JP2020075873A - Production method of benzothiazole derivative - Google Patents

Abstract

To provide: a production method of a benzothiazole derivative; as well as a production method of a polymerizable compound produced from the benzothiazole derivative; a polymerizable composition including the polymerizable compound; a polymer obtained by polymerizing the polymerizable composition; and an optical isomer utilizing the polymer.SOLUTION: A production method of a compound represented by the following general formula (III) is provided, and also a production method of a polymerizable compound produced from the compound represented by the general formula (III), a polymerizable composition, a polymer obtained by polymerizing the polymerizable composition, and an optical isomer utilizing the polymer are provided. When the polymerizable composition containing the compound is polymerized and the obtained film-like polymer is irradiated with ultraviolet light, change of color and change of phase difference scarcely take place.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a benzothiazole derivative, a method for producing a polymerizable compound using the benzothiazole derivative, a polymerizable composition produced by using the polymerizable compound, and an optical difference using the polymerizable composition. Regarding the cube.

  The compound having a polymerizable group (polymerizable compound) is used for various optical materials. For example, a polymer having a uniform orientation can be produced by aligning a polymerizable composition containing a polymerizable compound in a liquid crystal state and then polymerizing the same. Such a polymer can be used for a polarizing plate, a retardation plate, etc. necessary for a display. In many cases, two or more types of polymerization are required to meet the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, polymer transparency, mechanical strength, surface hardness, heat resistance and light resistance. A polymerizable composition containing a polymerizable compound is used. In that case, the polymerizable compound used is required to bring good physical properties to the polymerizable composition without adversely affecting other properties.

  When a polymerizable composition containing a polymerizable compound is used as an optical film material for a display or the like, it is preferable that the optical film is unlikely to undergo discoloration or retardation change after long-term use of the display product. As the cause of the color change and the change in phase difference, backlight, room light, ultraviolet light and backlight contained in sunlight, etc., due to heat from the surrounding environment, an extremely small amount of the polymerizable compound contained in the optical film is used. The alteration of impurities may be mentioned. When using an optical film that is prone to discoloration or change in phase difference for a display, the brightness and contrast of the display may deteriorate and the visibility may deteriorate due to long-term use, resulting in a large display product quality. There is a problem of lowering it.

  As an optical film material used for improving the viewing angle of a liquid crystal display and preventing reflection of external light of an organic electroluminescence element, various compounds having a birefringence index having a small or reverse wavelength dispersion have been developed. Of these compounds, a polymerizable compound having a benzothiazole structure has a suitable refractive index anisotropy and exhibits good reverse wavelength dispersion, and is useful as an optical film material. However, the conventionally known methods for producing a polymerizable compound having a benzothiazole structure have a problem of low yield (Patent Document 1). This is due to the low yield of the cyclization reaction. In the conventional method, a benzothiazole derivative (IIB) is produced by a cyclization reaction by the Jacobson method using a thioamide derivative (IIA) as a starting material. In the cyclization reaction, it is known that a by-product by a radical reaction is produced in addition to the desired benzothiazole derivative (IIB). Compound (IIBY) has been reported as an example of those by-products (Organic and Biomolecular Chemistry, 2004, No. 2, 3039-3043).

Various by-products including the compound (IIBY) are considered to contribute to the decrease in the yield of the cyclization reaction. Since the starting material (IIA) is expensive in the step of the cyclization reaction, a low yield is extremely disadvantageous in terms of cost.

  Further, when a benzothiazole derivative (IIB) produced by a conventional method is used to produce a polymerizable compound, and the obtained polymerizable compound is added to the polymerizable composition to produce a film, discoloration or discoloration of the film occurs. There is a problem that the phase difference is likely to change (Patent Document 1). Impurities derived from by-products by various radical reactions including the compound (IIBY) remained in a very small amount in the subsequent steps, and thus the produced polymerizable compound was added to the polymerizable composition to form a film. In this case, adverse effects such as discoloration of the film and changes in retardation are likely to occur. A compound having a benzothiazole structure has an absorption spectrum close to a visible light region, which is considered to be because deterioration due to an extremely small amount of impurities easily occurs with respect to light from the surrounding environment. Therefore, it has been required to develop a method for producing a benzothiazole derivative, which does not easily generate impurities that adversely affect the film and has a high yield.

JP, 2011-207765, A

  The problem to be solved by the present invention is to produce a polymerizable compound, and discoloration and retardation of the film-like polymer obtained by polymerizing a polymerizable composition containing the compound when irradiated with ultraviolet light. It is an object of the present invention to provide a method for producing a benzothiazole derivative that hardly changes. Further, a method for producing a polymerizable compound produced from the benzothiazole derivative, a polymerizable composition containing the polymerizable compound, a polymer obtained by polymerizing the polymerizable composition, and an optical using the polymer. It is to provide an anisotropic body.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, have developed a method for producing a compound represented by the following general formula (III). That is, the present invention has the following general formula (II)

(In the formula, PG ¹ and PG ² each independently represent a hydrogen atom or an organic group, and the ring B represents an aromatic group or a heteroaromatic group having 3 to 40 carbon atoms which may be substituted with L ^B. Represented by the general formula (III) below, wherein L ^B represents an organic group, and Y represents an oxygen atom or a sulfur atom.

(In the formula, rings B, Y, PG ¹ and PG ² each have the same meaning as rings B, Y, PG ¹ and PG ² in formula (II).) . In addition, a method for producing a polymerizable compound produced from the compound represented by the general formula (III), a resin using the polymerizable compound, a resin additive, an oil, a filter, an adhesive, a pressure-sensitive adhesive, a fat and oil, an ink, Pharmaceuticals, cosmetics, detergents, building materials, packaging materials, optical films, liquid crystal materials, organic EL materials, sealing materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, mechanical parts Provided are an agricultural chemical, a food, a product using them, a polymerizable composition, a polymer obtained by polymerizing the polymerizable composition, and an optical anisotropic body using the polymer.

  Since the production method of the present invention has a higher yield than the conventional methods, it is useful as a method for producing a benzothiazole derivative. Further, a polymerizable compound is produced because it is less likely to cause discoloration and a change in retardation when irradiated with ultraviolet light to a film-shaped polymer obtained by polymerizing a polymerizable composition containing the compound to produce a polymerizable compound. Is useful as a manufacturing method of. Further, an optical anisotropic body using a polymerizable composition containing a polymerizable compound produced by the production method of the present invention, because it is difficult to cause discoloration and change in phase difference when irradiated with ultraviolet light, etc. It is useful for optical film applications.

  The present invention provides a method for producing a compound represented by the general formula (III). In addition, a method for producing a polymerizable compound produced from the compound, a resin using the polymerizable compound, a resin additive, an oil, a filter, an adhesive, an adhesive, a fat, an ink, a drug, a cosmetic, a detergent, a building material. , Packaging materials, optical films, liquid crystal materials, organic EL materials, encapsulating materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals and food products, and their use The present invention provides a product, a polymerizable composition, a polymer obtained by polymerizing the polymerizable composition, and an optical anisotropic body using the polymer.

  In the production method of the present invention, it is preferable to carry out the cyclization reaction using an oxidizing agent. In the conventional production method, since the reaction point of the cyclization reaction is close to the alkoxy group, in the transition state of the cyclization reaction, the molecule of the oxidant is likely to coordinate with the oxygen atom of the alkoxy group, and the side reaction is likely to occur. .. In the production method of the present invention, the reaction point of the cyclization reaction is far from the alkoxy group on the benzene ring, as compared with the conventional production method. Therefore, it is considered that a side reaction is unlikely to occur, the yield is high, and impurities that adversely affect the formation of a film are unlikely to occur.

In formula (II), PG ¹ and PG ² each independently represent a hydrogen atom or an organic group. PG ¹ and PG ² are each independently substituted in view of ease of synthesis, availability of raw materials, and resistance to discoloration and retardation change when a polymerizable compound is produced into a film. Is preferably a hydrocarbon group or an optionally substituted silyl group, and PG ¹ and PG ² are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. An alkoxyalkoxyalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a tetrahydropyranyl group, a trialkylsilyl group having 3 to 20 carbon atoms More preferably, it represents an arylmethyl group having 4 to 30 carbon atoms or an acyl group having 1 to 20 carbon atoms, and PG ¹ and PG ² each independently represent an alkyl group having 1 to 20 carbon atoms. It is even more preferable that PG ¹ and PG ² each independently represent an alkyl group having 1 to 5 carbon atoms, and it is particularly preferable that PG ¹ and PG ² each represent a methyl group.

In formula (II), ring B represents a group containing an aromatic group or a heteroaromatic group having 3 to 40 carbon atoms, which may be substituted with L ^B. From the viewpoint of easiness of synthesis, availability of raw materials, and occurrence of discoloration and change of retardation when a polymerizable compound is produced into a film, ring B is represented by the following formula (B-1). B-10)

(Wherein, have one a bond at any position, any -CH = may be replaced each independently -N =, -CH 2 _- are each independently -O -, - S-, -NR ^B1-- (in the formula, R ^B1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), -CS- or -CO-, and these groups are not present. It may be substituted or may be substituted with one or more substituents L ^B ). The group represented by the above formula (B-1), from the following may be substituted by unsubstituted or substituted with one or more substituents L ^B formula (B-1-1) wherein (B -1-8)

(In the formula, one bond is present at any position, and R ^B1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from the above formula (B -2) is a group represented by the following formula (B-2-1) to formula (B-2-7) which may be unsubstituted or substituted by one or more substituents L ^B.

(In the formula, it has one bond at an arbitrary position.) It is preferable to represent a group selected from the above, and the group represented by the above formula (B-3) is an unsubstituted group or one group. The following formulas (B-3-1) to (B-3-9) that may be substituted by the above substituents L ^B

(In the formula, one bond is present at any position, and R ^B1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from the above formula (B -4) is a group represented by the following formula (B-4-1) to formula (B-4-9) which may be unsubstituted or substituted by one or more substituents L ^B.

(In the formula, one bond is present at any position, and R ^B1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from the above formula (B Examples of the group represented by -5) include the following formulas (B-5-1) to (B-5-13) which may be unsubstituted or substituted by one or more substituents L ^B.

(In the formula, one bond is provided at any position, and R ^B1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from the above formula (B Examples of the group represented by -6) include the following formulas (B-6-1) to (B-6-8) which may be unsubstituted or substituted by one or more substituents L ^B.

(In the formula, one bond is present at any position, and R ^B1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from the above formula (B Examples of the group represented by -7) are the following formulas (B-7-1) to (B-7-7) which may be unsubstituted or substituted by one or more substituents L ^B.

(In the formula, it has one bond at an arbitrary position.) It is preferable to represent a group selected from the above, and the group represented by the above formula (B-8) is an unsubstituted or one group. The following formula (B-8-1) to formula (B-8-4) which may be substituted by the above substituent L ^B

(In the formula, one bond is provided at any position, and R ^B1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from the above formula (B Examples of the group represented by -9) are the following formulas (B-9-1) to (B-9-8) which may be unsubstituted or substituted by one or more substituents L ^B.

(In the formula, it has one bond at any position.) It is preferable to represent a group selected from the group represented by the above formula (B-10), which is unsubstituted or The following formula (B-10-1) to formula (B-10-4) which may be substituted by the above substituent L ^B

(In the formula, it has one bond at an arbitrary position.) It is preferable to represent a group selected from.

In the general formula (II), L ^B represents an organic group, but when there are a plurality of L ^B, they may be the same or different. From the viewpoint of easiness of synthesis, availability of raw materials, and difficulty in causing discoloration and change in retardation when a polymerizable compound is produced into a film, when a plurality of L ^B are present, they may be the same. They may be different, and may be a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom substituted with a fluorine atom. Well, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—. S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH =. CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- is preferably an alkyl group having 1 to 20 carbon atoms which may be substituted, and L ^When a plurality of ^B are present, they may be the same or different, and are a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, or an arbitrary hydrogen atom. May be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—. , -OCO-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- may be substituted with an alkyl group having 1 to 20 carbon atoms. it is more preferable that represents, L ^B is they when there are a plurality of which may be the same or different and a fluorine atom, a chlorine atom, a cyano group, a nitro group, a dialkylamino group having 2 to 12 carbon atoms, More preferably, it represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkenyloxy group having 2 to 19 carbon atoms, and L ^B is , When they exist in plural, they may be the same or different and more preferably represent a fluorine atom, a chlorine atom or an alkyl group having 1 to 12 carbon atoms,
It is particularly preferable that L ^B represents an alkyl group having 1 to 8 carbon atoms.

  In the general formula (II), from the viewpoint of easiness of synthesis, availability of raw materials, and resistance to discoloration and phase difference change when the polymerizable compound is produced into a film, the polymerizable compound is produced. In view of solubility in a solvent, liquid crystallinity, and reverse wavelength dispersibility, the ring B is represented by the following formula (B-2-1-1) to formula (B-7-1-2).

(In the formula, a broken line represents a bonding position, and when a plurality of L ^B1 are present, they may be the same or different, and a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, a substituent Optionally substituted amino group, any hydrogen atom may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. , -S-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C-. Also represents an alkyl group having 1 to 20 carbon atoms, r represents an integer of 0 to 4, s represents an integer of 0 to 3, t represents an integer of 0 to 2, u represents 0 to 6 More preferably, it represents a group selected from
Ring B is represented by the following formula (B-2-1-1-1) to formula (B-2-2-3-5).

(In the formula, a broken line represents a bonding position, and when a plurality of L ^B11 are present, they may be the same or different, and are a fluorine atom, a chlorine atom, a cyano group, a nitro group, or a carbon number of 2 to 12 Represents a dialkylamino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkenyloxy group having 2 to 19 carbon atoms. More preferably, it represents a selected group,
Ring B is represented by the following formula (B-A-1) to formula (B-A-8)

(In the formula, a broken line represents a bonding position, and when a plurality of L ^B12 are present, they may be the same or different and represent a fluorine atom, a chlorine atom or an alkyl group having 1 to 12 carbon atoms. More preferably, it represents a group selected from
Ring B is represented by the following formula (B-A1-1) and formula (B-A1-2).

