JP2013253041A - Method for producing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a compound having an ester bond and/or amide bond, with a small content of impurities in high yield; and to provide a high purity compound obtained by the method.SOLUTION: There is provided a method for producing a mixed acid anhydride (4) by adding a compound (1) having at least one carboxy group and a base (2) simultaneously without mixing in advance to an acid halide compound (3) to react them. Also a method for producing an ester compound and/or amide compound (6) is provided which comprises: adding a compound (1) having at least one carboxy group and a base (2) simultaneously without mixing in advance to an acid halide compound (3) to react them to produce a mixed acid anhydride (4); and thereafter reacting with a compound (5) having at least one group selected from a hydroxy group, mercapto group and/or amino group.

Description

  The present invention relates to a method for producing a compound having an ester bond or / and an amide bond, a composition containing a compound obtained by the production method, a pharmaceutical, an agrochemical, a liquid crystal material, a polymer, a resin, a pigment using the composition, The present invention relates to dyes, cosmetics, foods, inks, pressure-sensitive adhesives, adhesives, printed materials, optical anisotropic bodies, display elements, and electronic devices.

  Compounds having an ester bond or / and an amide bond are used in various applications including synthetic resins, liquid crystal materials, pharmaceuticals, agricultural chemicals, pigments, dyes, foods, synthetic fibers, plastics, additives or cosmetics. In any application, those compounds are desired to have high purity from the viewpoints of quality, safety and reliability. From the viewpoint of profitability, it is important to produce those compounds with good yield.

  In particular, in the field of electronic materials, it is desired that the compound used has a high purity. For example, polymerizable liquid crystal materials are used in the field of optical anisotropic bodies in the field of electronic materials. The optical anisotropic body can be obtained as a film or a resin having a uniform orientation by aligning the polymerizable liquid crystal composition in a liquid crystal state and then polymerizing it. The film and resin thus produced can be used for polarizing plates, retardation plates and the like necessary for liquid crystal displays. In many cases, two or more types of polymerizability are required to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, film transparency, mechanical strength, surface hardness, heat resistance and light resistance. Compositions consisting of compounds are used. However, if impurities are mixed in the polymerizable compound constituting the composition, problems such as unevenness and discoloration may occur in the produced film or resin. If a film with unevenness or discoloration is used as an optical film for a liquid crystal display, for example, the brightness of the screen will be uneven and the color of the display will become unnatural. I will let you. For this reason, when used in the field of electronic materials, management of impurities on the order of ppm is required.

  Various methods are known as a method for producing a compound having an ester bond or / and an amide bond, and a mixed acid anhydride of a precursor having a carboxyl group and a precursor having a hydroxyl group, an amino group and / or a mercapto group. A production method by reacting a product with a base in the presence of a base is widely used because the reaction conditions are mild and the raw materials used are inexpensive. However, when the production method is carried out under known reaction conditions, a purification step for removing unreacted raw materials is necessary because the conversion rate to the target compound is low, and the isolation yield becomes low. There has been a problem that the purity of the target compound is lowered. Further, there is a problem that unreacted raw materials and by-products remain even after purification. Films prepared using a polymerizable liquid crystal composition containing a compound having such an ester bond or / and an amide bond are uneven, subjected to post-baking treatment after polymerization or for complete curing. Then, discoloration occurs, and when such a film is used as a member of a liquid crystal display, for example, there is a problem that the quality of the product is greatly deteriorated. Therefore, a production method capable of obtaining a compound having an ester bond or / and an amide bond with high yield and high purity has been demanded.

JP 2011-057635 A WO2009-122868A1 Japanese Patent Laid-Open No. 9-104642

The Journal of Organic Chemistry, 1991, 56 (1), 405-411.

  The problem to be solved by the present invention is to provide a method for producing a compound having an ester bond or / and an amide bond with a high yield and a low impurity content, and a high-purity compound obtained by the production method.

  Provided is a production method characterized in that at least one compound having a carboxyl group and a base are added and reacted simultaneously with an acid halogen compound without mixing in advance, and a high-purity compound obtained by the production method, Furthermore, the compound which uses the said high purity compound as an intermediate, its manufacturing method, and the high purity composition which uses the said high purity compound are provided.

  A compound having an ester bond or / and an amide bond produced by the production method of the present invention is useful as a component of various compositions because of its high yield and low impurity content. In addition, the composition containing the compound produced by the production method of the present invention is a pharmaceutical, agricultural chemical, liquid crystal material, polymer, resin, pigment, dye, cosmetics, food, ink, adhesive, adhesive, printed matter, optical anisotropic Useful for body, display element and electronic device applications.

  Provided is a method for producing a mixed acid anhydride (4) in which a compound (1) having at least one carboxyl group and a base (2) are added and reacted simultaneously with an acid halogen compound (3) without being mixed in advance. In addition, after the compound (1) having at least one carboxyl group and the base (2) are not mixed in advance, the acid halide compound (3) is simultaneously added and reacted to form a mixed acid anhydride (4). And a method for producing an ester compound and / or an amide compound (6), wherein the compound (5) having a group selected from at least one hydroxyl group, mercapto group and / or amino group is further reacted.

  In these embodiments, the compound (1) having at least one carboxyl group is preferably an aromatic carboxylic acid or an aliphatic carboxylic acid.

  The compound (5) having a group selected from at least one hydroxyl group, mercapto group and / or amino group may be an alcohol, a phenol, a thiol, a thiophenol, an aromatic amine and / or an aliphatic amine. preferable.

  The acid halogen compound (3) is preferably a sulfonic acid halogen compound, a carboxylic acid halogen compound or a halogen formate compound.

  The base (2) is preferably an amine, amide, carbamate, imide, sulfonamide, guanidine, hydrazone, hydrazide, hydrazine, heterocyclic amine, a salt thereof, a metal alkoxide or a metal hydroxide.

  Furthermore, the compound (1) having at least one carboxyl group is preferably a compound represented by the following general formula (I).

(In the formula, G ¹ represents the following formula (i)

(In the formula, each A ¹ is independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [ 2.2.2] Octylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2 , 5-diyl group, 1,3-dioxane-2,5-diyl group or a single bond, these groups are unsubstituted or each independently halogen, cyano group, nitro group, pentafluorosulfuranyl The alkyl group may be substituted by a group or an alkyl group having 1 to 10 carbon atoms, and each of these alkyl groups may be independently substituted with one or more hydrogen atoms by fluorine atoms or chlorine atoms. The above 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) Or A ¹ represents a group represented by P-Sp- (wherein P represents the following formula (P-1) to formula (P-17)).

And Sp represents one —CH ₂ — or two or more non-adjacent —CH ₂ — 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-, -CY = CY- or -C≡C- (wherein Y is independently a hydrogen atom, an alkyl having 1 to 12 carbon atoms) Represents a group, a fluorine atom, a chlorine atom or a cyano group.) Represents an alkylene group having 1 to 20 carbon atoms which may be substituted, or a single bond. Z ¹¹ and Z ¹² 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 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 - _{COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -C _{O -, - CH 2 -OCO -} , - CY = CY- ( wherein, Y each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group.) , —C≡C—, —CH═N—, —N═CH—, —N═N—, —CH═N—N═CH—, an alkylene group having 1 to 20 carbon atoms or a single bond. In this alkylene group, one or more hydrogen atoms may each independently be replaced by a fluorine atom or a chlorine atom, and one —CH ₂ — or two or more — CH ₂ — is 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) Or represents a cyano group.), And m11 represents an integer of 0 to 8. R ¹ and W ¹ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, or an alkyl having 1 to 20 carbon atoms. during group or P-Sp- (wherein, P is the same meaning as P in a ^1, Sp is a ¹ has the same meaning as Sp in. However there be the same group or different groups The alkyl groups each independently represent one or more hydrogen atoms replaced by fluorine or chlorine atoms, and one —CH ₂ — or adjacent group on the alkyl group. 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom or carbon atom number) 1 to 12 represents an alkyl group, a fluorine atom, a chlorine atom or a cyano group.) At least ^one of R ¹ and W ¹ represents a carboxyl group. )
Furthermore, the compound (5) having a group selected from at least one hydroxyl group, mercapto group and / or amino group is preferably a compound represented by the following formula (II).

