JP6102423B2 - Polymerizable compound and optical element - Google Patents

Description

  The present invention relates to a polymerizable compound, a liquid crystal material using the polymerizable compound, a resin, a resin additive, an oil, an oil filter, an oil, an ink, a pharmaceutical product, a cosmetic, a detergent, an agrochemical, a food, and various products.

  A PSA (Polymer Sustained Alignment) type liquid crystal display element, which is one of the types of TFT liquid crystal display elements, has a polymer structure for controlling the pretilt angle in the cell, enabling high-contrast display and high-speed response. is there. This device is produced by injecting a liquid crystal composition to which a polymerizable compound is added into a cell, and performing UV irradiation in a state where a voltage is applied to polymerize the polymerizable compound.

  As a problem of such a liquid crystal display element, image sticking that occurs when the same display is continued for a long time is known. One reason for this is that the pretilt angle changes with time because the polymer structure is unstable. In order to form a stable polymer structure, it is necessary to completely polymerize the added polymerizable compound and to use a polymerizable compound in which the polymer structure does not easily change when polymerized. In order to completely polymerize the added polymerizable compound, it is effective to irradiate high-intensity UV or longer UV, but on the other hand, deterioration of the liquid crystal material due to UV is promoted. End up. Therefore, in order to prevent burn-in without deteriorating the liquid crystal material, the development of a polymerizable compound that is polymerized by UV irradiation as low as possible and as short as possible, and the polymer structure formed by polymerization is stable and the pretilt angle is difficult to change. Is required.

  A polymerizable compound generally known in the field has a problem that solubility in a liquid crystal material is insufficient and an uncured monomer tends to remain (Patent Document 1). A compound has been reported that introduces a mesogenic skeleton with absorption at a long wavelength and has improved photosensitization, but the compound has insufficient solubility in liquid crystal materials and low stability of the pretilt angle. (Patent Document 2). Moreover, although the compound which improved the reactivity by increasing the number of polymerizable functional groups has been reported, there existed a problem which image sticking occurred by the display for a long time (patent document 3).

JP 2003-307720 A Special table 2011-515543 gazette Special table 2010-536894 gazette

  The problem to be solved by the present invention is that the solubility in a liquid crystal material is high, the amount of uncured monomer is small when added to the liquid crystal material to produce a PSA type display element, and the stability of the pretilt angle is high. It is to provide a polymerizable compound that hardly causes seizure. Moreover, it is providing the liquid crystal material containing the said polymeric compound.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polymerizable compound having a specific structure can solve the above-mentioned problems, and have completed the present invention.

  The present invention relates to the general formula (I)

(In the formula, R ¹ is a group represented by P-Sp-, 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, -N. (Y ² ) ₂ , —Si (Y ² ) ₃ , one —CH ₂ — or an alkyl group having 1 to 20 carbon atoms, but two or more —CH that are not adjacent to each other in the alkyl group ₂ may be each independently replaced by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O-, and the alkyl group may be linear or branched. (Wherein Y ² is a group represented by P-Sp-, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, hydroxyl group) Groups, straight or branched alkyls of 1 to 20 carbon atoms Represents a, they may be different even in the same case where Y ² there are a plurality.),
m ¹ represents 0 or 1, m ² represents an integer of 1 to 4,
A ¹ and A ³ are each independently 1,2-phenylene, naphthalene-1,2-diyl, naphthalene-2,3-diyl, naphthalene-2,8-diyl, naphthalene-1,8-diyl, naphthalene. -1,7-diyl, cyclohexane-1,2-diyl, 1,2-cyclohexenylene, decahydronaphthalene-1,2-diyl, decahydronaphthalene-1,8-diyl, decahydronaphthalene-2,3 -Diyl, decahydronaphthalene-1,7-diyl, decahydronaphthalene-2,8-diyl, indan-1,7-diyl or indan-1,2-diyl, these groups being unsubstituted or 1 One or more ═CH— in these ring structures may be substituted with ═N—, or one or more in these ring structures may be substituted by one or more L. Nonconsecutive -CH ₂ - are each independently -NH -, - may be substituted by O- or -S-,
A ² represents 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, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane -2,5-diyl, thiophene-2,5-diyl or fluorene-2,7-diyl, but these groups may be unsubstituted or substituted by one or more L, in these ring structures One or more ═CH— may be substituted with ═N—, or one or more non-sequential —CH ₂ — in these groups may each independently be —NH—, —O—, or —S—. May be replaced, ^{If 2} is A ² represents a 2-4 there are a plurality thereof may be the same or different and
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═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 - or an -C≡C- (wherein, Y Is a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group, n1 represents an integer of 1 to 6, even they are the same if Y ¹ there are a plurality of May be different.), When m ² represents ² to 4 and a plurality of Z ² are present, they may be the same or different,
The L is a group represented by P-Sp-, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, hydroxyl group, -N (Y ³ ). ₂ , —Si (Y ³ ) ₃ , one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—. , -OCO-, -OCO-O-, a linear or branched alkyl group having 1 to 20 carbon atoms (wherein Y ³ is a group represented by P-Sp-, 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, Y ³ If there are multiple, they are the same but different Which may be.) Represent, they will when L there are a plurality may be the same or different and
The Sp represents a spacer group or a single bond, and when a plurality of Sp are present, they may be the same or different, and the P represents a polymerizable group, but when a plurality of P are present, they are May be the same or different. ), A polymerizable composition containing the polymerizable compound, a liquid crystal composition containing the polymerizable compound, an optical element using the polymerizable compound, and a liquid crystal containing the polymerizable compound An optical element using the composition is provided.

  The polymerizable compound of the present invention is useful as a material for a PSA type liquid crystal display element because it is polymerized by low-intensity and short-time UV irradiation, has a high pretilt angle stability, and hardly causes image sticking. In addition, because it is highly soluble in other components, it can be used for liquid crystal materials, resins, resin additives, oils, oil filters, oils and fats, inks, pharmaceuticals, cosmetics, detergents, agricultural chemicals, foods, and products that use them. Useful.

  The present invention provides a polymerizable compound represented by the general formula (I), and also provides a polymerizable composition containing the compound and a liquid crystal display device containing the polymerizable composition.

In the general formula (I), R ¹ is a group represented by P-Sp-, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfur, from the viewpoint of solubility in other components. furanyl group, a nitro group, a cyano group, a hydroxyl _{^{group, -N (Y 2) 2,}} -Si (Y 2) 3, 1 single -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- (In the formula, each Y ² is independently a group represented by P-Sp-, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, or a hydroxyl group. Groups, straight or branched alkyls of 1 to 20 carbon atoms Preferably represents an indicative.) A group represented by P-Sp-, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, a nitro group, a cyano group, one -CH _2- or two or more non-adjacent —CH ₂ — may be independently replaced by —O—, —S—, —CO—, —COO—, —OCO—, or —OCO—O—. More preferably, it represents a linear or branched alkyl group having 1 to 20 carbon atoms, and is a group represented by P—Sp—, a fluorine atom, a chlorine atom, one —CH ₂ — or adjacent. Linear or branched having 1 to 20 carbon atoms in which two or more —CH ₂ — may be independently replaced by —O—, —COO—, —OCO—, —OCO—O— More preferably, it represents an alkyl group, a group represented by P-Sp-, Tsu atom, one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently of -O -, - COO -, - OCO- to carbon atoms which may be replaced 1 It is even more preferable that a linear alkyl group of 1 to 10 is represented, a group represented by P—Sp—, a fluorine atom, one —CH ₂ — or two or more —CH ₂ — that are not adjacent to each other. It is even more preferable that each independently represents a linear alkyl group having 1 to 10 carbon atoms which may be replaced by -O-, -COO-, or -OCO-, and a group represented by P-Sp- Or more preferably it represents a linear alkyl group having 1 to 8 carbon atoms in which one —CH ₂ — may be replaced by —O—, a group represented by P—Sp— or a carbon atom It is particularly preferable to represent a linear alkyl group having a number of 1 to 6.

m ¹ represents 0 or 1, and more preferably represents 0 from the viewpoint of ease of synthesis and solubility in other components.

m ² represents an integer of 1 to 4, but is more preferably an integer of 1 to 3 from the viewpoint of ease of synthesis and solubility in other components, and ease of synthesis and dissolution with other components. It is even more preferable to represent 1 or 2 from the viewpoint of sex.

m ¹ + m ² is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less, from the viewpoint of ease of synthesis and solubility in other components.

A ¹ and A ³ are each independently 1,2-phenylene, naphthalene-1,2-diyl, naphthalene-2,3-diyl, naphthalene-2,8-diyl, naphthalene-1,8-diyl, naphthalene. -1,7-diyl, cyclohexane-1,2-diyl, 1,2-cyclohexenylene, piperidine-2,3-diyl, decahydronaphthalene-1,2-diyl, decahydronaphthalene-1,8-diyl , Decahydronaphthalene-2,3-diyl, decahydronaphthalene-2,7-diyl, decahydronaphthalene-2,8-diyl or indan-1,2-diyl, wherein A ¹ and A ³ are each independently And one or more ═CH— groups may be substituted with ═N— or one or more sequences in these groups may be unsubstituted or substituted by one or more L. The —CH ₂ — groups that are not may each be independently substituted with —O— or —S—.

  From the viewpoint of ease of synthesis and solubility in other components, 1,2-phenylene, naphthalene-1,2-diyl, naphthalene-2,3-, which may be unsubstituted or substituted by one or more Ls Preferably represents diyl, naphthalene-2,8-diyl, naphthalene-1,8-diyl, naphthalene-1,7-diyl, cyclohexane-1,2-diyl, unsubstituted or substituted by one or more L More preferably represents 1,2-phenylene, naphthalene-1,2-diyl, naphthalene-2,3-diyl, naphthalene-1,8-diyl, which may be unsubstituted or substituted by one or more L. It is even more preferable to represent 1,2-phenylene which may be substituted, and even more preferable to represent 1,2-phenylene which may be unsubstituted or substituted with 1 to 3 Ls. It is even more preferable to represent 1,2-phenylene which may be unsubstituted or substituted by 1 or 2 L, and may be 1,2-phenylene which may be unsubstituted or substituted by 1 L. Even more preferably, it represents 1,2-phenylene substituted by one L, and particularly preferred.

A ² represents 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, and when there are a plurality of A ^{2 s} , they may be the same or different. May be unsubstituted or substituted by one or more L, and one or more ═CH— groups may be substituted by ═N— or one or more non-contiguous —CH in these groups. ₂ -group is Each may be independently substituted with -O- or -S-.

From the viewpoint of ease of synthesis and compatibility with other components, A ² may be unsubstituted or substituted with one or more L, 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 Preferably represents -diyl or fluorene-2,7-diyl and is unsubstituted or optionally substituted by one or more L, 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-2,6 More preferably represents -diyl, cyclohexane-1,4-diyl, fluorene-2,7-diyl, 1,4-phenylene or naphthalene-2, which may be unsubstituted or substituted by one or more L More preferably, it represents 6-diyl, and even more preferably represents 1,4-phenylene or naphthalene-2,6-diyl.

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; To an integer of 6 to 6), and when there are a plurality of Z ^{2 s} , they may be the same or different.

Z ¹ and Z ² are single bonds, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO— from the viewpoints of solubility in other components and difficulty of image sticking to the panel. , —COO—, —OCO—, —CF ₂ O—, —OCF 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-, -CY ¹ = CY ¹ -or -C≡C- is preferred (wherein Y ¹ independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom or a chlorine atom, n1 represents an integer of 1 to 6), a single _{bond, -OCH 2 -., - CH} 2 O-, _{CO -, - COO -, -} OCO -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH ^{= CH -, - CY 1 =} CY 1 - or more preferably representing a -C≡C- (. wherein, ^{Y 1} is each independently a hydrogen atom, a fluorine atom or a methyl group), a single bond, _{-OCH 2 -, - CH 2 O} -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - OCO-CH = CH -, - CH = CH It is even more preferred to represent —, —CF═CF— or —C≡C—, a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —CH. Even more preferably represents ═CH— or —C≡C—, a single bond, —COO—, Still more preferably represents an OCO-, and particularly preferably a single bond.