(In the formula, a broken line represents a bonding position.) It is particularly preferable to represent a group selected from the following.

  In the general formula (II), Y represents an oxygen atom or a sulfur atom. From the viewpoint of easiness of synthesis, yield, difficulty in causing discoloration and change in retardation when a polymerizable compound is produced into a film, and solubility in a solvent when a polymerizable compound is produced, liquid crystal It is particularly preferable that Y represents a sulfur atom from the viewpoint of the property and the reverse wavelength dispersibility.

  Specific examples of the compound represented by the general formula (II) include the following formula (II-1) to formula (II-20).

The compound represented by

  It is preferable to produce the compound represented by the general formula (III) from the compound represented by the general formula (II). In the ring B of the general formula (II), among the carbon atoms adjacent to the carbon atom bonded to the nitrogen atom bonded to the ring B, the carbon atom bonded to the hydrogen atom and the group represented by Y react with each other, Form a fused ring. In the ring B of the general formula (II), when there are two carbon atoms to which a hydrogen atom is bonded among the carbon atoms adjacent to the carbon atom bonded to the nitrogen atom bonded to the ring B, two reaction points are formed. Become. When the ring B in the general formula (II) has C2 symmetry about the bond between the bonded nitrogen atom and the carbon atom, the product has one kind, and when the ring B has no C2 symmetry, the product has two kinds. ..

  In the general formula (III), when the ring B represents a group selected from the above formulas (B-1) to (B-10), it has two bonds on any adjacent carbon atoms. In the general formula (III), the ring B is the above formula (B-1-1) to the formula (B-1-8), the formula (B-2-1) to the formula (B-2-7), the formula (B). B-3-1) to formula (B-3-9), formula (B-4-1) to formula (B-4-9), formula (B-5-1) to formula (B-5-13) ), Formula (B-6-1) to formula (B-6-8), formula (B-7-1) to formula (B-7-7), formula (B-8-1) to formula (B -8-4), a group selected from the formula (B-9-1) to the formula (B-9-8) and the formula (B-10-1) to the formula (B-10-4) is optional. Has two bonds on adjacent carbon atoms of.

  In the general formula (II), when the ring B represents a group selected from the above formulas (B-2-1-1) to (B-7-1-2), the ring B in the general formula (III) is Is from the following formula (C-2-1-1) to formula (C-7-1-2)

(Wherein the dashed line represents a bond ^position, L B1, r, s, t and u, ^L in each formula from the above formula (B-2-1-1) (B- 7-1-2) B1 , R, s, t, and u have the same meaning.).

  In the general formula (II), when the ring B represents a group selected from the above formulas (B-2-1-1-1) to the formula (B-2-2-3-5), the general formula (III) In the formula, ring B is represented by the following formula (C-2-1-1-1) to formula (C-2-2-3-6).

(In the formula, a broken line represents a bonding position, and L ^B11 has the same meaning as L ^B11 in the formula (B-2-1-1-1) to the formula (B-2-2-3-5), respectively. Represents a group selected from

  In the general formula (II), when the ring B represents a group selected from the above formulas (BA-1) to (BA-8), in the general formula (III), the ring B has the following formula. From (C-A-1) to formula (C-A-8)

(In the formula, the broken line represents the bonding position, and L ^B12 represents the same meaning as L ^B12 in the formula (BA-1) to the formula ( ^BA -8), respectively). Represent

  In the general formula (II), when the ring B represents a group selected from the above formulas (B-A1-1) and (B-A1-2), in the general formula (III), the ring B has the following formula. (C-A1-1)

(In the formula, the broken line represents the bonding position).

  Specific examples of the compound represented by the general formula (III) include the following formula (III-1) to formula (III-20).

The compound represented by

The compound represented by the general formula (III) can be produced from the compound represented by the general formula (II) by the following production method.
(Production method 1) Production of compound represented by formula (S-2)

(Represented in the formula, ring B, ring B in PG ¹ and PG ² are each the formula (II), the same meaning as PG ¹ and PG ^2.) Equation presence oxidizing agent a compound represented by (S-1) The compound represented by the formula (S-2) can be obtained by cyclizing underneath. Examples of the reaction conditions include an oxidation reaction with oxygen in the presence of copper trifluoromethanesulfonate.
(Production method 2) Production of compound represented by formula (S-5)

(In the formula, ring B, PG ¹ and PG ² each have the same meaning as ring B, PG ¹ and PG ² in formula (II).)
By converting the carbonyl group of the compound represented by formula (S-3) into a thiocarbonyl group, the compound represented by formula (S-4) can be obtained. Examples of the reaction conditions include a method of heating in the presence of Lawesson's reagent.

  The compound represented by formula (S-5) can be obtained by cyclizing the compound represented by formula (S-4) in the presence of a base and an oxidizing agent. Examples of the base include sodium hydroxide. Examples of the oxidizing agent include potassium ferricyanide.

  From the compound represented by the general formula (III), the following general formula (IV)

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen atom in the group is a fluorine atom. It may be substituted with an atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O. -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 - _{, -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CF- or -C≡C-, or a group represented by P ^1- [Sp ¹ -X ¹ ] _k ^1- ( In the formula, P ¹ represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ¹ may have any hydrogen atom in the group substituted with a fluorine atom, and one —CH ₂ — or adjacent Two or more —CH ₂ — which are not independently each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O. -CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or a straight chain having 2 to 20 carbon atoms which may be replaced by -C≡C-. A branched or branched alkylene group, when multiple Sp ^1's are present, they may be the same or different, and X ^1's are —O—, —S—, —OCH ₂ —, —CH ₂ O. -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 - _{, -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH-, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - _{, -OCO-CH 2 -, -} CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF-, -C≡C- or a single bond, but when a plurality of X ^1's are present, they may be the same or different (provided that P ^1- [Sp ¹ -X ¹ ] _k ¹ -is -O. Does not include an -O- bond. ), K1 represents an integer of 0 to 5. ),
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen atom in the group is substituted with a fluorine atom. Alternatively, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO. -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 _{S -, - CF 2 O -} , - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - _{OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, _{-OCO-CH 2 -, - CH} 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF- or - A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by C≡C-, or a group represented by-[X ² -Sp ² ] _k2- P ² (in the formula, P ² represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ² may have any hydrogen atom in the group substituted with a fluorine atom, and one —CH ₂ — or non-adjacent 2 more than five -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or straight-chain or branched-chain having 2 to 20 carbon atoms which may be replaced by -C≡C-. It represents an alkylene group, but when a plurality of Sp ² are present, they may be the same or different, and X ² is —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO. -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 _{S -, - CF 2 O -} , - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO- _{CH = CH -, - COO-} CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO _{-CH 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡ C- or a single bond is represented, but when a plurality of X ² are present, they may be the same or different (provided that-[X ² -Sp ² ] _k2- P ² is -O-O-. Does not include joins. ) And k2 represent an integer of 0 to 5. ),
A ¹ and A ² are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, tetrahydro Represents a pyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group, which may be unsubstituted or substituted by one or more substituents L ² . When there are a plurality of A ^1, they may be the same or different, and when there are a plurality of A ^2, they may be the same or different,
L ² is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom may be substituted with a fluorine atom, 1 number of -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH -, - CH = CH -, - CF = CF- or -C≡C- alkyl group having 20 good 1 -C be replaced by, ^or, P ^L - [Sp L - X ^L] kL _- in the group represented by (wherein, P ^L is radical polymerization, represents a polymerized group by cationic polymerization or anionic polymerization, Sp ^L is even any hydrogen atom in the radicals substituted by fluorine atoms Well, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—. S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- also represents a good straight-chain or branched alkylene group having a carbon number of 2 to 20, Sp ^L is those if there exist a plurality may be different even in the same, X ^L is -O -, - S _{-, - OCH 2 -, -} CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH- _{, -NH-CO -, - SCH} 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO -CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - _{CH 2 CH 2 -OCO -, -} COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH-, -CF = CF-, -C = C- or a single bond, but when a plurality of X ^L are present, they may be the same or different (provided that P ^L - ^{[Sp L} -X L ] _KL- does not include a —O—O— bond. ), KL represents an integer of 0 to 5. ), When ^two or more L ^2's are present, they may be the same or different,
Ax is the following formula (IV-Ax)

(In the formula, the broken line represents a bonding position, and the rings B and Y have the same meanings as the rings B and Y in the general formula (III) respectively.),
Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, —OCO—, —CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, _{-NH-O -, - O-} NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 _{-COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N - , - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{if Z 1} there are a plurality of They may be the same or different, and when a plurality of Z ² are present, they may be the same or different,
m1 and m2 each independently represent an integer of 0 to 6, while m1 + m2 represents an integer of 1 to 6,
However, there is at least one polymerizable group selected from P ¹ , P ² and P ^L. It is preferable to produce the compound represented by

In formula (IV), R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen in the group. An atom may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —OCH ₂ —, —. _{CH 2 O -, - CO -} , - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - _{SCH 2 -, - CH 2 S} -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, _{-COO-CH 2 -, - OCO} -CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH-, -CF = CF- or a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -C≡C-, or represented by P ^1- [Sp ¹ -X ¹ ] _k ^1- . Represents a group. R ¹ is a hydrogen atom or fluorine from the viewpoint of easiness of synthesis, resistance to discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersibility. An atom, a cyano group, a nitro group, or any hydrogen atom in the group may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently. _, - - S _-, - _-O and OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O-CO- _{O -, - CO-NH -} , - NH-CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH-, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - _{, -OCO-CH 2 -, -} CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF- or from a good 1 -C be replaced by -C≡C- 20 linear or branched alkyl group or a group represented by P ^1- [Sp ¹ -X ¹ ] _k ^1- is preferable, and R ¹ represents a hydrogen atom, a fluorine atom, or a group in the group. Any hydrogen atom may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO—. , A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -CH = CH- or -C≡C-, or P ^1- [Sp ¹ -X ¹ ] _k1- It is more preferable that R ¹ represents one of —CH ₂ — or two or more non-adjacent —CH ₂ — which may each independently be substituted by —O—. More preferably, it represents a linear or branched alkyl group of 1 to 20, or a group represented by P ^1- [Sp ¹ -X ¹ ] _k ^1- , and R ¹ represents one -CH ₂ -or. Two or more non-adjacent —CH ₂ — may be each independently substituted by —O—, a linear alkyl group having 1 to 12 carbon atoms, or P ^1- [Sp ¹ -X ¹ ] _{k1 -} is still more preferably represent a group represented by, R ¹ is a linear alkyl group having 1 to 12 carbon atoms, Alternatively, it is particularly preferable to represent the group represented by P ^1- [Sp ¹ -X ¹ ] _k ^1- .

In the general formula (IV), R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen in the group. An atom may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —OCH ₂ —, —. _{CH 2 O -, - CO -} , - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - _{SCH 2 -, - CH 2 S} -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, _{-COO-CH 2 -, - OCO} -CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH-, linear or branched alkyl group of -CF = CF- or -C≡C- 20 from a good 1 -C be replaced by, ^or - is represented by _{^{[X 2 -Sp 2] k2 -P}} 2 Represents a group. R ² is a hydrogen atom or fluorine from the viewpoint of easiness of synthesis, resistance to discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersibility. An atom, a cyano group, a nitro group, or any hydrogen atom in the group may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently. _, - - S _-, - _-O and OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O-CO- _{O -, - CO-NH -} , - NH-CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH-, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - _{, -OCO-CH 2 -, -} CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF- or from a good 1 -C be replaced by -C≡C- linear or branched alkyl group having 20 ^or, - preferably represents a group represented by _{^{[X 2 -Sp 2] k2 -P}} 2, R 2 is a hydrogen atom, a fluorine atom, or, in the radical Any hydrogen atom may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO—. , straight-chain or branched alkyl group of -CH = CH- or -C≡C- 20 from a good 1 -C be replaced by, ^or - Table in _{^{[X 2 -Sp 2] k2 -P}} 2 It is more preferred that R ² represents one group, and R ² is the number of carbon atoms in which one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently substituted by —O—. linear or branched alkyl group having 1 to 20, ^or - more preferably represents a group represented by _{^{[X 2 -Sp 2] k2 -P}} 2, R 2 is one -CH ₂ - or Two or more —CH ₂ — which are not adjacent to each other may each independently be substituted by —O—, a linear alkyl group having 1 to 12 carbon atoms, or — [X ² —Sp ² ] _k2. Even more preferably, it represents a group represented by —P ² , R ² is a linear alkyl group having 1 to 12 carbon atoms, or , ^- and particularly preferably a group represented by _{^{[X 2 -Sp 2] k2 -P}} 2.

In the general formula (IV), A ¹ and A ² are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine. -2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group, tetrahydropyran-2,5-diyl group or 1,3-dioxane-2,5-diyl group, which groups are unsubstituted or one or more substituents L ² When there are a plurality of A ^1, they may be the same or different, and when there are a plurality of A ^2, they may be the same or different. From the viewpoint of ease of synthesis, resistance to color change and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersion, A ¹ and A ² are plural. If present, they may be the same or different and each independently are unsubstituted or may be substituted by one or more substituents L ² , a 1,4-phenylene group, 1,4 -Cyclohexylene group, naphthalene-2,6-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group are preferred, and there are plural A ¹ and A ^2. If they are the same, they may be the same or different, and each of them independently represents the following formula (A-1) to formula (A-14).