(In the formula, G ² represents the following formula (ii)

(In the formula, each A ² is independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [ 2.2.2] Octylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2 , 5-diyl group, 1,3-dioxane-2,5-diyl group or a single bond, these groups are unsubstituted or each independently halogen, cyano group, nitro group, pentafluorosulfuranyl The alkyl group may be substituted by a group or an alkyl group having 1 to 10 carbon atoms, and each of these alkyl groups may be independently substituted with one or more hydrogen atoms by fluorine atoms or chlorine atoms. The above 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) or a cyano group.) may be replaced by, ^{a 2} is in the P-Sp- (wherein, P is the same meaning as P in ^{a 1,} Sp is the same meaning as Sp in the ^{a 1} represents. However may be either the same group different group.) it may be had be substituted by a group represented by, Z ²¹ and Z ² Each independently _-O is _{-, - 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 ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═ _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CY = CY- ( wherein, Y each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group. ), —C≡C—, —CH═N—, —N═CH—, —N═N—, —CH═N—N═CH—, an alkylene group having 1 to 20 carbon atoms or a single bond. Each of the alkylene groups independently may have one or more hydrogen atoms replaced by fluorine or chlorine atoms, and one —CH ₂ — or two or more non-adjacent ones on the alkylene group. —CH ₂ — is 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-, -CY = CY- or- C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, Represents a cyano group), and m21 represents an integer of 0 to 8. R ² and W ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, or an alkyl having 1 to 20 carbon atoms. during group or P-Sp- (wherein, P is the same meaning as P in a ^1, Sp is a ¹ has the same meaning as Sp in. However there be the same group or different groups The alkyl groups each independently represent one or more hydrogen atoms replaced by fluorine or chlorine atoms, and one —CH ₂ — or adjacent group on the alkyl group. 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom or carbon atom number) Represents an alkyl group of 1 to 12, a fluorine atom, a chlorine atom or a cyano group.), But at least one of R ² and W ² is selected from a hydroxyl group, a mercapto group and / or an amino group. Represents a group. )
Furthermore, the acid halogen compound (3) is preferably a compound represented by the following formula (III-1) or formula (III-2).

(In the formula, U ¹ represents an organic group, U ² represents a hydrogen atom or an organic group, and V represents a halogen.)
The mixed acid anhydride (4) is preferably a compound represented by the following general formula (IV).

(Wherein R ³ , G ³ and W ³ each represent the same meaning as R ¹ , G ¹ and W ^{1 in} formula (I), but in formula (I) R ¹ and / or W ¹ is carboxyl When a group is represented, the corresponding R ³ and / or W ³ is represented by the following formula (IV-1) or (IV-2)

(Wherein, ^{U 1} and ^{U 2} is the formula (III-1) and formula (III-2) represent the same meaning as ^{U 1} and ^{U 2} in.) Represented by. )
The ester compound and / or amide compound (6) is preferably a compound represented by the following general formula (V-1) to general formula (V-3).

(Wherein, ^{G 1} has the same meaning as ^{G 1} in the general formula (I), ^{G 2} has the same meaning as ^{G 2} in the general formula (II), ^{Q 1} and ^{Q 2} are each independently -COO -, -OCO-, -CONH-, -NHCO-, -COS- or -SCO-, wherein R ⁴ and W ⁴ are each independently R ¹ or W ¹ in formula (I) or formula (II) ) Represents the same meaning as R ² or W ^2. ) The group represented by P is cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13) or formula (P-15) are preferred, and formula (P-1), formula (P-2), formula (P-7), formula (P P-11) or formula (P-13) is more preferred, and formula (P-1) or formula (P-2) is particularly preferred.

Sp represents one —CH ₂ — or two or more non-adjacent —CH ₂ — 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) Or a cyano group), which represents an alkylene group having 1 to 20 carbon atoms or a single bond, which may be replaced with a cyano group, but when the compound produced by the production method of the present invention is used for a liquid crystal material, a liquid crystal sex and -CH view of compatibility one with the other ingredients 2 _- or two or more nonadjacent -CH ₂ - are each independently -O -, - COO -, - OCO -, - OCO-O -, - CH = CH-COO -, - OCO-CH = CH -, - CY = CY- Or -C≡C- (wherein each Y independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), an alkylene group having 1 to 12 carbon atoms or a single bond Preferably, one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —COO— or —OCO—. 12 alkylene groups or a single bond are more preferable, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently replaced with —O—, —COO— or —OCO—. An alkylene group having 1 to 8 carbon atoms or a single bond may be particularly preferable. Arbitrariness.

Furthermore, the compounds represented by the general formula (I) and the general formula (II) are each independently A ¹ and A ² from the viewpoint of ease of synthesis and from the viewpoint of liquid crystallinity when used in a liquid crystal material. Unsubstituted or each independently a cyano group, a nitro group, each independently one or more hydrogen atoms may be replaced by a fluorine atom or a chlorine atom or / and one —CH ₂ on this alkyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO- from a good carbon atoms 1 be replaced by 10 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexeni group which may be substituted by an alkyl group of the above or a group represented by P-Sp- Ren group, 1,4-bicyclo [2.2. ] Octylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5-diyl group 1,3-dioxane-2,5-diyl group, preferably each independently unsubstituted or each independently cyano group, nitro group, each independently one or more hydrogen atoms are fluorine atoms or may be replaced by chlorine atoms and / or one -CH on the alkyl group 2 _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S-, 1,4-phenylene group, naphthalene-2,6-diyl group, which may be substituted by an alkyl group having 1 to 10 carbon atoms which may be replaced by -CO-, -COO-, -OCO-, 4-cyclohexyle More preferably is a group, each independently unsubstituted or, respectively even independently one or more hydrogen atoms are replaced by fluorine atoms may or / and one -CH ₂ on the alkyl group - Alternatively, two or more non-adjacent —CH ₂ — may be independently replaced with —O—, —S—, —CO—, —COO—, —OCO—. Particularly preferred is a 1,4-phenylene group or a naphthalene-2,6-diyl group which may be substituted by an alkyl group,
Z ¹¹ , Z ¹² , Z ²¹ and Z ²² 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 ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF ₂ CF 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 -, - CY = CY- ( wherein , Y each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.), —C≡C—, —CH═N—, — = CH -, - N = N -, - CH = N-N = CH-, be each independently one or more hydrogen atoms are replaced by fluorine atom or chlorine atom may and / or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - COO -, - OCO- the replaced be an alkylene group having 1 to 20 carbon atoms Or a single bond is preferable, and each independently represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH ₂ CH 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 -, - CY = CY -(Wherein Y is independently a hydrogen atom, an alkyl having 1 to 12 carbon atoms, -C≡C-, -CH = N-, -N = CH-, -N = N-, -CH = N-N = CH-, each independently one or more hydrogen atoms Is more preferably an alkylene group having 1 to 20 carbon atoms which may be replaced by a fluorine atom or a single bond,
m11 and m21 are each independently preferably an integer of 1 to 5, more preferably an integer of 1 to 3, particularly preferably 1 or 2.
R ¹ and W ¹ are each independently R ¹ and W ¹ both represent a carboxyl group, or ^one of R ¹ and W ¹ represents a carboxyl group, the other is a hydrogen atom, a fluorine atom, a chlorine atom , A cyano group, or each independently one or more hydrogen atoms may be replaced by a fluorine atom or a chlorine atom or / and one —CH ₂ — or two or more —CH ₂ — not adjacent to each other. Each independently can be replaced by -O-, -S-, -COO-, -OCO-, or an alkyl group having 1 to 20 carbon atoms or R ¹ and W ¹ are represented by P-Sp- In the case of a group, preferably both of R ¹ and W ¹ represent a carboxyl group, or ^one of R ¹ and W ¹ represents a carboxyl group, and the other represents a hydrogen atom, a fluorine atom, or each independently One or more hydrogen atoms It is more preferable that R ¹ and W ¹ represent a group represented by P-Sp-, or an alkyl group having 1 to 12 carbon atoms which may be replaced by a fluorine atom,
R ² and W ² each independently both hydroxyl groups of R ² and W ^2, or represent a group selected from mercapto and / or amino group, one hydroxyl group of R ² and W ^2, Represents a group selected from a mercapto group and / or an amino group, the other being a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or each independently one or more hydrogen atoms being replaced by a fluorine atom or a chlorine atom And / or one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently replaced with —O—, —S—, —COO—, —OCO—. Preferably, the alkyl group having 1 to 20 carbon atoms or R ² and W ² represents a group represented by P—Sp—, and both of R ² and W ² represent a hydroxyl group, or R ² and W ² One represents a hydroxyl group, and the other represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms may be each independently replaced by a fluorine atom, or R ² and W ² is more preferably a group represented by P-Sp-,
If both R ¹ and W ¹ represents a carboxyl group, if it represents a group only one of R ² and W ² is selected from hydroxyl group, a mercapto group and / or amino group are preferred, R ² and W ² More preferably, only one of these represents a hydroxyl group,
When both R ² and W ² represent a group selected from a hydroxyl group, a mercapto group and / or an amino group, it is preferable that only ^one of R ¹ and W ¹ represents a carboxyl group.

