JPH01242552A - Biphenyl derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (A is H, halogen, 1-4C alkyl or 1-4C alkoxyl; R is lower alkyl). EXAMPLE:4-(1-Acetoxyethyl)-4'-beozyloxybiphenyl. USE:Useful as a synthetic intermediate for organic electronic materials, especially liquid crystal compounds and also for medicines, agricultural chemicals, etc. PREPARATION:A (1-hydroxyethyl)biphenyl derivative expressed by formula II is acylated with lower aliphatic carboxylic acids (e.g., acetic acid) in the presence or absence of a solvent (e.g., THF) using a catalyst, such as dimethylaminopyridine, at -30-100 deg.C to afford the aimed compound expressed by formula I. The lower aliphatic carboxylic acids are used in an amount of 1.2-2 equiv. based on the compound expressed by formula II.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention relates to the general formula (1) (wherein A is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms). The alkoxyl group, R
' represents a lower alkyl group) and a method for producing the same.

<Prior Art> The biphenyl derivative represented by the above general formula is a new compound that has not been described in any literature, and not only its production method but also its usefulness as a compound have not been known at all.

<I1 experience to be solved by the invention> The biphenyl derivative represented by the general formula (1) can be asymmetrically hydrolyzed using, for example, an esterase to form an optically active alcohol represented by the following formula and the acyl of the alcohol which is its enantiomer. They are useful as intermediates for medicines, agricultural chemicals, etc., and are particularly useful as intermediates for organic electronic materials, especially liquid crystal compounds.

For example, the optically active alcohol described above can be led to a liquid crystal compound by the method shown in the following formula, and this compound has excellent properties as a ferroelectric liquid crystal.

Means for Solving the Problems> The present invention provides a novel compound represented by the general formula (1) which is useful not only as such a medical and agricultural intermediate but also as an intermediate for organic electronic materials, especially liquid crystal compounds. The present invention provides biphenyl derivatives.

The biphenyl derivative represented by the general formula (1) is a 4-biphenyl derivative represented by the general formula (1) (wherein A has the same meaning as above).
It can be produced by reacting a (1-hydroxyethyl)biphenyl derivative with a lower aliphatic carboxylic acid to acylate it.

Here, 4-(l-
Hydroxyethyl)biphenyl derivatives are produced by converting 4-acetylbiphenyl derivatives l (in the above formula, A has the same meaning as above) with a reducing agent such as sodium borohydride, which is a metal hydride, as shown below. It can be easily produced by reducing a ketone in an organic solvent.

In addition, its raw material, 4-acetylbiphenyl derivative (
For example, as shown in (in the above formula, A has the same meaning as above and X represents a halogen atom), the hydroxyacetylbiphenyl surface is reacted with benzyl halides under basic conditions. It can be easily produced by benzylation.

4-(1-hydroxyethyl)biphenyl derivative (il
) with lower aliphatic carboxylic acids is carried out by acylation using a catalyst in the presence of a solvent or in the absence of pressure.

Here, as the lower aliphatic carboxylic acids, lower aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, their acid anhydrides or acid halides (for example, acid chloride, acid bromide) are used. The amount used is 4-(1-hydroxyethyl)biphenyl derivative (1
), and is usually used in a range of 1.2 to 2 equivalents, but the upper limit is not particularly limited.

When a solvent is used in this reaction, the solvent may be an aliphatic or aromatic solvent such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, hexane, etc. Examples include solvents that are inert to the reaction, such as group hydrocarbons, ethers, and halogenated hydrocarbons, either alone or as a mixture. Regarding usage 1, it can be used without any particular restrictions.

Examples of the catalyst include organic or inorganic basic substances such as dimethylaminopyridine, triethylamine, tri-n-butylamine, pyridine, picoline, lysine, imidazole, sodium chloride, sodium methylate, and potassium bicarbonate. Furthermore, organic acids or inorganic acids such as toluenesulfonic acid, methanesulfonic acid, and sulfuric acid can also be used as catalysts.

When using such a melting medium, for example, when an acid halide is used as the lower aliphatic carboxylic acid, pyridine is particularly preferably used.

The amount of catalyst used varies depending on the combination of lower aliphatic carboxylic acids and the catalyst used, and cannot necessarily be specified, but for example, when using an acid halide as the lower aliphatic carboxylic acid, 1 equivalent or more is used.

In addition, when lower aliphatic carboxylic acids are used as the lower aliphatic carboxylic acids, the reaction is carried out in the presence of a dehydrating agent, and as the dehydrating agent, carbodiimide derivatives such as dicyclohexylcarbodiimide are preferably used. The amount used is usually 1 equivalent or more relative to the lower aliphatic carboxylic acid. In this case, the combination of the above-mentioned basic catalyst is effective in improving the reaction rate and yield, and the amount used in this case is 0.01 times or more, preferably 0.01 equivalent to the lower aliphatic carboxylic acid. It is in the range of ~1 equivalent.