(In the formula, a broken line represents a bonding position, and when a plurality of L ² exists, they may be the same or different.) It is more preferable to represent a group selected from the above, and A ¹ and A ² are plural. When present, they may be the same or different, and it is further preferred that each independently represent a group selected from formula (A-1) to formula (A-12), and A ¹ and A ² are When a plurality of them are present, they may be the same or different, and it is even more preferable that each independently represent a group selected from formula (A-1) to formula (A-8), and A ¹ and A ^When a plurality of ² are present, they may be the same or different and it is particularly preferable that each independently represent a group selected from formula (A-1) or formula (A-2).

In formula (IV), L ² is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom is a fluorine atom. It may be substituted, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-,-. COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or an alkyl group having 1 to 20 carbon atoms which may be substituted by -C≡C-, or _{^{P L - [Sp L -X L}} ] kL - in represents a group represented, they may be the same or different ^{if L 2} there are a plurality. A plurality of L ^{2 s} are present from the viewpoint of easiness of synthesis, resistance to color change and retardation change when formed into a film, and solubility from solvent, liquid crystallinity and reverse wavelength dispersion. In these cases, they may be the same or different, and a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an amino group which may be substituted, or an arbitrary hydrogen atom is substituted with a fluorine atom. Alternatively, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —. CO-NH -, - NH- CO -, - CH = CH -, - CF = CF- or -C≡C- alkyl group having 20 good 1 -C be replaced by, ^{or, P} L - [ Sp ^L —X ^L ] _kL- is preferably represented, and when ^two or more L ² are present, they may be the same or different, and are a fluorine atom, a chlorine atom, a cyano group, or a nitro group. A group, a dialkylamino group having 2 to 12 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkyl group having 2 to 19 carbon atoms It is more preferable to represent an alkenyloxy group, and when ^two or more L ² are present, they may be the same or different, and an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 11 carbon atoms More preferably, L ² may be the same or different when a plurality of L ² are present, and represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. Is more preferable, and when a plurality of L ² are present, they may be the same or different and it is particularly preferable that they represent a methyl group, an ethyl group, a propyl group or a methoxy group.

In the general formula (IV), Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—. , -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-,-. NH-CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 _{-, - CH 2 CH 2 -COO} -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- or a single bond, When there are a plurality of Z ^1, they may be the same or different, and when there are a plurality of Z ^2, they may be the same or different. From the viewpoint of ease of synthesis, resistance to discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersibility, Z ¹ and Z ² are plural. when present they may be the same or different and each independently _{-OCH 2 -, - CH 2 O} -, - CH 2 CH 2 -, - COO -, - OCO -, - CO-NH _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH _{2 -, - CH 2 CH 2} -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - CF = CF -, - C≡C- or preferably a single bond, ^{Z 1} and When a plurality of Z ^2's are present, they may be the same or different and each independently -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, _{-COO-CH 2 CH 2 -,} - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - it is more preferable that represent _CH 2 CH 2 -OCO- or a single bond, ^{Z 1} and ^{Z 2} is -OCH ₂ they if there exist a plurality may be the same or different and each independently _{-, - CH 2 O -,} - COO -, - OCO- or more preferably a single bond, When a plurality of Z ¹ and Z ² are present, they may be the same or different and each independently represent -OCH _2- , -CH ₂ O-, -COO- or -OCO-. More preferably, when a plurality of Z ¹ and Z ² are present, they may be the same or different, and it is particularly preferable that they each independently represent —COO— or —OCO—.

  In the general formula (IV), m1 and m2 each independently represent an integer of 0 to 6, while m1 + m2 represents an integer of 1 to 6. M1 and m2 are independent of each other from the viewpoint of ease of synthesis, resistance to discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersion. It is more preferable that m1 and m2 each independently represent 1, 2 or 3, and it is further preferable that m1 and m2 each independently represent 1 or 2. It is particularly preferred that m1 and m2 each represent 2. m1 + m2 preferably represents an integer of 2 to 6, m1 + m2 more preferably represents an integer of 2 to 5, m1 + m2 more preferably represents 2, 3 or 4, and m1 + m2 represents 2 or 4. Even more preferably, m1 + m2 particularly preferably represents 4.

In the general formula (IV), P ¹ , P ² and P ^L represent a group polymerized by radical polymerization, cationic polymerization or anionic polymerization. From the viewpoint of ease of synthesis, resistance to discoloration and change of phase difference when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersion, P ¹ , P ² and P ^L independently represents the following formula (P-1) to formula (P-20)

(Wherein the broken line represents the bonding position), it is preferable that P ¹ , P ² and P ^L each independently represent formula (P-1), formula (P-2), formula (P-3), Formula (P-4), Formula (P-5), Formula (P-7), Formula (P-11), Formula (P-13), Formula (P-15), Formula ( preferably represents a group selected from ^{P-18), P 1,} P 2 and ^{P L} each independently formula (P-1), formula (P-2), formula (P-3), formula ( P-7), formula (P-11), formula (P-13) and formula (P-18) are more preferably represented, and P ¹ , P ² and P ^L are each independently a formula. It is more preferable to represent a group selected from (P-1), formula (P-2), formula (P-3) and formula (P-18), and P ¹ , P ² and P ^L are each independently. It is particularly preferable to represent a group selected from formula (P-1) and formula (P-2).

In the general formula (IV), Sp ¹ , Sp ² and Sp ^L may each independently have any hydrogen atom in the group replaced by a fluorine atom, and one —CH ₂ — or non-adjacent 2 more than five -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or straight-chain or branched-chain having 2 to 20 carbon atoms which may be replaced by -C≡C-. It represents an alkylene group, and when plural Sp ¹ are present, they may be the same or different, and when plural Sp ² are present, they may be the same or different, and Sp ^L is plural. If present, they may be the same or different. From the viewpoint of ease of synthesis, resistance to color change and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersion, Sp ¹ , Sp ² and Sp. ^When a plurality of ^L's are present, they may be the same or different, and each independently represents one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O. -, -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO- or -CH = CH- straight chain having 2 to 20 carbon atoms which may be substituted. Or a branched alkylene group is preferable, and when plural Sp ¹ , Sp ² and Sp ^L are present, they may be the same or different and each independently one —CH ₂ — or Two or more —CH ₂ — which are not adjacent to each other may each independently be substituted by —O—, —COO—, —OCO— or —O—CO—O—, and are directly a group of 2 to 12 carbon atoms. It is more preferable to represent a chain or branched alkylene group, and when a plurality of Sp ¹ , Sp ² and Sp ^L are present, they may be the same or different, and each independently one --CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO- or -OCO- represents a linear alkylene group which may carbon atoms 2 to 12 be replaced by More preferably, when a plurality of Sp ¹ , Sp ² and Sp ^L are present, they may be the same or different, each independently one —CH ₂ — or two or more that are not adjacent. of -CH ₂ - is still more preferably represent a straight-chain alkylene group which may carbon atoms 2 to 12 be replaced each by independently -O- ^is, Sp 1, Sp ² and Sp ^L is plurality of If so, they may be the same or different and it is particularly preferred that they represent a straight-chain alkylene group having 4 to 8 carbon atoms.

In the general formula (IV), X ¹ , X ² and ^XL are each independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-. , -CO-S -, - S -CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O-, _{-OCF 2 -, - CF 2 S} -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO _{-CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH _{2 -COO -, - CH 2 -OCO} -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond However, when a plurality of X ^1's are present, they may be the same or different (provided that P ^1- [Sp ¹ -X ¹ ] _k ¹ -does not include a —O—O— bond). If X ² there are a plurality thereof may be different even in the same _{^{(although, -. [X 2 -Sp 2}} ] k2 in -P ² containing no -O-O- bonds), ^{X L} there they If there are multiple may be different even in the same ^{(however, P L - [Sp L -X} L] kL - to contain no -O-O- bond.). From the viewpoints of ease of synthesis, resistance to discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersion, X ¹ , X ² and X ^L is those when there are a plurality may be the same or different and each independently _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - COO -, - OCO-, -CO-S -, - S- CO -, - OCO-O -, - CO-NH -, - NH-CO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, -CH ₂ CH ₂ -COO _{-, -} it is preferable to represent a _CH 2 CH 2 -OCO- or a single ^bond, even if the X 1, ^{X 2} and ^{X L} is there are a plurality of them are be the same or different may each independently _{-O -, - OCH 2 -,} - CH 2 O -, - COO -, - OCO -, - OCO-O -, - COO-CH 2 CH 2 -, - OCO-CH _{2 CH 2 -, - CH 2} CH 2 -COO -, - CH 2 CH 2 -OCO- or more preferably a single ^bond, X 1, ^{X 2} and ^{X L} is a those when a plurality present in the same Or may be different, more preferably each independently represents -O-, -COO-, -OCO-, -O-CO-O- or a single bond, and X ¹ , X ² and X ^L are When a plurality of them are present, they may be the same or different, and it is even more preferable that each independently represent -O-, -COO-, -OCO- or a single bond, and X ¹ , X ² and X It is particularly preferred that each ^L independently represents -O- or a single bond.

  In the general formula (IV), k1, k2 and kL each independently represent an integer of 0 to 5. From the standpoint of ease of synthesis, resistance to discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersion, k1, k2 and kL are respectively It is preferable that each independently represent an integer of 1 to 3, it is more preferable that k1, k2 and kL each independently represent 1 or 2, and it is particularly preferable that k1, k2 and kL represent 1.

  From the viewpoint of easiness of synthesis, occurrence of discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersibility, a compound represented by the general formula (IV) is used. The compound represented by the following formula (IV-i)

(In the formula, P ¹¹ and P ²¹ each independently represent a group selected from the formula (P-1) to the formula (P-20),
When a plurality of Sp ¹¹ and Sp ²¹ are present, they may be the same or different and each independently has one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently. Then, from 2 carbon atoms which may be replaced by -O-, -COO-, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-. Represents a linear or branched alkylene group of 20,
X ¹¹ and ^{X 21} are those when there are a plurality of which may be the same or different and each independently _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - COO-, -OCO -, - CO-S - , - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - COO-CH 2 CH 2 -, - OCO-CH 2 _{CH 2 -, - CH 2 CH} 2 -COO -, - CH 2 CH 2 -OCO- or a single bond,
k11 and k21 each independently represent an integer of 1 to 3,
When a plurality of A ¹¹ and A ²¹ are present, they may be the same or different, each independently unsubstituted or may be substituted by one or more substituents L ²¹ 1,4 -Phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group,
When a plurality of L ^21's are present, they may be the same or different, and are a fluorine atom, a chlorine atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, or any hydrogen. An atom may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO. -, -OCO-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C = C- alkyl group which may be substituted by 1 to 20 carbon atoms. ^or, P L ^- represents a group represented _{^{by, - [Sp L -X L]}} kL
Ax ¹ is the following formula (IV-Ax-i)

(In the formula, the broken line represents a bonding position, the ring B ¹ represents a group selected from the formula (B-1) to the formula (B-10), and Y ¹ represents an oxygen atom or a sulfur atom). Represents the group represented,
Z ¹¹ and ^{Z 21} are those when the presence of a plurality may be different even in the same, -OCH ₂ each independently _{-, - CH 2 O -,} - CH 2 CH 2 -, - COO -, - _{OCO -, - CO-NH -} , - NH-CO -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - CF = CF -, - C≡C- or a single bond ,
m11 and m21 each independently represent an integer of 1 to 4, while m11 + m21 represents an integer of 2 to 6. ) Is preferably represented by the following general formula (IV-i-i)

(In the formula, P ¹¹¹ and P ²¹¹ are each independently the above formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5). Represents a group selected from formula (P-7), formula (P-11), formula (P-13), formula (P-15) and formula (P-18),
When a plurality of Sp ¹¹¹ and Sp ²¹¹ are present, they may be the same or different and each independently has one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently. And represents a linear or branched alkylene group having 2 to 12 carbon atoms which may be substituted by -O-, -COO-, -OCO- or -O-CO-O-.
X ¹¹¹ and ^{X 211} are those when there are a plurality of which may be the same or different and each independently _{-O -, - OCH 2 -,} - CH 2 O -, - COO -, - OCO-, _{-O-COO -, - COO-} CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or a single bond,
k111 and k211 each independently represent 1 or 2,
When a plurality of A ¹¹¹ and A ²¹¹ are present, they may be the same or different and each is independently a group selected from the above formulas (A-1) to (A-14) (in the formula, The group represented by L ² means a group represented by L ^211. )
When a plurality of L ²¹¹ are present, they may be the same or different, and are a fluorine atom, a chlorine atom, a cyano group, a nitro group, a dialkylamino group having 2 to 12 carbon atoms, or 1 to 20 carbon atoms. Represents an alkyl group having 1 to 19 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkenyloxy group having 2 to 19 carbon atoms,
Ax ¹¹ is the following formula (IV-Ax-i-i).