  When a plurality of P appear, they may be the same or different, and each independently represents a polymerizable group. The polymerizable group means a group showing a polymerizable property commonly known in the art, but it is easy to synthesize, has a small amount of unreacted monomer, and has a high pretilt angle stability. Therefore, when a plurality of occurrences occur, they may be the same or different from each other, and each of them is independently represented by the following formulas (P-1) to (P-18):

It is preferable to represent a group selected from Formula (P-1) to Formula (P-13), and each independently represents a group selected from Formula (P-1) and Formula (P-2). ), Formula (P-3), formula (P-4), formula (P-5), formula (P-6), formula (P-7), formula (P-11), formula (P-13) It is further preferable to represent a group selected from: a group selected from formula (P-1), formula (P-2), formula (P-7), formula (P-11), or formula (P-13). It is even more preferable to represent, and it is particularly preferable to represent a group selected from Formula (P-1) or Formula (P-2).

When a plurality of Sp appear, they may be the same or different and each independently represents a spacer group or a single bond. Here, the spacer group is, for example, Pure Appl. Chem. 73 (5), 845-895 (2001) and C.I. Tschierske, G.M. Pelzl, S.M. Diele, Angew. Chem. 2004, 116, pages 6340-6368 and the like, and means a flexible linking group commonly known in the art. From the viewpoint of solubility in other components and stability of the pretilt angle, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, It preferably represents an alkylene group having 1 to 20 carbon atoms or a single bond which may be replaced by —OCO— or —OCO—O—, one —CH ₂ — or two or more non-adjacent — It is more preferable that CH ₂ — each independently represents an alkylene group having 1 to 10 carbon atoms or a single bond that may be independently replaced by —O—, —COO— or —OCO—, and one —CH ₂ It is more preferable that two or more non-adjacent —CH ₂ — each independently represent an alkylene group having 1 to 10 carbon atoms and a single bond that may be independently replaced by —O—. 2 pcs or non-adjacent - -CH ₂ -CH 2 above _- is still more preferable to represent are each independently -O- alkylene group or a single bond from a good 1 -C 8 be replaced, one -CH adjacent to the ring structure It is particularly preferable that _2- represents an alkylene group having 1 to 8 carbon atoms in which -O- is substituted or a single bond.

When a plurality of L appear, they may be the same or different, and each independently represents a group represented by P-Sp-, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a pentafluorosulfura. Nyl group, nitro group, cyano group, hydroxyl group, —N (Y ³ ) ₂ , —Si (Y ³ ) ₃ , one —CH ₂ —, or two or more —CH ₂ — that are not adjacent to each other. A linear or branched alkyl group having 1 to 20 carbon atoms which may be independently replaced with -O-, -S-, -CO-, -COO-, -OCO-, -OCO-O- ( In the formula, Y ³ is a group represented by P-Sp-, 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, and the number of carbon atoms. Represents 1 to 20 linear or branched alkyl groups However, in the case where a plurality of Y ³ are present, they may be the same or different.) From the viewpoint of ease of synthesis and solubility in other components, P-Sp Group, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. Represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be replaced by -COO- or -OCO-, a group represented by P-Sp-, a hydrogen atom, a fluorine atom , A chlorine atom, one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —COO— or —OCO—. More preferably represents a linear alkyl group of from 1 to 10, and P-Sp- A group represented by a hydrogen atom, a fluorine atom, one -CH 2 _- is more preferable to represent a linear alkyl group having 10 good 1 -C be replaced by -O-, P-Sp It is even more preferable that the group represented by —, a hydrogen atom, a fluorine atom, or one —CH ₂ — represents a linear alkyl group having 1 to 10 carbon atoms in which —O— may be substituted, A group represented by P-Sp-, a hydrogen atom, a fluorine atom, a methyl group or a methoxy group is particularly preferred.

  In the compound represented by the general formula (I), L is preferably contained in an amount of 0 to 5, more preferably 1 to 4 from the viewpoint of ease of synthesis and solubility in other components. Preferably, 1 to 3 is more preferable, and 1 to 2 is particularly preferable. Moreover, it is preferable to contain 1-4 groups represented by P-Sp- among this L.

As a compound represented by the general formula (I), A ³ may be unsubstituted or substituted by one or more L 1,2-phenylene, naphthalene-1,2-diyl or naphthalene-2 , 3-diyl compounds are preferred.

  When a plurality of P are present in the molecule, they may be the same or different.

  When there are a plurality of Sps in the molecule, they may be the same or different.

  Moreover, as a compound represented by general formula (I), the compound represented by the following general formula (Ig) to (Ik) is more preferable.

(Wherein R ¹ , A ¹ , A ² , Z ¹ , Z ² , P, Sp, m ¹ and m ² each independently represent the same as defined above.)

(In the formula, P, Sp, L, r and s each independently represent the same as defined above.)
As the compound represented by the general formula (Ih), a compound represented by the following general formula (Il) is even more preferable, and as the compound represented by the general formula (Ii), represented by the following general formula (Im) A compound is still more preferable, and a compound represented by the following general formula (In) is even more preferable as the compound represented by the general formula (Ij).

(In the formula, P and Sp each independently represent the same as defined above.)
In general formula (Il), general formula (Im), and general formula (In), it is more preferable that Sp is a single bond.

  Specifically, as the compound represented by the general formula (I), compounds represented by the following formulas (I-1) to (I-40) are preferable.

Although the manufacturing method of the compound of this invention is not specifically limited, It can manufacture with the following manufacturing methods.
(Production method 1) Production of a compound represented by the following formula (S-10)

By protecting the hydroxyl protecting group PG ¹ of the compound represented by the formula (S-1), it is possible to obtain a compound represented by the formula (S-2). The protecting group PG ¹ is not particularly limited as long as it can stably protect the hydroxyl group in the subsequent reaction, but, for example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS). , Theodora W. GREENE, A John Wiley & Sons, Inc., Publication). Specific examples of the protecting group PG ¹ include a methyl group, a methoxymethyl group, a benzyloxymethyl group, a methoxyethoxymethyl group, a 2- (trimethylsilyl) ethoxymethyl group, a methylthiomethyl group, a phenylthiomethyl group, an azidomethyl group, and a cyanomethyl group. 2,2-dichloro-1,1-difluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, tert-butyldiphenylsilylethyl group, tetrahydropyranyl group, 1-ethoxyethyl group, phenacyl group, 4-bromophenacyl Group, cyclopropylmethyl group, allyl group, prenyl group, 2-cyclohexen-1-yl group, propargyl group, isopropyl group, benzyl group, 2,4-dimethylbenzyl group, 4-methoxybenzyl group, o-nitrobenzyl group , P-nitrobenzyl group, 2,6-dic Lorobenzyl group, 3,4-dichlorobenzyl group, 4- (dimethylamino) carbonylbenzyl group, 4-methylsulfinylbenzyl group, 9-anthrylmethyl group, 4-picolyl group, heptafluoro-p-tolyl group, tetrafluoro -4-pyridyl group, trimethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triisopropylsilyl group, formyl group, acetyl group, rubrinyl group, pivalonyl group, benzoyl group, 9-fluorene carboxyl group, xanthene Carboxyl group, methoxycarboxyl group, tert-butoxycarboxyl group, 1-adamantoxycarboxyl group, 2,4-dimethyl-3-pentoxycarboxyl group, allyloxycarboxyl group, 4-methylsulfinylbenzyloxy Ruboxyl group, 2,2,2-trichloroethoxycarboxyl group, vinyloxycarboxyl group, benzyloxycarboxyl group, carbamate, dimethylphosphinyl group, dimethylphosphinothioyl group, diphenylphosphinothioyl group, methanesulfonyl group, Examples thereof include a trifluoromethanesulfonyl group, a toluenesulfonyl group, a 2-formylbenzenesulfonyl group, a benzylsulfonyl group, an ethyl group, a propyl group, an alkyl group, an alkenyl group, and an alkynyl group.

  A compound represented by the formula (S-3) is obtained by inducing a compound represented by the formula (S-2) into a Grignard reagent, reacting with trimethyl borate to form a borate ester, and then hydrolyzing with hydrochloric acid. Can be obtained. Tributyl borate instead of tributyl borate, tridecyl borate, triethyl borate, trihexadecyl borate, trihexyl borate, triisopropyl borate, trioctadecyl borate, trioctyl borate, triphenyl borate, triborate borate Propyl, tris borate (hexafluoroisopropyl), tritetradecyl borate, tri-o-tolyl borate, tris borate (4-chlorophenyl) and the like may be used.

  The boric acid ester may be hydrolyzed or may be used for the next reaction without hydrolysis. When hydrolyzing, the acids include hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromine Acid, hypoiodous acid, iodic acid, iodic acid, periodic acid, sulfuric acid, fluorosulfonic acid, nitric acid, phosphoric acid, hexafluoroantimonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chromic acid, boric acid, Methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, sodium polystyrene sulfonate, acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid, ascorbic acid, meldrum acid Etc. may be used. Further, when the boric acid ester is synthesized, a method of reacting an aromatic halide with diboron in the presence of a metal catalyst may be used. Examples of diboron include bis (neopentylglycolato) diboron, bis (catecholato) diboron, bis (hexylene glycolato) diboron, and bis (pinacolato) diboron. As the aromatic halide, an equivalent such as a fluorinated product, a chlorinated product, a brominated product, an iodinated product, or a triflate can be used. Examples of the metal catalyst 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) dichloro 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- Diphenyl-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- -[(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, bromide Palladium (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 sulfate, palladium / calcium carbonate, palladium hydroxide / carbon, palladium / silica gel, and a palladium catalyst palladium / SH silica gel. Besides palladium catalyst, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, molybdenum, ruthenium, rhodium, silver, tin, cerium, lanthanum, neodymium, thulium, ytterbium, hafnium, iridium, Platinum etc. are mentioned. As the catalyst form, in addition to the above, a polymer-supported catalyst, an amphiphilic complex catalyst, and the like can be used.

  The compound represented by the formula (S-5) can be obtained by reacting the compound represented by the formula (S-3) with the compound represented by the formula (S-4). For example, a method of cross-coupling in the presence of a metal catalyst and a base is efficient. As the metal catalyst, for example, those described above can be used. 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, etc. can be used. .

The compound represented by the formula (S-7) can be obtained by reacting the compound represented by the formula (S-5) with a compound represented by the formula (S-6) in the presence of a base. Here, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. As the base, the above-mentioned bases can be used. From the viewpoint of yield, secondary amines, tertiary amines or aromatic amines are preferable, and tertiary amines or aromatic amines are more preferable.

A compound represented by the formula (S-8) can be obtained by deprotecting the protecting group PG ¹ of the compound represented by the formula (S-7). Examples of the deprotection method include GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEORODA W. GREENE, A John Wiley & c., Ins.). Is preferred.

  The compound represented by the formula (S-10) can be obtained by reacting the compound represented by the formula (S-8) with a compound represented by the formula (S-9) in the presence of a base. As the base, the above-mentioned bases can be used. From the viewpoint of yield, secondary amines, tertiary amines or aromatic amines are preferable, and tertiary amines or aromatic amines are more preferable.

