JP5740928B2 - Method for producing carboxylic acid and intermediate carboxylic acid allyl ester - Google Patents

Description

  The present invention provides a method for producing an aromatic / alkyl carboxylic acid having a (meth) acryloyloxy group, which is a useful intermediate of a polymerizable liquid crystal compound, and a (meth) acryloyloxy group which is an intermediate in the production method. Aromatic / alkylcarboxylic acid allyl esters having the formula:

  Polymerizable liquid crystal compositions have been used as materials for optical compensation films used for the purpose of, for example, widening the viewing angle of TFT (Thin Film Transistor) liquid crystal displays (TFT-LCDs). General formula (V) as an important intermediate of the polymerizable compound used in the polymerizable liquid crystal composition

(Wherein, ^{A 2} of the general formula ^(A 2 -1) ~ formula ^(A 2 -4)

(In the formula, the phenylene group and the naphthyl group may be substituted by one or more fluorine atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and Z ² is a hydrogen atom. Or general formula (Z ² -1)

(Wherein R ¹ and L ² represent the same meaning as R ¹ and L ² in formula (III), and Y ¹ independently represents a single bond, —O— or —OCO—). Represents a substituent. The substituent represented by this is represented. L ¹ represents a single bond, —CH ₂ — or —C ₂ H ₄ —. Aromatic / alkyl carboxylic acids represented by:

  It was very difficult to produce an aromatic / alkyl carboxylic acid having a (meth) acryloyloxy group in high yield and high purity.

  Several methods for producing aromatic / alkyl carboxylic acids having a (meth) acryloyloxy group have been known so far (Patent Documents 1 to 5, Non-Patent Documents 1 to 3). These techniques include the steps of reacting mono / polyhydroxybenzoic acid or the corresponding methyl / ethyl ester with ω-halogenoalkyl-1-alcohol, pretreatment step to obtain mono / polyω-hydroxybenzoic acid, the desired compound A condensation step of benzoic acid and acrylic acid or acrylic acid chloride obtained to obtain This process has several drawbacks. For example, when ω-halogenoalkyl-1-ol such as 2-halogenoethane-1-ol or 4-halogenotan-1-ol is used, the yield is low. For example, when acrylic acid is used, it takes a long time to complete the condensation reaction, but an oligomer is formed at that time. Furthermore, when acrylic acid chloride is used, the addition reaction of hydrogen chloride proceeds as a side reaction.

(In the formula, R ¹¹ independently represents a hydrogen atom, an ethyl group or a methyl group, Z ¹¹ represents a hydrogen atom or HO— independently of each other, but at least one Z ¹¹ represents HO—, and Z ²¹ Independently represent a hydrogen atom, HO (CH ₂ ) _n —, n represents a natural number of 1 to 12, and Z ³¹ independently represents a hydrogen atom or a general formula (Z ³¹ -1)

(In the formula, R ²¹ represents a hydrogen atom or a methyl group, and L ²¹ represents an alkylene group having 1 to 12 carbon atoms.)
As another method, there is disclosed a method for producing a target product by oxidation of a benzaldehyde derivative having a (meth) acryloyloxy group using hydroxybenzaldehyde as a starting material (Patent Documents 4, 6, 7 and 8).

(In the formula, R ³¹ represents a hydrogen atom or a methyl group, and L ³¹ represents a methylene group having 1 to 12 carbon atoms.)
In the oxidation step, Jones reagent, potassium permanganate, peracid, permanganate, chromic acid, bromine, silver oxide, sodium chlorite in phosphate buffer, and the like are used. However, Jones reagent and chromate are expensive and their use is not preferred. Moreover, potassium permanganate, bromine, etc. may oxidize the double bond of a (meth) acryl group. Furthermore, there is a problem that raw materials indispensable for producing a compound having a tri (meth) acryloyloxy group contained in the compound represented by the general formula (V) cannot be obtained.

