JPH0788329B2 - Optically active phenyl ether compound - Google Patents

Description

The present invention relates to a specific optically active phenyl ether compound, and more particularly to a hydroquinone monoether compound having an alkyl group having an asymmetric carbon atom and a chlorine atom.

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

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 alkoxyphenol 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, R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents an asymmetric carbon.) Hereinafter, the present invention having the above gist will be described in more detail.

The compound represented by the general formula (I) is, for example, prepared by converting the corresponding 6-chloro-4-methylalkanol into a sulfonic acid ester, reacting it with hydroquinone monobenzyl ether, and then debenzylating by hydrogenation. It can be easily produced by a conventional monoetherification reaction such as.

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 Production of (R) -4- (6'-chloro-4'-methylhexyloxy) phenol 100 ml of dioxane [α] _D = -3.76 ° (27 ° C, C =
2. Chloroform solution) 9.14 g (0.03 mol) of para-toluene sulfonic acid ester synthesized from (R) -6-chloro-4-hexanol and 9.01 g (0.045 mol) of hydroquinone monobenzyl ether were dissolved and further pulverized. 2.40 g (0.06 mol) of sodium hydroxide was added, and the mixture was stirred under reflux for 3 hours. After desolvation, extract with 50 ml of toluene,
It was washed with 5% aqueous sodium hydroxide solution, 5% hydrochloric acid and saturated brine in this order, dried and then desolvated to obtain 9.35 g of crude ether.

This crude ether was added to n-hexane / diethyl ether (95
/ 5) was purified with a silica gel column using a developing solvent to obtain (R) -4- (6'-chloro-4'-methylhexyloxy) phenylbenzyl ether.

3.0 g of the above benzyl ether, 5% palladium carbon
0.3 g and 30 ml of ethanol were taken and hydrogenated at 60 ° C. and normal pressure. The obtained product was purified by a silica gel column using n-hexane / diethyl ether (70/30) as a developing solvent to obtain 2.1 g of (R) -4- (6'-chloro-4'-methylhexyloxy) phenol. Obtained.

The results of infrared spectroscopy (IR) and NMR are as follows:
It was confirmed that it was the target product.

IR: 3350 (s), 3050 (vw), 2950 (s), 2900 (w), 1605 (w), 1510 (s), 1470 (w), 1445 (m), 1385 (w), 1355 (w ), 1295 (w), 1230 (s), 1105 (w), 1010 (m), 920 (w), 830 (s), 770 (m), 725 (m), 655 (w), 520 (w ) ¹ H-NMR (carbon tetrachloride): δ = 6.55 (4H, s), 6.32 (1H, s), 3.76 (2H, t, J = 5.
8), 3.40 (2H, t, J = 6.5), 2.03 to 0.93 (7H, m), 0.79
(3H, d, J = 5.6) The optical rotation of the obtained product is shown below.

[Α] _D = + 2.02 ° (24 ° C., C = 1, chloroform solution) Example 2 (R) -4- (6′-chloro-4′-methyloctoxy)
Production of Phenol [α] _D = + 0.75 ° (28 ° C, C = 1, chloroform solution) Paratoluenesulfonic acid ester synthesized from (R) -6-chloro-4-methyloctanol 9.99 g (0.0
3 mol) and 9.01 g (0.045 mol) of hydroquinone monobenzyl ether were used as starting materials, and in exactly the same manner as in Example 1, the desired (R) -4- (6′-chloro-4′-methyloctoxy) was obtained. ) Obtained phenol.

The results of infrared spectroscopy (IR) and NMR are as follows:
It was confirmed that it was the target product.

IR: 3350 (s), 3040 (vw), 2925 (s), 2890 (m), 1600 (w), 1505 (s), 1450 (s), 1380 (m), 1355 (m), 1295 (w ), 1225 (s), 1100 (w), 1030 (m), 900 (w), 825 (s), 770 (m), 730 (w), 660 (w), 605 (w), 515 (w ) ¹ H-NMR (carbon tetrachloride): δ = 6.53 (4H, s), 5.83 (1H, s), 4.08 to 3.27 (3H,
m), 2.23 to 1.10 (9H, m), 1.10 to 0.60 (6H, m) The optical rotations of the obtained products are shown below.

[Α] _D = + 5.82 ° (26 ° C., C = 1, chloroform solution) Example 3 (R) -4- (6′-chloro-4′-methyldecyloxy)
Phenol production [α] _D = -1.95 ° (26 ° C, C = 1, chloroform solution) 10.83 g (0.03 g) of paratoluenesulfonic acid ester synthesized from (R) -6-chloro-4-methyldecanol
Mol) and 9.01 g (0.045 mol) of hydroquinone monobenzyl ether as raw materials, and in exactly the same manner as in Example 1, the target (R) -4- (6′-chloro-4′-methyldecyloxy) was obtained. Obtained phenol.

The results of infrared spectroscopy (IR) and NMR are as follows:
It was confirmed that it was the target product.

IR: 3350 (s), 3040 (vw), 2930 (s), 2880 (m), 1605 (w), 1510 (s), 1460 (s), 1380 (m), 1360 (m), 1300 (w ), 1220 (s), 1105 (w), 1020 (m), 935 (w), 830 (s), 770 (m), 735 (m), 665 (w), 520 (w) ¹ H-NMR (Carbon tetrachloride): δ = 6.54 (4H, s), 6.00 (1H, s), 4.05 to 3.52 (3H, s)
m), 2.16 to 1.03 (13H, m), 1.03 to 0.62 (6H, m) The optical rotation of the obtained product is shown below.

[Α] _D = + 2.00 ° (26 ° C, C = 1, chloroform solution)

Claims (1)

[Claims] 1. An optically active phenyl ether compound represented by the following general formula (I). (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents an asymmetric carbon.)