(In the formula, the broken line represents the bonding position, the ring B ¹¹ represents the formula (B-1-1) to the formula (B-1-8), and the formula (B-2-1) to the formula (B-2-). 7), formula (B-3-1) to formula (B-3-9), formula (B-4-1) to formula (B-4-9), formula (B-5-1) to formula (B-5-1). B-5-13), formula (B-6-1) to formula (B-6-8), formula (B-7-1) to formula (B-7-7), formula (B-8-1) ) To formula (B-8-4), formula (B-9-1) to formula (B-9-8), formula (B-10-1) to formula (B-10-4) And Y ¹¹ represents a group represented by an oxygen atom or a sulfur atom).
Z ¹¹¹ and ^{Z 211} are those when there are a plurality may be different even in the same, -OCH ₂ each independently _{-, - CH 2 O -,} - CH 2 CH 2 -, - COO -, - _{OCO -, - COO-CH 2} CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or a single bond,
m11 and m21 each independently represent 1, 2 or 3, and m11 + m21 represents an integer of 2 to 5. ) Is more preferable, and a compound represented by the following general formula (IV-ii)

(In the formula, P ¹² and P ²² are each independently the above formula (P-1), formula (P-2), formula (P-3), formula (P-7), formula (P-11). Represents a group selected from formula (P-13) and formula (P-18):
Sp ¹² and Sp ²² each independently represent one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently substituted by —O—, —COO— or —OCO—. Also represents a linear alkylene group having 2 to 12 carbon atoms,
X ¹² and X ²² each independently represent -O-, -COO-, -OCO-, -O-CO-O- or a single bond,
A ¹²¹ , A ¹²² , A ²²¹ and A ²²² are each independently a group selected from formula (A-1) to formula (A-12) (in the formula, the group represented by L ² is represented by L ^22). Represents a group selected from
When a plurality of L ²² are present, they may be the same or different and each represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 11 carbon atoms,
Ring C represents a group selected from the above formula (C-2-1-1) to formula (C-7-1-2),
Y ¹² represents an oxygen atom or a sulfur atom,
^{Z 121,} Z 122, Z ²²¹ and ^{Z 222} are each independently _{-OCH 2 -, - CH 2 O} -, - COO -, - OCO- or a single bond. ) Is more preferably represented by the following general formula (IV-iii):

(In the formula, P ¹³ and P ²³ each independently represent a group selected from the above formula (P-1), formula (P-2), formula (P-3), and formula (P-18),
Each of Sp ¹³ and Sp ²³ independently has one —CH ₂ — or two or more —CH ₂ — which are not adjacent to each other and each independently have —2—12 carbon atoms which may be substituted by —O—. Represents a linear alkylene group of
X ¹³ and X ²³ each independently represent -O-, -COO-, -OCO- or a single bond,
A ¹³¹ , A ¹³² , A ²³¹ and A ²³² are each independently a group selected from formula (A-1) to formula (A-8) (in the formula, the group represented by L ² is represented by L ^23). Represents a group selected from
When a plurality of L ^23's are present, they may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 5 carbon atoms,
Ring C ¹ represents a group selected from the above formula (C-2-1-1-1) to formula (C-2-2-3-6),
Y ¹³ represents an oxygen atom or a sulfur atom,
^{Z 131,} Z 132, Z ²³¹ and ^{Z 232} are each independently _{-OCH 2 -, - CH 2 O} -, - COO- or an -OCO-. It is even more preferable to represent the compound represented by the formula (), and the following general formula (IV-iv-1) and general formula (IV-iv-2)

(In the formula, P ¹⁴ and P ²⁴ each independently represent a group selected from formula (P-1) and formula (P-2),
Sp ¹⁴ and Sp ²⁴ each independently represent a linear alkylene group having 4 to 8 carbon atoms,
Ring C ² represents a group selected from the above formulas (C-1) to (C-9). It is particularly preferred to represent a compound selected from

  Specific examples of the compound represented by the general formula (IV) include the following formulas (IV-1) to (IV-11).

The compound represented by

  From the compound represented by the general formula (III), the following general formula (III ′)

A compound represented by the formula can be produced.

  The compound represented by the general formula (IV) includes a compound represented by the general formula (III '), the following general formula (III'a-1) and general formula (III'a-2).

(In the formula, R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , m 1 and m ² are each R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² in the general formula (IV). represents the same meaning as m1 and ^m2, -Z ^{1 -X III'a1} reacts with the compound represented by formula (III ') -Z ¹ - represents a group forming ^{a, X III'a2} -Z ^2- represents a group which reacts with the compound represented by the general formula (III ′) to form —Z ² —).

  Further, the compound represented by the general formula (IV) includes a compound represented by the general formula (III ′), the following general formula (III′b-1) and general formula (III′b-2).

(In the formula, A ¹ , A ² , Z ¹ and Z ² each have the same meaning as A ¹ , A ² , Z ¹ and Z ² in formula (IV), and m 1a and m 2a each independently represent 0 to 0; represents an integer of 6, m1a + m2a represents an integer of from 1 to ^6, -Z ^{1 -X III'b1} general formula reacts with the compound represented by (III ') -Z ¹ - represents a group capable of forming a , ^{X III'b2} -Z ² - is the general formula (III ') to react with a compound represented by -Z ² - represents a group forming ^{a, X III'c1} - the general formula (III'c- reacts with ^-Z 1 ^{-X III'd1} in 1) -Z ¹ - represents a group forming ^{a, -X III'b1} the ^{X III'd2} -Z ² in the general formula (III'c-2) - the reaction was -Z 2 and ^-. is reacted with the compound represented by the representative) a group forming a compound represented by the following general formula (IV ')

^{(Wherein, A 1, A 2, Ax} , Z 1 and ^{Z 2} represent each ^A 1 in the general formula ^{(IV), A 2, Ax} , the same meaning as ^{Z 1} and ^{Z 2, m1a, m2a, X} III ^'c1 - and ^{-X III'b1} each m1a in formula (III'b1) and the general formula ^{(III'b-2), m2a,} X III'c1 - and the same meaning as ^{-X III'b1} The compound represented by general formula (IV ′) is produced, and the compound represented by general formula (IV ′) and the following general formula (III′c-1) and general formula (III′c-2)

^{(Wherein, R 1, R 2, A} 1, A 2, Z 1 and ^{Z 2} each ^R 1 in the general formula ^{(IV), R 2, A} 1, A 2, same meaning as ^{Z 1} and ^{Z 2} , M1b and m2b each independently represent an integer of 0 to 6, m1b + m2b represents an integer of 1 to 6, m1a + m1b = m1, m2a + m2b = m2,
-Z ¹ -X ^III'd1 the general formula ^X in the compound represented by (IV ') ^III'c1 - reacted with -Z ¹ - represents a group forming ^{a, X III'd2} -Z ² - is generally It represents a group which reacts with -X ^III'b1 in the compound represented by the formula (IV ') to form -Z ^2- . ) It can manufacture by reacting with the compound represented by.

More specifically, the compound represented by the general formula (IV) can be produced from the compound represented by the general formula (III) by the following production method.
(Production method 3) Production of compound represented by formula (S-9)

(In the formula, PG ¹ and PG ² each have the same meaning as PG ¹ and PG ² in the general formula (II), and P ¹⁴ , Sp ¹⁴ and ring C ² are the general formula (IV-iv-1) and the general formula. (It has the same meaning as P ¹⁴ , Sp ¹⁴ and ring C ² in (IV-iv-2).)
The compound represented by formula (S-7) can be obtained by removing the groups represented by PG ¹ and PG ² of the compound represented by formula (S-6). As the reaction conditions, GREEN'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODORA W. GREENE co-authored, A John Wiley & c., Inc., Sons, Inc., Sons, Inc., P.S. , For example, reaction with boron tribromide, formic acid or pyridinium chloride.

The compound represented by formula (S-9) can be obtained by reacting the compound represented by formula (S-7) with the compound represented by formula (S-8). The reaction conditions are, for example, a method using a condensing agent, or a compound represented by the formula (S-8) is converted to an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride, and then represented by the formula (S-7). And a reaction with a compound in the presence of a base. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the base include triethylamine, diisopropylethylamine and pyridine.
(Production method 4) Production of compound represented by formula (S-15)

^(Wherein the same meanings as P 14, ^{Sp 14} and ring ^{C 2} is the general formula (IV-iv-1) and ^P 14, ^{Sp 14,} and ring ^{C 2} in the general formula (IV-iv-2). )
The compound represented by formula (S-12) can be obtained by reacting the compound represented by formula (S-10) with the compound represented by formula (S-11) in the presence of a base. Examples of the base include potassium carbonate and cesium carbonate.

  By hydrolyzing the tert-butyl group of the compound represented by formula (S-12), the compound represented by formula (S-13) can be obtained. Examples of the reaction conditions include a method using formic acid or trifluoroacetic acid.

  The compound represented by formula (S-15) can be obtained by reacting the compound represented by formula (S-13) with the compound represented by formula (S-14). The reaction conditions include, for example, a method using a condensing agent or a compound represented by the formula (S-14) after the compound represented by the formula (S-13) is converted into an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride. And the reaction in the presence of a base. The condensing agent and the base are the same as above.

  Examples of reaction conditions other than those described in Processes 1 to 4 include, for example, Experimental Chemistry Course (edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic. (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) conditions described in literature etc. or SciFinder (Chemical Abstracts Examples include conditions provided by online search services such as Service, American Chemical Society, and Reaxys (Elsevier Ltd.).

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

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

  The compound represented by the general formula (IV) is preferably used in a nematic liquid crystal composition, a smectic liquid crystal composition, a chiral smectic liquid crystal composition and a cholesteric liquid crystal composition. A compound other than the compound represented by the general formula (IV) may be added to the liquid crystal composition using the compound represented by the general formula (IV). Examples of the compound other than the compound represented by the general formula (IV) include the following general formula (X1)

(In the formula, P ^x1 and P ^x2 each independently represent a group polymerized by radical polymerization, cationic polymerization or anionic polymerization,
Each of Sp ^x1 and Sp ^x2 may independently have any hydrogen atom in the group substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are independently each other. Then, -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH. -CO-, -CH = CH-, -CF = CF- or -C = C- represents a linear or branched alkylene group having 2 to 20 carbon atoms which may be replaced by -C≡C-, but Sp ^x1 is plural. When present, they may be the same or different, and when there are a plurality of Sp ^x2, they may be the same or different,
X ^x1 and ^{X x2} are each independently _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S- CO -, - O-CO- O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- _{, -SCF 2 -, - CH =} CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, -CH = CH-, -N = N-, -CH = NN-CH =, -CF = CF-, -C≡C- or a single bond, but when there are a plurality of X ^1's, _{May be the} same or different (provided that P ^x1- [Sp ^x1 -X ^x1 ] _kx1 − does not include a —O—O— bond), and when there are a plurality of X ^x2, they are the same. even differ also good -, ^{(where, [X} _{x2 -Sp x2]} kx2 in ^{-P x2} does not contain -O-O- bond.)
kx1 and kx2 each independently represent an integer of 0 to 5,
A ^x1 and A ^x2 are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, tetrahydro Represents a pyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group, which may be unsubstituted or substituted by one or more substituents L ^x2 , When there are a plurality of A ^x1, they may be the same or different, and when there are a plurality of A ^x2, they may be the same or different,
L ^x2 is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom may be replaced by a fluorine atom, 1 number of -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, or an alkyl group having 1 to 20 carbon atoms which may be substituted by -C≡C-, or ^PxL- [ ^SpxL-. X ^xL ] _kxL − (wherein P ^xL represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ^xL represents a group in which any hydrogen atom in the group is substituted with a fluorine atom). Well, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—. S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- Also represents a straight-chain or branched alkylene group having 2 to 20 carbon atoms, and when there are a plurality of Sp ^xL, they may be the same or different, and X ^xL is —O—, —S. _{-, - OCH 2 -, -} CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH- _{, -NH-CO -, - SCH} 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO -CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - _{CH 2 CH 2 -OCO -, -} COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but when a plurality of X ^xL are present, they may be the same or different (provided that P ^xL − [Sp ^xL −X ^xL ] _kxL − does not include a —O—O— bond. ), KxL represents an integer of 0 to 5. ), When there are a plurality of L ^x2, they may be the same or different,
Ax ^x1 is the following formula (X1-Ax1)

(Wherein the dashed line represents a bonding position, any -CH = may be replaced each independently -N =, -CH ₂ - are each independently -O -, - S -, - NR ^xT- (in the formula, R ^xT represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), -CS-, or -CO-, and these groups are unsubstituted or 1 One or more substituents L ^xG (where L ^xG is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom is a fluorine atom) May be substituted with one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO. -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- represents an alkyl group having 1 to 20 carbon atoms which may be substituted. However, when there are a plurality of L ^xG, they may be the same or different, and T ^x1 may be replaced by the following formula (Tx1-1) to formula (Tx1-6).

(Wherein, have one a bond at any position, any -CH = may be replaced each independently -N =, -CH 2 _- are each independently -O -, - S-, ^-NRxT- (in the formula, ^RxT represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), -CS- or -CO-. Is an unsubstituted or one or more substituents L ^xW (where L ^xW is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, any optional The hydrogen atom may be replaced by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —. COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH =. 1 to 20 carbon atoms optionally substituted by CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-. Represents an alkyl group of, and when there are a plurality of L ^xW, they may be the same or different, and may be substituted with)). ) Represents a group represented by
Z ^x1 and ^{Z x2} are each independently _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - CO -, - COO -, - OCO -, - CO -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, _{-NH-O -, - O-} NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 _{-COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- or represents a single bond, but when there are a plurality of Z ^x1. They may be the same or different, and when a plurality of Z ^x2's are present, they may be the same or different,
mx1 and mx2 each independently represent an integer of 0 to 6, while mx1 + mx2 represents an integer of 1 to 6. However, the compound represented by the general formula (IV) is excluded. ). From the viewpoint of ease of synthesis, resistance to discoloration and change in retardation when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersion, the formula (X1) is used. Are represented by the following general formula (X1-i)

(In the formula, P ^x11 and P ^x21 each independently represent a group selected from the above formula (P-1) and formula (P-2),
Sp ^x11 and Sp ^x21 each independently represent a linear alkylene group having 4 to 8 carbon atoms,
T ^x11 is the following formula (Tx1-1-1) to formula (Tx1-5-1).

(In the formula, these have one bond at any position, and these groups are unsubstituted or one or more substituents L ^xW1 (in the case where a plurality of L ^xW1's are present, they may be the same or different. Well, fluorine atom, chlorine atom, cyano group, nitro group, dialkylamino group having 2 to 12 carbon atoms, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 19 carbon atoms, and 2 carbon atoms It represents an alkenyl group having 20 or an alkenyloxy group having 2 to 19 carbon atoms, which may be the same or different when a plurality of L ^xW1's are present. Represents a group represented by It is preferable that it is a compound represented by these.