JP-A-7-306317 JP 2004-323729 A JP 2004-277488 A US 5087672 US 2002-0036285 JP 59-70643 A WO00 / 05198 Publication EP1174411

Macromolecule. Chem. 179 (1978) p273. Macromolecule. Chem. , 183 (1982) p2311. Liquid Crystals (2004) 31 (2) p185-199

  The problem to be solved by the present invention is to provide a method for producing an aromatic / alkyl carboxylic acid having a (meth) acryloyloxy group, which is a useful intermediate of a polymerizable liquid crystal compound, and also to provide an intermediate in the production method. It is to provide an aromatic / alkylcarboxylic acid allyl ester having a certain (meth) acryloyloxy group.

  As a result of various studies, the inventors of the present application have found that a compound having a specific structure can solve the above-mentioned problems, and at the same time, completed a method for producing the compound.

The manufacturing method of carboxylic acid represented by general formula (V) including the process of following (1)-(3) and the compound represented by intermediate general formula (IV) are provided.
(1) General formula (I)

(In the formula, L ¹ represents a single bond, —CH ₂ — or —C ₂ H ₄ —, and A ¹ is represented by General Formula (A ¹ -1) to General Formula (A ¹ -4)). Represents a substituent,

(In the formula, the phenylene group and the naphthyl group may be substituted by one or more fluorine atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and Z ¹ is independently selected. Represents a hydrogen atom, a hydroxyl group or HOCO-, at least one of which represents a hydroxyl group or HOCO-). The compound represented by formula (II) is esterified with allyl alcohol or allyl halide.

(Wherein, A ¹ and L ¹ represent the same meaning as A ¹ and L ¹ in formula (I)).
(2) Compound represented by general formula (II) and general formula (III)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, L ² represents — (CH ₂ ) n —, n represents 0 to 12, and X represents a chlorine atom when n represents 1 to 12). Represents a bromine atom, an iodine atom, a hydroxyl group, a hydrogen atom, an alkanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group, and when n represents 0, X represents an alkanesulfonyl group, a p-toluenesulfonyl group or A trifluoromethanesulfonyl group) is reacted, and the hydroxyl group and HOCO- in Z ¹ are esterified to give a general formula (IV)

(Wherein, ^{L 1} represents the same meaning as ^{L 1} in the general formula (I), ^{A 2} of the general formula ^(A 2 -1) ~ formula ^(A 2 -4)

(In the formula, the phenylene group and the naphthyl group may be substituted by one or more fluorine atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and Z ² is a hydrogen atom. Or general formula (Z ² -1)

(Wherein R ¹ and L ² represent the same meaning as R ¹ and L ² in formula (III), and Y ¹ independently represents a single bond, —O— or —OCO—). Represents a substituent. The substituent represented by this is represented. ).
(3) Deprotecting the carboxylic acid ester compound represented by the general formula (IV) with a palladium catalyst in the presence of a base, the general formula (V)

(Wherein A ² and L ¹ represent the same meaning as A ² and L ¹ in formula (IV)).

  The production method of the present invention makes it possible to produce an aromatic / alkylcarboxylic acid having a (meth) acryloyloxy group, which is a useful intermediate of a polymerizable liquid crystal compound, in high yield and high purity. Further, it is possible to provide an aromatic / alkylcarboxylic acid allyl ester having a (meth) acryloyloxy group which is an important intermediate. As a result, a polymerizable liquid crystal compound having a plurality of ester bonds in the molecule, which has been difficult to produce, can be easily produced.

  The compound represented by the general formula (II) can be obtained by esterification of the compound represented by the general formula (I) with allyl alcohol or allyl halide.

  In the esterification, it is preferable to heat and reflux the compound represented by the general formula (I) in the presence of Lewis acid such as concentrated sulfuric acid or p-toluenesulfonic acid or Bronsted acid.

  The compound represented by the general formula (II) can also be obtained by reacting the compound represented by the general formula (I) with allyl halide in the presence of a base.

  In this reaction, the solvent is preferably acetone, acetonitrile, benzene, toluene, xylene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, or N-methylpyrrolidone, and N, N-dimethylformamide, N, N- More preferred are dimethylacetamide and N-methylpyrrolidone.

  As the allyl halide, allyl chloride, allyl bromide and allyl iodide are preferable, and allyl chloride is more preferable.

  As the base, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium carbonate and calcium carbonate, and organic bases such as pyridine, pyrimidine, triethylamine and diethylamine are preferable. Sodium, sodium bicarbonate, potassium carbonate, potassium bicarbonate and pyridine are preferred.