  More specific embodiments will be described below. For simplicity, the compound (1) having at least one carboxyl group is converted to a group selected from carboxylic acid, at least one hydroxyl group, mercapto group and / or amino group. The compound (4) having is represented as a nucleophile.

  The acid halogen compound (3) is preferably a sulfonic acid halogen compound or a carboxylic acid halogen compound, but reacts with a carboxylic acid in the presence of a base to give a carboxylic acid derivative having a detachable substituent, Furthermore, it is preferable that the carboxylic acid derivative reacts with a nucleophile so that the detachable substituent is efficiently eliminated. Examples of readily available acid halogen compounds include methanesulfonic acid chloride, toluenesulfonic acid chloride, acetyl chloride, and the like.

  The amount of the acid halogen compound (3) to be used is not particularly limited, but if it is less than 1 equivalent to the carboxylic acid, unreacted carboxylic acid remains after the reaction. Therefore, unreacted carboxylic acid must be removed by purification after the reaction. Usually, the carboxylic acid can be removed by a method such as column chromatography, recrystallization, reprecipitation, distillation, sublimation or the like. On the other hand, when the amount of the acid halogen compound is more than 1 equivalent with respect to the carboxylic acid, the acid halogen compound remains after the reaction. In that case, purification can be performed by the same method. Preferably it is 0.1-10 equivalent with respect to carboxylic acid, More preferably, it is 0.5-2 equivalent from a viewpoint of the ease of refinement | purification, More preferably, it is 0.8-1.5 equivalent.

  The base (2) is preferably an amine, amide, carbamate, imide, sulfonamide, guanidine, hydrazone, hydrazide, hydrazine, heterocyclic amine, a salt thereof, a metal alkoxide or a metal hydroxide. From the viewpoint, tertiary amines or aromatic amines and the amine salts are more preferable. Examples of easily available bases include trimethylamine, N, N-dimethylethylamine, N, N-diethylmethylamine, triethylamine, N, N-dimethylpropylamine, N, N-dimethylbutylamine, N, N-dimethylpentylamine, N , N-diethylpropylamine, N, N-dipropylethylamine, N, N-dipropylmethylamine, N, N-diethylpentylamine, N-ethyl-N-methylpentylamine, tributylamine, N, N-dibutyl Methylamine, N, N-dibutylethylamine, N, N-dibutylpropylamine, N-ethyl-N-methylpropylamine, N, N-dipropylmethylamine, N, N-dipropylethylamine, tripropylamine, tripropylamine Isopropylamine, N-methyldiisopropyla , N-ethyldiisopropylamine, N-propyldiisopropylamine, N-butyldiisopropylamine, pyridine, N-methylpyridine, 2-chloropyridine, 2-bromopyridine, piperidine, pyrimidine, quinoline, acridine, N, N-dimethyl Examples include -4-aminopyridine, picoline, bipyridine, 2,6-lutidine, pyridinium chlorochromate, pyridinium paratoluenesulfonate, and the like. Only one type of base may be used, or two or more types may be used. In the case of carrying out a production method comprising a step of reacting with an acid halogen compound without adding a carboxylic acid and a base in advance and a step of reacting a nucleophile, the base is added to the first step ( May be used only in the step of obtaining the mixed acid anhydride (4) from the compound (1) having at least one carboxyl group, the base (2) and the acid halogen compound (3), or the first step and the second step. Step (Step of obtaining ester compound and / or amide compound (6) from compound acid anhydride (4) and compound (5) having a group selected from at least one hydroxyl group, mercapto group and / or amino group) It may be used in both.

  In both the first step and the second step, the reaction temperature is usually from −50 ° C. to 150 ° C., but when a solvent is used, the reaction temperature is from −50 ° C. to the reflux temperature of the solvent. From the viewpoint of yield, −50 ° C. to 60 ° C. is preferable, and from the viewpoint of work efficiency, −10 ° C. to 40 ° C. is more preferable.

  The acid halogen compound (3) may be used as it is, dissolved in a solvent and used as a solution, suspended in a solvent and used as a suspension, but from the viewpoint of yield and reaction control, the solution or suspension It is preferable to use as.

  Carboxylic acid, base (2) and nucleophile may be used as they are, dissolved in a solvent and used as a solution, suspended in a solvent and used as a suspension. From the viewpoint, it is preferably used as a solution or suspension, and more preferably used as a solution.

The first step of adding and reacting the carboxylic acid and the base to the acid halogen compound without mixing them in advance is the following chemical formula (carboxylic acid) + k (acid halogen compound) + k (base) → (mixed acid anhydride) + k ( salt)
(Wherein, k represents the number of equivalents of acid halogen compound and base required for 1 equivalent of carboxylic acid). From the viewpoint of yield, it is preferable to add the carboxylic acid and the base simultaneously without mixing, and the dropping rate of the carboxylic acid and the base is
(Drop rate of carboxylic acid) :( Drip rate of base) = k: 1
It is more preferable that

The mixed acid anhydride (4) obtained in the first step may be isolated or may be used as it is for the second step without isolation. In the case of isolation, post-treatment and purification can be performed by a usual method. From the viewpoint of yield and work efficiency, a one-pot reaction that is directly used for the second step without isolation is preferred.
The second step of reacting the nucleophilic agent is the following chemical formula (mixed acid anhydride) + l (nucleophilic agent) + l (base) → (target product) + l (salt)
(Wherein 1 represents the number of equivalents of nucleophile and base required for 1 equivalent of mixed acid anhydride). The equivalent of the base required in the first step and the second step is (k + 1) times the carboxylic acid. When the reaction is carried out in one pot, (k + 1) equivalent base may be added in the first step, k equivalent base may be added in the first step, and 1 equivalent base may be added in the second step. In addition, the equivalent amount of the base may be a theoretically required amount, or a small excess or a large excess. From the viewpoint of yield and economy, the amount of base is preferably a small excess relative to the theoretically required amount.

  In both the first step and the second step, the reaction time is usually from several minutes to several days, although it depends on the compound, and preferably from several tens of minutes to several hours.

  The reaction solvent in both the first step and the second step is not particularly limited as long as it gives the target compound in the reaction process. Preferred reaction solvents include, for example, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane. 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethylene, 1-chlorobutane, carbon disulfide, acetone, acetonitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl Sulfoxide, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, o-di Lolobenzene, xylene, o-xylene, p-xylene, m-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl acetate, 2-methoxyethyl acetate, hexamethyl Phosphoric triamide, tris (dimethylamino) phosphine, cyclohexanone, 1,4-dioxane, styrene, tetrachloroethylene, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, 1,1,1-trichloroethane, toluene, hexane, pentane, cyclohexane , Cyclopentane, heptane, benzene, methyl isobutyl ketone, tert-butyl methyl ether, methyl ethyl ketone, methyl cyclohexanone, methyl butyl ketone, diethyl ketone, Sorin, coal tar naphtha, petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, and mineral spirits. From the viewpoint of compound solubility, chloroform, dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether, ethyl acetate , Butyl acetate, 1,4-dioxane, tetrahydrofuran, 1-methyl-2-pyrrolidinone, toluene, tert-butyl methyl ether, and methyl ethyl ketone are preferred.

  EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

Compound purity was analyzed by GC or HPLC. The analysis conditions are as follows.
(GC analysis conditions)
Column: J & W DB-1, 30 m × 0.25 mm × 0.25 μm
Temperature program: 100 ° C (1 minute)-(10 ° C / minute)-300 ° C (12 minutes)
Inlet temperature: 300 ° C
Detector temperature: 300 ° C
(HPLC analysis conditions)
Column: Inertsil ODS-3, 5 μm, 4.6 mmφ × 250 mm
Elution solvent: acetonitrile / water (90:10)
Flow rate: 0.5 mL / min
Detector: UV, 210nm
Column oven: 40 ° C
(Example 1) Production of compound represented by formula (I-1) (compound described in Patent Document 3)

To a reaction vessel equipped with a stirrer, a thermometer and two dropping funnels, 5.00 g (46 mmol) of ethyl chloroformate and 25 mL of tetrahydrofuran were added. While cooling with ice, 10 mL of a tetrahydrofuran solution of 2.77 g (46 mmol) of acetic acid and 20 mL of a tetrahydrofuran solution of 10.2 g (55 mmol) of tributylamine were separately added from a separate dropping funnel (acetic acid solution) :( tributylamine solution) = 1: It was dripped simultaneously with the dripping speed of 2. After stirring for 30 minutes under ice cooling, liquid separation treatment was performed using dichloromethane, and the solvent was distilled off to obtain 7.16 g of a compound represented by the formula (I-1). The yield was 98% and the purity was 99.97%. As a result of measuring ¹ H NMR, ¹³ C NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in Patent Document 3.
(Comparative Example 1) 5.00 g (46 mmol) of ethyl chloroformate and 25 mL of tetrahydrofuran were added to a reaction vessel equipped with a production stirrer described in Patent Document 3, a thermometer, and a dropping funnel. While cooling to −10 ° C., a solution consisting of 2.77 g (46 mmol) of acetic acid 10.2 g (55 mmol) of tributylamine and 20 mL of tetrahydrofuran was added dropwise at 0 ° C. or lower. After stirring for 30 minutes under ice cooling, liquid separation treatment was performed using dichloromethane, and the solvent was distilled off to obtain a compound represented by the formula (I-1). The yield was 92% and the purity was 99.89%.
(Example 2) Production of compound represented by formula (I-2) (compound described in Patent Document 3)