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)

The compound represented by the formula (S-12) can be obtained by reacting the compound represented by the formula (S-8) with a compound represented by the formula (S-11) in the presence of a base. Here, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and Sp represents the same one as defined in the general formula (I). As the base, the base described in production method 1 can be used, 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, water Sodium oxide, sodium hypochlorite, 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, acetate Um, potassium acetate, potassium carbonate, potassium bicarbonate, potassium formate, potassium oxalate, ammonium bicarbonate, ammonium carbonate, cesium carbonate, ammonium formate, ammonium sulfate or the like can be used. Solvents include 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, dimethyl sulfoxide, diethyl 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, hexamethylphosphoric triamide, tris (dimethylamino) phosphine, cyclohexanone, 1,4-dioxane, dichloromethane, styrene, tetrachloroethylene, tetrahydrofuran Pyridine, 1-methyl-2-pyrrolidinone, 1,1,1-trichloroethane, toluene, hexane, pentane, Rhohexane, 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 Etc. can be used. 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 Um hexafluorophosphate, tetramethylammonium hydrogen sulfate, tetramethylammonium perchlorate, tetramethylammonium p-toluenesulfonate, tetramethylammonium sulfate, tetramethylammonium tetrafluoroborate, tetramethylammonium triacetoxyborohydride , Tetrapropylammonium perruthenate, triethylmethylammonium tetrafluoroborate, trimethylphenylammonium tribromide, N, N-bis (3-D-gluconamidopropyl) coramide [BIGCHAP], N, N-bis (3-D -Gluconamidopropyl) deoxycoramide [Deoxy-BIGCHAP], NIKKOL BL-9EX [polyoxyethylene (9) lauryl ether ], Octanoyl-N-methylglucamide [MEGA-8], nonanoyl-N-methylglucamide [MEGA-9], decanoyl-N-methylglucamide [MEGA-10], polyoxyethylene (8) octylphenyl ether [Triton X-114], polyoxyethylene (9) octylphenyl ether [NP-40], polyoxyethylene (10) octylphenyl ether [Triton X-100], polyoxyethylene (20) sorbitan monolaurate [Tween 20], polyoxyethylene (20) sorbitan monopalmitate [Tween 40], polyoxyethylene (20) sorbitan monostearate [Tween 60], polyoxyethylene (20) sorbitan monooleate [Tween 80], Lioxyethylene 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, Digitonin, 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, heptadecafluorooctanesulfonic acid, lithium hepadecafluoro-1-octanesulfonate, pentadecafluorooctanoic acid, heptadecafluoro-1-octane Potassium sulfonate, 3- (hexadecyldimethylammonio) propanesulfonate, sodium cholate, sodium laurate, sodium myristate, sodium N-lauroylsarcosine, sodium oleate, sodium palmitate, sodium stearate, bissulfosuccinate (2-ethylhexyl) sodium, dodecene-1LAS, dimethylsodium 5-sulfoisophthalate, sodium 1-dodecanesulfonate, dodecylben Sodium sulfonate, sodium 1-hexadecane sulfonate, sodium 1-octadecane sulfonate, sodium 1-pentadecane sulfonate, sodium 1-tetradecane sulfonate, sodium 1-tridecane sulfonate, monododecyl sodium phosphate, monododecyl phosphate Sodium (mono, disodium mixture), sodium dodecyl sulfate, sodium hexadecyl sulfate, benzethonium chloride, hexadecyl pyridinium chloride, 1-dodecyl pyridinium chloride, hexadecyl pyridinium bromide, hexadecyl pyridinium chloride, monomyristine, monopalmitine, monostearin, Polyethylene glycol monostearate, polyethylene glycol monostearate (palmitate, stearate Sorbitan monolaurate [Span 20], sorbitan monopalmitate [Span 40], sorbitan monostearate [Span 60], sorbitan monooleate [Span 80], sorbitan sesquioleate [Span 83], sorbitan triole Art [Span 85], diethylene glycol monododecyl ether, ethylene glycol monododecyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monododecyl ether, polyethylene glycol mono-4-octylphenyl ether, tetraethyl glycol monododecyl ether, triethylene glycol monododecyl ether Examples include ether. Reaction conditions include, for example, an experimental chemistry course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publicization), and Beilstein Handbook of Organic Chemistry (Belgium Chemistry). , Springer-Verlag Berlin and Heidelberg GmbH & Co. K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.), etc. is there.

  The compound represented by the formula (S-14) can be obtained by reacting the compound represented by the formula (S-12) with a compound represented by the formula (S-13) in the presence of a base. As the base, a base described in Production Method 1 can be used, but from the viewpoint of yield, a secondary amine, a tertiary amine or an aromatic amine is preferable, and a tertiary amine or an aromatic amine is more preferable.

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.
(Manufacturing method 3) Manufacture of the compound represented by a following formula (S-29)

A compound represented by the formula (S-15) can be obtained by protecting ^one hydroxyl group of the compound represented by the formula (S-4) with a protecting group PG ¹ . The protecting group PG ¹ is not particularly limited as long as it can stably protect the hydroxyl group in the subsequent reaction, but, for example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS). , Theodora W. GREENE, A John Wiley & Sons, Inc., Publication). Specific examples of the protecting group PG ¹ include the protecting groups described in the above production method 1.

  The compound represented by the formula (S-17) can be obtained by reacting the compound represented by the formula (S-15) with a compound represented by the formula (S-16) in the presence of a base. Here, Sp represents the same one as defined in the general formula (I). As the base, the solvent and, if necessary, the phase transfer catalyst, those described in the production method 1 can be used.

By protecting the hydroxyl protecting group PG ² of the compound represented by the formula (S-17), it is possible to obtain a compound represented by the formula (S-18). The protecting group PG ² is not particularly limited as long as it can stably protect the hydroxyl group in the subsequent reaction, but, for example, GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS). , Theodora W. GREENE, A John Wiley & Sons, Inc., Publication). Specific examples of the protecting group PG ² include a methyl group, a methoxymethyl group, a methylthiomethyl group, a (phenyldimethylsilyl) methoxymethyl group, a benzyloxymethyl group, a p-methoxybenzyloxymethyl group, [(3,4-dimethoxybenzyl )] Oxy] methyl group, p-nitrobenzyloxymethyl group, o-nitrobenzyloxymethyl group, [(R) -1- (2-nitrophenyl) ethoxy] methyl group, (4-methoxyphenoxy) methyl group, guaiacol Methyl group, [(p-phenylphenyl) oxy] methyl group, tert-butoxymethyl group, 4-pentenyloxymethyl group, siloxymethyl group, 2-methoxyethoxymethyl group, 2-cyanoethoxymethyl group, bis (2- Chloroethoxy) methyl group, 2,2,2-trichloroethoxymethyl group 2- (trimethylsilyl) ethoxymethyl group, menthoxymethyl group, O-bis (2-acetoxyethoxy) methyl group, tetrahydropyranyl group, fluorous tetrahydropyranyl group, 3-bromotetrahydropyranyl group, tetrahydrothiopyranyl Group, 1-methoxycyclohexyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 4-methoxytetrahydrothiopyranyl S, S-dioxide group, 1-[(2-chloro-4-methyl) ) Phenyl] -4-methoxy-4-piperidinyl group, 1- (2-fluorophenyl) -4-methoxy-4-piperidinyl group, 1- (4-chlorophenyl) -4-methoxy-4-piperidinyl group, 1, 4-dioxane-2-yl group, tetrahydrofuranyl group, tetrahydrothi Ofuranyl group, 2,3,3a, 4,5,6,7,7a-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl group, 1-ethoxyethyl group, 1- ( 2-chloroethoxy) ethyl group, 2-hydroxyethyl group, 2-bromoethyl group, 1- [2- (trimethylsilyl) ethoxy] ethyl group, 1-methyl-1-methoxyethyl group, 1-methyl-1-benzyloxy Ethyl group, 1-methyl-1-benzyloxy-2-fluoroethyl group, 1-methyl-1-phenoxyethyl group, 2,2,2-trichloroethyl group, 1,1-dianisyl-2,2,2- Trichloroethyl group, 1,1,1,3,3,3-hexafluoro-2-phenylisopropyl group, 1- (2-cyanoethoxy) ethyl group, 2-trimethylsilylethyl group, 2- Benzylthio) ethyl group, 2- (phenylselenyl) ethyl group, tert-butyl group, cyclohexyl group, 1-methyl-1′-cyclopropylmethyl group, allyl group, prenyl group, cinnamyl group, 2-phenaryl group, propargyl group Group, p-chlorophenyl group, p-methoxyphenyl group, p-nitrophenyl group, 2,4-dinitrophenyl group, 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl group, benzyl group P-methoxybenzyl group, 3,4-dimethoxybenzyl group, 2,6-dimethoxybenzyl group, o-nitrobenzyl group, p-nitrobenzyl group, pentadienylnitrobenzyl group, pentadienylnitropiperonyl group Halobenzyl group, 2,6-dichlorobenzyl group, 2,4-dichlorobenzyl group, 2,6-difur Robenzyl, p-cyanobenzyl, fluorousbenzyl, 4-fluoroalkoxybenzyl, trimethylsilylxyl, p-phenylbenzyl, 2-phenyl-2-propyl, p-acylaminobenzyl, p-azidobenzyl Group, 4-azido-3-chlorobenzyl group, 2-trifluoromethylbenzyl group, 4-trifluoromethylbenzyl group, p- (methylsulfinyl) benzyl group, p-cyletanylbenzyl group, 4-acetoxybenzyl group, 4- (2-trimethylsilyl) ethoxymethoxybenzyl group, 2-naphthylmethyl group, 2-picolyl group, 4-picolyl group, 3-methyl-2-picolyl-N-oxide group, 2-quinolinylmethyl group, 6-methoxy- 2- (4-methylphenyl) -4-quinolinemethyl group, 1-pyre Rumethyl group, diphenylmethyl group, 4-methoxydiphenylmethyl group, 4-phenyldiphenylmethyl group, p, p'-dinitrobenzhydryl group, 5-dibenzosuberyl group, triphenylmethyl group, tris (4-tert- Butylphenyl) methyl group, α-naphthyldiphenylmethyl group, p-methoxyphenyldiphenylmethyl group, di (p-methoxyphenyl) phenylmethyl group, tri (p-methoxyphenyl) methyl group, 4- (4′-bromophena) Siloxy) phenyldiphenylmethyl group, 4,4 ′, 4 ″ -tris (4,5-dichlorophthalimidophenyl) methyl group, 4,4 ′, 4 ″ -tris (levulinoyloxyphenyl) methyl group, 4,4 ′, 4 ″ -tris (benzoyloxyphenyl) methyl group, 4,4′-dimethoxy-3 ″-[N- (i Dazolylmethyl)] trityl group, 4,4′-dimethoxy-3 ″-[N- (imidazolylethyl) carbamoyl] trityl group, bis (4-methoxyphenyl) -1′-pyrenylmethyl group, 4- (17-tetrabenzo [ a, c, g, i] fluorenylmethyl) -4,4 ''-dimethoxytrityl group, 9-anthryl group, 9- (9-phenyl) xanthenyl group, 9-phenylthioxanthyl group, 9- ( 9-phenyl-10-oxo) anthryl group, 1,3-benzodithiolan-2-yl group, 4,5-bis (ethoxycarbonyl)-[1,3] -dioxolan-2-yl group, benzisothioazolyl -S, S-dioxide group, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilane Ryl group, dimethyl hexyl silyl group, 2-norbornyl dimethyl silyl group, tert-butyl dimethyl silyl group, tert-butyl diphenyl silyl group, tribenzyl silyl group, tri-p-xylyl silyl group, triphenyl silyl group, diphenyl Methylsilyl group, di-tert-butylmethylsilyl group, bis (tert-butyl) -1-pyrenylmethoxysilyl group, tris (trimethylsilyl) silyl group, (2-hydroxystyryl) dimethylsilyl group, (2-hydroxystyryl) ) Diisopropylsilyl group, tert-butylmethoxyphenylsilyl group, tert-butoxydiphenylsilyl group, 1,1,3,3-tetraisopropyl-3- [2- (triphenylmethoxy) ethoxy] disiloxane-1-yl group , Fluorosilyl group, Mill group, benzoylformyl group, acetyl group, chloroacetyl group, dichloroacetyl group, trichloroacetyl group, trichloroacetamidyl group, trifluoroacetyl group, methoxyacetyl group, triphenylmethoxyacetyl group, phenoxyacetyl group, p-chloro Phenoxyacetyl group, phenylacetyl group, p-P-phenylacetyl group, diphenylacetyl group, 3-phenylpropionyl group, bisfluorus chain type propanoyl group, 4-pentenoyl group, 4-oxopentanoyl group, 4,4- ( Ethylenedithio) pentanoyl group, 5- [3-bis (4-methoxyphenyl) hydroxymethylphenoxy] rubulinoyl group, pivaloyl group, 1-adamantoyl group, crotonyl group, 4-methoxycrotonyl group, benzoyl group, p-phenyl Nzoyl group, 2,4,6-trimethylbenzoyl group, 4-bromobenzoyl group, 2,5-difluorobenzoyl group, p-nitrobenzoyl group, picolinoyl group, nicotinoyl group, 2- (azidomethyl) benzoyl group, 4-azidobutyroyl Group, (2-azidomethyl) phenylacetyl group, 2-{[(tritylthio) oxy] methyl} benzoyl group, 2-{[(4-methoxytritylthio) oxy] methyl} benzoyl group, 2-{[methyl (tritylthio) ) Amino] methyl} benzoyl group, 2-{{[(4-methoxytrityl) thio] methylamino} -methyl} benzoyl group, 2- (allyloxy) phenylacetyl group, 2- (prenyloxymethyl) benzoyl group, 6 -(Rubulinyloxymethyl) -3-methoxy-2-nitrobenzoyl group , 6- (rubrinyloxymethyl) -3-methoxy-4-nitrobenzoyl group, 4-benzyloxybutyroyl group, 4-trialkylsiloxybutyroyl group, 4-acetoxy-2,2-dimethylbutyroyl group, 2,2-dimethyl-4-pentenoyl group, 2-iodobenzoyl group, 4-nitro-4-methylpentanoyl group, o- (dibromomethyl) benzoyl group, 2-formylbenzenesulfonyl group, 4- (methylthiomethoxy) Butyroyl group, 2- (methylthiomethoxymethyl) benzoyl group, 2- (chloroacetoxymethyl) benzoyl group, 2-[(2-chloroacetoxy) ethyl] benzoyl group, 2- [2- (benzyloxy) ethyl] benzoyl group , 2- [2- (4-methoxybenzyloxy) ethyl] benzoyl group, 2,6-dichloro -4-methylphenoxyacetyl group, 2,6-dichloro-4- (1,1,3,3-tetramethylbutyl) phenoxyacetyl group, 2,4-bis (1,1-dimethylpropyl) phenoxyacetyl group, Chlorodiphenylacetyl group, isobutyroyl group, monosuccinoyl group, (E) -2-methyl-2-butenoyl group, o- (methoxycarbonyl) benzoyl group, p-P-benzoyl group, α-naphthoyl group, nitroyl group, alkyl N , N, N ′, N′-tetramethylphosphorodiamidyl group, 2-chlorobenzoyl group, allylsulfonyl group, methanesulfonyl group, benzylsulfonyl group, tosyl group, 2-[(4-nitrophenyl) ethyl] sulfonyl Group, 2-trifluoromethylsulfonyl group, 4-monomethoxytritylsulfenyl group, alkyl , 4-dinitrophenylsulfenyl group, 2,2,5,5-tetramethylpyrrolidin-3-one-1-sulfinyl group, boronyl group, dimethylphosphinothioyl group, methoxycarbonyl group, methoxymethoxycarbonyl group, 9 -Fluorenylmethoxycarbonyl group, ethoxycarbonyl group, bromoethoxycarbonyl group, 2- (methylthiomethoxy) ethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, 1,1-dimethyl-2,2,2- Trichloroethoxycarbonyl group, 2- (trimethylsilyl) ethoxycarbonyl group, 2- [dimethyl (2-naphthylmethyl) silyl] ethoxycarbonyl group, 2- (phenylsulfonyl) ethoxycarbonyl group, 2- (triphenylphosphino) ethoxycarbonyl Group cis- 4-[[(methoxytrityl) sulfenyl] oxy] tetraidfuran-3-yl] oxy group, isobutyloxycarbonyl group, tert-butyloxycarbonyl group, vinyloxycarbonyl group, allyloxycarbonyl group, cinnamyloxycarbonyl Group, propargyloxycarbonyl group, p-chlorophenyloxycarbonyl group, p-nitrophenyloxycarbonyl group, 4-ethoxy-1-naphthoxycarbonyl group, 6-bromo-7-hydroxycoumarin-4-ylmethoxycarbonyl group, benzyl Oxycarbonyl group, o-nitrobenzyloxycarbonyl group, p-nitrobenzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, 3,4-dimethoxybenzyloxycarbonyl group, anthraquinone-2-yl Methoxycarbonyl group, 2-dansylethoxycarbonyl group, 2- (4-nitrophenyl) ethoxycarbonyl group, 2- (2,4-dinitrophenyl) ethoxycarbonyl group, 2- (2-nitrophenyl) propyloxycarbonyl group, 2- (3,4-methylenedioxy-6-nitrophenyl) propyloxycarbonyl group, 2-cyano-1-phenylethoxycarbonyl group, 2- (2-pyridyl) amino-1-phenylethoxycarbonyl group, 2- [N-methyl-N- (2-pyridyl)] amino-1-phenylethoxycarbonyl group, phenacyloxycarbonyl group, 3 ′, 5′-dimethoxybenzoinoxycarbonyl group, benzylthioxycarbonyl group, dimethylthiocarbonyl group N-phenylaminocarbonyl group, N-methyl-N- o- nitrophenyl) aminocarbonyl group.