  The reaction temperature is preferably less than the boiling point of the solvent and allyl halide used at atmospheric pressure. For example, when reacting with allyl chloride in a N, N-formamide solvent, the temperature is preferably 30 ° C to 140 ° C, more preferably 50 ° C to 80 ° C.

  In the compound represented by the general formula (III), X represents a leaving group, and can be obtained by esterification with ω-halogenoalkyl-1-alcohol in the presence of an acid.

  In this esterification, benzene, toluene, xylene, pentane, hexane, cyclohexane, heptane or octane can be used as an organic solvent alone or as a mixed solvent.

  The reaction temperature can be carried out below the boiling point or azeotropic temperature of the organic solvent used. For example, in the case of a mixed solvent of cyclohexane and toluene, it is preferably 70 to 150 ° C, more preferably 80 to 120 ° C.

  As the acid, Lewis acid and Bronsted acid can be used, and concentrated sulfuric acid or p-toluenesulfonic acid is preferable.

  The compound represented by the general formula (IV) can be obtained by etherifying the compound represented by the general formula (II) and the compound represented by the general formula (III) in the presence of a base.

  In this reaction, acetone, acetonitrile, tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are preferable as the organic solvent, and N, N-dimethylformamide, N , N-dimethylacetamide and N-methylpyrrolidone are more preferred.

  As the base, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium carbonate and calcium carbonate, and organic bases such as pyridine, pyrimidine, triethylamine and diethylamine are particularly preferable. Sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and pyridine are preferred.

  The reaction temperature is preferably from room temperature to 180 ° C, more preferably from 70 to 140 ° C.

  The compound represented by the general formula (V) can be obtained by removing the allyl group of the compound represented by the general formula (IV) using a palladium catalyst in the presence of a base.

  As the organic solvent to be used, tetrahydrofuran, acetonitrile, benzene, toluene, xylene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, ethyl acetate, methanol or ethanol are preferable. They may be used or mixed.

  As the base to be used, allyloxyaniline, 4-bromo-N-methylaniline, 2-fluoro-N-methylaniline, 4-fluoro-N-methylaniline, 4-methoxy-N-methylaniline, 2-methyl- N-methylaniline, N-methylaniline, N-ethylaniline, N-butylaniline, aniline, diphenylamine, diethylamine, triethylamine and the like can be mentioned, preferably 2-methyl-N-methylaniline, N-methylaniline, N-ethylaniline, N-butylaniline and diphenylamine, which may be used alone or in combination.

  Palladium complexes used as catalysts include tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis [(diphenylphosphino) ethane] palladium, dichlorobis [(diphenylphosphino) propane] palladium, dichlorobis [( Diphenylphosphino) butane] palladium, dichlorobis [(diphenylphosphino) ferrocene] palladium, palladium acetate or palladium chloride are preferred, and these may be used alone or in combination, and trialkylphosphine or tria as a ligand. Reel phosphine may be included, and tetrakis (triphenylphosphine) palladium or palladium acetate having triphenylphosphine as a ligand is particularly preferable.

  As a catalyst amount to be used, it is preferable that it is 1-10 mol% with respect to the compound represented by general formula (IV).

  The amount of the base used is preferably 0.8 to 3 mol with respect to 1 mol of the compound represented by the general formula (IV).

  As reaction temperature, -10-100 degreeC is preferable and 0-40 degreeC is still more preferable.

Formula Examples of the compound represented by the general formula (IV) as the ring structure ^{A 2 (A 2 -1),} (A 2 -3) or a compound represented by ^(A 2 -4) are preferred.

EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, the purity of the obtained compound was determined by gas chromatography (hereinafter GC) (column: DB-1 30 m, film thickness 0.25 μm, inner diameter 0.25 mm, detector: FID) and high performance liquid chromatography (hereinafter HPLC) ( Column: Wakosil-II 5SIL-120 φ4.6 mm × 250 mm, developing solvent: hexane / dichloromethane).
Example 1 Method for Producing 6-Chlorohexyl Acrylate

108 g of acrylic acid, 136.5 g of 6-chlorohexane-1-ol, 19 g of 4-toluenesulfonic acid, and 0.5 g of hydroquinone monomethyl ether were dissolved in 700 mL of cyclohexane and heated to reflux with stirring for 7 hours. The water distilling out on the way was removed. The reaction solution was diluted with ethyl acetate, washed with water, and the organic phase was separated. An organic substance was extracted from the aqueous phase with ethyl acetate, and all the organic phases were combined, and then washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic phase was dehydrated with anhydrous magnesium sulfate, the solid content was filtered off, the solvent was distilled off, and 185 g of 6-chlorohexyl acrylate (yield: 81.7%, purity (GC): 92.2). %).
(Example 2) Method for producing 10-bromodecyl acrylate

10-Bromodecyl acrylate (yield: 90%, purity (GC): 89.9%) was used in the same manner except that 10-bromodecan-1-ol was used instead of 6-chlorohexane-1-ol in Example 1. )
(Example 3) Method for producing 3-chloropropyl acrylate

In the same manner as in Example 1 except that 3-chloropropan-1-ol was used instead of 6-chlorohexane-1-ol, 3-chloropropyl acrylate (yield: 96.6%, purity (GC): 96. 8%).
(Example 4) Method for producing 3-chloropropyl methacrylate

In Example 3, 3-chloropropyl methacrylate (yield: 92.5%, purity (GC): ˜100%) was obtained in the same manner except that methacrylic acid was used instead of acrylic acid.
(Example 5) Method for producing allyl 4-hydrobenzoate

34.5 g of 4-hydroxybenzoic acid, 22.8 g of allyl chloride and 32 g of sodium bicarbonate were added to 200 mL of DMF, heated to 60 ° C. and stirred overnight. The reaction solution was cooled to room temperature, diluted with ethyl acetate, and the solid content was filtered off. The obtained organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. After dehydration with anhydrous sodium sulfate, the solid content was filtered off, and the solvent was distilled off to obtain a milky white solid. The obtained solid was rinsed with hexane to obtain 31.5 g of allyl 4-hydrobenzoate (yield: 70.8%, purity (HPLC): 97.2%).
(Example 6) Method for producing allyl 3,4-dihydroxybenzoate

25 g of 3,4-dihydroxybenzoic acid, 136 g of allyl alcohol and 2 mL of concentrated sulfuric acid were heated to reflux with stirring for 20 hours. Thereafter, allyl alcohol was distilled off under reduced pressure. After dilution with ethyl acetate, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine. After dehydration with anhydrous sodium sulfate, the solid content was filtered off, and the solvent was distilled off to obtain a milky white solid. The obtained solid was rinsed with heptane to obtain 22.8 g of allyl 3,4-dihydroxybenzoate (yield: 72.4%, purity (HPLC): 98.2%).
(Example 7) Method for producing allyl 3,4,5-trihydroxybenzoate

In Example 6, allyl 3,4,5-trihydroxybenzoate (yield: 76.2) was obtained in the same manner except that 3,4,5-trihydroxybenzoic acid was used instead of 3,4-dihydroxybenzoic acid. %, Purity (HPLC): 98.3%).
(Example 8) Method for producing allyl 3- (4-hydroxyphenyl) propionic acid

In Example 6, allyl 3- (4-hydroxyphenyl) propionic acid was used in the same manner except that 3- (4-hydroxyphenyl) propionic acid was used instead of 3,4-dihydroxybenzoic acid (yield: 96. 5%, purity (HPLC): 95.1%).
Example 9 Allyl 4′-hydroxybiphenyl-4-carboxylic acid

In Example 6, allyl 4′-hydroxybiphenyl-4-carboxylic acid (yield: 78.78%) was used in the same manner except that 4′-hydroxybiphenyl-4-carboxylic acid was used instead of 3,4-dihydroxybenzoic acid. 3%, purity (HPLC): 95.2%).
Example 10 Allyl 4- (3- (acryloyloxy) propoxy) benzoic acid

