Propanol derivatives and perfumes containing the same

Details Propanol derivatives and perfumes containing the same Propanol derivatives and perfumes containing the same

1998-07-08

2001-05-01

Reamer, James H. (Department: 1614)

Perfume compositions

Perfume compositions

Ring containing active ingredient

C568S822000

Reissue Patent

active

RE037159

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a novel propanol derivative useful for perfume cosmetics, etc., and a perfume containing the same as an active ingredient.
BACKGROUND OF THE INVENTION
Some naturally-occurring compounds exhibit various characteristics attributed to their asymmetric structure. Of physiologically active substances having an asymmetric structure, many of those useful for humans are confined to the respective specific antipode. This tendency is particularly conspicuous in the field of pharmaceuticals, agricultural chemicals, pheromones, and food additives. It is known in these fields that a racemic mixture may have a markedly reduced effect or rather exhibit a counter effect. The field of perfumes is no exception to this tendency. For example, 1-menthol has the odor of mint; d-carvone has the odor of Caraway L.; and d-nootkatone has the odor of grapefruit. Each of these optical antipodes is different from or stronger than the respective other optical antipodes in odor. The latest examples of such a phenomenon are observed in &agr;-ionine, hydroxycitronellal, and rose oxide. For the detail, reference can be made to Kaqaku Sosetsu, No. 14, Ch. 6 “Aji to Nioi no Kagaku” (1976).
Therefore, development of optically active perfume components as well as development of novel perfumes would lead to development of optical antipodes having a new odor or usefulness and are of industrial significance.
With respect to 3-(2,2,6-trimethylcyclohexan-1-yl)propanol derivatives, compounds known to have a wood-like fragrance or an amber-like fragrance include 1-(2,2,6-trimethylcyclohexan-1-yl)pentan-3-ol having an ethyl group as the alkyl moiety (see West German Patent Application (OLS) No. 2,455,761), 1-(2,2,6-trimethylcyclohexan-1-yl)hexan-3-ol having a propyl group as the alkyl moiety (see JP-A-62-70314, JP-B-1-38438, JP-B-59-18373, JP-A-61-191636, and JP-B-62-16935; the terms “JP-A” and “JP-B” as used herein mean an “unexamined published Japanese patent application” and an “examined Japanese patent publication”, respectively), and 5-methyl-1-(2,2,6-trimethylcyclohexan-1-yl(hexan-3-ol having an isobutyl group as the alkyl moiety (See USSR Patent 1,082,780).
JP-B-1-38438 discloses a composition of 1-(2,2,6-trimethylcyclohexan-1-yl)hexan-3-ol comprising 80% or more of a trans isomer and not more than 20% of a cis isomer.
Since these cis and trans isomers each has an asymmetric carbon atom in the molecule thereof, it is expected that there are a pair of enantiomers, i.e., (+)-isomer and (−)-isomer. However, the compounds disclosed in the above-cited references exist as a racemic mixture. No other study has been reported on synthesis or properties of the individual optical isomers.
The recent diversity of cosmetics and sanitary goods has created a new increasing demand for a perfume material which has a high diffusibility, unique scent, high tastiness, high retention, satisfactory stability, and high safety. In particular, perfume materials having an amber-like fragrance and satisfying these requirements have been wanted.
SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to provide an optically active compound which is capable of imparting an amber-like fragrance while meeting the above-described demand.
Another object of this invention is to provide a perfume comprising the above-described optically active compound as an active ingredient.
In the light of the above-mentioned circumstances, the inventors have conducted extensive investigations and, as a result, succeeded to synthesize an optically active isomer of a 3-(2,2,6-trimethylcyclohexan-1-yl)propanol derivative and found that the 6(S)-isomer of the compound has a sharp and highly diffusible amber fragrance free from a wood-like fragrance accompanied by the dim odor of mold and is useful as a perfume. The present invention has been completed based on this finding.
The present invention relates to an optically active 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]propanol derivative represented by formula (I):
wherein R
1
represents a lower alkyl group.
The present invention further relates to a perfume containing the optically active compound of formula (I) as an active ingredient.
DETAILED DESCRIPTION OF THE INVENTION
In formula (I), the lower alkyl group as represented by R
1
preferably contains from 1 to 4 carbon atoms, and specific examples thereof include a methyl group, and ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
The optically active 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]propanol derivative of formula (I) can be synthesized, for example, in the following reaction scheme.
wherein R
1
is as defined above; and X represents a halogen atom.
The above active optically active propanol derivatives of formula (
I
)
can also be represented by the following formula
(
A
):
In the above formula
(
A
)
, the wavy line means a bond whose direction is not specified in the formula. It thus includes both the trans and cis forms of the compounds of formula
(
I
)
as reflected in Synthesis Examples
7
-
17
.
That is, the optically active 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]propanol derivative of formula (I) can easily be synthesized by reacting an optically active 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]propanal represented by formula (2) with an alkylmagnesium halide represented by the formula, R
1
MgX, wherein R
1
and X are the same as defined above.
The starting compound, 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]propanal (2), is a novel compound and can be synthesized in the following reaction scheme:
wherein R
2
represented a hydrogen atom or a methyl group; Ac represents an acetyl group; Et represents an ethyl group; and the wavy line indicates a trans- and/or cis-position.
While an optically active 1-[6(S)-2,2,6-trimethylcyclohexan]carbaldehyde (5) as an intermediate compound of the above reaction route is known to by synthesized by starting with optically active citronellal as described in JP-A-63-44544, it can easily be synthesized in a high yield by starting with optically active 1-methoxycitronellal (3) which is used on an industrial scale as a perfume or juvenile pheromone of mosquito larvae. Namely, 1-methoxycitronellal (3) is reacted with acetic anhydride to obtain an enol acetate (4) which, as produced, is then subjected to cyclization in the presence of a phosphoric acid catalyst to obtain the compound (5).
The compound (5) is then reacted with triethyl phosphonoacetate (6) by utilizing the Wittig reaction described, e.g., In Herbert O. House, Modern Synthetic Reaction, p. 690, W. A. Benjamin, Inc., Menlo Park, Calif., U.S.A. (1972) by synthesize optically active ethyl 3-[6(S)-2,2,6-trimethylcyclohexan-1yl]acrylate (7).
The compound (7) is reduced by using sodium borohydride or sodium bis(2-methoxyethoxy)aluminum hydride to synthesize optically active 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]-2-propen-1-ol (8) which is then oxidized with manganese dioxide to obtain optically active 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]-2-propen-1-al (9). The compound (9) is then hydrogenated in the presence of a palladium-on-carbon as a catalyst to synthesize optically active 3-[6(S)-2,2,6-trimethylcyclohexan-1-yl]propanal (2).
While the above description relates to synthesis of the 6(S)-compound, a 6(R)-compound can be obtained in the similar manner by starting with d-methoxycitronellal in place of 1-methoxycitronellal.
It surprisingly turned out that the scent given off by the thus obtained 3-[2,2,6-trimethylcyclohexan-1-yl]propanol derivatives utterly differs between different optical antipodes. More specifically, the 6(S)-compounds have a sharp amber fragrance with very high diffusibility in common, though somewhat different in strength and quality depending on the kind of R
1
. On the other hand, the 6(R)-compounds basically produce no amber fragrance and give off a powerless wood-like fragrance with a little moldiness. The racem

Affiliated with

Also associated with

Rating

Propanol derivatives and perfumes containing the same does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Propanol derivatives and perfumes containing the same, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Propanol derivatives and perfumes containing the same will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2559138