JP2800302B2 - Optically active phenol derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel optically active phenol derivative useful as an intermediate of an organic electronic material, especially a liquid crystal compound.

<Prior art> Various compounds have been conventionally developed as liquid crystal compounds.However, there are very few compounds which are excellent in characteristics such as high-speed response and which become ferroelectric liquid crystals in a low temperature region, and are intermediates of the liquid crystal compounds. Since the development of this intermediate is not yet sufficient, it has been desired to develop this intermediate and an industrially advantageous production method thereof.

<Problems to be Solved by the Invention> An object of the present invention is to provide a novel optically active phenol derivative which is a ferroelectric liquid crystal in a low-temperature region, and is useful as an intermediate of a ferroelectric liquid crystal compound having excellent characteristics as described above. Another object of the present invention is to provide a production method, and also provide an intermediate of the optically active phenol derivative and a production method thereof.

<Means for Solving the Problems> That is, the present invention provides a compound represented by the general formula [I]: (In the formula, R ^* represents an optically active alkyl group or an alkoxyalkyl group having 3 to 15 carbon atoms which may be substituted with a halogen atom, and n represents an integer of 1 to 6.) The present invention relates to a novel phenol derivative and a method for producing the same.

 Hereinafter, the present invention will be described in detail.

The esterification reaction, which is the first step of the present invention, has a general formula (IV) (Wherein, n represents the same meaning as described above), and an alcohol represented by the general formula [III] R ^* COOH [III] (wherein, R ^* has the same meaning as described above). The reaction is performed by reacting an optically active carboxylic acid or a derivative thereof in the presence of a catalyst or a condensing agent.

The debenzylation reaction of the second step of the present invention is represented by the general formula (II) (Wherein R ^* and n have the same meanings as described above). The reaction is carried out in the presence of a hydrogenation catalyst and hydrogen.

In addition, these alcohols [IV] correspond to the corresponding 4-
Hydroxyalkylphenols can be easily produced by benzylation by a known method.

In the esterification reaction between the alcohol [IV] and the optically active carboxylic acid [III] in the first step, a solvent may be used, and when a solvent is used, the solvent may be, for example, tetrahydrofuran, ethyl Reaction of aliphatic or aromatic hydrocarbons such as ether, acetone, methyl ethyl ketone, toluene, benzene, chloroform, chlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride, dimethylformamide, hexane, ether, ketone, amide or halogenated hydrocarbon Inactive solvents are used alone or as a mixture, and the amount used is not particularly limited. When an acid anhydride or an acid halide is used in this reaction, the reaction is performed using a catalyst.

The amount of the acid anhydride or acid halide to be used must be at least 1 equivalent times the alcohol [IV], and the upper limit is not particularly limited, but is preferably at most 4 equivalent times.

Examples of the catalyst include dimethylaminopyridine, triethylamine, tri-n-butylamine, picoline,
Organic or inorganic basic substances such as imidazole, sodium carbonate or potassium hydrogencarbonate can be mentioned, and organic or inorganic acids such as toluenesulfonic acid, methanesulfonic acid and sulfuric acid can be mentioned.

Although the amount of the catalyst used is not particularly limited, for example, when an acid halide is used, it is 1 equivalent or more times the acid halide.

When an optically active carboxylic acid [III] is used in the reaction, the reaction is performed using a condensing agent.

The amount of the carboxylic acid to be used is usually 1 to 2 equivalents relative to the alcohol [IV].

As the condensing agent, carbodiimides such as N, N'-dicyclohexylcarbodiimide and N-cyclohexyl-N '-(4-diethylamino) cyclohexylcarbodiimide are preferably used, and if necessary, organic bases such as 4-pyrrolidinopyridine, pyridine and triethylamine. Are used together. The amount of the condensing agent to be used is 1 to 1.2 equivalent times that of the optically active carboxylic acid [III].

When an organic base is used, the amount used is 0.01 to 0.2 equivalent times the condensing agent.

The reaction temperature is usually -80C to 120C, preferably -20C to 9C.
0 ° C.

The reaction time is not particularly limited, and the time when the alcohol [IV] is no longer detected from the reaction system is defined as the reaction end point.

The benzyloxybenzene derivative [II] can be obtained by subjecting the reaction mixture thus obtained to a usual post-treatment operation such as extraction, liquid separation, concentration, recrystallization or column chromatography.

