JPS63190839A - Optically active alcohol compound - Google Patents

Abstract

NEW MATERIAL:An optically active alcohol compound shown by I (R is H or 1-18C straight-chain alkyl; * is asymmetric carbon). EXAMPLE:6-Chloro-4-methyloctanol. USE:Useful for various industrial chemicals such as an intermediate for cosmetics and drugs. Further useful as an intermediate for liquid crystal compound or as an optical resolving agent or an auxiliary for asymmetric synthesis. Being expected to have physiological activities. PREPARATION:For example, (R)-(+)-citronellic acid or an R-2,6-dimethyl-8-oxo- alkene obtained by alkylating (R)-(+)-citronellic acid is reduced or optically active 3,7-dimethyl-6-octenal is reduced to give a compound, which is chlorinated to give a 2,6-dimethyl-8-chloroalkene-2. This compound is oxidized and reduced to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a specific optically active alcohol compound, and more particularly to a 4-methyl-6-chloroalkanol compound containing an asymmetric carbon.

Alcohol compounds having a methyl branch are useful as various industrial chemicals such as intermediate raw materials for cosmetics and pharmaceuticals, and in particular, optically active alcohol compounds have recently attracted particular attention as intermediates for liquid crystal chemicals. For example, alkoxyphenylpyrimidine compounds, alkoxybenzoic acid derivatives, and the like are known as ferroelectric liquid crystal chemical substances.

The alkoxy group in these liquid crystal compounds is 2
- Alkoxy groups derived from alcohols with a relatively small number of carbon atoms such as methylbutoxy or 6-methyloctoxy are known, but these compounds have problems such as an inappropriate usable temperature range. , which was not practically satisfactory.

As a result of repeated studies on optically active alcohol compounds having a methyl branch, the present inventors found that a compound represented by the following -m formula (I) has excellent optical activity.

HO (CHz): + CHCHz-C1l R(1)
CH, c+ (In the formula, R represents a hydrogen atom or a linear alkyl group having 1 to 18 carbon atoms, and * represents an asymmetric carbon.) The optically active alcohol of the present invention is an important substance as an industrial chemical. be. For example, in addition to the above intermediates for liquid crystal compounds, they are useful as optical resolution agents or auxiliary agents for asymmetric synthesis, and are also expected to have various physiological activities.

The present invention will be explained in more detail below.

Examples of the alkyl group represented by R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl groups.

Therefore, as a compound represented by the above general formula (1),
6-chloro-4-methylhexanol, 6-chloro-4
-Methyloctatool, 6-chloro-4-methylnonanol, 6-chloro-4-methyldecanol, 6-chloro-4-methyldodecanol, 6-chloro-4-methyloctadecanol, and the like.

These compounds are, for example, (R)-(I)-citronel acid or (R)-2,6-dimethyl-8-oxoalkene-2 obtained by alkylating it.
or optically active 3,7-dimethyl-6-octenal or optically active 2,6-dimethyl-8-oxoalkene-2 obtained by alkylating it. Active 2,6-dimethyl-8-hydroxyalkene-2 is chlorinated to form 2,6-dimethyl-8-chloroalkene-2.
It can be produced by producing 2, followed by oxidation and reduction.

Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these examples.

Example 1 ■ Two-pronged Yutan ↓ Two-pronged Earth Oe-sha J2y ■ Examination (112,
Synthesis of 6-dimethyl-8-hydroxydecene-2 18.
2 g of optically active 2,6-dimethyl-8-oxodecene-2 in 50 m7 of ethanol? Comprehensive, 19 in 7 dishes
After adding g of sodium borohydride over 5 minutes,
The mixture was stirred at room temperature for 2 hours.

After sufficiently concentrating the reaction mixture, 50 u/h of water was added, extracted with diethyl ether, washed with saturated brine, and dried.

Distilled after removing the solvent, boiling point 79-80"c/1
15.5 g of 2.6-dimethyl-8-hydroxydecene-2 was obtained as a distillate of 11 g mm.