The reaction temperature is usually -80°C to 100°C, preferably -25°C to 80°C.

The reaction time is not particularly limited, and the end point of the reaction can be set at the time when the raw material 4-(1-hydroxyethyl)biphenyl derivative (1) disappears.

After the reaction is completed, the desired general formula (1
) can be isolated,
If necessary, it can be purified by column chromatography or the like.

In this way, the biphenyl derivative represented by the general formula (1) can be easily produced in a good yield. Oxybiphenyl, 4-(1-acetoxyethyl)-4'-methylbenzyloxybiphenyl, 4-(1-acetoxyethyl)-41-methoxybenzyloxybiphenyl, 4-(1-acetoxyethyl)-4' -fluorobenzyloxybiphenyl, 4-(1-acetoxyethyl)
-4'chlorobenzyloxybiphenyl, 4-(1-acetoxyethyl)-4'-bromobenzyloxybiphenyl, 4-(1-acetoxyethyl)-4'-iodobenzyloxybiphenyl and acetoxyethyl group in each of the above compounds Examples include compounds in which is substituted with a propionyloxyethyl, butyryloxyethyl, valeryloxyethyl, hexanoyloxyethyl group, or the like.

<Effects of the Invention> According to the method of the present invention, biphenyl derivative (1), which is a novel compound, can be obtained in good yield, and the biphenyl derivative (1) thus produced can be used not only as a pharmaceutical and agrochemical intermediate but also as a liquid crystal compound. It can be used as an intermediate for organic electronic materials such as

<Examples> The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Performed @1 4-(1-hydroxyethyl)-4-benzyloxybiphenyl 91.251! (800 mmol) was dissolved in a mixture of 400 dJ3 of dry toluene and io,x/ of pyridine, and 25°9 of acetyl chloride
f (330E remol) is added over a period of 2 hours at 15-20°C. After that, at the same temperature for 1 hour and at 40-50℃ for 2 hours.
Keep warm for hours. After the reaction is completed, the mixture is cooled to below 10'C and 800% of water is added. The separated 13jm was sequentially washed with 2N-hydrochloric acid, water, 5% sodium carbonate, and water, concentrated under reduced pressure, and further purified by column chromatography to obtain 4-(1
-acetoxyethyl)-4'-benzyloxybiphenyl 101.6f (yield 97.8%) was obtained.

Melting point 184-185°C Example 2 4-(1-hydroxyethyl)-4-benzyloxybiphenyl was converted to 4-(1-hydroxyethyl)-4
'-(4-chlorobenzyloxy)biphenyl101.
4-(1-acetoxyethyl)-
4'-(4-chlorobenzyloxy)biphenyl ia
, 5fI (quantitative) was obtained.

Melting point 140.5-142'C Example 8 4.56 g (154 ot) of 4-(1-hydroxyethyl)-4'-benzyloxybiphenyl was dissolved in 50% of completely dry dichloromethane and dicyclohexylcarbodiimise8. 5 g (17IIllO6), 0.1 da of 4-pyrrolidinopyridine and III acetate were added and stirred at room temperature for 12 hours.

After separating the P from the resulting precipitate, the F solution was mixed with water, 5% acetic acid, and 6%
After sequentially washing with aqueous sodium bicarbonate and water, it was dried over anhydrous magnesium sulfate and condensed under reduced pressure.

The obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate) to obtain 4.8 IC of 4-(1-acetoxyethyl)-4-benzyloxybiphenyl.
A yield of 92%) was obtained.

Example 4 18.81 (0.04 mol) of 4-(1- and droxyethyl i4'-(4-methoxybenzyl)oxybia) was dissolved in 100 g of pyridine, and 6,01 (0,0, After 05, the reaction solution was diluted with 4N hydrochloric acid 300
Extract with 800% of toluene. The organic layer was washed successively with IN hydrochloric acid, water, 5% sodium bicarbonate solution, and water, and then concentrated under reduced pressure to obtain 4-(1-isovaleroyloxyethyl)-4'-(4-methoxybenzyl) as a pale yellow solid. )
Oxybiphenyl 16.8N (yield quantitative) was obtained.

Melting point 108.5-105°C Example 5 4-(1-hydroxyethyl)-4'-(4- 12.7f (0.04 mol) of methylbenzyl)oxybiphenyl was reacted and post-treated in accordance with Example 4, except that 4.6 g (0.05 mol) of propanoyl chloride was used in isovaleric acid. and 4-(1-propanoyloxyethyl)-4'-(4-methylbenzyl)oxybiphenyl 1 as a pale yellow solid.
5.0 pieces (yield 97%) were obtained.

-Point 111~112°C (Margin below)

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 4 carbon atoms, R
represents a lower alkyl group). (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 4 carbon atoms) 2. The method for producing a biphenyl derivative according to claim 1, wherein the (1-hydroxyethyl)biphenyl derivative is acylated by reacting with a lower aliphatic carboxylic acid.