31.5 g of allyl 4-hydroxybenzoic acid, 31.4 g of 3-chloropropyl acrylate and 36.6 g of potassium carbonate were added to 200 mL of N, N-dimethylformamide, heated to 80 ° C. and stirred overnight. After cooling to room temperature, the mixture was diluted with ethyl acetate and washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine. After dehydration with anhydrous sodium sulfate, the solid content was filtered off and the solvent was distilled off. The residue was purified by column chromatography (silica gel, developing solvent: gradient from heptane to 10% ethyl acetate / 90% heptane) to give 22.8 g of allyl 4- (3- (acryloyloxy) propoxy) Benzoic acid (yield: 84.8%, purity (HPLC): 97.3%) was obtained.
¹ H NMR (CDCl ₃ ) δ 8.02 (d, 2H), 6.91 (d, 2H), 6.43 (d, 1H), 6.12 (dd, 1H), 6.02 (m, 1H) ), 5.83 (d, 1H), 5.41 (d, 1H), 5.27 (d, 1H), 4.79 (d, 2H), 4.36 (t, 2H), 4.11 (T, 2H), 2.18 (m, 2H)
(Example 11) Method for producing allyl 3,4-bis (6- (acryloyloxy) hexyloxy) benzoic acid

In Example 10, allyl 3,4 is similarly used except that allyl 3,4-dihydroxybenzoic acid is used instead of allyl 4-hydroxybenzoic acid, and 6-chlorohexyl acrylate is used instead of 3-chloropropyl acrylate. -Bis (6- (acryloyloxy) hexyloxy) benzoic acid (yield: 63.2%, purity (HPLC): 95.2%) was obtained.
¹ H NMR (CDCl ₃ ) δ 7.68 (d, 1H), 7.55 (s, 1H), 6.87 (d, 1H), 6.39 (d, 2H), 6.13 (dd, 2H) ), 6.03 (m, 1H), 5.81 (d, 2H), 5.39 (d, 1H), 5.27 (d, 1H), 4.79 (d, 2H), 4.16 (T, 4H), 4.05 (t, 4H), 1.60 (m, 16H)
(Example 12) Method for producing allyl 3,4,5-tris (6- (acryloyloxy) hexyloxy) benzoic acid

In the same manner as in Example 11, except that allyl 3,4,5-trihydroxybenzoic acid is used instead of allyl 3,4-dihydroxybenzoic acid, allyl 3,4,5-tris (6- (acryloyloxy) hexyl is used. Oxy) benzoic acid (yield: 79.3%, purity (HPLC): 96.8%) was obtained.
¹ H NMR (CDCl ₃ ) δ 7.28 (s, 2H), 6.40 (d, 3H), 6.13 (dd, 3H), 6.03 (m, 1H), 5.81 (d, 3H) ), 5.40 (d, 1H), 5.39 (d, 1H), 4.81 (d, 2H), 4.17 (m, 6H), 4.02 (m, 6H), 1.69 (M, 24H)
(Example 13) Method for producing allyl 3,4-bis (10- (acryloyloxy) decyloxy) benzoic acid

In the same manner as in Example 11 except that 10-bromodecyl acrylate is used instead of 6-chlorohexyl acrylate, allyl 3,4-bis (10- (acryloyloxy) decyloxy) benzoic acid (yield: 68.2) %, Purity (HPLC): 98.0%).
¹ H NMR (CDCl ₃ ) δ 7.66 (d, 1H), 7.55 (s, 1H), 6.86 (d, 1H), 6.39 (d, 2H), 6.12 (dd, 2H ), 6.04 (m, 1H), 5.81 (d, 2H), 5.39 (d, 1H), 5.27 (d, 1H), 4.79 (d, 2H), 4.15 (M, 4H), 4.03 (m, 4H), 1.82 (m, 4H), 1.66 (m, 4H), 1.47 (m, 4H), 1.27 (m, 20H)
(Example 14) Method for producing allyl 3,4,5-tris (10- (acryloyloxy) decyloxy) benzoic acid

In the same manner as in Example 13, except that allyl 3,4,5-trihydroxybenzoic acid is used instead of allyl 3,4-dihydroxybenzoic acid, allyl 3,4,5-tris (10- (acryloyloxy) decyloxy is used. ) Benzoic acid (yield: 95.2%, purity (HPLC): 95.0%) was obtained.
(Example 15) Method for producing allyl 3- (4- (6- (acryloyloxy) hexyloxy) phenyl) propionic acid

