JPH0657667B2 - Optically active phenyl ether compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a specific optically active phenyl ether compound, and more particularly to a halogenated phenyl ether compound having an alkyl 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, alkoxybenzoic acid derivatives and the like are known as ferroelectric smectic liquid crystal chemical substances.

As the alkoxy group in these liquid crystal compounds, 6-
Methyloctoxy group, 2-methylbutoxy group, etc. are known, but these compounds have a problem that the usable temperature range is not appropriate, or the stability is poor, and they are practical Was not.

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 alkoxybenzene 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.

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

(In the formula, X represents a halogen atom, n represents 3 to 12, and * represents an asymmetric carbon.) Hereinafter, the present invention will be described in more detail.

Examples of the halogen atom represented by X include chlorine, bromine, iodine and fluorine, and a compound in which X is bromine is particularly preferable. Moreover, n shows 3-12, but especially a compound of 4-10 is preferable.

The compound represented by the general formula (I) can be easily produced by a well-known etherification reaction such as, for example, converting 4-methylalkanol into a sulfonic acid ester and then reacting with 4-halogenated phenol. it can.

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

Example 1 Preparation of 4-methyldecyl-4'-bromophenyl ether 172 g (1.0 mol) of 4-methyldecanol and 151.5 g (1.5 mol) of triethylamine were added to 1300 ml of dichloromethane.
, And cooled to 0-10 ° C. Methanesulfonyl chloride (149 g, 1.3 mol) was added dropwise, and after the addition, the mixture was stirred at the same temperature for 2 hours.

Dichloromethane (1000 ml) was added, and the mixture was washed with ice water, 10% hydrochloric acid, saturated aqueous sodium carbonate solution and saturated brine in that order, dried over magnesium sulfate, and desolvated to give 4-methyldecylmethanesulfonate.

125 g (0.5 mol) of 4-methyldecyl methanesulfonate, 95.1 g (0.55 mol) of 4-bromophenol, 30 g (0.75 mol) of powdered sodium hydroxide and 800 of dioxane
After taking up ml, the mixture was stirred under reflux for 8 hours, and after disappearance of the sulfonic acid ester was confirmed by gas chromatography, the produced sodium methanesulfonate was filtered off. The filtrate was desolvated, the resulting residue was extracted with 1000 ml of toluene, the toluene solution was washed with 5% hydrochloric acid and then with saturated saline, and desolvated.

Distillation under reduced pressure gave 4-methyldecyl-4'-bromophenyl ether as a fraction having a boiling point of 165 ° C / 1 mmHg.

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

1590 cm ^-1 and 820 cm ^-1 (benzene ring), 1380 cm ^-1 (methyl group), 1250 cm ^-1 (ether) Further, the following optical rotation of the resulting product.

[Α] _D = + 2.84 ° (chloroform) Example 2 Preparation of 4-methyldodecyl-4′-bromophenyl ether 4-methyldodecanol 2 was used instead of 4-methyldecanol.
In the same manner as in Example 1 except that 00 g (1.0 mol) was used,
The target product, 4-methyldodecyl-4'-bromophenyl ether, was obtained as a fraction having a boiling point of 175 ° C / 1 mmHg.

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

1590 cm ^-1 and 820 cm ^-1 (benzene ring), 1380 cm ^-1 (methyl group), 1250 cm ^-1 (ether) Further, the following optical rotation of the resulting product.

[Α] _D = + 1.99 ° (chloroform)

Claims (1)

[Claims] 1. An optically active phenyl ether compound represented by the following general formula (I). (In the formula, X represents a halogen atom, n represents 3 to 12, and * represents an asymmetric carbon.)