(2) Synthesis of 2,6-dimethyl-8-chlorodecene-2 13.8 g of 2,6-dimethyl-8-hydroxydecene-2 was dissolved in 75DI7 carbon tetrachloride, and 21.0 g of triphenylphosphine was added. , and stirred under reflux for 3 hours.

After the solvent was distilled off, the mixture was extracted with hexane, and after the hexane was distilled off, it was distilled to obtain 669 g of 2.6-dimethyl-8-chlorodecene-2 as a distillate with a boiling point of 118-120°C/16a+mHg.

(3) Synthesis of 6-chloro-4-methyloctatool Take 100% each of anhydrous methanol and anhydrous dichloromethane,
6.9 g of 2,6-dimethyl-8-chlorodecene-2 was dissolved therein. Cool this to -40℃ and weigh 0.04 g
Oxygen containing 1/l of ozone was blown in for 30 minutes at a rate of 12017 hours. After removing excess ozone by blowing nitrogen gas, sodium borohydride 4 was added at the same temperature.
．． 2 g was added, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 1 hour.

-After standing overnight, add 100m7 of toluene to the reaction solution and add 5%
The mixture was poured into 200ml of hydrochloric acid and stirred at room temperature for 1 hour.

The toluene layer was taken, washed with saturated brine, and then dried.

After removing toluene, it is distilled to a boiling point of 69-70℃10.
3.2 g of the target product, 6-chloro-4-methyloctatool, was obtained as a distillate of 111In+Hg.

I R(cs+-') 3325 (s), 2900 (s), 1455 (s
), 1380 (m), 1055 (s), 610 (
m) H-NMR (CC14) 64.03 (s: III, OH), 3.80 (
Town 1) 1. C11-CI), 3.43 (t, J=
6Hz; 21+, CHz-0), 2.00-1.06
(m; 9H, CH2 and CH), 0.96 (t,
J, 611□; 3tl, C1l+), 0.85
(d, J=5Hz; 311. CH3) Specific optical rotation (α) D= +0.75° (28°C, C=1,
CllCl:l solution) Example 2 Any 3 Ryo and - Ni no' So and L ± No 2 sori needle setting 2.6-
Instead of dimethyl-8-oxodecene-2, optically active 2
．． The boiling point was 71 to 72°C by the same procedure as in Example 1 except that 6-dimethyl-8-oxoundecene-2 was used.
The target object, 6-
Chloro-4-methylnonanol was obtained.

l R(cm-') 3325 (s), 2950 (s), 1460 (s
), 1380 (m), 1060 (s), 605 (
m) FI -N M R (CC1,) δ 4.00 Cm; 11. CI-CI), 3.5
8 (t, J=6Hz; 2H, Cl1g-0), 2
．． 77 (br-s; II (,0ff), 1.93~
1.10 (m; IIH, C1b and C11), 0.
93 (t, d=611z; 3H, C113), 0
．． 92 (d, J・5Hz; 3tL C1l:l)
Specific optical rotation [α]. --1,75° (27℃, C=2
, CClCl:l) Example 3 -Chloro-4-methylhexanol 9 Synthesis 2.In place of 6-dimethyl-8-oxodecene-2, optically active 3,
Example 1 except that 7-dimethyl-6-octenal is used.
The title compound was synthesized in exactly the same manner as above. However, the target product is ethyl acetate/n-hexane (25/75)
The product was purified by silica gel column chromatography using as a developing solvent.

T R (cm-') 3340 (s), 2925 (s), 1450 (s
), 1380 (m), 1055 (s), 650 (
m) HN M R (CC1a) 63.45 (t, J=6H,; 2+1. CH2
-0), 3.45 D, J=611□; 2H, C1
1z-CI), 3.13 (s; Ill, 01l)
, 2.00-1.10 (m; IH, C1l□ and C
)l), 0.88 (d, J・5.5Hz: 311
．． C1h) Specific rotation [α]. =-3,76° (27°C, C=2, CHC
l3 solution) Patent applicant: ADEKA ARGUS CHEMICAL CO., LTD.

Claims (1)

[Claims] An optically active alcohol compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R represents a hydrogen atom or a straight-chain alkyl group having 1 to 18 carbon atoms, and * represents an asymmetric carbon.)