  A compound represented by the formula (S-19) is obtained by inducing a compound represented by the formula (S-18) into a Grignard reagent, reacting with trimethyl borate to form a borate ester, and then hydrolyzing with hydrochloric acid. Can be obtained. A boron compound described in production method 1 may be used in place of trimethyl borate. The obtained boric acid ester may be hydrolyzed or may be used for the next reaction without hydrolysis. In the case of hydrolysis, for example, the acid described in the production method 1 can be used. Further, when the boric acid ester is synthesized, a method of reacting an aromatic halide with diboron in the presence of a metal catalyst may be used. As the metal catalyst, aromatic halide and diboron, those described in production method 1 can be used.

  The compound represented by the formula (S-21) can be obtained by reacting the compound represented by the formula (S-19) with the compound represented by the formula (S-20). For example, a method of cross-coupling in the presence of a metal catalyst and a base is efficient. As a metal catalyst and a base, the thing of the manufacturing method 1, for example can be used.

The compound represented by the formula (S-23) can be obtained by reacting the compound represented by the formula (S-21) with a compound represented by the formula (S-22) in the presence of a base. Here, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. As the base, a base described in Production Method 1 can be used, but from the viewpoint of yield, a secondary amine, a tertiary amine or an aromatic amine is preferable, and a tertiary amine or an aromatic amine is more preferable.

By deprotecting the protecting group PG ² of the compound represented by the formula (S-23), it is possible to obtain a compound represented by the formula (S-24). Examples of the deprotection method include GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEORODA W. GREENE, A John Wiley & c., Ins.). Is preferred.

  The compound represented by the formula (S-26) can be obtained by reacting the compound represented by the formula (S-24) with a compound represented by the formula (S-25) in the presence of a base. As the base, a base described in Production Method 1 can be used, but from the viewpoint of yield, a secondary amine, a tertiary amine or an aromatic amine is preferable, and a tertiary amine or an aromatic amine is more preferable.

A compound represented by the formula (S-27) can be obtained by deprotecting the protecting group PG ¹ of the compound represented by the formula (S-26). Examples of the deprotection method include GREEN'S PROTECTIVE GROUPS IN ORGANIG SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEORODA W. GREENE, A John Wiley & c., Ins.). Is preferred.

  The compound represented by the formula (S-29) can be obtained by reacting the compound represented by the formula (S-27) with a compound represented by the formula (S-28) in the presence of a base. As the base, a base described in Production Method 1 can be used, but from the viewpoint of yield, a secondary amine, a tertiary amine or an aromatic amine is preferable, and a tertiary amine or an aromatic amine is more preferable.

  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.

  The liquid crystal composition of the present invention may contain other compounds in an arbitrary range other than using one or more polymerizable compounds represented by the general formula (I) of the present invention. Specifically, the following general formula (II-1) and general formula (II-2)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, one existing in these groups) Or two or more methylene groups which are not adjacent to each other may be substituted with —O— or —S—, and one or more hydrogen atoms present in these groups are fluorine atoms. Or A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ and A ⁹ are each independently substituted with a chlorine atom,
(A) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom);
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and a group selected from the group consisting of decahydronaphthalene-2,6-diyl group,
The hydrogen atom contained in the group (a), group (b) or group (c) may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, respectively. ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH _2. -, -CH ₂ O-, -OCF _2- , -CF ₂ O- or -C≡C-, and A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and / or Z ⁸ , they may be the same or different, and L ¹ , L ² , L ³ , L ⁴ and L ⁵ are independent of each other. Represents a hydrogen atom, a trifluoromethyl group, a trifluoromethoxy group, a fluorine atom or a chlorine atom. It is not ^{the L 1} and ^{L 2} represent simultaneously hydrogen ^atoms, L 3, ^{L 4} and ^{which L 5} without simultaneously represent a hydrogen ^{atom, m 4, m 5, m} 6 and ^{m 7} are each independently , 0, 1, 2 or 3, m ⁴ + m ⁵ and m ⁶ + m ⁷ are 4 or less. In general formula (II-1), the compound represented by general formula (II-2) is excluded. ) A compound represented by

  Specific examples of the compounds represented by the general formula (II-1) and the general formula (II-2) include formulas (ii-1) to (ii-29).

(Wherein, alkyl represents an alkyl group having 1 to 10 carbon atoms and alkenyl represents an alkenyl group having 2 to 10 carbon atoms).

  General formula (III-1) and general formula (III-2)

(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkenyl group having 2 to 10 carbon atoms, and one methylene present in these groups) Two or more methylene groups which are not adjacent or adjacent to each other may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups are fluorine atoms or chlorine atoms. A ¹⁰ , A ¹¹ , A ¹² , A ¹³ , A ¹⁴ and A ¹⁵ are each independently
(A) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(B) 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group,
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and a group selected from the group consisting of decahydronaphthalene-2,6-diyl group,
The hydrogen atom contained in the group (a), group (b) or group (c) may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, respectively. ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH _2. -, -CH ₂ O-, -OCF _2- , -CF ₂ O- or -C≡C-, A ¹¹ , A ¹² , A ¹⁴ , A ¹⁵ , Z ⁹ , Z ¹¹ , Z ¹² and / or When a plurality of Z ¹⁴ are present, they may be the same or different, and L ⁶ , L ⁷ , L ⁸ , L ⁹ and L ¹⁰ each independently represent a hydrogen atom or a fluorine atom, and Y ¹ and Y ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom Cyano group, a thiocyanate group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a difluoromethoxy ^group, at least one fluorine atom of L 6, ^{L 7} or ^{Y 1,} chlorine atom, a cyano group, a thiocyanate group, a trifluoromethoxy group, a trifluoromethyl group, 2,2,2-trifluoroethyl group, or represents a difluoromethoxy group, at least one of the hydrogen atoms contained in the a ¹⁰ or a ¹² One represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, and at least one of L ⁸ , L ⁹ , L ¹⁰ or Y ² is a fluorine atom, a chlorine atom, a cyano group or a thiocyanato group. , Trifluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl Represents groups, or represents a difluoromethoxy group, at least one cyano group of the hydrogen atoms contained in A ^13, A ¹⁴ or A ^15, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, m ⁸ , M ⁹ , m ¹⁰ and m ¹¹ each independently represents 0, 1 or 2. In general formula (III-1), the compound represented by general formula (III-2) is excluded. ) A compound represented by

  Specific examples of the compounds represented by the general formula (III-1) and the general formula (III-2) include formulas (III-1-1) to (III-1-11).

(Wherein R ⁹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and X ^{31 to} X ³⁸ are each independently a hydrogen atom or fluorine. Z ³¹ represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.

(Wherein R ¹⁰ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group, and X ^{31 to} X ³⁸ are each independently a hydrogen atom or fluorine. Z ³¹ represents a fluorine atom, a trifluoromethoxy group, or a trifluoromethyl group), and a compound represented by formula (iii-1) to formula (iii-32) is more preferable.

(Wherein alkyl represents an alkyl group having 1 to 10 carbon atoms, alkenyl represents an alkenyl group having 2 to 10 carbon atoms, and Y ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, or trifluoro). It represents a methoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a difluoromethoxy group, but preferably represents a hydrogen atom, a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group. Can be mentioned.