In the same manner as in Example 11 except that allyl 3- (4-hydroxyphenyl) propionic acid is used instead of allyl 3,4-dihydroxybenzoic acid, allyl 3- (4- (6- (acryloyloxy) hexyloxy) is used. Phenyl) propionic acid (yield: 89.6%, purity (HPLC): 90.1%) was obtained.
¹ H NMR (CDCl ₃ ) δ 7.09 (d, 2H), 6.80 (d, 2H), 6.38 (d, 1H), 6.11 (dd, 1H), 6.90 (m, 1H) ), 5.78 (d, 1H), 5.27 (d, 1H), 5.20 (d, 1H), 4.56 (d, 2H), 4.16 (t, 2H), 3.92. (T, 2H), 2.89 (t, 2H), 2.61 (t, 2H), 1.77 (m, 2H), 1.70 (m, 2H), 1.46 (m, 4H)
(Example 16) Method for producing allyl 4 '-(6- (acryloyloxy) hexyloxy) biphenyl-4-carboxylic acid

In the same manner as in Example 11, except that allyl 4′-hydroxybiphenyl-4-carboxylic acid is used instead of allyl 3,4-dihydroxybenzoic acid, allyl 4 ′-(6- (acryloyloxy) hexyloxy) biphenyl- 4-carboxylic acid (yield: 84.0%, purity (HPLC): 98.7%) was obtained.
¹ H NMR (CDCl ₃ ) δ 8.12 (d, 2H), 7.64 (d, 2H), 7.58 (d, 2H), 7.01 (d, 2H), 6.42 (d, 1H ), 6.16 (dd, 1H), 6.11 (m, 1H), 5.84 (d, 1H), 5.47 (d, 1H), 5.33 (d, 1H), 4.87 (D, 2H), 4.21 (t, 2H), 4.03 (t, 2H), 1.85 (m, 2H), 1.75 (m, 2H), 1.55 (m, 4H)
(Example 17) Method for producing 4- (3- (acryloyloxy) propoxy) benzoic acid

8.1 g of allyl 4- (3- (acryloyloxy) propoxy) benzoic acid, 4.1 g of N-methylaniline, 0.28 g of palladium acetate and 0.66 g of triphenylphosphine are added to 50 mL of acetonitrile, and nitrogen is added. Stir overnight at room temperature under atmosphere. The reaction solution was diluted with ethyl acetate, washed with 5% hydrochloric acid and saturated brine, and then dried over anhydrous sodium sulfate.
The solid content was filtered off and the solvent was distilled off. The residue was purified by column chromatography (silica gel, developing solvent: dichloromethane) and 4.2 g of 4- (3- (acryloyloxy) propoxy) benzoic acid (yield: 80.0%, purity (HPLC): 93) 0.0%).
(Example 18) Method for producing 3,4-bis (6- (acryloyloxy) hexyloxy) benzoic acid

In the same manner as in Example 17, except that allyl 3,4-bis (6- (acryloyloxy) hexyloxy) benzoic acid was used instead of allyl 4- (3- (acryloyloxy) propoxy) benzoic acid, -Bis (6- (acryloyloxy) hexyloxy) benzoic acid (yield: 73.8%, purity (HPLC): 95.0%) was obtained.
(Example 19) Method for producing 3,4,5-tris (6- (acryloyloxy) hexyloxy) benzoic acid

In the same manner as in Example 17, except that allyl 3,4,5-tris (6- (acryloyloxy) hexyloxy) benzoic acid is used instead of allyl 4- (3- (acryloyloxy) propoxy) benzoic acid, 3 , 4,5-tris (6- (acryloyloxy) hexyloxy) benzoic acid (yield: 90.5%, purity (HPLC): 95.0%).
(Example 20) Method for producing 3,4-bis (10- (acryloyloxy) decyloxy) benzoic acid

In the same manner as in Example 17, except that allyl 3,4-bis (10- (acryloyloxy) decyloxy) benzoic acid was used instead of allyl 4- (3- (acryloyloxy) propoxy) benzoic acid, 3,4- Bis (10- (acryloyloxy) decyloxy) benzoic acid (yield: 77.4%, purity (HPLC): 98.0%) was obtained.
(Example 21) Method for producing 3,4,5-tris (10- (acryloyloxy) decyloxy) benzoic acid