  Specific examples of the compound represented by the general formula (X1) include the following formula (X1-1) to formula (X1-5).

The compound represented by

  A compound other than the compound represented by the general formula (IV) may be added to the liquid crystal composition using the compound represented by the general formula (IV). Examples of the compound other than the compound represented by the general formula (IV) include the following general formula (X2)

(In the formula, P ^x3 and P ^x4 each independently represent a group polymerized by radical polymerization, cationic polymerization or anionic polymerization,
Sp ^x3 and Sp ^x4 may each independently be replaced by any hydrogen atom in the group by a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently. Then, -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH. -CO-, -CH = CH-, -CF = CF- or -C≡C- represents a linear or branched alkylene group having 1 to 20 carbon atoms which may be replaced with a plurality of Sp ^x3. If present, they may be the same or different, and if there are a plurality of Sp ^x4, they may be the same or different,
X ^x3 and ^{X x4} are each independently _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S- CO -, - O-CO- O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- _{, -SCF 2 -, - CH =} CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, -CH = CH-, -N = N-, -CH = NN-CH-, -CF = CF-, -C≡C- or a single bond, but when a plurality of X ^x3 are present, they are _{May be the} same or different (provided that P ^x3 − (Sp ^x3 −X ^x3 ) _kx3 − does not include a —O—O— bond), and when a plurality of X ^x4 are present, they are the same. even differ also good -, (provided ^{that, (X} _{x4 -Sp x4)} ^kx4 the ^{-P x4} contains no -O-O- bonds.)
kx3 and kx4 each independently represent an integer of 0 to 5,
A ^x3 and A ^x4 are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, tetrahydro Represents a pyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group, which may be unsubstituted or substituted by one or more substituents L ^x3 , When there are a plurality of A ^x3, they may be the same or different,
L ^x3 is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfanyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropyl group. Amino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO. -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, Number of carbon atoms which may be substituted by -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-. Although 1 represents a linear or branched alkyl group of 20, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, the above _{^{P xL - [Sp xL -X xL}} ] kxL Represents a group represented ^{by-, and} when there are a plurality of L ^x3, they may be the same or different,
Z ^x3 is _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - CO -, - COO -, - OCO -, - CO-S -, - S- CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-,-. _{O-NH -, - SCH 2} -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 _{CH 2 -OCO -, - COO-} CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, -N = CH-, -CH = NN-CH-, -CF = CF-, -C [identical to] C- or represents a single bond, but when a plurality of ^Zx3's are present, they may be the same. Can be different,
mx3 represents an integer of 0 to 6. ). From the viewpoint of ease of synthesis, resistance to discoloration and retardation change when formed into a film, and solubility in a solvent, liquid crystallinity and reverse wavelength dispersibility, the formula (X2) is used. Are represented by the following general formula (X2-i)

(In the formula, P ^x31 and P ^x41 each independently represent a group selected from the above formula (P-1) or formula (P-2), and Sp ^x31 and Sp ^x41 each independently represent ^one- CH ₂ — or two or more non-adjacent —CH ₂ — each independently represent a linear alkylene group having 2 to 12 carbon atoms which may be substituted by —O—, and X ^x31 and X ^x41 Each independently represent ^-O- , ^-COO- , ^-OCO- or a single bond, and A ^x31 , A ^x32 and A ^x41 each independently represent the above formula (A-1) to formula (A-8). In the group, L ² represents L ^3, and when a plurality of L ³ are present, they may be the same or different and may be a fluorine atom, a chlorine atom, or a carbon atom number of 1. To a linear alkyl group having 1 to 7 carbon atoms and a linear alkoxy group having 1 to 7 carbon atoms, and Z ^x31 and Z ^x32 each independently represent ^-COO- , ^-OCO- or a single bond. The compound represented by the general formula (X2) is preferably a compound represented by the following general formula (X2-i-1) to general formula (X2-i-7).

(In the formula, P ^x32 and P ^x42 each independently represent a group selected from the above formula (P-1) or formula (P-2), and Sp ^x32 and Sp ^x42 each independently have 2 carbon atoms. To 12 in the formula, L ³¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, or a methoxy group.) Is more preferable.

  Specific examples of the compound represented by the general formula (X2) include the following formula (X2-1) to formula (X2-7).

The compound represented by

  When a compound other than the compound represented by the general formula (IV) is added to the liquid crystal composition using the compound represented by the general formula (IV), easiness of synthesis, discoloration and change in retardation when formed into a film. From the viewpoint of the occurrence of the occurrence of the above, and from the viewpoint of the solubility in a solvent, the liquid crystallinity and the reverse wavelength dispersion, the compound represented by the general formula (IV) in the liquid crystal composition is 0.01% by mass to 99. The content is preferably 99% by mass, more preferably 1.0% by mass to 99.9% by mass, further preferably 20% by mass to 99.5% by mass, and 50% by mass to 99% by mass. Is more preferable, and 70% by mass to 90% by mass is particularly preferable.

  Further, the compound of the present invention is preferably used in a nematic liquid crystal composition, a smectic liquid crystal composition, a chiral smectic liquid crystal composition and a cholesteric liquid crystal composition. It is also possible to add to the polymerizable liquid crystal composition containing the compound of the present invention, a polymerizable compound that does not exhibit liquid crystallinity to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples thereof include those described in "Data Book of Photocuring Technology, Materials (Monomers, Oligomers, Photopolymerization Initiators)" (Kunihiro Ichimura, Kiyomi Kato, Technonet).

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

  In addition, a stabilizer may be added to the polymerizable composition containing the compound 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, and nitroso compounds. Be done. When the stabilizer is used, the amount added is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5 mass% is more preferable. Further, one kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. As the stabilizer, specifically, the formula (X3-1) to the formula (X3-35)

(In the formula, n represents an integer of 0 to 20) and a compound represented by the formula is preferable.

  When the polymerizable liquid crystal composition containing the compound of the present invention is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents and synthetic resins, Metals, metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants according to their purpose. It is also possible to add an ion exchange resin, a metal oxide such as titanium oxide, or the like.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention and the polymerizable compound produced from the compound of the present invention can be used for various purposes. For example, a polymer obtained by polymerizing a polymerizable liquid crystal composition containing the compound of the present invention without aligning it can be used as a light scattering plate, a depolarizing plate, and a moire fringe preventing plate. Further, a polymer obtained by polymerizing after orientation is useful because it has optical anisotropy. Such an optically anisotropic substance is, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth or the like, a substrate having an organic thin film formed thereon, or an alignment film obtained by obliquely vapor-depositing SiO _2. It can be manufactured by carrying the polymerizable liquid crystal composition on a substrate having the same or by sandwiching it between the substrates.

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

  Examples of the alignment treatment other than the above include the use of fluid alignment of the liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. The shape of the substrate may have a curved surface as a constituent portion in addition to the flat plate. The material forming the substrate may be an organic material or an inorganic material. Examples of the organic material used as the material of the substrate include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetyl. Cellulose, cellulose, polyetheretherketone, etc. may be mentioned, and examples of the inorganic material include silicon, glass, calcite and the like.

When polymerizing the polymerizable liquid crystal composition containing the compound of the invention of the present application, it is desirable that the polymerization proceeds rapidly. Therefore, a method of irradiating with 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 liquid crystal composition is sandwiched between two substrates to carry out polymerization in a state, at least the substrate on the irradiation surface side must have appropriate transparency to active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as electric field, magnetic field or temperature, and further irradiation with active energy rays is performed. It is also possible to use a means of polymerizing the above. The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the invention is maintained. In particular, when an optically anisotropic substance is to be produced by photopolymerization, polymerization is performed at a temperature as close to room temperature as possible, that is, typically at a temperature of 25 ° C., in order to avoid unintended induction of thermal polymerization. Preferably. The intensity of the active energy ray is preferably 0.1 mW / cm ^{2 to 2} W / cm ² . When the strength is 0.1 mW / cm ² or less, a large amount of time is required to complete the photopolymerization, which deteriorates the productivity. When the strength is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

  The optical anisotropic body obtained by the polymerization can be subjected to heat treatment for the purpose of reducing the initial change in characteristics and achieving stable expression of characteristics. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

  The optical anisotropic body manufactured by such a method may be peeled from the substrate and used alone, or may be used without being peeled. Further, the obtained optically anisotropic body may be laminated or used by being attached to another substrate.

  In the present invention, the ring structure contained in the 1,4-cyclohexylene group, decahydronaphthalene-2,6-diyl group and 1,3-dioxane-2,5-diyl group is either trans or cis. From the viewpoint of liquid crystallinity, the content of the trans isomer is preferably higher than the content of the cis isomer, and the content of the trans isomer in the ring structure is more preferably 80% or more. The content of the trans isomer in the ring structure is more preferably 90% or more, more preferably the content of the trans isomer in the ring structure is 95% or more, and the content of the trans isomer in the ring structure is 98% or more. % Or more is particularly preferable. In the present invention, the following notation (CY-1)

(In the formula, a broken line represents a bonding position.) Means a trans isomer and / or a cis isomer of a 1,4-cyclohexylene group, and the following notation (CY-1-t) and notation (CY-1-c). )

(In the formula, a broken line represents a bonding position.) Means a trans isomer and a cis isomer of a 1,4-cyclohexylene group, respectively.

  In the present invention, having a bond at any position means having a necessary number of bonds at any position. For example, when it is a monovalent group, it is intended to have one bond at any position. Specifically, for example, the following formula (ex-sub)

When the group represented by is a monovalent group and has a bond at any position, the following formula (ex-sub-1) to formula (ex-sub-3)

(In the formula, the broken line represents a bonding position.), Which means to represent a group selected from the following.

  Further, in the present invention, each element may be replaced with an isotope of the same element.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Moreover, "%" in the compositions of the following Examples and Comparative Examples means "mass%". When handling a substance unstable to oxygen and / or water in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. The purity of each compound is UPLC (Waters ACQUITY UPLC BEH C ₁₈ , 2.1 × 100 mm, 1.7 μm, acetonitrile / water or acetonitrile / water containing 0.1% formic acid, PDA, column temperature 40 ° C.), GC (Agilent 6890A). , J & W DB-1, 30 m / 0.25 mm / 0.25 μm, carrier gas He, FID, 100 ° C. (1 minute) → temperature rise 10 ° C./minute→300° C. (12 minutes)) or ¹ H NMR (JEOL, 400 MHz).
(Example 1) Production of compound represented by formula (II-1)

  10.0 g of the compound represented by the formula (I-1) and 70 mL of the compound represented by the formula (I-1-1) were added to a reaction vessel, and the mixture was heated with stirring at 150 ° C. for 5 hours. After distilling off diethyl oxalate under reduced pressure, purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 13.2 g of the compound represented by the formula (I-1-2).

  13.2 g of the compound represented by the formula (I-1-2), 21.1 g of Lawesson's reagent, and 100 mL of toluene were added to a reaction vessel, and the mixture was heated under reflux for 8 hours. Purification by column chromatography (silica gel, hexane / ethyl acetate) gave 11.3 g of the compound represented by the formula (I-1-3).

  11.3 g of the compound represented by the formula (I-1-3), 50 mL of methanol, and 30 mL of 20% sodium hydroxide aqueous solution were added to a reaction vessel, and the mixture was heated and stirred at 50 ° C. for 3 hours. The mixture was neutralized with 5% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed successively with water and brine. After drying over sodium sulfate, the solvent was evaporated to obtain 9.1 g of the compound represented by the formula (I-1-4).

  9.1 g of the compound represented by the formula (I-1-4), 150 mL of water, and 6.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 33.4 g of potassium ferricyanide and 100 mL of methanol were added, and the mixture was heated and stirred at 40 ° C. for 10 hours. The reaction solution was poured into 5% hydrochloric acid, and the precipitated solid was filtered and washed with water. By drying, 4.0 g of a compound represented by the formula (I-1-5) was obtained.