15.0 g (0.13 mol) of methanesulfonyl chloride and 30 mL of tetrahydrofuran were added to a reaction vessel equipped with a stirrer, a thermometer and two dropping devices. While cooling with ice, 200 mL of a tetrahydrofuran solution of 34.6 g (0.13 mol) of the compound represented by formula (I-2-1) and 100 mL of a tetrahydrofuran solution of 28.9 g (0.16 mol) of tributylamine were separately added. From the dropping device, (the solution of the compound represented by the formula (I-2-1)) :( tributylamine solution) = 2: 1 at the same time. After stirring for 1 hour while cooling with ice, liquid separation treatment was performed using dichloromethane, and the solvent was distilled off to obtain 43.9 g of a compound represented by the formula (I-2). The yield was 98% and the purity was 95.53%. As a result of measuring ¹ H NMR, ¹³ C NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in Patent Document 3.
(Comparative Example 2)
A compound represented by the formula (I-2) was produced by the same method as in Comparative Example 1 with the same reaction scale as in Example 2. The yield was 94% and the purity was 95.50%.
Example 3 Production of Compound Represented by Formula (I-3)

To a reaction apparatus equipped with a stirrer, a thermometer and two dropping devices, 5.00 g (43.6 mmol) of methanesulfonyl chloride and 10 mL of tetrahydrofuran were added. While cooling with ice, 60 mL of a tetrahydrofuran solution of 12.9 g (44.1 mmol) of the compound represented by formula (I-3-1) and 30 mL of a tetrahydrofuran solution of 5.25 g (51.9 mmol) of triethylamine were separately added dropwise. From the apparatus, (solution of the compound represented by the formula (I-3-1)) :( triethylamine solution) = 2: 1 at the same time. After stirring for 1 hour while cooling with ice, 2.64 g (21.6 mmol) of 4-dimethylaminopyridine and 2.69 g (19.4 mmol) of 2- (4-hydroxyphenyl) ethanol were added. While cooling with ice, 5.25 g (51.9 mmol) of triethylamine was added dropwise. After stirring for 7 hours, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 12.2 g of a compound represented by the formula (I-3). The yield was 82% and the purity was 99.63%.
¹ H NMR (CDCl ₃ ) δ 1.45-1.54 (m, 8H), 1.72 (m, 4H), 1.83 (m, 4H), 3.08 (t, 2H), 4. 03 (quin, 4H), 4.18 (quin, 4H), 4.51 (t, 2H), 5.83 (d, 2H), 6.13 (dd, 2H), 6.38 (d, 2H) ), 6.89 (d, 2H), 6.96 (d, 2H), 7.15 (d, 2H), 7.32 (d, 2H), 7.96 (d, 2H), 8.13 (D, 2H) ppm.
LRMS (EI) m / z 686 (100).
(Comparative Examples 3-6)
A compound represented by the formula (I-3) was produced by changing the method of addition of the reagent in the first step only in the same reaction scale as in Example 3 to the following method.
How to add the reagent of Comparative Example 3: A tetrahydrofuran solution of triethylamine was added dropwise to a tetrahydrofuran solution in which methanesulfonyl chloride and a compound represented by the formula (I-3-1) were mixed.
How to add the reagent of Comparative Example 4: To a tetrahydrofuran solution of triethylamine, a tetrahydrofuran solution in which methanesulfonyl chloride and a compound represented by the formula (I-3-1) were mixed was added dropwise.
How to add the reagent of Comparative Example 5: A tetrahydrofuran solution of triethylamine was dropped into a tetrahydrofuran solution of methanesulfonyl chloride, and then a tetrahydrofuran solution of a compound represented by the formula (I-3-1) was dropped.
How to add the reagent of Comparative Example 6: To a tetrahydrofuran solution of methanesulfonyl chloride, a tetrahydrofuran solution in which triethylamine and a compound represented by the formula (I-3-1) were mixed was added dropwise.
The results are shown in Table 1.

Example 4 Production of Compound Represented by Formula (I-4)

A compound of the formula (I-4) was prepared in the same manner as in Example 3 except that the compound represented by the formula (I-3-1) in Example 3 was replaced with the compound represented by the formula (I-4-1). ) Was produced. The yield was 79% and the purity was 99.55%.
¹ H NMR (DMSO-d ₆ ) δ 2.11 (m, 4H), 3.05 (t, 2H), 4.15 (t, 2H), 4.18 (t, 2H), 4.28 ( m, 4H), 4.46 (t, 2H), 5.96 (d, 2H), 6.19 (dd, 2H), 6.32 (d, 2H), 7.04 (d, 2H), 7.12 (d, 2H), 7.19 (d, 2H), 7.39 (d, 2H), 7.88 (d, 2H), 8.06 (d, 2H) ppm.
¹³ C NMR (DMSO-d ₆ ) δ 28.3, 34.2, 61.5, 65.1, 65.3, 115.9, 115.1, 121.5, 122.2, 122.4 128.7, 130.3, 131.6, 132.0, 132.0, 132.4, 136.2, 149.7, 162.8, 163.5, 164.6, 165.7, 165. 9 ppm.
LRMS (EI) m / z 602 (100).
(Comparative Example 7)
A tetrahydrofuran solution in which triethylamine and a compound represented by the formula (I-4-1) were mixed with a tetrahydrofuran solution of methanesulfonyl chloride was added in the same reaction scale as in Example 4 except for adding the reagent in the first step. It changed into the method of dripping and the compound represented by Formula (I-4) was manufactured. The yield was 76% and the purity was 99.05%.
Example 5 Production of Compound Represented by Formula (I-5)

  A reaction solution containing the compound represented by the formula (I-4-2) was prepared by the same method as in Example 4. That is, 5.00 g (43.6 mmol) of methanesulfonyl chloride and 10 mL of tetrahydrofuran were added to a reactor equipped with a stirrer, a thermometer and two dropping devices. While cooling with ice, 50 mL of a tetrahydrofuran solution of 11.0 g (44.1 mmol) of the compound represented by the formula (I-4-1) and 25 mL of a tetrahydrofuran solution of 5.25 g (51.9 mmol) of triethylamine were separately added dropwise. From the apparatus, (solution of the compound represented by the formula (I-4-1)) :( triethylamine solution) = 2: 1 at the same time.

Thereafter, the mixture was stirred for 1 hour while cooling with ice, and 0.53 g (4.3 mmol) of 4-dimethylaminopyridine and 2.68 g (21.6 mmol) of methylhydroquinone were added. While cooling with ice, 5.25 g (51.9 mmol) of triethylamine was added dropwise. After stirring for 1 hour, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 12.3 g of a compound represented by the formula (I-5). The yield was 97% and the purity was 99.73%.
¹ H NMR (CDCl ₃ ) δ 2.22 (m, 7H), 4.17 (t, 4H), 4.39 (t, 4H), 5.85 (d, 2H), 6.14 (dd, 2H), 6.43 (d, 2H), 6.99 (dd, 4H), 7.08 (dd, 1H), 7.14 (d, 1H), 7.18 (d, 1H), 8. 16 (dd, 4H) ppm.
¹³ C NMR (CDCl ₃ ) δ 16.4, 28.5, 61.6, 64.6, 114.2, 114.3, 120.0, 121.7, 121.9, 122.9, 124. 1, 128.2, 131.0, 131.7, 132.3, 147.0, 148.4, 163.0, 163.1, 164.4, 164.8, 166.1 ppm.
LRMS (EI) m / z 588 (100).
(Comparative Example 8)
A tetrahydrofuran solution in which triethylamine and a compound represented by the formula (I-4-1) were mixed with a tetrahydrofuran solution of methanesulfonyl chloride only in the same manner as in Example 5 except that the reagent was added in the first step. It changed into the method of dripping and the compound represented by Formula (1-5) was manufactured. The yield was 93% and the purity was 99.65%.
Example 6 Production of Compound Represented by Formula (I-6)

  To a reaction vessel equipped with a stirrer, a thermometer and two dropping devices, 5.00 g (43.6 mmol) of methanesulfonyl chloride and 10 mL of tetrahydrofuran were added. While cooling with ice, 50 mL of a tetrahydrofuran solution of 7.95 g (44.1 mmol) of 4-acetoxybenzoic acid and 25 mL of a tetrahydrofuran solution of 5.25 g (51.9 mmol) of triethylamine were respectively added from separate dropping devices (4-acetoxybenzoic acid). Solution) :( triethylamine solution) = 2 at the same time as the dropping speed of 2: 1. After stirring for 30 minutes while cooling with ice, 0.53 g (4.3 mmol) of 4-dimethylaminopyridine and 5.32 g (43.6 mmol) of 2,4-dimethylphenol were added. While cooling with ice, 5.25 g (51.9 mmol) of triethylamine was added dropwise. After stirring for 1 hour, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 12.0 g (42 of compound represented by formula (I-6-2)) 0.2 mmol). The yield was 97% and the purity was 99.85%.

