1.16 g (1.00 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 90 ° C. for 5 hours. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 28.1 g (0.0801 mol) of a compound represented by the formula (I-9-2).

  To the reaction vessel were added 28.1 g (0.0801 mol) of the compound represented by the formula (I-9-2), 300 mL of ethanol, and 150 mL of 20% aqueous sodium hydroxide, and the mixture was heated to reflux for 5 hours. After neutralizing with hydrochloric acid, purification was performed by column chromatography (silica gel) and recrystallization to obtain 24.0 g (0.0777 mol) of the compound represented by the formula (I-9-3).

In a reaction vessel equipped with a thermometer and a dropping funnel, 10.0 g (0.0324 mol) of the compound represented by the formula (I-9-3) and the compound represented by the formula (I-9-4) 9. 47 g (0.0324 mol), 0.40 g (3.24 mmol) of N, N-dimethylaminopyridine and 200 mL of dichloromethane were added. While cooling with ice, 4.90 g (0.0389 mol) of diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 5 hours, purification was performed by column chromatography (silica gel) and recrystallization to obtain 13.2 g of a compound represented by the formula (I-9).
Phase transition temperature: C 100 N> 250 I
¹ H NMR (CDCl ₃ ) δ 1.48-1.57 (m, 4H), 1.73 (quin, 7.3 Hz, 2H), 1.86 (quin, 7.3 Hz, 2H), 3.84 (S, 3H), 4.07 (t, 6.5 Hz, 2H), 4.19 (t, 6.5 Hz, 2H), 5.82 (dd, 1.6, 10.5 Hz, 1H), 6 .13 (dd, 10.3, 17.2 Hz, 1H), 6.41 (dd, 1.4, 17.2 Hz, 1H), 6.91 (d, 8.9 Hz, 2H), 7.00 ( d, 8.9 Hz, 2H), 7.41 (d, 8.9 Hz, 1H), 7.52 (d, 8.9 Hz, 2H), 7.70 (dd, 1.5, 8.9 Hz, 1H) ), 7.78 (d, 9.0 Hz, 1H), 8.05 (s, 1H), 8.22-8.25 (m, 3H) ppm.
¹³ C NMR (CDCl ₃ ) δ 25.7, 25.7, 25.8, 28.5, 28.9, 55.3, 64.4, 68.1, 87.8, 90.8, 114. 1, 114.4, 115.0, 120.9, 121.7, 122.8, 123.4, 124.4, 127.5, 128.5, 130.1, 130.5, 130.6, 131.1, 132.0, 132.6, 133.2, 145.6, 159.8, 163.7, 164.1, 166.3 ppm.
LRMS: 582
HRMS: 582.18
Example 10 Production of Compound Represented by Formula (I-10)

  In a reaction vessel equipped with a thermometer, 30.0 g (0.108 mol) of the compound represented by the formula (I-10-1), 13.8 g (0.141 mol) of trimethylsilylacetylene, copper (I) iodide 0.41 g (2.16 mmol), N, N-dimethylformamide 150 mL, and triethylamine 50 mL were added. After nitrogen substitution, 1.25 g (1.08 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 90 ° C. for 10 hours. Purification was performed by column chromatography (silica gel) to obtain 23.9 g (0.0812 mol) of a compound represented by the formula (I-10-2).

  To the reaction vessel were added 23.9 g (0.0812 mol) of the compound represented by the formula (I-10-2), 16.8 g (0.122 mol) of potassium carbonate, and 200 mL of methanol, and the mixture was stirred at room temperature. Purification was performed by liquid separation washing and column chromatography (silica gel) to obtain 17.7 g (0.0795 mol) of a compound represented by the formula (I-10-3).

  In a reaction vessel equipped with a thermometer, 17.7 g (0.0795 mol) of the compound represented by the formula (I-10-3) and 25.7 g (0 of the compound represented by the formula (I-8-5)) 0.095 mol), 0.30 g (1.59 mmol) of copper (I) iodide, 150 mL of N, N-dimethylformamide, and 50 mL of triethylamine were added. After substituting with nitrogen, 0.92 g (0.80 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated and stirred at 90 ° C. for 9 hours. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 28.8 g (0.0620 mol) of a compound represented by the formula (I-10-4).