Under a nitrogen atmosphere, 4.0 g of the compound represented by the formula (I-1-5), 0.1 mL of N, N-dimethylformamide, and 40 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 2.6 g of oxalyl chloride was added dropwise, and the mixture was stirred at 40 ° C. for 2 hours. 2.0 g of pyridine was added. A solution prepared by dissolving 2.0 g of the compound represented by the formula (I-1-6) in 10 mL of dichloromethane was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into 5% hydrochloric acid and extracted with dichloromethane. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 4.3 g of the compound represented by the formula (II-1).
LC-MS: 315 [M + 1]
(Example 2) Production of compound represented by formula (II-2)

By a method similar to that in Example 1, a compound represented by the formula (I-2-5) was produced. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-2-5), 2.5 g of the compound represented by the formula (I-2-6), 0.3 g of 4-dimethylaminopyridine in a reaction vessel, 40 mL of dichloromethane was added. While cooling with ice, 3.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 5.5 g of the compound represented by the formula (II-2).
LC-MS: 343 [M + 1]
(Example 3) Production of compound represented by formula (II-3)

The compound represented by the formula (I-3-5) was produced by the same method as in Example 1. In a nitrogen atmosphere, 5.0 g of a compound represented by the formula (I-3-5), 2.5 g of a compound represented by the formula (I-3-6), 0.3 g of 4-dimethylaminopyridine in a reaction vessel, 40 mL of dichloromethane was added. While cooling with ice, 3.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 5.0 g of a compound represented by the formula (II-3).
LC-MS: 343 [M + 1]
(Example 4) Production of compound represented by formula (II-4)

By a method similar to that in Example 1, the compound represented by the formula (I-4-5) was produced. Under a nitrogen atmosphere, 5.0 g of a compound represented by the formula (I-4-5), 2.5 g of a compound represented by the formula (I-4-6), 0.3 g of 4-dimethylaminopyridine in a reaction vessel, 40 mL of dichloromethane was added. While cooling with ice, 3.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 4.7 g of a compound represented by the formula (II-4).
LC-MS: 343 [M + 1]
(Example 5) Production of compound represented by formula (II-5)

A compound represented by the formula (I-5-5) was produced by the same method as in Example 1. In a reaction vessel under a nitrogen atmosphere, 5.0 g of a compound represented by formula (I-5-5), 2.5 g of a compound represented by formula (I-5-6), 0.3 g of 4-dimethylaminopyridine, 40 mL of dichloromethane was added. While cooling with ice, 3.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 4.8 g of a compound represented by the formula (II-5).
LC-MS: 343 [M + 1]
(Example 6) Production of compound represented by formula (II-6)

By a method similar to that in Example 1, a compound represented by the formula (I-6-5) was produced. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-6-5), 2.8 g of the compound represented by the formula (I-6-6) and 0.3 g of 4-dimethylaminopyridine in a reaction vessel. 40 mL of dichloromethane was added. While cooling with ice, 3.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 5.3 g of a compound represented by the formula (II-6).
LC-MS: 357 [M + 1]
(Example 7) Production of compound represented by formula (II-7)

By a method similar to that in Example 1, the compound represented by the formula (I-7-5) was produced. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-7-5), 3.1 g of the compound represented by the formula (I-7-6), 0.3 g of 4-dimethylaminopyridine, and 0.3 g in a reaction vessel. 40 mL of dichloromethane was added. While cooling with ice, 3.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 5.4 g of a compound represented by the formula (II-7).
LC-MS: 371 [M + 1]
(Example 8) Production of compound represented by formula (II-8)

Represented by formula (I-8-5) in the same manner as in Example 1 except that the compound represented by formula (I-1) was replaced with the compound represented by formula (I-8). The compound was prepared. In a reaction vessel under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-8-5), 3.0 g of the compound represented by the formula (I-8-6), 0.3 g of 4-dimethylaminopyridine, 40 mL of dichloromethane was added. While cooling with ice, 3.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 5.0 g of a compound represented by the formula (II-8).
LC-MS: 411 [M + 1]
(Example 9) Production of compound represented by formula (II-9)

The compound represented by the formula (I-9) was produced by the method described in WO2017 / 062581A1. Represented by formula (I-9-5) in the same manner as in Example 1 except that the compound represented by formula (I-1) was replaced with the compound represented by formula (I-9). The compound was prepared. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-9-5), 1.2 g of the compound represented by the formula (I-9-6) and 0.2 g of 4-dimethylaminopyridine in a reaction vessel. 40 mL of dichloromethane was added. While cooling with ice, 1.9 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 4.5 g of the compound represented by the formula (II-9).
LC-MS: 468 [M + 1]
(Example 10) Production of compound represented by formula (II-10)

  Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (I-10-1), 3.2 g of pyridinium p-toluenesulfonate, and 100 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 13.6 g of 3,4-dihydro-2H-pyran was added dropwise, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution and extracted with dichloromethane. The organic layer was washed successively with water and brine. By purification by column chromatography (Wakogel 50NH2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., dichloromethane / hexane), 17.7 g of the compound represented by the formula (I-10-2) was obtained.

  To the pressure resistant reactor, 17.7 g of the compound represented by the formula (I-10-2), 1.8 g of 5% Pd / C (en) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 100 mL of tetrahydrofuran were added, and the hydrogen pressure was 0. The mixture was stirred at 0.5 MPa for 20 hours. After removing the catalyst by filtration, the solvent was distilled off under reduced pressure. By refining by column chromatography (Wakogel 50NH2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hexane / ethyl acetate), 12.9 g of the compound represented by the formula (I-10) was obtained.

Represented by formula (I-10-7) in the same manner as in Example 1 except that the compound represented by formula (I-1) was replaced with the compound represented by formula (I-10). The compound was prepared. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-7), 30 mL of thionyl chloride, and 0.1 mL of N, N-dimethylformamide were added to a reaction vessel, and the mixture was heated under reflux for 4 hours. After the solvent was distilled off, 40 mL of tetrahydrofuran was added and dissolved. A solution prepared by dissolving 1.2 g of the compound represented by the formula (I-10-8) in 10 mL of tetrahydrofuran was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 5% hydrochloric acid and extracted with dichloromethane. The organic layer was washed successively with water and brine. Purification by column chromatography (Wakogel 50NH2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hexane / ethyl acetate) gave 3.0 g of the compound represented by the formula (II-10).
LC-MS: 456 [M + 1]
(Example 11) Production of compound represented by formula (II-11)

5.0 g of the compound represented by formula (II-1), 9.6 g of Lawesson's reagent, and 100 mL of toluene were added to a reaction vessel, and the mixture was heated under reflux for 8 hours. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 4.2 g of the compound represented by the formula (II-11).
LC-MS: 331 [M + 1]
(Example 12) Production of compound represented by formula (II-12)

A compound represented by the formula (II-12) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-2). Manufactured.
LC-MS: 359 [M + 1]
(Example 13) Production of compound represented by formula (II-13)

A compound represented by the formula (II-13) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-3). Manufactured.
LC-MS: 359 [M + 1]
(Example 14) Production of compound represented by formula (II-14)

A compound represented by the formula (II-14) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-4). Manufactured.
LC-MS: 359 [M + 1]
(Example 15) Production of compound represented by formula (II-15)

A compound represented by the formula (II-15) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-5). Manufactured.
LC-MS: 359 [M + 1]
(Example 16) Production of compound represented by formula (II-16)

A compound represented by the formula (II-16) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-6). Manufactured.
LC-MS: 373 [M + 1]
(Example 17) Production of compound represented by formula (II-17)

A compound represented by the formula (II-17) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-7). Manufactured.
LC-MS: 387 [M + 1]
(Example 18) Production of compound represented by formula (II-18)

A compound represented by the formula (II-18) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-8). Manufactured.
LC-MS: 427 [M + 1]
(Example 19) Production of compound represented by formula (II-19)

A compound represented by the formula (II-19) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-9). Manufactured.
LC-MS: 484 [M + 1]
(Example 20) Production of compound represented by formula (II-20)

A compound represented by the formula (II-20) was prepared in the same manner as in Example 11 except that the compound represented by the formula (II-1) was replaced with the compound represented by the formula (II-10). Manufactured.
LC-MS: 472 [M + 1]
(Example 21) Production of compound represented by formula (III-11)

5.0 g of the compound represented by the formula (II-11), 75 mL of water, and 3.0 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (14.9 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 4.5 g of a compound represented by the formula (III-11) was obtained.
LC-MS: 329 [M + 1]
(Example 22) Production of compound represented by formula (III-12)

5.0 g of the compound represented by the formula (II-12), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 4.5 g of a compound represented by the formula (III-12) was obtained.
LC-MS: 357 [M + 1]
(Example 23) Production of compound represented by formula (III-13)

5.0 g of the compound represented by the formula (II-13), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 4.4 g of a compound represented by the formula (III-13) was obtained.
LC-MS: 357 [M + 1]
(Example 24) Production of compound represented by formula (III-14)

5.0 g of the compound represented by the formula (II-14), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 4.0 g of the compound represented by the formula (III-14) was obtained.
LC-MS: 357 [M + 1]
(Example 25) Production of compound represented by formula (III-15)

5.0 g of the compound represented by the formula (II-15), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 4.2 g of the compound represented by the formula (III-15) was obtained.
LC-MS: 357 [M + 1]
(Example 26) Production of compound represented by formula (III-16)

5.0 g of the compound represented by the formula (II-16), 75 mL of water, and 2.7 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 13.3 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.9 g of a compound represented by the formula (III-16) was obtained.
LC-MS: 371 [M + 1]
(Example 27) Production of compound represented by formula (III-17)

5.0 g of the compound represented by the formula (II-17), 75 mL of water, and 2.6 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 13.3 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.8 g of a compound represented by the formula (III-17) was obtained.
LC-MS: 385 [M + 1]
(Example 28) Production of compound represented by formula (III-18)

5.0 g of the compound represented by the formula (II-18), 75 mL of water, and 2.3 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 11.6 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 4.1 g of a compound represented by the formula (III-18) was obtained.
LC-MS: 425 [M + 1]
(Example 29) Production of compound represented by formula (III-19)

5.0 g of the compound represented by the formula (II-19), 75 mL of water, and 2.1 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 10.2 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.6 g of a compound represented by the formula (III-19) was obtained.
LC-MS: 482 [M + 1]
(Example 30) Production of compound represented by formula (III-20)

5.0 g of the compound represented by the formula (II-20), 75 mL of water, and 2.1 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 10.5 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated with stirring at 40 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 2.7 g of a compound represented by the formula (III-20) was obtained.
LC-MS: 470 [M + 1]
(Example 31) Production of compound represented by formula (III-2)

5.0 g of the compound represented by the formula (II-2), 1.1 g of copper trifluoromethanesulfonate and 100 mL of xylene were added to a reaction vessel, and the mixture was heated and stirred at 140 ° C. for 30 hours in an oxygen atmosphere. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, dichloromethane) to obtain 3.3 g of the compound represented by the formula (III-2).
LC-MS: 341 [M + 1]
(Example 32) Production of compound represented by formula (IV-1)

  Under a nitrogen atmosphere, 4.0 g of the compound represented by the formula (III-11) and 80 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 9.1 g of boron tribromide was added dropwise, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.9 g of a compound represented by the formula (III-11-1).

The compound represented by the formula (III-11-2) was produced by the method described in WO2015 / 147243A1. In a reaction vessel under a nitrogen atmosphere, 5.0 g of a compound represented by formula (III-11-1), 16.3 g of a compound represented by formula (III-11-2), 0.2 g of 4-dimethylaminopyridine, 100 mL of dichloromethane was added. While cooling with ice, 4.6 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) yielded 14.5 g (purity 99.78%) of the compound represented by formula (IV-1).
LC-MS: 1245 [M + 1]
(Example 33) Production of compound represented by formula (IV-2)

  To the reaction vessel, 4.0 g of the compound represented by the formula (III-12) and 40.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 3.3 g of the compound represented by the formula (III-12-1).

The compound represented by the formula (III-12-2) was produced by the method described in WO2009 / 116657A1. In a reaction vessel under a nitrogen atmosphere, 5.0 g of a compound represented by formula (III-12-1), 12.7 g of a compound represented by formula (III-12-2), and 0.2 g of 4-dimethylaminopyridine. 100 mL of dichloromethane was added. While cooling with ice, 4.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) yielded 12.0 g of a compound represented by the formula (IV-2) (purity 99.87%).
LC-MS: 1129 [M + 1]
(Example 34) Production of compound represented by formula (IV-3)

  To the reaction vessel, 3.8 g of the compound represented by the formula (III-13) and 38.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.9 g of a compound represented by the formula (III-13-1).

The compound represented by the formula (III-13-2) was produced by the method described in WO2009 / 116657A1. In a reaction vessel under a nitrogen atmosphere, 5.0 g of a compound represented by formula (III-13-1), 12.7 g of a compound represented by formula (III-13-2), 0.2 g of 4-dimethylaminopyridine, 100 mL of dichloromethane was added. While cooling with ice, 4.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 11.5 g (purity 99.84%) of the compound represented by the formula (IV-3).
LC-MS: 1129 [M + 1]
(Example 35) Production of compound represented by formula (IV-4)

  3.7 g of the compound represented by formula (III-14) and 37.0 g of pyridinium chloride were added to a reaction vessel, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.8 g of a compound represented by the formula (III-14-1).

  The compound represented by the formula (III-14-2) was produced by the method described in JP-A-2017-210409. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-14-1), 8.9 g of the compound represented by the formula (III-14-2), 12.4 g of cesium carbonate and 100 mL of dimethyl sulfoxide were placed in a reaction vessel. Was added and the mixture was heated with stirring at 80 ° C. for 8 hours. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 6.6 g of a compound represented by the formula (III-14-3).

  6.6 g of the compound represented by formula (III-14-3), 30 mL of dichloromethane, and 30 mL of formic acid were added to a reaction vessel, and the mixture was heated under reflux for 5 hours. After the solvent was distilled off under reduced pressure, the residue was washed with water. By drying, 4.4 g of a compound represented by the formula (III-14-4) was obtained.

The compound represented by the formula (III-14-5) was produced by the method described in WO2017 / 169839A1. In a nitrogen atmosphere, 4.4 g of the compound represented by the formula (III-14-4), 3.9 g of the compound represented by the formula (III-14-5), and 0.1 g of 4-dimethylaminopyridine in a reaction vessel under a nitrogen atmosphere. 60 mL of dichloromethane was added. While cooling with ice, 2.0 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 5.6 g of a compound represented by the formula (IV-4) (purity 99.76%).
LC-MS: 1101 [M + 1]
(Example 36) Production of compound represented by formula (IV-5)

  To the reaction vessel, 3.7 g of the compound represented by the formula (III-15) and 37.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.9 g of a compound represented by the formula (III-15-1).

The compound represented by the formula (III-15-2) was produced by the method described in WO2009 / 116657A1. Under a nitrogen atmosphere, 5.0 g of the compound represented by formula (III-15-1), 12.7 g of the compound represented by formula (III-15-2) and 0.2 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 4.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 10.4 g of a compound represented by the formula (IV-5) (purity 99.72%).
LC-MS: 1129 [M + 1]
(Example 37) Production of compound represented by formula (IV-6)

  3.8 g of the compound represented by the formula (III-16) and 38.0 g of pyridinium chloride were added to a reaction vessel, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.6 g of a compound represented by the formula (III-16-1).

