JP2531228B2 - Biphenyl derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (I) (Wherein 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), and a method for producing the same.

<Prior Art> The biphenyl derivative represented by the general formula (I) is a novel compound which has not been described in any literature, and it has been heretofore known not only of its production method but also of its usefulness as a compound.

<Problems to be Solved by the Invention> The biphenyl derivative represented by the general formula (I) is useful as an intermediate for medicines, agricultural chemicals, etc., but is particularly useful as an intermediate for organic electronic materials, especially liquid crystal compounds. is there.

For example, the biphenyl derivative can be typically introduced into a novel liquid crystal compound by a method represented by the following formula, and the compound has very excellent properties as a ferroelectric liquid crystal.

<Means for Solving the Problems> The present invention is of course applicable to such medical and agricultural chemical intermediates.
The present invention provides a biphenyl derivative represented by the general formula (I), which is a novel compound useful as an organic electronic material, especially as an intermediate for liquid crystal compounds.

The biphenyl derivative represented by the general formula (I) is 4-
Acetyl-4'-hydroxybiphenyl and general formula (II) (Wherein A has the same meaning as described above, X represents a halogen atom or —OSO ₂ R, where R represents a lower alkyl group or an optionally substituted phenyl group). It can be produced by reacting with an agent.

This reaction is usually carried out in the presence of a basic substance, and examples of the basic substance include alkali metal hydrides such as sodium hydride and potassium hydride, alkaline earth metal hydrides such as calcium hydride, and lithium. , Alkali metal or alkaline earth metal such as sodium, potassium and calcium, alkali metal alcoholate such as sodium methylate and sodium ethylate, alkali metal carbonate such as sodium carbonate and potassium carbonate, sodium hydroxide,
Examples thereof include alkali metal hydroxides such as potassium hydroxide and organic metals such as butyllithium and methyllithium.

Such basic substances are usually 4-acetyl-4'-
It is used in 1 equivalent or more times that of hydroxybiphenyl,
The upper limit is not particularly limited, but it is preferably double equivalent.

The benzylating agent used in this reaction is a halide such as chloride, bromide, or iodine, or a sulfuric acid ester (methanesulfonic acid ester, ethanesulfonic acid ester, benzenesulfonic acid ester, toluenesulfonic acid ester, etc.). Specifically, benzyl chloride, benzyl bromide, benzyl tosylate, benzyl mesylate, 4-methylbenzyl chloride, 4-methylbenzyl bromide, 4-methoxybenzyl fluoride, 2-chlorobenzyl chloride, 4-chlorobenzyl chloride, 4- Chlorbenzyl bromide, 4-
Examples include ethoxybenzyl chloride, 4-propoxybenzyl chloride, 4-butoxybenzyl chloride, 4-ethoxybenzyl bromide, 4-propoxybenzyl bromide, 4-butoxybenzyl bromide and the like.

The amount of such a benzylating agent used is 4-acetyl-
The amount is 1 equivalent or more with respect to 4'-hydroxybiphenyl, but is usually in the range of 1 to 2 equivalents.

As the solvent, for example, methanol, ethanol, 2
-Propanol, tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chloroform, chlorobenzene, dichloromethane,
Dichloroethane, carbon tetrachloride, aliphatic or aromatic hydrocarbons such as hexane, ether, inert to the reaction of halogenated hydrocarbons, etc. are used alone or in a mixture of solvents,
The amount used is not particularly limited. Furthermore, in addition to the above, dimethylformamide, dimethylsulfoxide,
A polar solvent such as hexamethylphosphorylamide or N-methylpyrrolidone can also be used.

Although water alone or a mixture of water and the above organic solvent can be used as a solvent, when the mixture is used, in a two-phase system with an organic solvent, particularly an organic solvent immiscible with water (for example, toluene, benzene, etc.). Can be efficiently benzylated by coexistence with a phase transfer catalyst (eg, tetrabutylammonium chloride, benzyltrimethylammonium chloride).

The reaction temperature is generally -50 ° C to 120 ° C, preferably -30 ° C.
The range is up to 100 ° C.

After completion of the reaction, usual separation means such as extraction, liquid separation,
The biphenyl derivative (I) can be obtained in good yield by an operation such as concentration, and can be purified by column chromatography, recrystallization or the like, if necessary.

<Effects of the Invention> Thus, according to the method of the present invention, a novel compound, a biphenyl derivative represented by the general formula (I), can be industrially advantageously produced, and the compound of the present invention is useful as a liquid crystal material. In addition, it can be used as an intermediate for agricultural chemicals, pharmaceuticals, and the like.

<Example> Hereinafter, the present invention will be described with reference to Examples.

Example 1 A 4-necked flask equipped with a stirrer and a thermometer was charged with 2-acetyl-4'-hydroxybiphenyl (21.2 g, 0.1 mol) and dimethylformamide (200 ml), and anhydrous potassium carbonate (41.5 g, 0.3 mol) was added. And stir. After the temperature was raised to 50 ° C, 15.2 g of benzyl chloride was added dropwise, and the temperature was raised to 7
React for hours. After completion of the reaction, the reaction solution was poured into 500 ml of water and stirred, and the resulting precipitate was collected, washed well with water and dried to obtain 28.9 g of a white solid. This was recrystallized from ethanol to obtain 26.3 g (yield 87%) of 4-acetyl-4'-benzyloxybiphenyl.

Melting point 170-172 ° C. Example 2 4-acetyl-4 ′-(4-chlorobenzyl) was reacted and worked up in the same manner as in Example 1 except that 20.6 g of 4-chlorobenzyl chloride was used instead of benzyl chloride. 80.0 g (yield 89.5%) of (oxy) biphenyl was obtained.

Melting point 178-179.5 ° C Example 3 Sodium hydroxide (60%) in place of anhydrous potassium carbonate
The same reaction as in Example 1 except that 4.4 g (0.11 mol) was used (however, the reaction time was 3 hours) and post-treatment was carried out to give 4-
27.0 g of acetyl-4'-benzyloxybiphenyl was obtained.

Example 4 Sodium hydride (60%) instead of anhydrous potassium carbonate
The reaction was performed in the same manner as in Example 1 except that 17.2 g of p-methoxybenzyl chloride was used in place of benzyl chloride instead of 4.4 g (0.11 mol), and the post-treatment was carried out to obtain The pale yellow solid was recrystallized from ethanol to give 4-acetyl-4 '-(p-methoxybenzyl).
26.0 g (yield 79%) of oxybiphenyl was obtained.

Melting point 195-197 ° C. Example 5 Reaction and post-treatment were carried out in the same manner as in Example 1 except that 16.8 g of p-methylbenzyl chloride was used instead of benzyl chloride, and the obtained pale yellow solid was recrystallized from ethanol. , 4-acetyl-4 '-(p-methylbenzyl)
25.6 g (yield 81%) of oxybiphenyl was obtained.

Melting point 179-181.5 ° C

Claims (2)

(57) [Claims] 1. A general formula (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. 4-Acetyl-4'-hydroxybiphenyl and the general formula (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, and X represents a halogen atom or -OSO ₂ R. Here, R
Represents a lower alkyl group or an optionally substituted phenyl group), and a general formula characterized by reacting a benzylating agent represented by (Wherein A has the same meaning as described above).