In Example 17, except that allyl 3,4,5-tris (10- (acryloyloxy) decyloxy) benzoic acid was used instead of allyl 4- (3- (acryloyloxy) propoxy) benzoic acid, 4,5-Tris (10- (acryloyloxy) decyloxy) benzoic acid (yield: 75.2%) was obtained.
(Example 22) Method for producing 3- (4- (6- (acryloyloxy) hexyloxy) phenylpropionic acid

In Example 17, in place of allyl 4- (3- (acryloyloxy) propoxy) benzoic acid, allyl 3- (4- (6- (acryloyloxy) hexyloxy) phenylpropionic acid was used in the same manner. (4- (6- (acryloyloxy) hexyloxy) phenylpropionic acid (yield: 83.3%, purity (HPLC): 97.0%) was obtained.
(Example 23) 4 '-(6- (acryloyloxy) hexyloxy) biphenyl-4-carboxylic acid production method

In the same manner as in Example 17, except that allyl 4 ′-(6- (acryloyloxy) hexyloxy) biphenyl-4-carboxylic acid is used instead of allyl 4- (3- (acryloyloxy) propoxy) benzoic acid, 4 '-(6- (acryloyloxy) hexyloxy) biphenyl-4-carboxylic acid (yield: 83.0%, purity (HPLC): 97.0%) was obtained.
(Comparative Example 1)
A reaction vessel equipped with a stirrer, a cooler, and a thermometer was charged with 13.8 g (100 mmol) of 4-hydroxybenzoic acid, 2.5 g of potassium iodide, 0.7 g of tetrabutylammonium bromide, and 400 ml of ethanol and stirred at room temperature. did. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 50 ° C., and 14 g (150 mmol) of 3-propylhexanol was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further heated to 70 ° C. and further reacted for 3 hours. After completion of the reaction, the reaction mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to give 4- (3-hydroxypropoxy) benzoic acid (yield: 65.0%, purity) (HPLC): 95.0%) was obtained.

  Then, 12 g (61 mmol) of 4- (3-hydroxypropoxy) benzoic acid, 10 g (140 mmol) of acrylic acid, 1 g of p-toluenesulfonic acid, toluene in a reaction vessel equipped with a stirrer, a condenser and a Dean stack. 100 ml was charged. The reaction vessel was heated to reflux with toluene and allowed to react for 4 hours. After completion of the reaction, the reaction solution was washed with saturated sodium hydrogen carbonate, neutralized with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 11.4 g of 4- (3- (acryloyloxy) propoxy) benzoic acid (yield: 75.0%, purity (HPLC): 88.0%). Compared with the production method of the present invention, the yield and purity were low.

(Comparative Example 2)
In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 21.4 g (100 mmol) of (4′-hydroxy) biphenyl-4-carboxylic acid, 2.5 g of potassium iodide, 0.7 g of tetrabutylammonium bromide, 400 ml of ethanol was charged and stirred at room temperature. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 50 ° C., and 20.5 g (150 mmol) of 6-chlorohexanol was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further heated to 70 ° C. and further reacted for 3 hours. After completion of the reaction, the reaction mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to give (4 ′-(6-hydroxyhexyloxy) biphenyl-4-carboxylic acid (yield : 65%, purity (HPLC): 86.0%) was synthesized in an amount of 20.4 g.

  Subsequently, 20 g (63 mmol) of 4 ′-(6-hydroxyhexyloxy) biphenyl-4-carboxylic acid, 10 g of acrylic acid (140 mmol), p- 1 g of toluenesulfonic acid and 100 ml of toluene were charged. The reaction vessel was heated to reflux with toluene and allowed to react for 4 hours. After completion of the reaction, the reaction solution was washed with saturated sodium hydrogen carbonate, neutralized with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 16.6 g of 4 ′-(6- (acryloyloxy) hexyloxy) biphenyl-4-carboxylic acid (yield: 72%, purity (HPLC): 86.0%). . Compared with the production method of the present invention, the yield and purity were low.