  12.0 g (42.2 mmol) of the compound represented by the formula (I-6-2) was added to a reaction vessel equipped with a stirrer and a dropping device, and dissolved in 20 mL of toluene and 20 mL of tetrahydrofuran. 4.62 g (63.3 mmol) of butylamine was added dropwise and stirred at room temperature for 7 hours. After separation and washing with 5% hydrochloric acid and brine, purification was performed by recrystallization (methanol / water), and 10.0 g (41.3 mmol) of the compound represented by the formula (I-6-3) was obtained. Obtained.

10.0 g (41.3 mmol) of the compound represented by the formula (I-6-3) and the compound represented by the formula (I-4-1) in a reaction vessel equipped with a stirrer, a thermometer and a dropping device. 10.3 g (41.3 mmol) and 4-dimethylaminopyridine 0.50 g (4.1 mmol) were added and suspended in 50 mL of dichloromethane. While cooling with ice, 6.25 g (49.5 mmol) of N, N′-diisopropylcarbodiimide was added dropwise so that the reaction temperature did not exceed 15 ° C. After stirring at room temperature for 5 hours, the solvent was distilled off and the residue was purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 16.9 g (35.5) of the compound represented by the formula (I-6). Mmol).
¹ H NMR (CDCl ₃ ) δ 2.19-2.25 (m, 5H), 2.34 (s, 3H), 4.17 (t, 2H), 4.39 (t, 2H), 5. 85 (dd, 1H), 6.14 (dd, 1H), 6.42 (dd, 1H), 6.98 to 7.08 (m, 5H), 7.36 (d, 2H), 8.16 (D, 2H), 8.29 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 16.1, 20.8, 28.5, 61.1, 64.7, 113.1, 114.3, 121.3, 121.6, 122.0, 127. 0, 127.5, 128.2, 129.8, 131.0, 131.7, 131.8, 132.4, 135.6, 147.2, 155.2, 163.3, 164.2 164.3, 166.1 ppm.
LRMS (EI) m / z 474 (100)
(Comparative Example 9)
Only the method of adding the reagent in the first step with the same reaction scale as in Example 6 was changed to a method in which a tetrahydrofuran solution in which triethylamine and 4-acetoxybenzoic acid were mixed was dropped into a tetrahydrofuran solution of methanesulfonyl chloride. A compound represented by (I-6-2) was produced. The yield was 94% and the purity was 99.68%.

Thereafter, a compound represented by formula (I-6) was produced in the same manner as in Example 6.
(Example 7) Production of compound represented by formula (I-7) (compound described in Academic Literature 1)

  A compound represented by formula (I-7-1) was produced by the method described in Academic Literature 1.

  To a reaction vessel equipped with a stirrer, a thermometer and two dropping devices, 11.6 mL (150 mmol) of methyl chloroformate and 50 mL of dichloromethane were added. While cooling with ice, 50 mL of a tetrahydrofuran solution of 14 g (75.2 mmol) of the compound represented by the formula (I-7-1) and 25 mL of a tetrahydrofuran solution of 21 mL (150 mmol) of triethylamine were respectively added from separate dropping devices (formula (I The solution of the compound represented by -7-1)): (triethylamine solution) = 2: 1 was added dropwise at the same time. After stirring for 2 hours while cooling with ice, the solvent was distilled off. It was suspended in diethyl ether, filtered and concentrated to obtain 17.1 g (69.9 mmol) of a compound represented by the formula (I-7-2).

The compound 71 represented by the formula (I-7) was reduced by the method described in the academic literature 1 using 17.1 g (69.9 mmol) of the compound represented by the formula (I-7-2) obtained. .82 g was obtained. The yield was 65% and the purity was 99.98%. As a result of measuring ¹ H NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in Non-Patent Document 1.
¹ H NMR δ 5.86 (m, 1H), 5.46 (d, 1H), 5.28 (d, 1H), 3.29 (d, 1H), 2.44 (s, 1H), 1 .51 (s, 1H), 1.44 (s, 3H), 1.33 (s, 3H) ppm.
LRMS (EI) m / z 173, 157, 141, 83, 69.
(Comparative example 10) The manufacturing method of a nonpatent literature 1 The compound represented by Formula (I-7-1) by the method of the nonpatent literature 1 was manufactured.

In a reaction vessel equipped with a stirrer, a thermometer and a dropping device, 21 mL (150 mmol) of triethylamine and 50 mL of a dichloromethane solution of 14 g (75.2 mmol) of the compound represented by the formula (I-7-1) were cooled with ice. 11.6 mL (150 mmol) of methyl chloroformate was added dropwise. After stirring for 2 hours while cooling with ice, the solvent was distilled off. 16.4 g of a compound represented by the formula (I-7-2) was obtained by suspending in diethyl ether, filtering and concentrating. Using 16.4 g of the compound represented by the formula (I-7-2) thus obtained, the compound was reduced by the method described in Non-Patent Document 1 to obtain 7.03 g of a compound represented by the formula (I-7). . The yield was 54% and the purity was 99.34%.
(Example 8) Production of compound represented by formula (I-8) (compound described in Patent Document 2)

In the production method described in Patent Document 2, 50 mL of a tetrahydrofuran solution of 3,4-di- (6-acryloyloxyhexyloxy) benzoic acid and 50 mL of a tetrahydrofuran solution of diisopropylethylamine were respectively added from separate dropping devices (3,4-di- (6-acryloyloxyhexyloxy) benzoic acid solution): (diisopropylethylamine solution) = A compound represented by the formula (I-8) was produced by the same method except that it was dropped simultaneously at a dropping rate of 1: 1. . The yield was 46% and the purity was 99.30%. As a result of measuring the IR spectrum, ¹ H NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in Patent Document 2.
IR (KBr) 2937, 1717, 1632, 1598, 1516, 1495, 1474, 1410, 1295, 1265, 1207, 1189, 1160, 1078, 992, 812, 756 cm ⁻¹ .
¹ H NMR δ 0.95 (t, 3H), 1.50-1.91 (m, 18H), 2.63 (q, 2H), 4.08-4.21 (m, 8H), 5. 82-6.44 (m, 8H), 6.70 (d, 1H), 6.95 (d, 1H), 7.41-7.17 (m, 4H), 7.69 (d, 1H) , 7.73 (d, 1H), 7.84-8.23 (m, 4H), 8.82 (s, 1H) ppm. LRMS (EI) m / z 820 (100).
(Comparative Example 11) Process described in Patent Document 2 At 0 ° C. or lower, a tetrahydrofuran solution of 3,4-di- (6-acryloyloxyhexyloxy) benzoic acid and diisopropylethylamine was added dropwise to a tetrahydrofuran solution of methanesulfonic acid chloride. did. After completion of the dropwise addition, the mixture was stirred as it was for 30 minutes, and a mixed solution of 4-dimethylaminopyridine, diisopropylethylamine, and tetrahydrofuran in a piece of microspatula was added dropwise while maintaining at -10 ° C or lower. After stirring for 2 hours as it was, the reaction solution was washed with water, 1% hydrochloric acid and toluene were added, and after oil-water separation, the organic layer was washed twice with water. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: toluene), then reprecipitated from methanol, and the precipitate was filtered to produce a compound represented by the formula (I-8). did. The yield was 26% and the purity was 99.31%.
(Example 9) Production of compound represented by formula (I-9) (compound described in Patent Document 1)