  Formula (IV)

(Wherein R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, but one —CH ₂ — or not adjacent 2 One or more of —CH ₂ — may be replaced with an oxygen atom or a sulfur atom, and a hydrogen atom present in these groups may be replaced with a fluorine atom or a chlorine atom, and A ¹⁶ , A ¹⁷ and A ¹⁸ are each independently
(A) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ), (B) 1,4-phenylene group (one —CH═ or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1,4- Phenylene group and 3,5-difluoro-1,4-phenylene group and (c) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl A group selected from the group consisting of a group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, m ¹² represents 0 or 1, Z ¹⁵ and Z ¹⁶ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —CF ₂ CF ₂ —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CH═N—, —N═CH—, —CH═N—N═CH— or —C≡C—. In the case where a plurality of Z ¹⁶ and / or A ¹⁸ are present, they may be the same or different. In general formula (IV), the compounds represented by general formula (II-1), general formula (II-2), general formula (III-1), and general formula (III-2) are excluded. ) A compound represented by

  Specific examples of the compound represented by the general formula (IV) include formulas (iv-1) to (iv-13).

(Wherein, alkyl represents an alkyl group having 1 to 10 carbon atoms and alkenyl represents an alkenyl group having 2 to 10 carbon atoms).

  The liquid crystal composition is a compound selected from the group consisting of a compound represented by formula (IV), a compound represented by formula (II-1) and a compound represented by formula (II-2), or a formula (III-1) And preferably containing at least one compound selected from the group consisting of compounds represented by formula (III-2), and containing one or more compounds represented by formula (IV) Furthermore, when the compound selected from the group consisting of the compounds represented by the general formula (II-1) and the general formula (II-2) is contained alone or in combination, or represented by the general formula (IV) The compound may contain one or more compounds, and may further contain one or more compounds selected from the group consisting of compounds represented by formula (III-1) and formula (III-2). More preferred. The lower limit of the content of each compound represented by the general formula (IV) is preferably 2% by mass, more preferably 3% by mass, and more preferably 5% by mass with respect to the total amount of the liquid crystal composition of the present invention. 6 mass% is more preferable, and the upper limit is preferably 40 mass%, more preferably 30 mass%, more preferably 25 mass%, and more preferably 20 mass%. The lower limit of the total content of each compound represented by the general formula (IV) is preferably 5% by mass, more preferably 7% by mass, and more preferably 10% by mass with respect to the total amount of the liquid crystal composition of the present invention. The upper limit is preferably 95% by weight, more preferably 90% by weight, more preferably 85% by weight, and more preferably 80% by weight. 2 mass% is preferable with respect to the total amount of the liquid-crystal composition of this invention, and, as for the lower limit of content of each compound represented by general formula (II-1) and general formula (II-2), 3 mass% Is more preferable, 5 mass% is more preferable, 6 mass% is more preferable, and the upper limit is preferably 40 mass%, more preferably 30 mass%, more preferably 25 mass%, and more preferably 20 mass%. 5 mass% is preferable with respect to the total amount of the liquid-crystal composition of this invention, and, as for the lower limit of the total content of each compound represented by general formula (II-1) and general formula (II-2), 7 mass % Is more preferable, 10 mass% is more preferable, 15 mass% is more preferable, and the upper limit is preferably 95 mass%, more preferably 90 mass%, more preferably 85 mass%, and more preferably 80 mass%. 2 mass% is preferable with respect to the total amount of the liquid-crystal composition of this invention, and, as for the lower limit of content of each compound represented by general formula (III-1) and general formula (III-2), 3 mass% Is more preferable, 5 mass% is more preferable, 6 mass% is more preferable, and the upper limit is preferably 40 mass%, more preferably 30 mass%, more preferably 25 mass%, and more preferably 20 mass%. 5 mass% is preferable with respect to the total amount of the liquid-crystal composition of this invention, and, as for the lower limit of the total content of each compound represented by general formula (III-1) and general formula (III-2), 7 mass % Is more preferable, 10 mass% is more preferable, 15 mass% is more preferable, and the upper limit is preferably 95 mass%, more preferably 90 mass%, more preferably 85 mass%, and more preferably 80 mass%.

  The liquid crystal composition of the present invention may contain other polymerizable compounds in an arbitrary range other than containing at least one or two or more polymerizable compounds represented by the general formula (I). Examples of other polymerizable compounds include the following general formulas (V-1) to (V-10):

(In the formula, P ¹ and P ² are the same as those defined as P in the general formula (I), and Sp ¹ and Sp ² are the same as those defined as Sp in the general formula (I). Wherein r represents an integer from 0 to 4, s represents an integer from 0 to 3, and R ¹ , R ² , Z ¹ , Z ² and L are the same as defined in general formula (I) Is preferable).

  The two substrates used for the display element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

  The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each color, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate via a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant. As a method for sandwiching a liquid crystal composition for a PS (polymer stabilization) type or PSA (polymer sustaining alignment) type liquid crystal display element between two substrates, a vacuum injection method, a liquid crystal dropping (ODF) method, or the like is used. Can do.

  As a method for polymerizing a polymerizable compound, since rapid progress of polymerization is desirable, 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 be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask during 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. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating current to the polymerizable compound-containing liquid crystal composition. The alternating current to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the MVA mode liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89 degrees from the viewpoint of alignment stability and contrast.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Most preferably, the polymerization is carried out at a temperature close to room temperature, that is, typically at a temperature of 15 ° C to 60 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is preferably 100W / cm ² from 0.1 mW / cm ^2, and more preferably 80W / cm ² from 2 mW / cm ^2. Energy of ultraviolet light irradiation, can be appropriately adjusted, is preferably 10000 mJ / cm ² from 10 mJ / cm ^2, from 100mJ / cm ² 7000mJ / cm ² is more preferable. When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays, but is preferably 10 seconds to 600 seconds.

  Further, the liquid crystal display element of the present invention obtained by polymerization can be subjected to heat treatment for the purpose of reducing the initial characteristic change and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 ° C. to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

  The polymerizable compound used in the present invention needs to control the orientation of the liquid crystal material after polymerization and maintain the orientation state for a long time. For this reason, the alignment control force of liquid crystal and the mechanical strength of the cured product are required. In addition, if an uncured polymerizable compound or a large amount of a polymerization initiator remains after curing, a display defect is caused. Therefore, polymerization proceeds without using a small amount of polymerization initiator or polymerization initiator. It is required to do.

  A compound having a polymerizable functional group and not showing liquid crystallinity can also be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. However, after the polymerizable compound is cured, the liquid crystal layer must exhibit a liquid crystal phase. For this reason, when adding a non-polymerizable liquid crystal composition, it is necessary to adjust the addition amount so as to exhibit liquid crystallinity. The polymerizable compound contains at least one kind, but preferably contains 1 to 5 kinds, more preferably 1 to 3 kinds. In addition, if the content of the polymerizable compound is small, the alignment regulating force on the liquid crystal molecules is weak, and if it is too large, the required energy during polymerization increases, and the amount of the polymerizable compound that remains without polymerization increases. Therefore, the lower limit is preferably 0.01% by mass, more preferably 0.03% by mass, and the upper limit is preferably 2.0% by mass, and is 1.0% by mass. Is more preferable.

  The compound represented by the general formula (I) can be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added depending on the purpose. In this case, the concentration of the photopolymerization initiator is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 10% by mass with respect to the compound represented by the general formula (I). 4 to 5% by mass is more preferable. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Examples of the thermal polymerization initiator include azobisisobutyronitrile and benzoyl peroxide. One type of photopolymerization initiator may be used, or two or more types of photopolymerization initiators may be used in combination.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651), 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), and 2-hydroxy-2-methyl. -1-phenylpropan-1-one (DAROCUR 1173), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE 2959), 2- Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (IRGACURE 127), methyl phenylglyoxylate (DAROCUR MBF), 2-methyl -1- (4-methylthiophenyl) -2-mol Horinopropan-1-one (IRGACURE 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (IRGACURE 369), 2- (dimethylamino) -2-[(4-methyl Phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379EG), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (LUCIRIN TPO), bis (2,4,6- Trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819), IRGACURE 819DW, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl)- Phenyl) Titanium (IRGAC RE 784), benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene] amino (IRGACURE OXE 01), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl acetate ] Ethylideneamino (IRGACURE OXE 02), IRGACURE 754, IRGACURE 500, IRGACURE 250, IRGACURE 270, acetophenone, p-anisyl, benzyl, benzoin, benzophenone, 2-benzoylbenzoic acid, 4,4'-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, -Benzoylbenzoic acid, methyl 2-benzoylbenzoate, 4,4'-dichlorobenzophenone, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthen-9-one, 2-ethylanthraquinone, 2-isonitrosopro Piophenone, 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, 2- (1,3-benzodioxol-5-yl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 4-benzoyl 4'-methyldiphenyl sulfide, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, 2,2'-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra Phenyl-1,2'-biimidazole, (±) -camphorquinone, 2-chlorobenzophenone, 4-chlorobenzophenone, 2-chlorothiaxanthone, dibenzosuberone, 2- (3,4-dimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate 9-fluorenone, 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 4-isopropyl-4′-methyldiphenyliodonium tetrakis ( Pentafluo Rophenyl) borate, 2-isopropylthioxanthone, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, 10-methyl-9 (10H) -acridone, 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2-methyl-4′-methylthio-2-morpholinopropiophenone, nifedipine, 2-pyridyl tribromomethyl sulfone, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, tribromomethyl Phenyl sulfone, triphenylsulfonium tetrafluoroborate, tri-p-to Rusuruhoniumu hexafluorophosphate, tri -p- tolyl sulfonium trifluoromethanesulfonate, and the like are preferable.

  In addition, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.5% by mass, and 0.03% by mass relative to the composition. To 0.1% by mass is more preferable. One kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination.

  Specifically, as the stabilizer, the formula (VI-1) to the formula (VI-36)

The compound represented by these is preferable.

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 the flask, 20.0 g (0.12 mol) of the compound represented by the formula (I-1a) and 2.91 g (0.012 mol) of p-toluenesulfonic acid pyridinium salt were added and dissolved in dichloromethane. While cooling with ice, 12.6 g (0.15 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 6 hours, the mixture was washed with an aqueous sodium bicarbonate solution and brine and the solvent was distilled off to obtain 29.4 g (0.11 mol) of the compound represented by the formula (I-1b). Here, THP represents a tetrahydropyranyl group.

  To a reaction vessel purged with nitrogen, 3.62 g (0.15 mol) of magnesium and 6 mL of tetrahydrofuran were added. A tetrahydrofuran solution of 29.4 g (0.11 mol) of the compound represented by the formula (I-1b) was gradually added to prepare a Grignard reagent. A tetrahydrofuran solution of 17.8 g (0.17 mol) of trimethyl borate was added dropwise and stirred for 3 hours. 10% hydrochloric acid was added dropwise to make the reaction solution acidic. After washing with brine, the solvent was distilled off to obtain 24.3 g (0.10 mol) of the compound represented by the formula (I-1c).

  In a reaction vessel purged with nitrogen, 24.3 g (0.10 mol) of the compound represented by the formula (I-1c), 19.3 g (0.10 mol) of 4-bromoresorcinol and 21.1 g (0. 15 mol) was added and suspended in 120 mL of ethanol. Tetrakis (triphenylphosphine) palladium (0) (3.53 g, 3.1 mmol) was added, and the mixture was heated to reflux for 10 hours. After neutralization with an aqueous ammonium chloride solution, toluene was added and the mixture was washed with brine. Purification was performed by column chromatography (alumina) to obtain 24.8 g (0.087 mol) of a compound represented by the formula (I-1d).

To the flask, 24.8 g (0.087 mol) of the compound represented by the formula (I-1d) and 11.4 g (0.11 mol) of triethylamine (Et ₃ N) were added and dissolved in 100 mL of tetrahydrofuran. While cooling with ice, a solution of 21.7 g (0.21 mol) of methacryloyl chloride in tetrahydrofuran was added dropwise. After stirring at room temperature for 6 hours, 10% hydrochloric acid was added and stirred at room temperature for 5 hours. After the solvent was distilled off, it was dissolved in dichloromethane. By washing with brine, 27.8 g (0.082 mol) of the compound represented by the formula (I-1f) was obtained.