The compound represented by the formula (III-16-2) was produced by the method described in WO2015 / 147243A1. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-16-1), 14.3 g of the compound represented by the formula (III-16-2) and 0.2 g of 4-dimethylaminopyridine in a reaction vessel, 100 mL of dichloromethane was added. While cooling with ice, 4.1 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. By purifying by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol), 13.2 g (purity 99.68%) of the compound represented by the formula (IV-6) was obtained.
LC-MS: 1287 [M + 1]
(Example 38) Production of compound represented by formula (IV-7)

  3.7 g of the compound represented by the formula (III-17) and 37.0 g of pyridinium chloride were added to a reaction vessel, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.4 g of a compound represented by the formula (III-17-1).

The compound represented by the formula (III-17-2) was produced by the method described in WO2009 / 116657A1. In a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-17-1), 11.7 g of the compound represented by the formula (III-17-2), and 0.2 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 3.9 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 11.4 g of a compound represented by the formula (IV-7) (purity 99.69%).
LC-MS: 1157 [M + 1]
(Example 39) Production of compound represented by formula (IV-8)

  Under a nitrogen atmosphere, 3.5 g of the compound represented by the formula (III-18) and 80 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 6.2 g of boron tribromide was added dropwise, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.6 g of a compound represented by the formula (III-18-1).

The compound represented by the formula (III-18-2) was produced by the method described in JP-A-2016-047813. In a nitrogen atmosphere, 5.0 g of a compound represented by the formula (III-18-1), 10.6 g of a compound represented by the formula (III-18-2), 0.2 g of 4-dimethylaminopyridine in a reaction vessel, 100 mL of dichloromethane was added. While cooling with ice, 3.8 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 10.6 g of a compound represented by the formula (IV-8) (purity 99.56%).
LC-MS: 1113 [M + 1]
(Example 40) Production of compound represented by formula (IV-9)

  To a pressure-resistant reaction vessel, 4.0 g of the compound represented by the formula (III-19), 50 mL of tetrahydrofuran, 25 mL of methanol, 0.4 g of 5% palladium carbon were added, and the mixture was stirred for 10 hours at 50 ° C. at a hydrogen pressure of 0.3 MPa. The catalyst was removed by filtration and the solvent was distilled off under reduced pressure. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 1.7 g of a compound represented by the formula (III-19-1).

The compound represented by the formula (III-19-2) was produced by the method described in WO2014 / 010325A1. Under a nitrogen atmosphere, 5.0 g of a compound represented by the formula (III-19-1), 14.8 g of a compound represented by the formula (III-19-2) and 0.2 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 4.6 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 13.4 g (purity 99.34%) of the compound represented by the formula (IV-9).
LC-MS: 1158 [M + 1]
(Example 41) Production of compound represented by formula (IV-10)

  3.7 g of the compound represented by formula (III-20), 30 mL of tetrahydrofuran, 30 mL of methanol, and 1 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 10 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 1.5 g of a compound represented by the formula (III-20-1).

The compound represented by the formula (III-20-2) was produced by the method described in WO2009 / 116657A1. Under a nitrogen atmosphere, 5.0 g of the compound represented by formula (III-20-1), 13.9 g of the compound represented by formula (III-20-2), and 0.2 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 4.6 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) yielded 12.8 g (purity 98.94%) of the compound represented by formula (IV-10).
LC-MS: 1102 [M + 1]
(Example 42) Production of compound represented by formula (IV-11)

  2.8 g of the compound represented by the formula (III-2) and 28.0 g of pyridinium chloride were added to a reaction vessel, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 1.8 g of the compound represented by the formula (III-2-1).

The compound represented by the formula (III-2-2) was produced by the method described in WO2009 / 116657A1. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-2-1), 13.4 g of the compound represented by the formula (III-2-2), 0.2 g of 4-dimethylaminopyridine in a reaction vessel, 100 mL of dichloromethane was added. While cooling with ice, 4.4 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 12.5 g of a compound represented by the formula (IV-11) (purity 98.49%).
LC-MS: 1113 [M + 1]
(Comparative Example 1) Production of compound represented by formula (IV-R-1)

  To the reaction vessel, 10.0 g of the compound represented by the formula (I-R-1-1) and 70 mL of the compound represented by the formula (I-R-1-2) were added, and the mixture was heated with stirring at 150 ° C for 5 hours. After distilling off diethyl oxalate under reduced pressure, purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 14.5 g of a compound represented by the formula (IR-1-3).

  14.5 g of the compound represented by the formula (I-R-1-3), 45.6 g of Lawesson's reagent, and 100 mL of toluene were added to a reaction vessel, and the mixture was heated under reflux for 8 hours. Purification by column chromatography (silica gel, hexane / ethyl acetate) gave 12.6 g of a compound represented by the formula (IR-1-4).

  12.6 g of the compound represented by the formula (IR-1-4), 50 mL of methanol, and 30 mL of 20% aqueous sodium hydroxide solution were added to a reaction vessel, and the mixture was heated and stirred at 50 ° C. for 3 hours. The mixture was neutralized with 5% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed successively with water and brine. After drying over sodium sulfate, the solvent was distilled off to obtain 9.8 g of a compound represented by the formula (IR-1-5).

  9.8 g of the compound represented by the formula (I-R-1-5), 150 mL of water, and 10.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 53.5 g of potassium ferricyanide and 10 mL of methanol were added, and the mixture was heated and stirred at 40 ° C. for 10 hours. The reaction solution was poured into 5% hydrochloric acid, and the precipitated solid was filtered and washed with water. By drying, 7.8 g of a compound represented by the formula (IR-1-6) was obtained.

  In a nitrogen atmosphere, 7.8 g of the compound represented by the formula (I-R-1-6), 10.0 g of the compound represented by the formula (I-R-1-7), and 4-dimethylaminopyridine in a reaction vessel. 0.5 g and 100 mL of dichloromethane were added. While cooling with ice, 6.6 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 9.6 g of a compound represented by the formula (II-R-1).

  9.6 g of the compound represented by the formula (II-R-1), 7.4 g of Lawesson's reagent, and 100 mL of toluene were added to a reaction vessel, and the mixture was heated under reflux for 8 hours. Purification by column chromatography (silica gel, hexane / ethyl acetate) gave 9.9 g of a compound represented by the formula (II-R-11).

9.9 g of the compound represented by formula (II-R-11), 150 mL of water, and 6.0 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 29.6 g of potassium ferricyanide and 30 mL of methanol were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 8.5 g of a compound represented by the formula (III-R-11) was obtained.
LC-MS: 329 [M + 1]
Under a nitrogen atmosphere, 4.0 g of the compound represented by the formula (III-R-11) and 80 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 9.1 g of boron tribromide was added dropwise, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.9 g of a compound represented by the formula (III-R-11-1).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-R-11-1), 16.3 g of the compound represented by the formula (III-R-11-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.6 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) yielded 14.5 g of a compound represented by the formula (IV-R-1) (purity 96.79%).
LC-MS: 1245 [M + 1]
(Comparative Example 2) Production of compound represented by formula (IV-R-2)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced by the compound represented by the formula (I-R-2-1), and the same procedure as in the formula (II- A compound represented by R-12) was produced. 5.0 g of the compound represented by the formula (II-R-12), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.5 g of a compound represented by the formula (III-R-12) was obtained.
LC-MS: 357 [M + 1]
To the reaction vessel, 4.0 g of the compound represented by the formula (III-R-12) and 40.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 3.3 g of a compound represented by the formula (III-R-12-1).

In a nitrogen atmosphere, 5.0 g of a compound represented by the formula (III-R-12-1), 12.7 g of a compound represented by the formula (III-R-12-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 12.0 g (purity 94.88%) of the compound represented by the formula (IV-R-2).
LC-MS: 1129 [M + 1]
(Comparative Example 3) Production of compound represented by formula (IV-R-3)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced with the compound represented by the formula (I-R-3-1) by the same method, and the compound represented by the formula (II- A compound represented by R-13) was produced. 5.0 g of the compound represented by the formula (II-R-13), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.4 g of a compound represented by the formula (III-R-13) was obtained.
LC-MS: 357 [M + 1]
To the reaction vessel, 3.8 g of the compound represented by the formula (III-R-13) and 38.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.9 g of a compound represented by the formula (III-R-13-1).

In a nitrogen atmosphere, 5.0 g of a compound represented by the formula (III-R-13-1), 12.7 g of a compound represented by the formula (III-R-13-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 11.5 g (purity 97.84%) of the compound represented by the formula (IV-R-3).
LC-MS: 1129 [M + 1]
(Comparative Example 4) Production of compound represented by formula (IV-R-4)

In Comparative Example 1, a compound represented by the formula (II-R-1-1) was replaced with a compound represented by the formula (I-R-4-1) by the same method as in the formula (II-). A compound represented by R-14) was produced. 5.0 g of the compound represented by the formula (II-R-14), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.2 g of the compound represented by the formula (III-R-14) was obtained.
LC-MS: 357 [M + 1]
To the reaction vessel, 3.7 g of the compound represented by the formula (III-R-14) and 37.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.8 g of a compound represented by the formula (III-R-14-1).

  Under a nitrogen atmosphere, 5.0 g of a compound represented by the formula (III-R-14-1), 8.9 g of a compound represented by the formula (III-R-14-2), and 12.4 g of cesium carbonate in a reaction vessel. , 100 mL of dimethyl sulfoxide were added, and the mixture was heated with stirring at 80 ° C. for 8 hours. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) yielded 6.6 g of a compound represented by the formula (III-R-14-3).

  6.6 g of the compound represented by the formula (III-R-14-3), 30 mL of dichloromethane and 30 mL of formic acid were added to a reaction vessel, and the mixture was heated under reflux for 5 hours. After the solvent was distilled off under reduced pressure, the residue was washed with water. By drying, 4.4 g of a compound represented by the formula (III-R-14-4) was obtained.

In a nitrogen atmosphere, 4.4 g of the compound represented by the formula (III-R-14-4), 3.9 g of the compound represented by the formula (III-R-14-5), and 4-dimethylaminopyridine in a reaction vessel. 0.1 g and 60 mL of dichloromethane were added. While cooling with ice, 2.0 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 5.6 g of a compound represented by the formula (IV-R-4) (purity 97.76%).
LC-MS: 1101 [M + 1]
(Comparative Example 5) Production of compound represented by formula (IV-R-5)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced by the compound represented by the formula (I-R-5-1), and the same method as in the formula (II- A compound represented by R-15) was produced. 5.0 g of the compound represented by the formula (II-R-15), 75 mL of water, and 2.8 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. Potassium ferricyanide (13.8 g) and methanol (15 mL) were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.3 g of a compound represented by the formula (III-R-15) was obtained.
LC-MS: 357 [M + 1]
To the reaction vessel, 3.7 g of the compound represented by the formula (III-R-15) and 37.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.9 g of a compound represented by the formula (III-R-15-1).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-R-15-1), 12.7 g of the compound represented by the formula (III-R-15-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 10.4 g (purity 98.72%) of the compound represented by the formula (IV-R-5).
LC-MS: 1129 [M + 1]
(Comparative Example 6) Production of compound represented by formula (IV-R-6)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced with the compound represented by the formula (I-R-6-1) by the same method as in the formula (II- A compound represented by R-16) was produced. 5.0 g of the compound represented by the formula (II-R-16), 75 mL of water, and 2.7 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 13.3 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated and stirred at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.1 g of the compound represented by the formula (III-R-16) was obtained.
LC-MS: 371 [M + 1]
To the reaction vessel, 3.8 g of the compound represented by the formula (III-R-16) and 38.0 g of pyridinium chloride were added, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.6 g of a compound represented by the formula (III-R-16-1).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-R-16-1), 14.3 g of the compound represented by the formula (III-R-16-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.1 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. By purifying by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol), 13.2 g (purity 98.68%) of the compound represented by the formula (IV-R-6) was obtained.
LC-MS: 1287 [M + 1]
(Comparative Example 7) Production of compound represented by formula (IV-R-7)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced with the compound represented by the formula (I-R-7-1) by the same method, and the compound represented by the formula (II- A compound represented by R-17) was produced. 5.0 g of the compound represented by the formula (II-R-17), 75 mL of water, and 2.6 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 13.3 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated and stirred at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.0 g of the compound represented by the formula (III-R-17) was obtained.
LC-MS: 385 [M + 1]
3.7 g of the compound represented by the formula (III-R-17) and 37.0 g of pyridinium chloride were added to a reaction vessel, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.4 g of a compound represented by the formula (III-R-17-1).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-R-17-1), 11.7 g of the compound represented by the formula (III-R-17-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 3.9 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) yielded 11.4 g of a compound represented by the formula (IV-R-7) (purity 98.69%).
LC-MS: 1157 [M + 1]
(Comparative Example 8) Production of compound represented by formula (IV-R-8)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced with the compound represented by the formula (I-R-8-1) by the same method as in the formula (II- A compound represented by R-18) was produced. 5.0 g of the compound represented by the formula (II-R-18), 75 mL of water, and 2.3 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 11.6 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.4 g of a compound represented by the formula (III-R-18) was obtained.
LC-MS: 425 [M + 1]
Under a nitrogen atmosphere, 3.5 g of the compound represented by the formula (III-R-18) and 80 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 6.6 g of boron tribromide was added dropwise, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 2.6 g of a compound represented by the formula (III-R-18-1).

Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-R-18-1), 10.6 g of the compound represented by the formula (III-R-18-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 3.8 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) yielded 10.6 g of a compound represented by the formula (IV-R-8) (purity 98.56%).
LC-MS: 1113 [M + 1]
(Comparative Example 9) Production of compound represented by formula (IV-R-9)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced by the compound represented by the formula (I-R-9-1), and the same procedure as in the formula (II- A compound represented by R-19) was produced. 5.0 g of the compound represented by the formula (II-R-19), 75 mL of water, and 2.1 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 10.2 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated and stirred at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.0 g of a compound represented by the formula (III-R-19) was obtained.
LC-MS: 482 [M + 1]
To a pressure-resistant reaction vessel, 4.0 g of the compound represented by the formula (III-R-19), 50 mL of tetrahydrofuran, 25 mL of methanol, 0.4 g of 5% palladium carbon were added, and the mixture was stirred at 50 MPa for 50 hours at a hydrogen pressure of 0.3 MPa. did. The catalyst was removed by filtration and the solvent was distilled off under reduced pressure. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 1.7 g of a compound represented by the formula (III-R-19-1).