In a reaction vessel equipped with a thermometer and a dropping funnel, 28.8 g (0.0620 mol) of the compound represented by the formula (I-10-4), 12.0 g (0.0931 mol) of diisopropylethylamine, and 200 mL of dichloromethane were added. added. While cooling with ice, 7.30 g (0.0807 mol) of acryloyl chloride was added dropwise. After stirring at room temperature, liquid separation washing was performed, and purification was performed by column chromatography (silica gel) and recrystallization to obtain 20.9 g of a compound represented by the formula (I-10).
LRMS: 518
HRMS: 518.28
Example 11 Production of Compound Represented by Formula (I-11)

In Example 10, the compound represented by the formula (I-10-1) is converted into the compound represented by the formula (I-11-1), and the compound represented by the formula (I-8-5) is converted into 4-iodo. A compound represented by the formula (I-11) was obtained by the same method except that it was replaced with phenol.
LRMS: 402
HRMS: 402.14 It is represented by the following formulas (I-12) to (I-42) using the same method as in Examples 1 to 11, a known method, and a method based on the known method. The compound was prepared.

(Examples 12-22, Comparative Examples 1-3)
Compounds represented by Formula (I-1) to Formula (I-11) described in Example 1 to Example 11, Compound (R-1) and Compound (R-2) described in Patent Document 1, Patent Document The compound (R-3) described in 2 was used as an evaluation target compound.

  In order to evaluate the storage stability, the stable storage concentration of the compound to be evaluated was measured. The stable storage concentration was determined by preparing a composition in which the compound to be evaluated was added to the base liquid crystal in increments of 10% from 10% to 50%, and after leaving the prepared composition at 15 ° C. for 500 hours, Is defined as the maximum concentration of the compound at which no occurrence occurs. A compound having a large maximum addition concentration has a high stable storage concentration, meaning that no crystal precipitation occurs even after long-term storage.

  In order to measure the stable storage concentration, a liquid crystal composition comprising the following compound (X-1): 30%, compound (X-2): 30% and compound (X-3): 40% was used as the base liquid crystal (X). It was. The measurement results are shown in Table 1 below.

From Table 1, formula (I-1) to formula (I-5), formula (I-7), which is the present invention described in Examples 12 to 16, Example 18, Example 19, and Example 21, The compounds represented by the formula (I-8) and the formula (I-10) are both crystalline as compared with (R-1) and (R-3) which are the compounds described in Comparative Examples 1 to 3. It can be seen that the maximum addition concentration at which precipitation does not occur is high and shows high storage stability.
(Examples 23 to 33, Comparative Examples 4 to 6)
3% of photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to each of the compositions prepared by adding 30% of the target compound to the base liquid crystal (X) and then dissolved in cyclopentanone. A 25% solution was obtained. This solution was applied to a glass with polyimide subjected to a rubbing treatment by a spin coating method and dried at 65 ° C. for 3 minutes. The obtained coating film was placed on a hot plate at 60 ° C. and irradiated with ultraviolet rays at an intensity of 20 mW / cm ² for 60 seconds. The obtained polymer was evaluated for haze value and unevenness. The haze value is the following formula haze (%) = Td / Tt × 100
(In the formula, Td represents diffuse transmittance, and Tt represents total light transmittance.) For measurement, a haze measuring device (NHD2000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used, and measurement was performed at the center of the substrate. . In addition, if there is no unevenness or the like on the film by visual inspection, it is ◎, if there is slight unevenness, ○, if slightly unevenness is found, Δ, if very unevenness is seen. Is x. The results are shown in Table 2 below.

From Table 2, the compounds represented by the formulas (I-1) to (I-4) according to the present invention described in Examples 23 to 26 are all compounds described in Comparative Examples 4 to 6. It can be seen that the haze is low and the unevenness is small as compared with (R-1) to (R-3). In addition, formulas (I-5) to (I-8), (I-10) and (I-11) according to the present invention described in Examples 27 to 30, 32 and 33 are used. It can be seen that the compounds represented by the formulas (H-1) and (R-3) are the compounds described in Comparative Example 4 to Comparative Example 6 and the haze is the same or lower and the unevenness is the same or less.
The obtained polymer was post-baked at 200 ° C. for 60 minutes. In order to compare the magnitude of the phase difference change of the film after post-baking, the phase difference Re (550) at 550 nm before and after post-baking was measured, and the phase difference Re (550) before and after post-baking was measured. Retention rate (retardation retention rate (%) = (Re (550) (after post-baking)) / (Re (550) (before post-baking))) × 100) was calculated. For measuring the phase difference, RETS-100 manufactured by Otsuka Electronics Co., Ltd. was used. The results are shown in Table 3 below.