27.8 g (0.082 mol) of the compound represented by the formula (I-1f) and 10.8 g (0.11 mol) of triethylamine were added to the flask and dissolved in 120 mL of dichloromethane. While cooling with ice, a solution of 9.68 g (0.11 mol) of acryloyl chloride in dichloromethane was added dropwise. The mixture was stirred at room temperature for 6 hours, and washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and brine. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 22.5 g of the target compound represented by formula (I-1).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 392
HRMS: 392.13
Example 2 Production of Compound Represented by Formula (I-2)

10.0 g (0.030 mol) of the compound represented by the formula (I-1f) and 3.89 g (0.38 mol) of triethylamine were added to the flask, and dissolved in 50 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 4.02 g (0.38 mol) of methacryloyl chloride was added dropwise. The mixture was stirred at room temperature for 6 hours, and washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and brine. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 8.51 g of the target compound represented by formula (I-2).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 406
HRMS: 406.14
Example 3 Production of Compound Represented by Formula (I-3)

By the same method as in Example 1 except that the compound represented by the formula (I-1a) was replaced with the compound represented by the formula (I-3a), methacryloyl chloride was replaced with acryloyl chloride, and acryloyl chloride was replaced with methacryloyl chloride. A compound represented by the formula (I-3) was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 428
HRMS: 428.13
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 acryloyl chloride was replaced with methacryloyl chloride and methacryloyl chloride was replaced with acryloyl chloride.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 442
HRMS: 442.14
Example 5 Production of Compound Represented by Formula (I-5)

A compound represented by the formula (I-5) was obtained in the same manner as in Example 1 except that the compound represented by the formula (I-1a) was replaced with a compound represented by the formula (I-5a). .
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 468
HRMS: 468.16
Example 6 Production of Compound Represented by Formula (I-6)

The compound represented by the formula (I-5f) was reacted with methacryloyl chloride in the presence of triethylamine in the same manner as in Example 1 to obtain the compound represented by the formula (I-6).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
¹ H NMR (CDCl ₃ ) δ 1.92 (s, 3H), 2.08 (s, 3H), 2.09 (s, 3H), 5.65 (m, 1H), 5.79 (m, 2H), 6.19 (m, 1H), 6.38 (m, 2H), 7.09 (d, 1H), 7.15 (dd, 1H), 7.21 (m, 2H), 7. 49 (m, 3H), 7.60 (m, 2H), 7.64 (m, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 18.3, 18.4, 18.4, 116.6, 119.5, 121.9, 126.9, 127.4, 127.7, 127.7, 128. 0, 129.4, 131.1, 131.8, 135.3, 135.5, 135.7, 135.8, 138.2, 139.3, 148.1, 150.4, 150.4, 165.3, 165.5, 165.9 ppm.
LRMS: 482
HRMS: 482.17
Example 7 Production of Compound Represented by Formula (I-7)

A compound represented by the formula (I-7) was obtained in the same manner as in Example 1 except that the compound represented by the formula (I-1a) was replaced with a compound represented by the formula (I-7a). .
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 810, 750, 690 cm ⁻¹ .
LRMS: 420
HRMS: 420.16
Example 8 Production of Compound Represented by Formula (I-8)

To the flask, 7.00 g (0.035 mol) of the compound represented by the formula (I-8a) and 0.44 g (1.74 mmol) of p-toluenesulfonic acid pyridinium salt were added and dissolved in 50 mL of dichloromethane. While cooling with ice, 3.81 g (0.045 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 6 hours, the mixture was washed with saturated aqueous sodium hydrogen carbonate and brine. Purification by column chromatography (alumina) yielded 9.73 g (0.034 mol) of the compound represented by formula (I-8b).

22.2 g (0.045 mol) of 3-benzyloxypropyltriphenylphosphonium bromide was added to a nitrogen-substituted reaction vessel and suspended in 60 mL of tetrahydrofuran. The mixture was cooled to −30 ° C., and 5.08 g (0.045 mol) of potassium tert-butoxide ( ^t BuOK) was added. After stirring for 1 hour, a tetrahydrofuran solution of 9.73 g (0.034 mol) of the compound represented by the formula (I-8b) was added dropwise. After stirring at room temperature for 3 hours, the solvent was distilled off. Hexane was added, the precipitate was filtered off, and the mother liquor was purified by column chromatography (alumina) to obtain 12.4 g (0.030 mol) of the compound represented by the formula (I-8c).

  12.4 g (0.030 mol) of the compound represented by the formula (I-8c) was added to the flask, and dissolved in 30 mL of tetrahydrofuran and 30 mL of methanol. 1 mL of concentrated hydrochloric acid was added and stirred at room temperature for 7 hours. The solvent was distilled off, redissolved in toluene, and washed with brine. By purification by column chromatography (alumina), 9.60 g (0.029 mol) of the compound represented by the formula (I-8d) was obtained.

  9.60 g (0.029 mol) of a compound represented by the formula (I-8d), 6.88 g (0.029 mol) of a compound represented by the formula (I-1c), potassium carbonate in a reaction vessel substituted with nitrogen 5.97 g (0.043 mol) was added and dissolved in 50 mL of tetrahydrofuran and 50 mL of water. Tetrakis (triphenylphosphine) palladium (0) (1.66 g, 1.44 mmol) was added, and the mixture was heated to reflux for 7 hours. Toluene was added, washed with a saturated aqueous ammonium chloride solution and brine, and purified by column chromatography (alumina) to obtain 9.42 g (0.022 mol) of the compound represented by the formula (I-1c). It was.

  To the autoclave, 9.42 g (0.022 mol) of a compound represented by the formula (I-1c) and 0.94 g of 5% palladium carbon (Pd / C) were added and suspended in 50 mL of tetrahydrofuran. The mixture was heated and stirred at 50 ° C. for 6 hours under a hydrogen pressure of 5 atmospheres. Purification by column chromatography (alumina) yielded 7.42 g (0.022 mol) of the compound represented by formula (I-8f).

  To the reaction vessel, 7.42 g (0.022 mol) of the compound represented by the formula (I-8f) and 5.12 g (0.051 mol) of triethylamine were added and dissolved in 50 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 5.06 g (0.048 mol) of methacryloyl chloride was added dropwise. The mixture was stirred at room temperature for 6 hours, washed with a saturated aqueous ammonium chloride solution and brine, purified by column chromatography (alumina), and 9.23 g (0.019 mol) of the compound represented by the formula (I-8 g) was obtained. Obtained.

  To the flask, 9.23 g (0.019 mol) of a compound represented by the formula (I-8 g) was added and dissolved in 30 mL of tetrahydrofuran and 30 mL of methanol. 1 mL of concentrated hydrochloric acid was added and stirred at room temperature for 6 hours. After the solvent was distilled off, the residue was redissolved in toluene and washed with brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 7.38 g (0.019 mol) of a compound represented by the formula (I-8h).

To the reaction vessel, 7.38 g (0.019 mol) of the compound represented by the formula (I-8h) and 2.84 g (0.028 mol) of triethylamine were added and dissolved in 50 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 2.20 g (0.024 mol) of acryloyl chloride was added dropwise. The mixture is stirred at room temperature for 5 hours, washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate and brine, purified by column chromatography (silica gel) and recrystallization, and compound 5 represented by the target formula (I-8). .87 g was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 810, 750, 690 cm ⁻¹ .
LRMS: 448
HRMS: 448.19
Example 9 Production of Compound Represented by Formula (I-9)

  To the flask, 10.0 g (0.14 mol) of the compound represented by the formula (I-9a) and 1.79 g (7.1 mmol) of p-toluenesulfonic acid pyridinium salt were added and dissolved in 50 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 15.6 g (0.19 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 6 hours, the mixture was washed with saturated aqueous sodium hydrogen carbonate and brine. By distilling off the solvent, 21.8 g (0.14 mol) of the compound represented by the formula (I-9b) was obtained.

  To the reaction vessel, 21.8 g (0.14 mol) of the compound represented by the formula (I-9b) and 17.8 g (0.071 mol) of the compound represented by the formula (I-9c) were added, and 30 mL of triethylamine and Dissolved in 90 mL of N, N-dimethylformamide. After making the inert atmosphere, 0.54 g (2.8 mmol) of copper (I) iodide and 1.63 g (1.4 mmol) of tetrakis (triphenylphosphine) palladium (0) were added, and the mixture was heated at 90 ° C. for 9 hours. Stir with heating. Toluene was added, and the mixture was washed with a saturated aqueous ammonium chloride solution and brine, and then purified by column chromatography (alumina) to obtain 18.3 g (0.046 mol) of the compound represented by the formula (I-9d).

  To the autoclave, 18.3 g (0.046 mol) of the compound represented by the formula (I-9d) was added and dissolved in 100 mL of tetrahydrofuran. 5% Pd / C (1.8 g) was added and reacted at a hydrogen pressure of 5 atm for 8 hours. After filtering the catalyst, the solvent was distilled off and the residue was purified by column chromatography (alumina) to obtain 18.3 g (0.045 mol) of the compound represented by the formula (I-9e).

  To the flask, 18.3 g (0.045 mol) of a compound represented by the formula (I-9e) and 4.63 g (0.058 mol) of pyridine were added and dissolved in 80 mL of dichloromethane. While cooling with ice, 16.5 g (0.058 mol) of trifluoromethanesulfonic anhydride was added dropwise. The mixture was stirred at room temperature for 6 hours, washed with brine, and purified by column chromatography (alumina) to obtain 23.0 g (0.043 mol) of the compound represented by the formula (I-9f).

  To the flask, 23.0 g (0.043 mol) of the compound represented by the formula (I-9f) was added and dissolved in 50 mL of tetrahydrofuran and 50 mL of methanol. 1 mL of concentrated hydrochloric acid was added and stirred at room temperature for 7 hours. The solvent was distilled off, redissolved in ethyl acetate and washed with brine, and then the solvent was distilled off to obtain 15.5 g (0.042 mol) of the compound represented by the formula (I-9g).

  In a reaction vessel, 15.5 g (0.042 mol) of a compound represented by the formula (I-9g), 10.0 g (0.042 mol) of a compound represented by the formula (I-1c), 8.68 g of potassium carbonate (0.063 mol) was added. Tetrahydrofuran (100 mL) and water (100 mL) were added to make the atmosphere inert, then tetrakis (triphenylphosphine) palladium (0) (2.42 g, 2.1 mmol) was added, and the mixture was heated to reflux for 7 hours. Toluene was added and washed with brine, and then purified by column chromatography (alumina) to obtain 12.5 g (0.031 mol) of the compound represented by the formula (I-9h).

  To the reaction vessel, 12.5 g (0.031 mol) of the compound represented by the formula (I-9h) and 7.21 g (0.071 mol) of triethylamine were added and dissolved in 80 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 7.13 g (0.068 mol) of methacryloyl chloride was added dropwise. After stirring at room temperature for 5 hours, the mixture was washed with a saturated aqueous ammonium chloride solution and brine, and the solvent was distilled off to obtain 15.7 g (0.029 mol) of the compound represented by the formula (I-9i).

  To the flask, 15.7 g (0.029 mol) of the compound represented by the formula (I-9i) was added and dissolved in 50 mL of tetrahydrofuran and 50 mL of methanol. 1 mL of concentrated hydrochloric acid was added and stirred at room temperature for 7 hours. The solvent was distilled off, redissolved in ethyl acetate and washed with brine, and then the solvent was distilled off. Purification by column chromatography (silica gel) gave 9.82 g (0.022 mol) of the compound represented by the formula (I-9j).