Claims (10)

The manufacturing method of carboxylic acid represented by general formula (V) including the process of following (1)-(3).
(1) General formula (I)

(Wherein, ^{L 1} is a single bond, -CH ₂ - or _-C 2 _{H 4} - represents, ^{A 1} is represented by the general formula ^(A 1 -1) or the general formula ^{(A 1} - is represented by 3) Represents a substituent,

(In the formula, the phenylene group may be substituted by one or more fluorine atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and each Z ¹ is independently a hydrogen atom. , A hydroxyl group or HOCO-, at least one of which represents a hydroxyl group or HOCO-))) and a compound represented by the general formula (II):

(Wherein, A ¹ and L ¹ represent the same meaning as A ¹ and L ¹ in formula (I)).
(2) Compound represented by general formula (II) and general formula (III)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, L ² represents — (CH ₂ ) n —, n represents 0 to 12, and X represents a chlorine atom when n represents 1 to 12). Represents a bromine atom, an iodine atom, a hydroxyl group, a hydrogen atom, an alkanesulfonyloxy group, a p-toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group, and when n represents 0, X represents an alkanesulfonyl group, a p-toluenesulfonyl group or A trifluoromethanesulfonyl group) is reacted, and the hydroxyl group and HOCO- in Z ¹ are esterified to give a general formula (IV)

(Wherein, ^{L 1} represents the same meaning as ^{L 1} in the general formula (I), ^{A 2} of the general formula ^(A 2 -1) or the general formula ^(A 2 - 3)

(In the formula, the phenylene group may be substituted by one or more fluorine atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and Z ² is a hydrogen atom or a general formula (Z ² -1)

(Wherein R ¹ and L ² represent the same meaning as R ¹ and L ² in formula (III), and Y ¹ independently represents a single bond, —O— or —OCO—). Represents a substituent. The substituent represented by this is represented. ).
(3) Deprotecting the carboxylic acid ester compound represented by the general formula (IV) with a palladium catalyst in the presence of a base, the general formula (V)

(Wherein A ² and L ¹ represent the same meaning as A ² and L ¹ in formula (IV)). In order to obtain the carboxylic acid ester represented by the general formula (IV) according to claim 1, the compound represented by the general formula (II) according to claim 1 is reacted with the compound represented by the general formula (III). And then deprotecting the carboxylic acid ester represented by the general formula (IV) using a palladium complex (Pd (0) Ln) as a catalyst in the presence of a base, the carboxylic acid represented by the general formula (V) Manufacturing method. Carboxyl represented by the general formula (V) for deprotecting the carboxylic acid ester represented by the general formula (IV) according to claim 1 using a palladium complex (Pd (0) Ln) as a catalyst in the presence of a base. Acid production method. The production method according to claim 1, wherein an amine is used as the base. General formula (VI) as base

(Wherein, R ³ and R ⁴ are each independently hydrogen,. Represents an alkyl group or a phenyl group having 1 to 12 carbon atoms) A process according to any one of claims 1 to 4 using a compound represented by . The production method according to claim 1, wherein the ligand (Ln) of the palladium complex (Pd (0) Ln) is a trialkylphosphine or a triarylphosphine. The manufacturing method in any one of Claims 1-6 which perform a deprotection process at 0-40 degreeC. The production method according to any one of claims 1 to 7, wherein the amount of the palladium complex is 1 to 10 mol% with respect to the compound represented by the general formula (IV). The production method according to any one of claims 1 to 8, wherein the amount of the amine used is 0.8 to 3 mol with respect to 1 mol of the compound represented by the general formula (IV). Formula (IV)

(In the formula, L ¹ represents a single bond, —CH ₂ — or —C ₂ H ₄ — , and A ² represents a substitution represented by the general formula (A ² -1) or the general formula (A ² -3 )). Represents a group,

(In the formula, the phenylene group may be substituted by one or more fluorine atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and each Z ² is independently a hydrogen atom. Or general formula (Z ² -1)

Wherein R ¹ and L ² represent the same meaning as R ¹ and L ² in the general formula (III) according to claim ^1, and Y ¹ each independently represents a single bond, —O— or —OCO—. )) , At least one of the substituents is represented by the general formula (Z ² -1) . ) A compound represented by