JPS5822450B2 - Isolongiphoran-3-ol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound inlongiphoran-3-ol represented by the following formula (I).

Conventionally, isolongifolane ketone represented by the following formula (II) has an excellent aroma, and it has been reported that inlongifolane can be prepared in formic acid or acetic acid in the presence or absence of a strong acid such as sulfuric acid, hydrogen peroxide, or an organic peracid. Or, it is known that it can be obtained by oxidation with sodium dichromate etc. (US Pat. No. 371,869).
No. 8, Special Publication No. 4-7-20639, Japanese Patent Publication No. 49-80
No. 057).

As a result of various studies aimed at synthesizing isolonghiphoran ketone by another method, the present inventors succeeded in heating inlonghiphoran epoxide represented by the following formula (m) in a hydrogen atmosphere using palladium-carbon as a catalyst. For example, isolonghiphoran ketone (TI) can be obtained, and the product purified by ordinary vacuum distillation has an excellent amber-like and patchouli-like aroma in addition to the woody aroma of isolonghiphoran ketone. It was discovered that it also has a scent tone.

Therefore, the inventor searched for the original area and found that
It is difficult to separate and purify using ordinary vacuum distillation, but as a result of analysis using gas chromatography, which has a high separation ability, it was found that isolonghiphoran-4-ol (IV and inlongiphoran-4-ol represented by inlongiphoran) was present in the product. It was confirmed that 3-ol (■) was contained in an amount of 5 to 10%, and that these together produced the above-mentioned excellent fragrance tone.

The present inventor isolated this new compound, inlonkiphoran-3-ol, and confirmed its properties, and found that it is a fragrant substance with a unique aroma reminiscent of patchouli alcohol, and it can be used as a fragrance ingredient. It was discovered that it has high industrial value, and furthermore, by reducing isolongifolane eboxide (III) with lithium aluminum hittride, inlongifolen-3-ol (■
) could be obtained in high yield, and completed the present invention.

The compound inlongiphoran-3-ol (I) of the present invention can be produced using inlongiphoran epoxide (■) as a raw material.

Longifolene, a bicyclic sesquiterpene produced as an essential oil component of pine resin, is easily isomerized to inlongifolene using an acid catalyst.

By treating this inlongifolene with peracetic acid in an inert solvent such as chloroform, inlongifolene epoxide (III) is easily prepared.

Inlongiphoran eboxide (III) is reacted with lithium aluminum hittride using a solvent such as tetrahydrofuran.

That is, lithium aluminum hittride is added to tetrahydrofuran in advance, and a tetrahydrofuran solution of isolongiphoran epoxiside is gradually added thereto.

It is appropriate to maintain the reaction temperature at about 30°C.

After the reaction is completed, the solvent is collected, decomposed with hydrochloric acid, extracted with a solvent such as n-hexane, distilled off, and then distilled under reduced pressure to precipitate 100-b. Point 7
White crystals of inlongifolen-3-ol are obtained at a temperature of 1.5-72.0°C.

There is almost no difference in the aroma of the products obtained by distillation purification alone and by adding recrystallization purification, so when using it as an industrial fragrance substance, distillation purification should be used. That's enough.

Next, an example will be given and explained.

Example 1 11 of tetrahydrofuran was placed in a 5F reaction kolben,
Add to this lithium aluminum Hitler 100P (2,
6 mol) was added little by little under water cooling.

This was heated to 30° C., and 1 kg (5.0 mol) of inlongiphoran epoxide] in tetrahydrofuran solution 11 was added over 1 hour while stirring.

After the reaction, the mixture was allowed to stand for 12 hours], and n-hexane was added to the tetrahydrogen residue from the reaction solution at 50 mvtHg to form a slurry, which was poured into ice water little by little with vigorous stirring.

Add 4.0% concentrated hydrochloric acid to this. Add 50 ml of acidic water layer and n-
The hexane layer was separated.

The aqueous layer was further extracted with n-hexane, combined with the n-hexane layer, washed with sodium carbonate water, and then distilled.
Collect hexane and then 100-107°c/0
．． 5 mmHg fraction 9]. 2. ! I got l.

This product crystallizes when left to stand, and then recrystallizes from 90% ethanol to crystallize 377 with a melting point of 71 and a temperature of 5 to 72.0°C.
, 5F was obtained.

Concentration of the recrystallization mother liquor further yielded 1102 as crystals with a purity of 99% or higher.

The immediate and MS spectra of this product were as follows, and it was confirmed that it was inlongifolen-3-ol.

NMR spectrum (CDCl2): 0.86 (s,
3H), 0,91 (s,6H), 0.98(s,3H
), ],, 16 (s, OH), 0.9 8 ~ 2.1
2 (m, 13H).

MS spectrum (m/e): 2 2 2 (M+
), 207, 189, 179, 161, 153, 139
, 111, 109, 98.

This product has an excellent patchouli-like aroma.

Example 2 Perfume for Detergents By using the above formulation, a perfume for detergents having excellent patchouli-like fragrance retention and a clean feeling after washing was obtained.

Claims (1)

[Claims] 1 The following formula (I) Inlongiphoran-3-ol represented by