  From Table 3, from the formula (I-1) to the formula (I-4), the formula (I) of the present invention described in the examples 23 to 26, the example 28, the example 29, the example 31 and the example 32. -6), Formula (I-7), Formula (I-9), and the film containing the compound represented by Formula (I-10) are all the compounds described in Comparative Example 4 to Comparative Example 6 (R As compared with the film containing -1) to (R-3), the retardation retention was high. Moreover, all the films containing the compound represented by the formula (I-5), the formula (I-8) and the formula (I-11) which are the inventions of Examples 27, 30 and 33 are all included. Compared with the film containing (R-1) to (R-3), which are the compounds described in Comparative Examples 4 to 6, the retardation retention was equal or higher. Thus, all the films containing the compounds represented by formula (I-1) to formula (I-11), which are the inventions described in Examples 23 to 33, all exhibit high retardation retention. I understand.

  From the above results, the compounds represented by the formulas (I-1) to (I-11), which are the inventions of the present invention described in Examples 1 to 11, have storage stability when constituting a polymerizable composition. The optically anisotropic body using the compound of the present invention has less haze and unevenness, and it is understood that the decrease in retardation is small even when heat-treated. Therefore, the compound of the present invention is useful as a constituent member of the polymerizable composition. Moreover, the optical anisotropic body using the composition containing the compound of this invention is useful for uses, such as an optical film.

Claims (16)

Formula (I)

(Wherein P represents a polymerizable group,
Sp represents a spacer group or a single bond, and when a plurality of Sp are present, they may be the same or different,
X represents —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 -, - (C (Y ¹ ) ₂ ) _n1 −, —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 -, - CY 1}} = CY 1 - ( wherein, ^{Y 1} are each independently hydrogen atom, 12 Al of from 1 carbon atoms Group, a fluorine atom, a chlorine atom or a cyano group, n1 represents an integer of 1 to 6, if Y ¹ there are a plurality thereof may be different even in the same.) Or a single bond In the case where a plurality of Xs are present, they may be the same or different,
A ¹ and A ⁴ are each independently 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, cyclohexane-1,4-diyl, 1,4-cyclohexenylene, bicyclo [ 2.2.2] Octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, thiophene-2,5-diyl or fluorene-2,7-diyl, these groups being unsubstituted or one or more And one or more ═CH— groups in these ring structures may be substituted with ═N—, or one or more non-consecutive —CH ₂ — groups in these groups may be Independent May be substituted with -O- or -S-, and when a plurality of A ¹ and A ⁴ are present, they may be the same or different,
A ² and A ³ are each independently 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, cyclohexane-1,4-diyl, 1,4-cyclohexenylene, bicyclo [ 2.2.2] Octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, thiophene-2,5-diyl or fluorene-2,7-diyl, these groups being unsubstituted or one or more And one or more ═CH— groups in these ring structures may be substituted with ═N—, or one or more non-consecutive —CH ₂ — groups in these groups may each be Independent May be substituted with -O- or -S-
At least one of A ² and A ³ represents naphthalene-2,6-diyl which may be unsubstituted or substituted by one or more Ls;
Z ¹ and Z ² are each independently a single bond, —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 —, — (C (Y ¹ ) ₂ ) _n1 —, —CH ₂ CF ₂ —, —CF ₂ CH 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 -, - CY 1 = C Y ¹ — or —C≡C— (wherein Y ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group; 6 represents an integer of 6; when a plurality of Y ¹ are present, they may be the same or different.) When a plurality of Z ¹ and Z ² are present, they are the same or different. Well,
n represents an integer of 0 to 10,
m1 and m2 represent integers from 0 to 5,
R represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 20 carbon atoms, and two or more non-adjacent —CH ₂ — in the alkyl group are each independently -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O- may be substituted, and the alkyl group may be linear or branched. The hydrogen atom bonded to the carbon atom in the group may be replaced by a fluorine atom, but when R represents a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a methoxy group or a thiomethoxy group, m1 is from 1 Represents an integer of 5,
L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, —N (Y ³ ) ₂ , —Si (Y ³ ) ₃ , one —CH ₂ —. Or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O—. A linear or branched alkyl group having 1 to 20 atoms (wherein Y ³ is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, A cyano group, a hydroxyl group, a linear or branched alkyl group having 1 to 20 carbon atoms, and when there are a plurality of Y ^3, they may be the same or different), a hydroxyl group or Represents a mercapto group. ) A compound represented by In the general formula (I), A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , m ¹ , m ² n and L represent the same as defined in claim 1,
P is the following formula (P-1) to formula (P-18)

Represents a group selected from
When a plurality of Sps appear, they may be the same or different, and each independently represents one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O—, The compound according to claim 1, which represents an alkylene group having 1 to 20 carbon atoms or a single bond which may be replaced by -COO-, -OCO- or -OCO-O-. The compound of Claim 1 or Claim 2 represented by the following general formula (i-1) to (i-9).