In the production method described in Patent Document 1, 300 mL of a tetrahydrofuran solution of the compound represented by the formula (I-3-1) and 100 mL of a tetrahydrofuran solution of triethylamine are respectively supplied from different dropping devices (represented by the formula (I-3-1)). The compound represented by the formula (I-9) was produced by the same method except that the solution was added dropwise at a dropping rate of 3: 1: (triethylamine solution) = 3: 1. The yield was 82% and the purity was 99.35%. As a result of measuring ¹ H NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in Patent Document 1.
¹ H NMR (CDCl ₃ ) δ 8.70 (s, 2H), 8.49 (s, 1H), 8.18-8.11 (m, 4H), 7.93 (d, 2H), 7. 40-7.26 (m, 4H), 6.99 (d, 4H), 6.41 (d, 2H), 6.13 (dd, 2H), 5.83 (d, 2H), 4.20 -4.06 (m, 8H), 3.60 (s, 3H), 1.85-1.70 (m, 8H), 1.57-1.20 (m, 8H) ppm.
LRMS (EI) m / z 846 (100).
(Comparative Example 12)
A compound represented by the formula (I-9) was produced on the same scale as in Example 9 by the same production method as in Comparative Example 1. The yield was 72% and the purity was 99.31%.
(Example 10) Production of a compound represented by the formula (I-10) (compound described in EP 0888281B1)

  A solution of the compound represented by formula (I-3-2) was prepared in the same manner as in Example 3. That is, 5.00 g (43.6 mmol) of methanesulfonyl chloride and 10 mL of tetrahydrofuran were added to a reactor equipped with a stirrer, a thermometer and two dropping devices. While cooling with ice, 60 mL of a tetrahydrofuran solution of 12.9 g (44.1 mmol) of the compound represented by formula (I-3-1) and 30 mL of a tetrahydrofuran solution of 5.25 g (51.9 mmol) of triethylamine were separately added dropwise. From the apparatus, (solution of the compound represented by the formula (I-3-1)) :( triethylamine solution) = 2: 1 at the same time.

Then, after stirring for 1 hour while cooling with ice, 0.54 g (4.41 mmol) of 4-dimethylaminopyridine and 9.52 g (43.6 mmol) of the compound represented by the formula (I-10-1) were added. added. While cooling with ice, 5.25 g (51.9 mmol) of triethylamine was added dropwise. After stirring for 3 hours, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 19.5 g of a compound represented by the formula (I-10). The yield was 91% and the purity was 99.43%. As a result of measuring ¹ H NMR, ¹³ C NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in JP 2000-507932 A.
¹ H NMR (CDCl ₃ ) δ 0.91 (t, 3H), 1.09 (m, 2H), 1.19-1.54 (m, 12H), 1.73 (quin, 2H), 1. 86 (m, 6H), 2.49 (t, 1H), 4.05 (t, 2H), 4.18 (t, 2H), 5.82 (d, 1H), 6.12 (dd, 1H) ), 6.40 (d, 1H), 6.95 (d, 2H), 7.10 (d, 2H), 7.24 (d, 2H), 8.13 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 14.4, 20.0, 25.7, 25.7, 28.5, 29.0, 33.5, 34.4, 37.0, 39.7, 44. 1, 64.4, 68.0, 114.2, 121.3, 121.8, 127.7, 128.5, 130.5, 132.2, 145.2, 148.9, 163.3 165.1, 166.3 ppm.
LRMS (EI) m / z 492 (100).
(Comparative Example 13)
It is represented by the formula (I-10) by the same method as in Example 10, except that a tetrahydrofuran solution in which the compound represented by the formula (I-3-1) and triethylamine are mixed is dropped on the same scale as in Example 10. The resulting compound was prepared. The yield was 87% and the purity was 99.41%.
(Comparative Example 14) Production method described in EP0888281B1 A compound represented by the formula (I-10) was produced by the method described in EP0888281B1 on the same scale as in Example 10. The yield was 70% and the purity was 99.01%.
(Example 11) Production of compound represented by formula (I-11) (compound described in EP 1786888B1)

In Example 10, the compound represented by formula (I-11-1) was represented by formula (I-11) by the same method as in Example 10 except that the compound represented by formula (I-10-1) was replaced by formula (I-11-1). A compound was prepared. The yield was 87% and the purity was 99.41%. As a result of measuring ¹ H NMR, ¹³ C NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in EP178688B1.
¹ H NMR (CDCl ₃ ) δ 1.51 (m, 4H), 1.73 (quin, 2H), 1.85 (quin, 2H), 3.84 (s, 3H), 4.06 (t, 2H), 4.19 (t, 2H), 5.82 (d, 1H), 6.12 (dd, 1H), 6.40 (d, 1H), 6.89 (d, 2H), 6. 98 (d, 2H), 7.25 (d, 1H), 7.43 (m, 3H), 7.62 (d, 1H), 8.17 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 25.7, 25.7, 28.5, 28.9, 55.3, 64.4, 68.1, 86.2, 90.5, 114.0, 114. 4, 114.7, 120.7, 122.6, 123.9, 127.1, 128.5, 130.5, 130.7, 132.5, 132.9, 133.1, 147.0, 159.9, 163.7, 163.8, 166.3 ppm.
LRMS (EI) m / z 532 (100).
(Comparative Example 15)
It is represented by the formula (I-11) by the same method as in Example 11 except that a tetrahydrofuran solution in which the compound represented by the formula (I-3-1) and triethylamine are mixed is dropped on the same scale as in the example 11. The resulting compound was prepared. The yield was 85% and the purity was 99.40%.
(Comparative Example 16) Production method described in EP178688B1 A compound represented by the formula (I-11) was produced by the method described in EP178688B1 on the same scale as in Example 11. The yield was 65% and the purity was 98.60%.
(Example 12) Production of compound represented by formula (I-12) (compound described in WO2009-060843)

To a reaction vessel equipped with a stirrer, a thermometer, and two dropping devices, 5.00 g (43.6 mmol) of methanesulfonyl chloride and 10 mL of dichloromethane were added. While cooling with ice, 20 mL of a tetrahydrofuran solution of 5.72 g (43.6 mmol) of the compound represented by the formula (I-12-1) and 20 mL of a tetrahydrofuran solution of 5.29 g (52.3 mmol) of triethylamine were separately added dropwise. The solution was dropped simultaneously at a dropping rate of (solution of compound represented by formula (I-12-1)) :( triethylamine solution) = 1: 1 from the apparatus. After stirring for 30 minutes while cooling with ice, 0.53 g (4.3 mmol) of 4-dimethylaminopyridine and 8.43 g (43.6 mmol) of the compound represented by the formula (I-12-2) were added. . While cooling with ice, 5.29 g (52.3 mmol) of triethylamine was added dropwise. After stirring for 1 hour, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) to obtain 11.2 g (42.2 mmol) of the compound represented by formula (I-12). The yield was 84% and the purity was 99.93%. As a result of measuring ¹ H NMR, ¹³ C NMR and mass spectrum of the obtained compound, it was consistent with the measurement data of the compound obtained by the method described in WO2009-060843.
(Comparative Example 17)
It is represented by the formula (I-12) by the same method as in Example 12, except that a tetrahydrofuran solution in which the compound represented by the formula (I-12-1) and triethylamine are mixed is dropped on the same scale as in Example 12. The resulting compound was prepared. The yield was 82% and the purity was 99.90%.
(Example 13) Production of compound represented by formula (I-13) (compound described in Journal of the American Chemical Society, vol. 131, p. 3812-3813 (2009))

To a reaction vessel equipped with a stirrer, a thermometer and two dropping devices, 7.50 g (65.5 mmol) of methanesulfonyl chloride and 10 mL of dichloromethane were added. While cooling with ice, 120 mL of a solution of 37.5 g (66.2 mmol) of the compound represented by the formula (I-13-1) and 60 mL of a dichloromethane solution of 7.29 g (72.1 mmol) of triethylamine were separately added dropwise. From the apparatus, (solution of the compound represented by the formula (I-13-1)) :( triethylamine solution) = 2: 1 at the same time. After stirring for 30 minutes while cooling with ice, 0.80 g (6.6 mmol) of 4-dimethylaminopyridine and 7.50 g (62.9 mmol) of the compound represented by the formula (I-13-2) were added. . While cooling with ice, 7.29 g (72.1 mmol) of triethylamine was added dropwise. After stirring for 1 hour, the solvent was distilled off and the residue was purified by column chromatography (silica gel) to obtain 36.9 g of a compound represented by the formula (I-13). The yield was 88% and the purity was 99.91%. As a result of measuring ¹ H NMR, ¹³ C NMR and mass spectrum of the obtained compound, Journal of the American Chemical Society, vol. 131, p. This coincided with the measurement data of the compound obtained by the method described in 3812-3813 (2009).
¹ H NMR (C ₆ D ₆ ) δ 7.82 (s, 1H), 7.15 (s, 1H), 6.90 (s, 1H), 6.78 (1H), 6.69 (dd, 1H), 5.82 (d, 1H), 5.65 (dd, 1H), 4.22 (m, 4H), 4.16 (d, 1H), 3.24 (m, 1H), 3. 14 (m, 1H), 3.12 (s, 3H), 3.02 (s, 2H), 2.80 (m, 1H), 2.66 (m, 1H), 1.49 (s, 3H) ), 1.47 (s, 3H), 0.94 (m, 4H), -0.07 (s, 9H), -0.11 (s, 9H) ppm.
¹³ C NMR (C ₆ D ₆ ) δ 201.1, 169.3, 154.1, 153.7, 152.6, 141.7, 140.5, 139.8, 130.5, 126.7, 126.2, 116.5, 116.0, 110.1, 88.2, 67.0, 63.3, 57.7, 46.2, 39.7, 27.6, 22.7, 18. 0, 17.6, 16.4, -1.6, -1.7 ppm.
LRMS (EI) m / z 666 (100).
(Comparative Example 18)
It is represented by the formula (I-13) by the same method as in Example 13 except that a dichloromethane solution in which the compound represented by the formula (I-13-1) and triethylamine are mixed is dropped on the same scale as in Example 13. The resulting compound was prepared. The yield was 85% and the purity was 99.88%.
Example 14 Production of Compound Represented by Formula (I-14)