To the reaction vessel, 9.82 g (0.022 mol) of the compound represented by the formula (I-9j) and 2.87 g (0.028 mol) of triethylamine were added and dissolved in 100 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 2.37 g (0.026 mol) of acryloyl chloride was added dropwise. The mixture was stirred at room temperature for 5 hours and then washed with 5% hydrochloric acid and brine. Purification by column chromatography (silica gel) gave 7.14 g of the compound represented by the target formula (I-9).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 504
HRMS: 504.25
Example 10 Production of Compound Represented by Formula (I-10)

A compound represented by the formula (I-10) was obtained in the same manner as in Example 4 except that acryloyl chloride was replaced with methacryloyl chloride.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 810, 750, 690 cm ⁻¹ .
¹ H NMR (CDCl ₃ ) δ 1.87 (s, 3H), 2.08 (s, 3H), 2.11 (s, 3H), 5.60 (m, 1H), 5.81 (m, 2H), 6.15 (m, 1H), 6.39 (m, 1H), 6.42 (m, 1H), 7.12 (d, 1H), 7.17 (dd, 1H), 7. 28 (dd, 1H), 7.54 (d, 1H), 7.56 (dd, 1H), 7.61 (d, 1H), 7.81 (d, 1H), 7.86 (d, 1H) ), 7.89 (d, 1H) ppm.
¹³ C NMR (CDCl ₃ ) δ 18.3, 18.4, 18.5, 116.7, 118.4, 119.6, 121.6, 127.5, 127.5, 127.7, 127. 8, 127.9, 129.6, 131.2, 131.4, 132.1, 132.9, 134.2, 135.2, 135.6, 135.8, 148.3, 148.8, 150.5, 165.3, 165.5, 166.1 ppm.

LRMS: 456
HRMS: 456.16
Example 11 Production of Compound Represented by Formula (I-11)

  In a flask, 10.0 g (0.058 mol) of the compound represented by the formula (I-1a), 7.10 g (0.075 mol) of 3-chloropropanol, 11.99 g (0.087 mol) of potassium carbonate, ethanol 100 mL was added and heated to reflux for 5 days. After filtration, the solvent was distilled off and redissolved in toluene. After washing with brine, purification was performed by column chromatography (silica gel) to obtain 10.7 g (0.046 mol) of a compound represented by the formula (I-11a).

  After the reaction vessel was purged with nitrogen, 10.7 g (0.046 mol) of the compound represented by the formula (I-11a), 6.82 g (0.069 mol) of trimethylsilylacetylene, tetrakis (triphenylphosphine) palladium (0 ) 0.54 g (46.3 mmol), 0.18 g (92.6 mmol) of copper (I) iodide, 20 mL of triethylamine and 60 mL of N, N-dimethylformamide were added and heated at 90 ° C. for 7 hours. Toluene 200 mL and water 200 mL were added for liquid separation treatment. The organic layer was washed with brine, and then purified by column chromatography (silica gel) to obtain 8.51 g (0.034 mol) of the compound represented by the formula (I-11b).

  To the reaction vessel, 8.51 g (0.034 mol) of a compound represented by the formula (I-11b) and 7.10 g (0.051 mol) of potassium carbonate were added and suspended in 50 mL of methanol. The mixture was stirred at room temperature for 8 hours and then filtered. The solvent was distilled off and the residue was purified by column chromatography (silica gel) to obtain 5.75 g (0.033 mol) of the compound represented by the formula (I-11c).

  To the flask were added 10.0 g (0.053 mol) of 4-bromoresorcinol, 13.0 g (0.14 mol) of 3-chloropropanol, 21.9 g (0.16 mol) of potassium carbonate, and 100 mL of ethanol for 8 days. Heated to reflux. After filtration, the solvent was distilled off and redissolved in toluene. After washing with brine, purification was performed by column chromatography (silica gel) to obtain 13.7 g (0.045 mol) of a compound represented by the formula (I-11d).

  After the reaction vessel was purged with nitrogen, 10.1 g (0.033 mol) of the compound represented by formula (I-11d), 5.75 g (0.033 mol) of the compound represented by formula (I-11c), Add tetrakis (triphenylphosphine) palladium (0) 0.38 g (33.0 mmol), copper (I) iodide 0.13 g (66.0 mmol), triethylamine 20 mL and N, N-dimethylformamide 60 mL, Heat at 10 ° C. for 10 hours. Toluene 200 mL and water 200 mL were added for liquid separation treatment. The organic layer was washed with brine, and then purified by column chromatography (silica gel) to obtain 9.25 g (0.023 mol) of the compound represented by the formula (I-11e).

To the flask, 9.25 g (0.023 mol) of the compound represented by the formula (I-11e) and 8.18 g (0.081 mol) of triethylamine were added and dissolved in 80 mL of dichloromethane. While cooling with ice, a solution of 8.45 g (0.081 mol) of methacryloyl chloride in dichloromethane was added dropwise. The mixture was stirred at room temperature for 6 hours, and washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and brine. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 9.79 g of the compound represented by the target formula (I-11).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 810, 750, 690 cm ⁻¹ .
LRMS: 604
HRMS: 604.27
Example 12 Production of Compound Represented by Formula (I-12)

  To a flask equipped with a Dean-Stark apparatus, 10.0 g (0.065 mol) of the compound represented by the formula (I-12a), 100 mL of ethanol and 1 mL of concentrated sulfuric acid were added, and ethanol was added while removing the reaction solution. Refluxing was carried out for an hour. The solvent was distilled off, redissolved in ethyl acetate, and washed with brine. The solvent was distilled off to obtain 11.5 g (0.063 mol) of a compound represented by the formula (I-12b).

  To the flask, 11.5 g (0.063 mol) of the compound represented by the formula (I-12b) and 0.79 g (3.1 mmol) of p-toluenesulfonic acid pyridinium salt were added and dissolved in 50 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 6.35 g (0.076 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 6 hours, the mixture was washed with saturated aqueous sodium hydrogen carbonate and brine. The solvent was distilled off to obtain 21.4 g (0.061 mol) of a compound represented by the formula (I-12c).

  To the flask, 21.4 g (0.061 mol) of the compound represented by the formula (I-12c) was added, 100 mL of methanol and 19.5 g of 25% aqueous sodium hydroxide solution were added, and the mixture was heated to reflux for 2 hours. After 10% hydrochloric acid was gradually added to neutralize, the mixture was extracted with ethyl acetate. By distilling off the solvent, 19.3 g (0.060 mol) of the compound represented by the formula (I-12d) was obtained.

  To the flask, 10.0 g (0.062 mol) of the compound represented by the formula (I-12e), 9.48 g (0.075 mol) of benzyl chloride and 12.9 g (0.094 mol) of potassium carbonate were added, and N, Suspended in 50 mL of N-dimethylformamide. After heating at 90 ° C. for 9 hours, toluene and water were added for liquid separation treatment. Purification by column chromatography (silica gel) gave 10.6 g (0.042 mol) of a compound represented by the formula (I-12f).

  To the flask, 10.6 g (0.042 mol) of the compound represented by the formula (I-12f) and 0.53 g (2.1 mmol) of p-toluenesulfonic acid pyridinium salt were added and dissolved in 50 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 4.64 g (0.055 mol) of 3,4-dihydro-2H-pyran was added dropwise. After stirring at room temperature for 6 hours, the mixture was washed with saturated aqueous sodium hydrogen carbonate and brine. By distilling off the solvent, 13.9 g (0.042 mol) of a compound represented by the formula (I-12 g) was obtained.

  To the autoclave, 13.9 g (0.042 mol) of a compound represented by the formula (I-12 g) and 1.3 g of 5% palladium carbon were added and suspended in 100 mL of tetrahydrofuran. The mixture was stirred at a hydrogen pressure of 0.5 MPa and 50 ° C. for 8 hours. After filtering the catalyst, the solvent was distilled off to obtain 10.2 g (0.042 mol) of a compound represented by the formula (I-12h).

  In a reaction vessel, 10.2 g (0.042 mol) of the compound represented by the formula (I-12h), 13.5 g (0.042 mol) of the compound represented by the formula (I-12d), N, N-dimethyl 0.51 g (4.2 mmol) of aminopyridine was added and suspended in 90 mL of dichloromethane. While cooling with ice, 6.30 g (0.050 mol) of N, N-diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 7 hours, the mixture was filtered and washed with 5% hydrochloric acid and brine. By recrystallization from a mixed solvent of dichloromethane and methanol, 18.3 g (0.033 mol) of the compound represented by the formula (I-12i) was obtained.

  To the flask, 18.3 g (0.033 mol) of the compound represented by the formula (I-12i) was added, and suspended in 50 mL of tetrahydrofuran and 50 mL of methanol. Concentrated hydrochloric acid (0.5 mL) was added, and the mixture was stirred at room temperature for 8 hours. The solvent was concentrated, dissolved in ethyl acetate and washed with brine. Purification by column chromatography (silica gel) yielded 9.57 g (0.032 mol) of the compound represented by formula (I-12j).

To the flask, 9.57 g (0.032 mol) of the compound represented by the formula (I-12j) and 8.18 g (0.12 mol) of triethylamine were added and suspended in 100 mL of dichloromethane. While cooling with ice, a dichloromethane solution of 12.1 g (0.12 mol) of methacryloyl chloride was added dropwise. The mixture was stirred at room temperature for 6 hours, and washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and brine. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 12.1 g of the compound represented by the target formula (I-12).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 810, 750, 690 cm ⁻¹ .
LRMS: 500
HRMS: 500.15
A method similar to that described in Example 1 to Example 12 is used to formula (I-13) to formula (I-40).

A polymerizable compound represented by the formula:
(Examples 13-24, Comparative Examples 1-3)
Polymerizable compound (I-1) to polymerizable compound (I-12) of the present invention, Comparative compound 1 described in Example 1 of Patent Document 1, Comparative compound 2 described in <Example 1> of Patent Document 2, and Patent Document Comparative compound 3 described in 3 of Example 6 was used as a polymerizable compound to be evaluated.

  A liquid crystal composition composed of the following compounds was prepared and used as a base liquid crystal (X1).

<< Solubility test of polymerizable compounds >>
A polymerizable liquid crystal composition was prepared by adding 5% of the polymerizable compound to be evaluated to the base liquid crystal (X1) and dissolving it. The solubility of the compound to be evaluated was evaluated by the presence or absence of precipitates after the prepared liquid crystal composition was stored at −30 ° C. for 60 days. When deposits were observed visually, the deposits were filtered and analyzed by gas chromatography (GC). The results are shown in the table below.

  When no precipitate was observed, ◎, when a minute amount was observed, ◯, when many were observed, ×.

As a result of analyzing the precipitate for the liquid crystal composition in which the precipitate was observed, all were polymerizable compounds to be evaluated. Thus, it can be seen that the polymerizable compound of the present invention has a solubility in the liquid crystal material equivalent to or higher than that of the comparative compound.
<< Production of display element >>
A polymerizable liquid crystal composition was prepared by adding 0.3% of the polymerizable compound to be evaluated to the base liquid crystal (X1) and dissolving it, to obtain a polymerizable liquid crystal composition to be evaluated. The polymerizable liquid crystal composition to be evaluated was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. While applying a rectangular wave of 1.8 V at a frequency of 1 kHz and irradiating UV of 320 nm or more at 10 mW / cm ² for 600 seconds using a high pressure mercury lamp, the PSA type vertical alignment liquid crystal display element (XI) to be evaluated Was made. The following table shows the relationship between the polymerizable compound to be evaluated and the liquid crystal display element.

<Evaluation of polymerizability>
In order to evaluate the ease of polymerization of the polymerizable compound, the liquid crystal composition obtained by disassembling the liquid crystal display element is analyzed using a liquid chromatograph (HPLC), and the amount of the uncured polymerizable compound is measured. did. It is intended that the greater the amount of uncured polymerizable compound, the less likely the polymerizable compound will polymerize. The results are shown in the table below.

Thus, since the display element produced by adding the polymerizable compound of the present invention has a small amount of the uncured polymerizable compound, the polymerizable compound of the present invention has a lower strength and shorter strength than the comparative compound 1. It turns out that it superposes | polymerizes by UV irradiation of time.
<Evaluation of pretilt angle stability>
In order to evaluate the stability of the pretilt angle of the liquid crystal display element, the produced display element was heated at 70 ° C. for 24 hours, and the pretilt angle before and after the heating was evaluated by a crystal rotation method. The results are shown in the table below.