Substituent R in optically active carboxylic acid [III]
^* Represents a carbon number of 3 to 5 which may be substituted with a halogen atom.
15 optically active alkyl groups or alkoxyalkyl groups, for example, the following:

1-methylpropyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,
2,3-dimethylbutyl, 1,2,2-trimethylbutyl, 1,2,
3-trimethylbutyl, 2,3,3-trimethylbutyl, 1-
Methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl,
1,2,2,3-tetramethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylxyl, 4-methylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethyl Hexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 1,3-dimethylheptyl, 1-methyloctyl, 2-methyloctyl, 3
-Methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 1,2-dimethyloctyl, 1,4-dimethyloctyl, 1-methylnonyl, 2-
Methylnonyl, 3-methylnonyl, 4-methylnonyl,
5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 1,2-dimethylnonyl, 1-methyldecyl, 2-methyldecyl, 3-methyldecyl, 4-methyldecyl, 5
-Methyldecyl, 6-methyldecyl, 7-methyldecyl, 8-methyldecyl, 1-methylundecyl, 9-methylundecyl, 1-methyldodecyl, 10-methyldodecyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxy Hexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, propoxyethyl, propoxypropyl, propoxybutyl, Propoxypentyl, propoxyhexyl, propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxyethyl, butoxypropyl Butoxybutyl, butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxydecyl, pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyoctyl, hexyloxydecyl, pentyl Oxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl,
Hexyloxyhexyl, heptyloxyethyl, heptyloxypropyl, heptyloxybutyl, heptyloxypentyl, octyloxyethyl, octyloxypropyl, decyloxyethyl, decyloxypropyl, 1-halopropyl, 1-halobutyl, 1-halopentyl, -Halohexyl, 1-haloheptyl, 1-halooctyl, 1-halo-2-methylpropyl, 1-halo-
2-methylbutyl, 1-halo-2-methylpentyl, 1
-Halo-2-methylhexyl, 1-halo-2-methylhexyl, 1-halo-2-methyloctyl, 2-trihalomethylpentyl, 2-trihalomethylhexyl, 2-trihalomethylheptyl, 2-halopropyl, -Halo-
2-methylpropyl, 2,3-dihalopropyl, 2-halobutyl, 3-halobutyl, 2,3-dihalobutyl, 2,4
-Dihalobutyl, 3,4-dihalobutyl, 2-halo-3-
Methylbutyl, 2-halo-3,3-dimethylbutyl, 2-
Halopentyl, 3-halopentyl, 4-halopentyl,
2,4-dihalopentyl, 2,5-dihalopentyl, 2-halo-3-methylpentyl, 2-halo-4-methylpentyl, 2-halo-3-monohalomethyl-4-methylpentyl, 2-halohexyl, 3-halohexyl , 4-halohexyl, 5-halohexyl, 2-haloheptyl, 2-halooctyl (however, in the above examples, halo represents fluorine, chlorine, bromine or iodine.) In this reaction, the carboxylic acid having these substituents Alternatively, anhydrides or acid halides such as acid chloride or acid bromide are used.

Some of the optically active carboxylic acids are obtained by oxidation of the corresponding alcohol or reductive deamination of the amino acid, and some are naturally occurring or
Alternatively, it can be derived from the following optically active amino acids or optically active oxyacids obtained by resolution.

Alanine, valine, leucine, isoleucine, phenylalanine, serine, threonine, allothreonine, homoserine, alloisoleucine, tert.-leucine, 2-
Aminobutyric acid, norvaline, norleucine, ornithine,
Lysine, hydroxylysine, phenylglycine, trifluoroalanine, aspartic acid, glutamic acid, lactic acid, mandelic acid, tropic acid, 3-hydroxybutyric acid, malic acid, tartaric acid, isopropyl malic acid and the like.

In the second step, the debenzylation reaction of the optically active benzyloxybenzene derivative [II], examples of the hydrogenation catalyst used include platinum-based catalysts such as PtO ₂ and Pt-C, Pd-C, Pd
-BaSO _4, palladium palladium black, etc., Rh-C, Rh
-Al ₂ O ₃ or the like rhodium, and is exemplified such as a nickel-based catalysts such as ruthenium-based or Raney nickel, etc. RuO _2, Ru-C, in particular a palladium catalyst is preferably used.

The hydrogenation catalyst is used in an amount of usually 0.01 to 100% by weight, preferably 0.1 to 50% by weight, based on the optically active benzyloxybenzene derivative represented by the general formula [II].

