JPH0737404B2 - Optically active biphenyl ether compound - Google Patents

Description

The present invention relates to a specific optically active biphenyl ether compound, and more particularly to a hydroxybiphenyl ether compound having an alkoxy group having an asymmetric carbon.

Alkoxybenzene derivatives having asymmetric carbon have attracted particular attention in recent years as intermediates for liquid crystal chemicals.
Alkoxybiphenyl compounds, alkoxyphenylpyrimidine compounds, and alkoxybenzoic acid derivatives are known as ferroelectric smectic liquid crystal chemicals.

The alkoxy group in these liquid crystal compounds is 6
-Methyloctoxy group, 2-methylbutoxy group and the like are known, but these compounds have a problem that the usable temperature range is not appropriate, or the orientation stability is poor, and they are practical. It wasn't.

Therefore, a ferroelectric liquid crystal compound including the basic skeleton of the compound is currently being studied.

As a result of intensive studies on the alkoxybiphenyl compound having an asymmetric carbon atom, the present inventors have found that the compound represented by the following general formula (I) has excellent optical activity.

Further, the compound represented by the general formula (I) has a highly reactive hydroxyl group as a nuclear substituent, and is therefore expected as an intermediate for a ferroelectric liquid crystal compound.

(In the formula, n represents 3 to 5, m represents 3 to 12, and * represents an asymmetric carbon.) Hereinafter, the present invention having the above gist will be described in more detail.

The compound represented by the above general formula (I) is, for example, 4,4 ′
It can be easily produced by reacting dihydroxybiphenyl with a halide or tosylate of an optically active alcohol in the presence of an alkali compound.

Next, the present invention will be described with reference to examples.

Example 1 Preparation of 4- (4 "-methyldodecyloxy) -4'-hydroxybiphenyl 3.72 g of 4,4'-dihydroxybiphenyl, 0.8 g of finely powdered sodium hydroxide and 50 ml of methyl ethyl ketone were taken and refluxed to 1 Stir for hours.

Here, optically active 4-methyldodecyl bromide 5.27
g was added, and the mixture was stirred at 80 ° C. for 15 hours.

The reaction mixture was poured into a large amount of 5% hydrochloric acid, and the precipitated solid was filtered. After washing with water and drying, n-hexane / ethyl acetate (85
/ 15) was purified with a silica gel column as a developing solvent to obtain 4- (4 "-methyldodecyloxy) -4'-hydroxybiphenyl as a white powder having a melting point of 125 to 126 ° C.

As a result of infrared spectroscopic analysis, the obtained product had the following characteristic absorptions and was confirmed to be the target product.

3400cm ^-1 (s), 3050cm ^-1 (w), 2975cm ^-1 (w), 29
40cm ^-1 (s), 2860cm ^-1 (m), 1610cm ^-1 (m), 1600
^{cm -1 (m), 1500cm -1} (s), 1470cm -1 (m), 1450cm
^-1 (m), 1380cm ^-1 (w), 1250cm ^-1 (s), 1040cm ^-1
(W) and 820 cm ^-1 (s) The optical rotation of the obtained product is shown below.

[Α] _D = + 0.69 ° (29 ° C., C = 1, chloroform solution) Example 2 Preparation of 4- (6 ″ -methyldecyloxy) -4′-hydroxybiphenyl 4,4′-dihydroxybiphenyl 4.1 g Then, 0.8 g of finely powdered sodium hydroxide and 50 ml of methyl ethyl ketone were taken and stirred under reflux for 1 hour.

To this was added 6.53 g of optically active p-toluenesulfonic acid ester of 6-methyldecanol, and the mixture was stirred at 82 ° C for 12 hours.

The reaction mixture was treated as in Example 1 and had a melting point of 119-120.
The target product, 4- (6 ″ -methyldecyloxy) -4′-hydroxybiphenyl, was obtained as a white powder at ℃.

As a result of infrared spectroscopic analysis, the obtained product had the following characteristic absorptions and was confirmed to be the target product.

3400cm ^-1 (s), 3050cm ^-1 (w), 2975cm ^-1 (w), 29
40cm ^-1 (s), 2860cm ^-1 (m), 1610cm ^-1 (m), 1600
^{cm -1 (m), 1500cm -1} (s), 1470cm -1 (m), 1450cm
^-1 (m), 1380cm ^-1 (w), 1250cm ^-1 (s), 1040cm ^-1
(W) and 820 cm ^-1 (s) The optical rotation of the obtained product is shown below.

[Α] _D = + 0.38 ° (28 ° C, C = 1, chloroform solution)

Claims (1)

[Claims] 1. An optically active biphenyl ether compound represented by the following general formula (I). (In the formula, n represents 3 to 5, m represents 3 to 12, and * represents an asymmetric carbon.)