Thus, the display element produced by adding the polymerizable compound of the present invention had a slight change in the pretilt angle before and after heating. On the other hand, in the display element XI-13 and the display element XI-14 manufactured by adding the comparative compound, the pretilt angle greatly changed by heating.
<Evaluation of burn-in>
In order to compare the difficulty of occurrence of image sticking in the liquid crystal display element, a voltage of 7.5 V was applied at 70 ° C., and evaluation was performed visually at each elapsed time. When there was no image sticking by visual observation, it was evaluated as “◯”, when image burn-in was slightly observed, “△”, and when image burn-in was observed strongly, “X”. The results are shown in the table below.

Thus, it can be seen that any liquid crystal display element manufactured by adding the compound of the present invention is less likely to cause image sticking. On the other hand, the liquid crystal display element manufactured by adding the comparative compound was seized by applying voltage for a long time.
(Examples 25-36, Comparative Examples 4-6)
The compound (I-1) to the compound (I-12) of the present invention and the comparative compound 1, the comparative compound 2, and the comparative compound 3 were used as the evaluation target compounds.

  A liquid crystal composition composed of the following compounds was prepared and used as a base liquid crystal (X2).

<< Solubility test of polymerizable compounds >>
A polymerizable liquid crystal composition was prepared by adding 5% of the polymerizable compound to be evaluated to the base liquid crystal (X2) and dissolving it. The solubility of the polymerizable compound to be evaluated was evaluated by the presence or absence of precipitates after the prepared liquid crystal composition was stored at −30 ° C. for 60 days. When deposits were observed visually, the deposits were filtered and analyzed by GC. The results are shown in the table below.

  When no precipitate was observed, ◎, when a minute amount was observed, ◯, when many were observed, ×.

As a result of analyzing the precipitate for the liquid crystal composition in which the precipitate was observed, all were polymerizable compounds to be evaluated. Thus, it can be seen that the compound of the present invention has a solubility in the liquid crystal material equivalent to or higher than that of the comparative compound.
<< Production of display element >>
A polymerizable liquid crystal composition was prepared by adding 0.3% of the polymerizable compound to be evaluated to the base liquid crystal (X2) and dissolving it, to obtain a polymerizable liquid crystal composition to be evaluated. The polymerizable liquid crystal composition to be evaluated was injected by a vacuum injection method into a cell having a comb-like electrode made of ITO coated with a polyimide alignment film that induces a homogeneous alignment with a cell gap of 3.5 μm. The liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a voltage of 1.6 V to the cell. A horizontal alignment liquid crystal display element (XII) in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized was obtained by adjusting the irradiation intensity of the cell surface to 10 mW / cm ² and irradiating for 600 seconds. The following table shows the relationship between the polymerizable compound to be evaluated and the liquid crystal display element.

<Evaluation of polymerizability>
In order to evaluate the ease of polymerization of the polymerizable compound, the liquid crystal composition obtained by disassembling the liquid crystal display element was analyzed using HPLC, and the amount of the uncured polymerizable compound was measured. It is intended that the greater the amount of uncured polymerizable compound, the less likely the polymerizable compound will polymerize. The results are shown in the table below.

Thus, since the display element produced by adding the compound of the present invention has a small amount of uncured polymerizable compound, the compound of the present invention has a lower intensity and shorter UV irradiation than the comparative compound 1. It can be seen that polymerization takes place.
<Evaluation of burn-in>
In order to compare the difficulty of occurrence of image sticking in the liquid crystal display element, a voltage of 7.5 V was applied at 70 ° C., and evaluation was performed visually at each elapsed time. When there was no image sticking by visual observation, it was evaluated as “◯”, when image burn-in was slightly observed, “△”, and when image burn-in was observed strongly, “X”. The results are shown in the table below.

Thus, it can be seen that any liquid crystal display element manufactured by adding the compound of the present invention is less likely to cause image sticking. On the other hand, the liquid crystal display element manufactured by adding the comparative compound was seized by applying voltage for a long time.
(Examples 37 to 48, Comparative Examples 7 to 9)
The compound (I-1) to the compound (I-12) of the present invention and the comparative compound 1, the comparative compound 2, and the comparative compound 3 were used as the evaluation target compounds.

  A liquid crystal composition composed of the following compounds was prepared and used as a base liquid crystal (X3).

3% of photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) is added to each of the compositions prepared by adding 20% of the target compound to the base liquid crystal (X3) 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. When the phase difference before heating of the obtained film was defined as 100%, the phase difference (%) after heating at 200 ° C. for 1 hour was measured. For measuring the phase difference, RETS-100 manufactured by Otsuka Electronics Co., Ltd. was used. The results are shown in the table below.

  Thus, the film prepared by adding the compound of the present invention is heat resistant because the decrease in retardation after heating is equivalent or small compared to the film prepared by adding the comparative compound. It turns out that it is excellent in property.

  From the above results, the compound of the present invention has high solubility in the liquid crystal material, and can be polymerized by low-intensity and short-time UV irradiation when added to the liquid crystal composition. It can also be seen that when a PSA type liquid crystal display device is manufactured using a liquid crystal composition to which the compound of the present invention is added, the stability of the pretilt angle is high and image sticking is unlikely to occur. Therefore, the compounds of the present invention are useful as liquid crystal materials, resins, resin additives, oils, oil filters, oils and fats, inks, pharmaceuticals, cosmetics, detergents, agricultural chemicals, foods, and various products.

Claims (10)

General formula (Ig)

(In the formula, ^{R 1} is the front base, human Dorokishiru group, a hydroxyalkyl group of carbon atom number of 1 to 20 represented by P-Sp-,
m ¹ represents 0 , m ² represents an integer of 1 to 2 ,
A ¹ is 1,2-phenylene, naphthalene-1,2-diyl, naphthalene-2,3-diyl, naphthalene-2,8-diyl, naphthalene-1,8-diyl or naphthalene-1,7-diyl . These groups may be unsubstituted or substituted by one or more L ,
A ² is represents a 1,4-phenylene, this group may be substituted by unsubstituted or one or more L,
Z ¹ and ^{Z 2} are each independently a single bond, - COO -, - OCO - or to display the -C≡C-, ^{if Z 2 m 2} represents 2 there are a plurality they had the same Can be different,
Wherein L is a group represented by P-Sp-, hydrogen atom, a fluorine atom, one -CH ₂ - is - O - from a good 1 -C be replaced with the 1 0 linear Joa alkyl group And when there are a plurality of L, they may be the same or different,
The Sp represents a single bond , alkylene, or oxyalkylene, and when a plurality of Sp are present, they may be the same or different, and the P is represented by the formula (P-1) or the formula (P-2). )

Represents a, P is they when there are a plurality of rather good even if the same or different and the groups represented by P-Sp- present is a two or three. ) A polymerizable compound represented by: A polymerizable composition comprising the polymerizable compound according to claim 1 . 1 type or 2 or more types of polymeric compounds of Claim 1, general formula (II-1), and general formula (II-2)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, one existing in these groups) -CH ₂ -or two or more methylene groups not adjacent to each other may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups are A fluorine atom or a chlorine atom, and A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ and A ⁹ are each independently
(A) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom);
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and a group selected from the group consisting of decahydronaphthalene-2,6-diyl group,
The hydrogen atom contained in the group (a), group (b) or group (c) may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, respectively. ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH _{2. -, - CH 2 O -,} - OCF 2 -, - CF 2 O- or represents ^{-C≡C-, a 5, a 6,} a 8, a 9, Z 3, Z 5, Z 6 , and / Or when a plurality of Z ⁸ are present, they may be the same or different, and L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a hydrogen atom, trifluoromethyl group, trifluoro methoxy group, represent a fluorine atom or a chlorine atom, L ¹ and L ² are simultaneously water Represent the atoms ^without, L 3, ^{L 4} and ^{which L 5} without simultaneously represent a hydrogen ^{atom, m 4, m 5, m} 6 and ^{m 7} are each independently 0, 1, 2 or 3 M ⁴ + m ⁵ and m ⁶ + m ⁷ are 4 or less. In general formula (II-1), the compound represented by general formula (II-2) is excluded. A liquid crystal composition containing one or more compounds selected from the group represented by: 1 type, or 2 or more types of polymeric compounds of Claim 1, general formula (III-1), and general formula (III-2)

(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkenyl group having 2 to 10 carbon atoms, and one methylene present in these groups) Two or more methylene groups which are not adjacent or adjacent to each other may be substituted with -O- or -S-, and one or more hydrogen atoms present in these groups are fluorine atoms or chlorine atoms. A ¹⁰ , A ¹¹ , A ¹² , A ¹³ , A ¹⁴ and A ¹⁵ are each independently
(A) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ),
(B) 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1 , 4-phenylene group, 3,5-difluoro-1,4-phenylene group,
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and a group selected from the group consisting of decahydronaphthalene-2,6-diyl group,
The hydrogen atom contained in the group (a), group (b) or group (c) may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH. _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O- or -C≡C-, and A ¹¹ , A ¹² , A ¹⁴ , A ¹⁵ , Z ⁹ , Z ¹¹ , Z ¹² and / or or ^{if Z 14} there are a plurality, they may be different may be the ^{same, L 6, L 7, L} 8, L 9 and ^{L 10} each represents a hydrogen atom or a fluorine atom each independently, ^{Y 1} And Y ² each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a difluoromethoxy group, L ^{6, L 7} or ^{Y 1} is at the same time It is not representative of the atom, or at least one of the hydrogen atoms contained in the A ¹⁰ or A ¹² represents a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom, L ^8, L ⁹ , L ¹⁰ or Y ² do not simultaneously represent a hydrogen atom, or at least one of the hydrogen atoms contained in A ¹³ , A ¹⁴ or A ¹⁵ is a cyano group, a fluorine atom, a trifluoromethyl group, trifluoro A methoxy group or a chlorine atom is represented, and m ⁸ , m ⁹ , m ¹⁰ and m ¹¹ each independently represent 0, 1 or 2. In general formula (III-1), the compound represented by general formula (III-2) is excluded. A liquid crystal composition containing one or more compounds selected from the group represented by: Formula (IV)

(Wherein R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, but one —CH ₂ — or not adjacent 2 One or more —CH ₂ — may be replaced with —O— or —S—, and a hydrogen atom present in these groups may be replaced with a fluorine atom or a chlorine atom, and A ¹⁶ , A ¹⁷ And A ¹⁸ are each independently
(A) trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other may be replaced by —O— or —S—). ), (B) 1,4-phenylene group (one —CH═ or two or more non-adjacent —CH═ may be replaced by a nitrogen atom), 3-fluoro-1,4- Phenylene group and 3,5-difluoro-1,4-phenylene group and (c) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl A group selected from the group consisting of a group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, m ¹² represents 0 or 1, Z ¹⁵ and Z ¹⁶ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —CF ₂ CF ₂ —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CH═N—, —N═CH—, —CH═N—N═CH— or —C≡C—. In the case where a plurality of Z ¹⁶ and / or A ¹⁸ are present, they may be the same or different. In general formula (IV), the compounds represented by general formula (II-1), general formula (II-2), general formula (III-1), and general formula (III-2) are excluded. The liquid crystal composition according to claim 3 or 4 , comprising one or more compounds selected from the group represented by: An optical element using the polymerizable compound according to claim 1 . An optical element using the liquid crystal composition according to any one of claims 3 to 5 . A cured product comprising two substrates each having a light-transmitting layer and an electrode, and the composition according to claim 6 cured between these substrates, or claims 3 to 5 . An optical element comprising a cured product obtained by curing the liquid crystal composition according to claim 1. The optical element according to any one of claims 6 to 8 , which is used for a PS (polymer stabilization) mold or a PSA (polymer sustaining alignment) mold. Liquid crystal materials, resins, resin additives, oils, oil filters, oils and fats, inks, pharmaceuticals, cosmetics, detergents, agricultural chemicals, and foods using the compound according to claim 1 or a cured product obtained by curing the compound. Product used.