Perfuming ingredients of woody, fruity odor

Details Perfuming ingredients of woody, fruity odor Perfuming ingredients of woody, fruity odor

1999-09-16

2001-05-22

Keys, Rosalynd (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acid esters

C568S665000, C568S820000

Reexamination Certificate

active

06235926

ABSTRACT:

TECHNICAL FIELD AND PRIOR ART
The present invention relates to novel perfuming ingredients. It relates, more particularly, to compounds of the general formula
as defined further on, and their use in perfumery.
The said compounds possess novel odoriferous properties, namely woody and, fruity odors this combination being unknown in the prior art compounds. The application also concerns syntheses and novel intermediate products which serve to prepare said compounds.
The compounds which are the object of the present invention show as a common feature the bicyclic carbon framework 7,7-dimethyl-10-methylene-bicyclo [4.3.1]decane which carries osmophoric groups comprising an oxygen atom in the exocyclic 3-position. The bicycle can, moreover, comprise other substituents, for example alkyl groups.
The use in perfumery of substances of similar structure, which comprise the bicyclic system 6,6-dimethyl-9-methylene-bicyclo[3.3.1]nonane, thus having one carbon atom less in the cycle carrying the osmophoric group, has been known for a long time. From an olfactive point of view, the most important substance of this well-known group is 2-ethoxy-2,6,6-trimethyl-9-methylene-bicyclo[3.3.1]nonane of formula
the synthesis of which was carried out for the first time in the fifties by Stoll et al. (see U.S. Pat. No. 2,803,662). Since then, several syntheses were described for this product, all leading to a mixture of the exo- and endo-ethoxy isomers, with the relative proportions between these 2 isomers varying considerably according to the synthesis which was chosen. A mixture of these isomers is, moreover, sold under the commercial name Physeol (origin: Firmenich SA, Geneva, Switzerland). This commercially available compound has a woody odor which is accompanied by an amber ether note.
We have now discovered that the presence of a supplementary carbon in the cycle carrying the osmophoric group gives rise to odoriferous properties which are clearly distinct from those of Physeol and of its analogues, namely woody and amber notes to which there is added an intense fruity note, in particular of the rhubarb or grapefruit type. In view of the knowledge of the odor properties of bicyclic compounds of the 6,6-dimethyl-9-methylene-bicyclo[3.3.1]nonane type, mentioned above, and of Physeol in particular, this result is thus very unexpected and renders the compounds (I) and (II) particularly useful in perfumery due to the combination of the above-mentioned odor characteristics.
DESCRIPTION OF THE INVENTION
The object of the present invention is thus to provide novel perfuming ingredients showing the above-mentioned specific odor, and the synthesis of said products.
Therefore, the present application describes compounds of the general formula
in which
R
1
and R
2
are identical or different and represent each a methyl or ethyl group,
R
3
represents hydrogen or an alkyl group from C
1
to C
4
, linear or branched,
R
4
represents hydrogen, an alkyl group from C
1
to C
4
, linear or branched, or an acyl group of formula R
5
C(O)—, R
5
being hydrogen or an alkyl group from C
1
to C
4
, linear or branched,
and their use in perfumery.
The common feature of the compounds of the present invention containing the bicycle 7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane oxo-substituted in position 3, is their olfactive character. Their odor can be described as a woody note, together with an intense fruity note. The quality and intensity of said fruity note can be of varied nature, but the woody bottom note is always clearly present, rendering said compounds particularly useful in perfumery.
Of course, in spite of the fact that the compounds of the present invention possess a common odor of the woody-fruity type, there are differences between the various products, and these can be quite pronounced. These differences cannot only reveal themselves between compounds of different chemical structure, but even between stereoisomers of a given compound.
The odoriferous properties of the compounds of the invention are best represented in 7,7-dimethyl-10-methylene-bicyclo[4.3.1]dec-3-yl acetate and in 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane. These two compounds are thus preferred according to the invention.
7,7-Dimethyl-10-methylene-bicyclo[4.3.1]dec-3-yl acetate, in the form of a mixture of isomers of the exo and endo configuration, develops a woody note which is accompanied by a note of the rhubarb type. The overall impression of the odor of this compound is that of a woody-rooty note of the Vetyver type, with the rooty character being accompanied by the mentioned fruity character. This olfactive character is very prized in fine perfumery.
The two exo and endo isomers of this compound show distinct odors. The exo isomer, in fact, develops an odor in which the woody, cedar character is more marked, whereas the endo isomer possesses a woody note in which the odor characters of the rhubarb and grapefruit types are very pronounced.
3-Methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane also exists in two stereoisomeric forms, namely as exo and endo configuration isomers, which show odoriferous features which are different from each other or even from those of their mixture. The endo isomer develops a citrus-grapefruit odor, reminiscent of nootkatone, which is very strong, whereas the exo isomer shows a warm, typical, woody note with an aspect reminiscent of AMBROX® (8,12-epoxy-13,14,15,16-tetranorlabdane, registered trademark of Firmenich SA, Geneva, Switzerland) and orris. The mixtures of these two isomers possess a voluminous odor wherein the woody and grapefruit notes are very substantive and tenacious. Generally, the two isomers as well as their mixtures, are all useful perfuming ingredients.
The compounds of formulae (I) and (II) can be used just as well in fine perfumery as in functional perfumery, and this in the form of one of their pure isomers or in form of a mixture of these. They have revealed themselves appropriate for the preparation of various perfuming compositions, bases and perfuming concentrates, as well as for perfumes and colognes, to which they confer a woody-fruity character. Their use for the perfuming of various articles, like soaps, bath or shower gels, shampoos, hair-conditioning creams and lotions, cosmetic preparations, body deodorants or air fresheners is also advantageous.
Moreover, they are also appropriate for the perfuming of detergents or fabric softeners and of all-purpose household cleaners.
The proportions in which the compounds of the present invention can be used in the various above-mentioned products varies within a wide range of values. These values depend on the nature of the product to be perfumed and the desired olfactive effect. They also depend on the nature of the coingredients in a given composition, when the compounds of the invention are used in admixture with other perfuming ingredients, solvents or adjuvants of current use in the art. The compounds of the present invention can of course also be added to the perfuming compositions or perfumed articles either as such or in solution in solvents of current use in the art.
As an example, there can be cited concentrations of the order from 1 to 10%, even 20% or more, by weight with respect to the perfuming composition into which they are incorporated. Much lower concentrations than those cited above can be used when the compounds are used for the perfuming of the various products cited above.
The invention also concerns a process for the preparation of a compound of formula
in which symbols R
1
to R
4
have the meaning as defined above, wherein said process comprises the following steps:
a) the reaction of a compound of formula
 in which R
1
and R
2
have the meaning indicated for formula (II), with a reducing agent, to obtain the corresponding compound of formula (II) in which R
3
and R
4
each represent hydrogen; or
b) the reaction of a compound of formula (I) with an appropriate organometallic compound to

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