In a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-R-19-1), 14.8 g of the compound represented by the formula (III-R-19-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.6 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 13.4 g (purity 98.64%) of the compound represented by the formula (IV-R-9).
LC-MS: 1158 [M + 1]
(Comparative Example 10) Production of compound represented by formula (IV-R-10)

In Comparative Example 1, the compound represented by the formula (I-R-1-1) was replaced with the compound represented by the formula (I-R-10-1) by the same method as in the formula (II- A compound represented by R-20) was produced. 5.0 g of the compound represented by the formula (II-R-20), 75 mL of water, and 2.1 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 10.5 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated and stirred at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 2.2 g of a compound represented by the formula (III-R-20) was obtained.
LC-MS: 470 [M + 1]
3.7 g of the compound represented by the formula (III-R-20), 30 mL of tetrahydrofuran, 30 mL of methanol, and 1 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 10 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 1.5 g of a compound represented by the formula (III-R-20-1).

In a nitrogen atmosphere, 5.0 g of a compound represented by the formula (III-R-20-1), 13.9 g of a compound represented by the formula (III-R-20-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.6 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 12.8 g (purity 98.35%) of the compound represented by the formula (IV-R-10).
LC-MS: 1102 [M + 1]
(Comparative Example 11) Production of compound represented by formula (IV-R-11)

  A compound represented by the formula (IR-11-3) was produced by a method similar to the method described in US2005 / 0143422A1. Under a nitrogen atmosphere, 5.0 g of a compound represented by the formula (I-R-11-3), 4.0 g of a compound represented by the formula (I-R-11-4), and 4-dimethylaminopyridine in a reaction vessel. 0.3 g and 40 mL of dichloromethane were added. While cooling with ice, 4.0 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 6.0 g of the compound represented by the formula (II-R-21).

  To the reaction vessel, 6.0 g of the compound represented by the formula (II-R-21), 11.1 g of Lawesson's reagent, and 100 mL of toluene were added, and the mixture was heated under reflux for 8 hours. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 5.0 g of a compound represented by the formula (II-R-31).

5.0 g of the compound represented by the formula (II-R-31), 75 mL of water, and 2.9 g of sodium hydroxide were added to a reaction vessel, and the mixture was stirred for 1 hour while cooling with ice. 14.5 g of potassium ferricyanide and 15 mL of methanol were added, and the mixture was heated with stirring at 50 ° C. for 30 hours. The reaction solution was poured into water, the precipitated solid was filtered, and washed with hexane. By drying, 3.2 g of the compound represented by the formula (III-R-2) was obtained.
LC-MS: 341 [M + 1]
2.8 g of the compound represented by formula (III-R-2) and 28.0 g of pyridinium chloride were added to a reaction vessel, and the mixture was heated with stirring at 180 ° C. for 3 hours. The reaction mixture was poured into water, the precipitated solid was filtered, and washed successively with water and hexane. Purification by column chromatography (silica gel, dichloromethane / ethyl acetate) gave 1.8 g of a compound represented by the formula (III-R-2-1).

In a nitrogen atmosphere, 5.0 g of the compound represented by the formula (III-R-2-1), 13.4 g of the compound represented by the formula (III-R-2-2), and 4-dimethylaminopyridine in a reaction vessel. 0.2 g and 100 mL of dichloromethane were added. While cooling with ice, 4.4 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 12.5 g of a compound represented by the formula (IV-R-11) (purity: 98.00%).
LC-MS: 1113 [M + 1]
The yields of the cyclization reactions in Examples 21 to 31 and Comparative Examples 1 to 11 are shown in the table below.

It can be seen that the production method of the present invention has a higher yield in the cyclization reaction than the production method of the comparative example.
(Examples 43 to 53, Comparative examples 12 to 22)
Compounds represented by Formulas (IV-1) to (IV-11) described in Examples 32 to 42 and Formulas (IV-R-1) to Formula (IV) described in Comparative Examples 1 to 11 The compound represented by IV-R-11) was used as a compound to be evaluated. The compound to be evaluated, the compound represented by the formula (X1-3), the compound represented by the formula (X1-4), the compound represented by the above formula (X2-6), 4-methoxyphenol and toluene. They were mixed and heated at 80 ° C. with stirring to dissolve them. After cooling to room temperature, a photopolymerization initiator Irgacure 907 (manufactured by BASF Japan Ltd.) was added, and the coating solution was prepared by stirring and dissolving at room temperature. The mixing ratio of each component is shown in the table below.

  A uniaxially stretched polyethylene terephthalate (PET) film having a thickness of 50 μm is rubbed using a commercially available rubbing device, and then a coating solution containing each compound is applied by a bar coating method (bar coater # 5) at 90 ° C. for 2 minutes. Dried. After cooling the obtained coating film to room temperature, it was polymerized by irradiating it with ultraviolet rays at a conveyor speed of 6 m / min using a UV conveyor device (manufactured by GS Yuasa Co., Ltd.) to produce a film to be evaluated.

In order to evaluate the discoloration of the obtained film and the change of the phase difference, the film to be evaluated was placed on a hot plate at 80 ° C. and irradiated with 60 mW of light for 50 hours by an LED lamp (365 nm). The yellowing index (YI) of the film before and after the heating irradiation was measured to determine the yellowing index (ΔYI). The degree of yellowness was calculated by measuring the absorption spectrum of the film with JASCO UV / VIS Spectrophotometer V-560. The formula is
YI = 100 (1.28X-1.06Z) / Y
(In the formula, YI represents yellowness, and X, Y, and Z represent tristimulus values in the XYZ color system (JIS K7373).). The degree of yellowing (ΔYI) means the difference between the yellowness before light irradiation and the yellowness after light irradiation (JIS K7373). Further, the retardation retention rate of the film before and after heating and irradiation was determined. The phase difference retention rate was measured by the phase difference measured by Otsuka Electronics Co., Ltd. RETS-100, and the following formula was used:
Retention rate of phase difference (%) = Re (b) / Re (a) × 100
(In the formula, Re (b) represents the phase difference at 450 nm after the heating irradiation, and Re (a) represents the phase difference at 450 nm before the heating irradiation). The yellowing degree (ΔYI) and retardation retention of each film are shown in the table below.

  Since the film containing the polymerizable compound produced by the production method of the present invention has a low degree of yellowing, it is understood that discoloration is unlikely to occur. Further, since the film containing the polymerizable compound produced by the production method of the present invention has a high retardation retention rate, it can be seen that the retardation is unlikely to change.

  From the above results, the production method of the present invention is high in yield as compared with the conventional method, and thus is useful as a method for producing a benzothiazole derivative. Further, a polymerizable compound is produced because it is less likely to cause discoloration and a change in retardation when irradiated with ultraviolet light to a film-shaped polymer obtained by polymerizing a polymerizable composition containing the compound to produce a polymerizable compound. Is useful as a manufacturing method of. Further, an optical anisotropic body using a polymerizable composition containing a polymerizable compound produced by the production method of the present invention, because it is difficult to cause discoloration and change in phase difference when irradiated with ultraviolet light, etc. It is useful for optical film applications.

Claims (7)

The following general formula (II)

(In the formula, PG ¹ and PG ² each independently represent a hydrogen atom or an organic group, and ring B represents an aromatic group or a heteroaromatic group having 3 to 40 carbon atoms which may be substituted with L ^B. And a compound represented by L ^B represents an organic group, and when there are a plurality of L ^B, they may be the same or different, and Y represents an oxygen atom or a sulfur atom. Manufactured by the following general formula (III):

(In the formula, rings B, Y, PG ¹ and PG ² each have the same meaning as rings B, Y, PG ¹ and PG ² in formula (II)). In formulas (II) and (III), PG ¹ and PG ² are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, or 3 to 20 carbon atoms. Alkoxyalkoxyalkyl group, alkenyl group having 2 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, tetrahydropyranyl group, trialkylsilyl group having 3 to 20 carbon atoms, and 4 to 30 carbon atoms 2. The production method according to claim 1, wherein the arylmethyl group or the acyl group having 1 to 20 carbon atoms is represented. In the general formula (II), ring B is represented by the following formula (B-1) to formula (B-10).

(Wherein, have one a bond at any position, any -CH = may be replaced each independently -N =, -CH 2 _- are each independently -O -, - S-, -NR ^B1- (in the formula, R ^B1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), -CS- or -CO-, and these groups are not present. Substituent, which may be substituted by one or more substituents L ^B ), is represented by the formula (1), the production method according to claim 1 or 2. From the step of producing the compound represented by the general formula (III) according to claim 1 from the compound represented by the general formula (II) according to claim 1, and from the compound represented by the general formula (III) The following general formula (IV)

(In the formula, R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen atom in the group is a fluorine atom. It may be substituted with an atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O. -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 - _{, -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CF- or -C≡C-, or a group represented by P ^1- [Sp ¹ -X ¹ ] _k ^1- ( In the formula, P ¹ represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ¹ may have any hydrogen atom in the group substituted with a fluorine atom, and one —CH ₂ — or adjacent Two or more —CH ₂ — which are not independently each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O. -CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or a straight chain having 2 to 20 carbon atoms which may be replaced by -C≡C-. A branched or branched alkylene group, when multiple Sp ^1's are present, they may be the same or different, and X ^1's are —O—, —S—, —OCH ₂ —, —CH ₂ O. -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 - _{, -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH-, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - _{, -OCO-CH 2 -, -} CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF-, -C≡C- or a single bond, but when a plurality of X ^1's are present, they may be the same or different (provided that P ^1- [Sp ¹ -X ¹ ] _k ¹ -is -O. Does not include an -O- bond. ), K1 represents an integer of 0 to 5. ),
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen atom in the group is substituted with a fluorine atom. Alternatively, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO. -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 _{S -, - CF 2 O -} , - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - _{OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, _{-OCO-CH 2 -, - CH} 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF- or - A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by C≡C-, or a group represented by-[X ² -Sp ² ] _k2- P ² (in the formula, P ² represents a group polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ² may have any hydrogen atom in the group substituted with a fluorine atom, and one —CH ₂ — or non-adjacent 2 more than five -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or straight-chain or branched-chain having 2 to 20 carbon atoms which may be replaced by -C≡C-. It represents an alkylene group, but when a plurality of Sp ² are present, they may be the same or different, and X ² is —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO. -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 _{S -, - CF 2 O -} , - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO- _{CH = CH -, - COO-} CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO _{-CH 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡ C- or a single bond is represented, but when a plurality of X ² are present, they may be the same or different (provided that-[X ² -Sp ² ] _k2- P ² is -O-O-. Does not include joins. ) And k2 represent an integer of 0 to 5. ),
A ¹ and A ² are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, tetrahydro Represents a pyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group, which may be unsubstituted or substituted by one or more substituents L ² . When there are a plurality of A ^1, they may be the same or different, and when there are a plurality of A ^2, they may be the same or different,
L ² is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom may be substituted with a fluorine atom, 1 number of -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH -, - CH = CH -, - CF = CF- or -C≡C- alkyl group having 20 good 1 -C be replaced by, ^or, P ^L - [Sp L - X ^L] kL _- in the group represented by (wherein, P ^L is radical polymerization, represents a polymerized group by cationic polymerization or anionic polymerization, Sp ^L is even any hydrogen atom in the radicals substituted by fluorine atoms Well, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—. S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- also represents a good straight-chain or branched alkylene group having a carbon number of 2 to 20, Sp ^L is those if there exist a plurality may be different even in the same, X ^L is -O -, - S _{-, - OCH 2 -, -} CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH- _{, -NH-CO -, - SCH} 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO -CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - _{CH 2 CH 2 -OCO -, -} COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH-, -CF = CF-, -C = C- or a single bond, but when a plurality of X ^L are present, they may be the same or different (provided that P ^L - ^{[Sp L} -X L ] _KL- does not include a —O—O— bond. ), KL represents an integer of 0 to 5. ), When ^two or more L ^2's are present, they may be the same or different,
Ax is the following formula (IV-Ax)

(In the formula, the broken line represents a bonding position, and the rings B and Y have the same meanings as the rings B and Y in the general formula (III) respectively.),
Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, —OCO—, —CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, _{-NH-O -, - O-} NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 _{-COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N - , - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{if Z 1} there are a plurality of They may be the same or different, and when a plurality of Z ² are present, they may be the same or different,
m1 and m2 each independently represent an integer of 0 to 6, while m1 + m2 represents an integer of 1 to 6,
However, there is at least one polymerizable group selected from P ¹ , P ² and P ^L. ) And a step of producing a compound represented by formula (4).   From the step of producing the compound represented by the general formula (III) according to claim 1 from the compound represented by the general formula (II) according to claim 1, and from the compound represented by the general formula (III) A polymerizable composition comprising a step of producing the compound represented by the general formula (IV) according to claim 4 and a step of producing a polymerizable composition containing the compound represented by the general formula (IV). Method of manufacturing things.   From the step of producing the compound represented by the general formula (III) according to claim 1 from the compound represented by the general formula (II) according to claim 1, and from the compound represented by the general formula (III) A step of producing a compound represented by the general formula (IV) according to claim 4, and a polymerizable composition containing the compound represented by the general formula (IV) by mixing the compound represented by the general formula (IV). A method for producing a polymer, which comprises a step of producing a composition and a step of polymerizing a polymerizable composition containing a compound represented by the general formula (IV).   The compound represented by the general formula (II) according to claim 1.