  In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 100 g (0.53 mol) of 6-hydroxy-2-naphthoic acid (a compound represented by the formula (I-14-1)), 300 mL of acetic acid, acetic anhydride 65.1 g (0.64 mol) and 5 g of sulfuric acid were added, heated to 60 ° C. and reacted for 8 hours. After adding 1 L of water to the reaction solution and stirring for 1 hour while cooling with ice, the precipitated solid was filtered. The obtained solid was dispersed and washed twice with 1 L of water. The solid was dried to obtain 118.7 g of a compound represented by the formula (I-14-2).

  To a reaction vessel equipped with a stirrer, a thermometer and two dropping devices, 5.00 g (43.6 mmol) of methanesulfonyl chloride and 10 mL of tetrahydrofuran were added. While cooling with ice, 50 mL of a tetrahydrofuran solution of 10.2 g (44.1 mmol) of the compound represented by the formula (I-14-2) and 25 mL of a tetrahydrofuran solution of 5.25 g (51.9 mmol) of triethylamine were separately added dropwise. From the apparatus, (4-acetoxybenzoic acid solution) :( triethylamine solution) was simultaneously added dropwise at a dropping rate of 2: 1. After stirring for 30 minutes while cooling with ice, 0.53 g (4.3 mmol) of 4-dimethylaminopyridine and 5.32 g (43.6 mmol) of 2,4-dimethylphenol were added. While cooling with ice, 5.25 g (51.9 mmol) of triethylamine was added dropwise. After stirring for 1 hour, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 14.1 g (42) of the compound represented by the formula (I-14-4) 0.2 mmol). The yield was 97% and the purity was 99.57%.

  14.1 g (42.2 mmol) of the compound represented by the formula (I-14-4) was added to a reaction vessel equipped with a stirrer and a dropping device, and dissolved in 30 mL of toluene and 30 mL of tetrahydrofuran. 4.62 g (63.3 mmol) of butylamine was added dropwise and stirred at room temperature for 7 hours. After separation and washing with 5% hydrochloric acid and brine, purification was performed by recrystallization (methanol / water) to obtain 12.1 g (41.3 mmol) of the compound represented by the formula (I-14-5). Obtained.

To a reaction vessel equipped with a stirrer, a thermometer, and two dropping devices, 4.73 g (41.3 mmol) of methanesulfonyl chloride and 10 mL of tetrahydrofuran were added. While cooling with ice, 50 mL of a tetrahydrofuran solution of 10.3 g (41.3 mmol) of the compound represented by the formula (I-14-6) and 25 mL of a tetrahydrofuran solution of 5.25 g (51.9 mmol) of triethylamine were separately added dropwise. From the apparatus, (4-acetoxybenzoic acid solution) :( triethylamine solution) was simultaneously added dropwise at a dropping rate of 2: 1. After stirring for 30 minutes while cooling with ice, 0.53 g (4.3 mmol) of 4-dimethylaminopyridine and 12.1 g (41.3 mmol) of the compound represented by the formula (I-14-5) were added. . While cooling with ice, 5.25 g (51.9 mmol) of triethylamine was added dropwise. After stirring for 1 hour, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 20.8 g (39.6) of the compound represented by the formula (I-14). Mmol). The yield was 96% and the purity was 99.68%.
¹ H NMR (CDCl ₃ ) δ 2.20 to 2.26 (m, 5H), 2.35 (s, 3H), 4.18 (t, 2H), 4.40 (t, 2H), 5. 85 (dd, 1H), 6.14 (dd, 1H), 6.43 (dd, 1H), 7.01 (d, 2H), 7.07 (s, 2H), 7.11 (s, 1H ), 7.46 (dd, 1H), 7.77 (d, 1H), 7.93 (d, 1H), 8.06 (d, 1H), 8.20 (d, 2H), 8.24 (Dd, 1H), 8.82 (d, 1H) ppm.
¹³ C NMR (CDCl ₃ ) δ 16.2, 20.8, 28.5, 61.1, 64.7, 114.3, 118.8, 121.6, 121.6, 122.5, 126. 2, 126.6, 127.5, 128.1, 128.2, 129.8, 130.4, 131.0, 131.6, 131.8, 132.4, 135.7, 136.4. 147.3, 150.8, 163.2, 164.7, 165.0, 166.1 ppm.
LRMS (EI) m / z 524 (100).
(Comparative Example 19)
Only in the step of obtaining the compound represented by formula (I-14-4) on the same reaction scale as in Example 14 and the step of obtaining the compound represented by formula (I-14), the addition of the reagent The method was changed to a method in which a tetrahydrofuran solution in which triethylamine and carboxylic acid were mixed was added dropwise to a tetrahydrofuran solution of sulfonyl chloride, to produce a compound represented by the formula (I-14). The compound obtained in each step had a yield of 95%, a purity of 98.57%, and a yield of 92% and a purity of 99.37%.
Example 15 Production of Compound Represented by Formula (I-14)

  A solution of the compound represented by formula (I-3-2) was prepared in the same manner as in Example 3. That is, 5.00 g (43.6 mmol) of methanesulfonyl chloride and 10 mL of tetrahydrofuran were added to a reactor equipped with a stirrer, a thermometer and two dropping devices. While cooling with ice, 60 mL of a tetrahydrofuran solution of 12.9 g (44.1 mmol) of the compound represented by formula (I-3-1) and 30 mL of a tetrahydrofuran solution of 5.25 g (51.9 mmol) of triethylamine were separately added dropwise. From the apparatus, (solution of the compound represented by the formula (I-3-1)) :( triethylamine solution) = 2: 1 at the same time.

Then, after stirring for 1 hour while cooling with ice, 0.54 g (4.41 mmol) of 4-dimethylaminopyridine and 10.6 g (43.6 mmol) of the compound represented by the formula (I-6-3) were added. added. While cooling with ice, 5.25 g (51.9 mmol) of triethylamine was added dropwise. After stirring for 3 hours, the solvent was distilled off, and dichloromethane and 5% hydrochloric acid were added for liquid separation. The organic layer was washed with brine and neutralized, and then purified by column chromatography (silica gel) and reprecipitation (dichloromethane / methanol) to obtain 21.6 g of a compound represented by the formula (I-15). The yield was 96% and the purity was 99.55%.
¹ H NMR (CDCl ₃ ) δ 1.45 to 1.57 (m, 4H), 1.73 (quin, 2H), 1.85 (quin, 2H), 2.19 (s, 3H), 2. 34 (s, 3H), 4.06 (t, 2H), 4.18 (t, 2H), 5.82 (dd, 1H), 6.12 (dd, 1H), 6.41 (dd, 1H) ), 6.97 to 7.08 (m, 5H), 7.36 (d, 2H), 8.15 (d, 2H), 8.29 (d, 2H) ppm.
¹³ C NMR (CDCl ₃ ) δ 16.1, 20.8, 25.6, 25.7, 28.5, 28.9, 64.4, 68.1, 114.3, 121.0, 121. 6,122.0,126.9,127.2,127.5,128.5,129.8,130.5,131.7,131.8,132.4,135.6,147.2 155.2, 163.7, 164.3, 164.3, 166.3 ppm.
LRMS (EI) m / z 516 (100).
(Comparative Example 20)
It is represented by formula (I-15) by the same method as in Example 15 except that a tetrahydrofuran solution in which a compound represented by formula (I-3-1) and triethylamine are mixed is added dropwise on the same scale as in Example 15. The resulting compound was prepared. The yield was 88% and the purity was 99.43%.
(Examples 16 to 25 and Comparative Examples 21 to 33) Evaluation of Films A matrix composition (M) comprising the following compound (A): 30%, compound (B): 40% and compound (C): 30% was prepared. did.