As the solvent, methanol, alcohols such as ethanol, dioxane, ethers such as tetrahydrofuran,
Benzene, aromatic hydrocarbons such as toluene, esters such as ethyl acetate, amides such as dimethylformamide,
Examples thereof include fatty acids such as acetic acid and water, and these may be used alone or as a mixture.

The above reaction is usually carried out at normal pressure or under pressure, and the pressure range is usually 1 to 200 atm.

The reaction temperature is generally 0-200 ° C, preferably 20-180 ° C.

Although the reaction time is not particularly limited, the time when the optically active benzyloxybenzene derivative [II] is no longer detected from the reaction system or the time when hydrogen absorption is stopped is defined as the reaction end point.

An optically active phenol derivative represented by the general formula [I] can be obtained by subjecting the thus obtained reaction mixture to a usual post-treatment operation such as filtration, concentration, recrystallization, distillation or column chromatography.

<Effects of the Invention> The novel optically active phenol derivative [I], which is a compound of the present invention, is obtained by, for example, a method shown by the following formula:
It can lead to a novel liquid crystal compound [V], which has very excellent properties as a ferroelectric liquid crystal.

(Here, Ar represents a phenylene group, a biphenylene group, a heterocyclic group, or the like, Y represents an alkyl group, an alkoxyl group, or the like. R ^* and n have the same meanings as described above.) Thereby, the phenol derivative [I] can be industrially advantageously produced.

Further, the novel optically active phenol derivative represented by the general formula [I] can also be used as an intermediate for agricultural chemicals, medicines and the like.

<Example> Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 1-benzyloxy-4- (3-hydroxypropyl) benzene was placed in a four-necked flask equipped with a thermometer and a stirrer.
4.85 g (200 mmol), 2.45 g of 2S-methylbutanoic acid (24 mmo
l) and 20 mg of 4-pyrrolidinopyridine were added at room temperature for 24 hours.
Stirred for hours.

After completion of the reaction, the reaction mixture was filtered, and the obtained filtrate was filtered for 5 hours.
% Acetic acid, water, 5% aqueous sodium bicarbonate, and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (eluent: toluene / ethyl acetate = 40/1) to give 1-benzyloxy-4- [3- (2S-methylbutanoyloxy)
Propyl] benzene [II-1] 5.55 g [85% yield, ▲
[Α] ²⁰ _D ▼ = + 7.6 ゜ (c = 1, CHCl ₃ ), ▲ n ²⁰ _D ▼ =
1.5311].

3.26 g (10 mmol) of the obtained [II-1] was added to ethanol 8
0%, added 0.3 g of 10% Pd / C, and added hydrogen pressure of 1-1.2.
Stir vigorously at atmospheric pressure for 12 hours.

After the completion of the reaction, Pd / C was separated by filtration, and the obtained filtrate was subjected to reduced pressure.
Concentrated. The obtained residue was subjected to silica gel column chromatography (eluent: toluene / ethyl acetate = 10/1) to give 2.24 g of 4- [3- (2S-methylbutanoyloxy) propyl] phenol [I-1] (yield 95%).

▲ [α] ²⁰ _D ▼ = + 32.3 ゜, (c = 1, CHCl ₃ ) ▲ n ²⁰ _D
▼ = 1.5058 Examples 2 to 5 In place of 2S-methylbutanoic acid used in Example 1, Table-
The reaction, post-treatment and purification were carried out in the same manner as in Example 1 except that the optically active carboxylic acid [III] described in 1 was used. The results are shown in Table 1.

Example 6 Example 1 was repeated except that 1-benzyloxy-4- (2-hydroxyethyl) benzene was used in place of 1-benzyloxy-4- (3-hydroxypropyl) benzene used as a raw material in Example 1. The reaction, post-treatment and purification were carried out in the same manner as described above, and 1-benzyloxy-4-
[2-2S-methylbutanoyl) ethyl] benzene [II-
6] 5.50 g (88% yield) was obtained. ▲ [α] ²⁰ _D ▼ = ＋ 8.2
゜ (c = 1, CHCl ₃ ) ▲ n ²⁰ _D ＝= 1.5340 The obtained [II-6] was used in Example 1 [II-
In place of [1], the reaction, work-up and purification were carried out, and 4- [2
2.18 g (98% yield) of-(2S-methylbutanoyloxy) ethyl] phenol [I-6] was obtained. ▲ [α] ²⁰ _D ▼ =
+33.8 ゜ (c = 1, CHCl ₃ ), {n ²⁰ _D ▼ = 1.066} Examples 7 to 8 Instead of 2S-methylbutanoic acid used in Example 6, the optically active carboxylic acid [Table 2] Reaction, post-treatment and purification were carried out in the same manner as in Example 6 except that III] was used. Table 2 shows the results.