Wherein R, P, Sp, X, A ¹ , A ⁴ , Z ¹ , Z ² , m 1, m ² and L are each independently the same as defined in claim 1 or claim 2. Each independently represents an integer from 0 to 4, and each s independently represents an integer from 0 to 3, provided that R represents a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group or a thiomethoxy group. (When expressed, m1 represents an integer of 1 to 5.) R is one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —COO—, —OCO—. The compound according to any one of claims 1 to 3, which represents a linear or branched alkyl group. L is a fluorine atom, a chlorine atom, one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently replaced with —O—, —COO—, or —OCO—. The compound according to any one of claims 1 to 4, which represents a linear or branched alkyl group having 1 to 10 carbon atoms. When a plurality of Sp are present, they may be the same or different, and each independently represents one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O—, The compound as described in any one of Claims 1-5 which represents the C1-C20 alkylene group which may be substituted by -COO-, -OCO-, or -OCO-O-.   When a plurality of Xs appear, they may be the same or different from each other, and each independently represents a single bond, —O—, —S—, —COO—, —OCO—, —CO—S— or —S—CO. The compound according to any one of claims 1 to 6, which represents-.   The compound according to any one of claims 1 to 7, wherein n represents 1. When a plurality of Z ¹ and Z ² appear, they may be the same or different, and each independently represents a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—. S -, - S-CO - , - CH = CH-COO -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO - or a compound according to any one of _-CH 2 _CH 2 -OCO- claims 1 to 8 representing the. The compound as described in any one of Claims 1-9 represented by the following general formula (ia-1) to (ia-3).

(Wherein P, Sp, X, L, r and s each independently represent the same as defined in claims 1 to 3, Z ^1a and Z ^2a are a single bond, —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 R ¹ represents carbon in which one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently replaced by —O—, —COO—, or —OCO—. Represents a linear or branched alkyl group having 1 to 10 atoms.)   The composition containing the compound as described in any one of Claims 1-10.   The liquid crystal composition containing a compound as described in any one of Claims 1-10. The liquid crystal composition has the general formula (II)

(Wherein P ¹ and P ² each independently represent the same meaning as P in formula (I), and S ¹ and S ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms) represents a one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced by a, ^{X 1} and X ² is each independently a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S. _{-CO -, - O-CO-} O -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CH = N _{-, - SCH 2 -, -} CH 2 S -, - 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—, —CF ₂ —, —CF ₂ O—, —OCF ₂ —, —CY ¹ = CY ¹ — Y ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group.) Or —C≡C—, and Z ³ each independently represents a single atom. _{bond, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O-CO- _{O -, - OCOOCH 2 -,} - CH 2 OCOO -, - CO-NH -, - NH-CO -, - SCH 2 _{-, - CH 2 S -,} - CH = N -, - SCH 2 -, - CH 2 S -, - 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—, —CF ₂ —, —CF ₂ O—, —OCF ₂ —, —CY ² = CY ² — (where Y ² Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group. ) Or -C≡C-, and A ⁵ and A ⁶ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5 - diyl group, naphthalene-2,6-diyl group, represents a tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, ^{a 5} and ^{a 6} are each independently unsubstituted May be substituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen atom, a cyano group, or a nitro group, m3 represents 0, 1, 2, or 3; When A represents 2 or 3, A ⁵ and / or Z ³ present in two or three may be the same or different, but the compound represented by the general formula (I) is excluded. The liquid crystal composition according to claim 12, comprising at least one selected from the group consisting of compounds represented by:   A polymer obtained by polymerizing the composition according to any one of claims 11 to 13.   An optical anisotropic body using the polymer according to claim 14.   A resin, a resin additive, an oil, an oil filter, an oil, an ink, a pharmaceutical, a cosmetic, a detergent, a liquid crystal material, an agrochemical and a food containing the compound according to any one of claims 1 to 10, and a product using them .