Maternal composition (M) 67.9%, formula (I-3), formula (I-4), formula (I-5), formula (I-6) produced by the production method of the present invention and known production methods ), Formula (I-8), Formula (I-9), Formula (I-10) and Formula (I-11), respectively, 29.1% of the compound and photopolymerization initiator Irgacure 907 (Ciba Specialty) A polymerizable composition (N) containing 3% of tea chemical was prepared. A cyclopentanone solution of the polymerizable composition (N) (concentration of the polymerizable composition (N) of 25%) was applied to glass with a rubbed polyimide by spin coating, and dried at 65 ° C. for 3 minutes. The obtained coating film was placed on a hot plate at 60 ° C. and irradiated with ultraviolet rays at an intensity of 20 mW / cm ² for 60 seconds. The appearance and yellow index (YI) of the obtained polymer were evaluated. If there was no unevenness or the like on the polymer by visual observation, it was marked as ◎, when unevenness was found slightly, Δ, and when much unevenness was observed as x. As for the yellow index, the absorption spectrum of the polymer was measured with JASCO UV / VIS Spectrophotometer V-560, and the yellowness (YI) was calculated with the attached color diagnostic program. YI is
YI = 100 (1.28X-1.06Z) / Y (JIS K7373)
Calculated from

  Thereafter, the obtained polymer was post-baked at 200 ° C. for 60 minutes. Similarly, YI after post-baking was calculated from the above formula.

  In addition, about the compound (I-9), since the compound itself is yellow, the measurement of YI was not performed. In addition, compound (I-3) whose production was examined in Comparative Example 5 was not evaluated because the reaction yield was low and isolation was difficult. The results are shown in the table below.

  As described above, the production method of the present invention was able to obtain the target compound in high yield. Moreover, it has also confirmed that the impurity content produced at the time of manufacture was small. When the impurity content is increased, unevenness occurs when the polymer is used, and YI deteriorates. The polymer produced using the polymerizable liquid crystal composition containing the compound obtained by the production method of the present application has no unevenness, and the yellow index after polymerization and after post-baking is sufficiently low, that is, almost no discoloration occurs. I understood. For this reason, the compound manufactured by the manufacturing method of this invention is especially useful for the use of a film.

Claims (11)

  A method for producing a mixed acid anhydride (4), wherein the compound (1) having at least one carboxyl group and the base (2) are added and reacted simultaneously with the acid halogen compound (3) without being mixed in advance.   The compound (1) having at least one carboxyl group and the base (2) are added to the acid halogen compound (3) at the same time without mixing in advance and reacted to form a mixed acid anhydride (4). A method for producing an ester compound and / or an amide compound (6), wherein a compound (5) having a group selected from two hydroxyl groups, mercapto groups and / or amino groups is further reacted.   The production method according to claim 1 or 2, wherein the compound (1) having at least one carboxyl group is an aromatic carboxylic acid or an aliphatic carboxylic acid.   The compound (5) having a group selected from at least one hydroxyl group, mercapto group and / or amino group is an alcohol, a phenol, a thiol, a thiophenol, an aromatic amine and / or an aliphatic amine. The manufacturing method of any one of Claims 1-3 characterized by these.   The production method according to any one of claims 1 to 4, wherein the acid halogen compound (3) is a sulfonic acid halogen compound, a carboxylic acid halogen compound, or a halogen formate compound.   The base (2) is an amine, amide, carbamate, imide, sulfonamide, guanidine, hydrazone, hydrazide, hydrazine, heterocyclic amine, salt thereof, metal alkoxide or metal hydroxide. The manufacturing method of any one of -5. Compound (1) having at least one carboxyl group is represented by the following general formula (I)

(In the formula, G ¹ represents the following formula (i)

(In the formula, each A ¹ is independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [ 2.2.2] Octylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2 , 5-diyl group, 1,3-dioxane-2,5-diyl group or a single bond, these groups are unsubstituted or each independently halogen, cyano group, nitro group, pentafluorosulfuranyl The alkyl group may be substituted by a group or an alkyl group having 1 to 10 carbon atoms, and each of these alkyl groups may be independently substituted with one or more hydrogen atoms by fluorine atoms or chlorine atoms. The above 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) Or A ¹ represents a group represented by P-Sp- (wherein P represents the following formula (P-1) to formula (P-17)).

And Sp represents one —CH ₂ — or two or more non-adjacent —CH ₂ — 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-, -CY = CY- or -C≡C- (wherein Y is independently a hydrogen atom, an alkyl having 1 to 12 carbon atoms) Represents a group, a fluorine atom, a chlorine atom or a cyano group.) Represents an alkylene group having 1 to 20 carbon atoms which may be substituted, or a single bond. Z ¹¹ and Z ¹² 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 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 - _{COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -C _{O -, - CH 2 -OCO -} , - CY = CY- ( wherein, Y each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group.) , —C≡C—, —CH═N—, —N═CH—, —N═N—, —CH═N—N═CH—, an alkylene group having 1 to 20 carbon atoms or a single bond. In this alkylene group, one or more hydrogen atoms may each independently be replaced by a fluorine atom or a chlorine atom, and one —CH ₂ — or two or more — CH ₂ — is 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) Or represents a cyano group.), And m11 represents an integer of 0 to 8. R ¹ and W ¹ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, or an alkyl having 1 to 20 carbon atoms. during group or P-Sp- (wherein, P is the same meaning as P in a ^1, Sp is a ¹ has the same meaning as Sp in. However there be the same group or different groups The alkyl groups each independently represent one or more hydrogen atoms replaced by fluorine or chlorine atoms, and one —CH ₂ — or adjacent group on the alkyl group. 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom or carbon atom number) 1 to 12 represents an alkyl group, a fluorine atom, a chlorine atom or a cyano group.) At least ^one of R ¹ and W ¹ represents a carboxyl group. The manufacturing method of any one of Claims 1-6 which are the compounds represented by this. The compound (5) having a group selected from at least one hydroxyl group, mercapto group and / or amino group is represented by the following general formula (II):

(In the formula, G ² represents the following formula (ii)

(In the formula, each A ² is independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [ 2.2.2] Octylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2 , 5-diyl group, 1,3-dioxane-2,5-diyl group or a single bond, these groups are unsubstituted or each independently halogen, cyano group, nitro group, pentafluorosulfuranyl The alkyl group may be substituted by a group or an alkyl group having 1 to 10 carbon atoms, and each of these alkyl groups may be independently substituted with one or more hydrogen atoms by fluorine atoms or chlorine atoms. The above 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) or a cyano group.) may be replaced by, ^{a 2} is in the P-Sp- (wherein, P is the same meaning as P in ^{a 1,} Sp is the same meaning as Sp in the ^{a 1} represents. However may be either the same group different group.) it may be had be substituted by a group represented by, Z ²¹ and Z ² Each independently _-O is _{-, - 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 ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═ _{CH -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- _{CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CY = CY- ( wherein, Y each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group. ), —C≡C—, —CH═N—, —N═CH—, —N═N—, —CH═N—N═CH—, an alkylene group having 1 to 20 carbon atoms or a single bond. Each of the alkylene groups independently may have one or more hydrogen atoms replaced by fluorine or chlorine atoms, and one —CH ₂ — or two or more non-adjacent ones on the alkylene group. —CH ₂ — is 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-, -CY = CY- or- C≡C— (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, Represents a cyano group), and m21 represents an integer of 0 to 8. R ² and W ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, or an alkyl having 1 to 20 carbon atoms. during group or P-Sp- (wherein, P is the same meaning as P in a ^1, Sp is a ¹ has the same meaning as Sp in. However there be the same group or different groups The alkyl groups each independently represent one or more hydrogen atoms replaced by fluorine or chlorine atoms, and one —CH ₂ — or adjacent group on the alkyl group. 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—, —CY═CY— or —C≡C— (wherein Y is independently a hydrogen atom or carbon atom number) Represents an alkyl group of 1 to 12, a fluorine atom, a chlorine atom or a cyano group.), But at least one of R ² and W ² is selected from a hydroxyl group, a mercapto group and / or an amino group. Represents a group. The production method according to claim 1, wherein the compound is represented by the formula:   Pharmaceuticals, agricultural chemicals, liquid crystal materials, polymers, resins, pigments, dyes, cosmetics, foods, inks, pressure-sensitive adhesives, adhesives, printed matter containing the compound produced by the production method according to any one of claims 1 to 8. , Optical anisotropic bodies, display elements or electronic devices.   The compound manufactured by using the compound manufactured by the manufacturing method in any one of Claims 1-8 as an intermediate body.   Pharmaceuticals, agricultural chemicals, liquid crystal materials, polymers, resins, pigments, dyes, cosmetics, foods, inks, adhesives, adhesives, printed materials, optical anisotropic bodies, display elements or electronic devices containing the compound according to claim 10.