Example 9 The reaction, post-treatment and purification were carried out in the same manner as in Example 1 except that 1-benzyloxy-4- (4-hydroxybutyl) benzene used as a raw material in the Example was used. 5.72 g of 4- [4- (2S-methylbutanoyl) butyl] benzene [II-9] (yield 84
%). ▲ [α] ²⁰ _D ▼ = + 7.1 ゜ (c = 1, CHC
l ₃ ), (n ²⁰ _D ) = 1.5322 The obtained [II-9] was used in Example 1 [II-1].
In place of 4- (4-)
2.40 g (96% yield) of (2S-methylbutanoyloxy) butyl) phenol [I-9] was obtained. ▲ [α] ²⁰ _D ▼ =
+29.8 ゜ (c = 1, CHCl ₃ ), {n ²⁰ _D ▼ = 1.5049 Examples 10 to 11 Instead of the 2S-methylbutanoic acid used in Example 9, the optically active carboxylic acid described in Table 3 [ Reaction, post-treatment and purification were carried out in the same manner as in Example 9 except that III] was used. The results are shown in Table-3.

Reference Example (Production Example of Liquid Crystal Compound) Reference Example 1 (−) in a four-necked flask equipped with a stirrer and a thermometer
1.18 g (5 mmol) of -4- [3- (2S-methylbutanoyloxy) propyl] phenol, 1.67 g (6 mmol) of 4-decyloxybenzoic acid and 30 ml of anhydrous dichloromethane are charged, and 1.22 g of N, N'-dicyclohexylcarbodiimide is added. 6m
mol) and 0.1 g of 4-pyrrolidinopyridine,
Stirred all day and night.

After completion of the reaction, the resulting precipitate was separated by filtration, diluted with 200 ml of toluene, and the obtained organic layer was washed with water, 5% aqueous acetic acid, water, 5% aqueous sodium hydrogen carbonate and water in that order, and dried over anhydrous magnesium sulfate. And concentrated under reduced pressure. This was purified by silica gel chromatography (eluent: toluene-ethyl acetate) to give (-)-4-decyloxybenzoic acid 4- [3- (2S-methylbutanoyloxy) propyl] phenyl ester 2.
16 g (87% yield) was obtained.

▲ [α] ²⁰ _D ▼ = -2.6 ゜ (c = 1, CHCl ₃ ) Reference Example 2 A reaction and a post-treatment were carried out in the same manner as in Reference Example 1 except that 4′-octyloxy-4-biphenylcarboxylic acid was used instead of 4-decyloxybenzoic acid used in Reference Example 1, and (−) ) -4'-Biphenylcarboxylic acid 4- [3
2.32 g (yield 85%) of-(2S-methylbutanoyloxy) propyl] phenyl ester was obtained.

▲ [α] ²⁰ _D ▼ = -1.9 ゜ (c = 1, CHCl ₃ ) phase series

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masayoshi Minami 3-1-198, Kasuganaka, Konohana-ku, Osaka-shi, Sumitomo Chemical Co., Ltd. (56) References JP-A-64-31891 (JP, A) JP-A-2-131443 (JP, A) JP-A-1-156722 (JP, A) Chem. Plarm, Bull. , 29 [11] (1981), 3202-3207 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 69/24 C07C 67/08

Claims (3)

(57) [Claims] 1. A compound of the formula [I] (In the formula, R ^* represents an optically active alkyl group or alkoxyalkyl group having 3 to 15 carbon atoms which may be substituted with a halogen atom, and n represents an integer of 1 to 6.) Phenol derivatives. 2. The general formula [II] (Wherein R ^* and n have the same meanings as described above), wherein the optically active benzyloxybenzene derivative is debenzylated in the presence of a hydrogenation catalyst and hydrogen. 5. The method for producing an optically active phenol derivative according to the above. 3. A compound of the general formula [IV] (Wherein n represents the same meaning as described above) and an optically active carboxylic acid represented by the general formula R ^* COOH (wherein R ^* has the same meaning as described above) or The derivative is reacted in the presence of a catalyst or a condensing agent to form an optically active benzyloxybenzene derivative represented by the general formula [II] according to claim 2, and the derivative is treated with a hydrogenation catalyst and hydrogen. The method for producing an optically active phenol derivative according to claim 1, wherein the phenol derivative is debenzylated below.