Perfume compositions – Perfume compositions – Ring containing active ingredient
Reexamination Certificate
1999-06-02
2001-06-05
Padmanabhan, Sreeni (Department: 1621)
Perfume compositions
Perfume compositions
Ring containing active ingredient
C512S009000, C512S017000, C568S343000, C568S374000, C568S375000, C568S356000, C568S445000, C568S446000, C585S360000
Reexamination Certificate
active
06242413
ABSTRACT:
FIELD OF THE INVENTION
The invention provides aldehydes and ketones having a bicyclo[6.4.0]dodec-1(8)-en-10-yl, bicyclo[5.4.0]undec-1(7)-en-9-yl, bicyclo[6.4.0]dodec-1(12)-en-10- yl or bicyclo [5.4.0]undec-1(11)-en-9-yl skeleton, especially 1-{bicyclo[6.4.0]dodec-1(8)-en-10-yl }ethan-1-ones, 1-{bicyclo[6.4.0]dodec-1(8)-en-10-yl}methanals, 1- {bicyclo[5.4.0]-undec-1(7)-en-9-yl }ethan-1-ones, 1-{bicyclo[5.4.0]undec-1(7)-en-9-yl }methanals, 1-{bicyclo[6.4.0]dodec-1(12)-en-10-yl}ethan-1-ones, 1-{bicyclo[6.4.0]dodec-1(12)-en-10-yl}methanals, 1-{bicyclo[5.4.0]undec-1(11)-en-9-yl}ethan-1-ones and 1-{bicyclo[5.4.0]-undec-1(12)-en-9-yl}methanals, which can be methyl- or ethyl-substituted on the six-membered ring, as well as their use as odorants.
BACKGROUND OF THE INVENTION
Ionones and their linear derivatives (for example, Raldeine® or Timberol®), as well as their cyclic derivatives (for example, Iso E Super®) play a central role in perfumery. In particular, in the last ten years the classical perfumes with top, middle and base notes have been superseded more and more by monolithic creations, which are build around a main accord from relatively few olfactory substances of which some can be present in an amount of up to 25% and more in a composition [R. R. Calkin, J. S. Jellinek, Perfumery—Practice and Principles, Wiley, New York 1994, 138-140].
Ionones and their derivatives are preferred olfactory substances for the composition of such accords and perfumes, as they combine harmonically with a large number of olfactory building blocks, confer transparency and warmth to the compositions and their soft, floral-woody notes themselves remain pleasant in high concentration.
On the other hand, ionones and ionone derivatives are a relatively old class of odorant substances and although they cover an entire spectrum from fresh floral to strong woody-amber like facets, there exists, however, a great need for novel compounds of similar tonality, but with new, individual olfactory characters in order to create new original accords which, in turn, can be used as components of new trend perfumes (for example, the so-called “sheer orientals”).
SUMMARY OF THE INVENTION
In one embodiment the invention is a compound of formula (I):
wherein
n is 1 or2;
R
1
and R
4
are independently H or CH
3
; and
R
2
and R
3
are independently H, CH
3
or CH
2
CH
3
.
Another embodiment of the invention is a compound having formula (I′):
wherein
n is 1 or 2;
R
4
is H or CH
3
; and
R
2
and R
3
are independently H, CH
3
or CH
2
CH
3
.
Another embodiment of the invention is a process for producing a R
1
-methyl substituted compound of formula (I′). This process includes reacting a spirocyclic vinylcyclopropane compound with a dienophile in the presence of a catalyst; and then producing regioselectively or Z-diastereoselectively, the compound of formula (I).
DETAILED DESCRIPTION OF THE INVENTION
In aldehydes and ketones having the bicyclo skeleton indicated in more detail below there has now been found a class of compounds which enriches the woody-floral olfactory spectrum of ionones and ionone derivatives by new facets and thereby satisfies the aforementioned requirements in an advantageous manner. This novel class of compounds is represented by formula (I):
wherein
n is 1 or 2;
R
1
and R
4
are independently H or CH
3
; and
R
2
and R
3
are independently H, CH
3
or CH
2
CH
3
The dotted line in formula (I) signifies a double bond between the two bridgehead atoms or between bridgehead atom 1 and ring atom 11 or 12.
The compounds of formula (I) are novel. Formula (I) accordingly embraces aldehydes, as well as methyl ketones and ethyl ketones with bicyclo[6.4.0]dodec-1(8)-en-10-yl or bicyclo[5.4.0]undec-1(7)-en-9-yl substituents or, respectively, bicyclo[6.4.0]dodec-1(12)-en-10-yl or bicyclo[5.4.0]undec-1(11 )-en-9-yl substituents, which can carry methyl or ethyl substituents on the cyclohexene ring. The following compounds numbered 1-14 are preferred examples of this novel class of compounds:
The compounds set forth above 1-14 are exemplary only and are not intended to limit the scope of the present invention in any way.
The compounds of formula (I) have woody-flowery notes, which are reminiscent of ionones, and in addition aldehydic, maritime, amber- and tobacco-like, to some extent also fruity-fresh, melon-like, or balsamic side-notes. In some cases, such as for example, in the case of compounds 3 and 4, the woody character dominates strongly and the total olfactory impression is woody-amber like to dry-frankincense like, reminiscent of Iso E Super®, as well as of vetiver oil.
In addition to compounds 3 and 4, the present invention also includes perfumistically aldehyde compounds, for example compounds 2 and 6, as well as the R
1
-methyl substituted compounds 5 and 10.
The compounds of formula (I), preferably compounds 1-13, are intended to embrace, in accordance with the invention, all possible stereomers and diastereomers of the respective compounds. In some instances, the compounds of the present invention differ greatly in their intensity and in their odor, but on the basis of their odor each of them can be used perfumistically. In the examples which follow, the respective olfactory intensity and interesting diastereomers are described and characterized in more detail.
The compounds of formula (I) harmonize with a large number of natural and/or synthetic raw materials which are frequently used in odorant compositions. Especially in the floral and chypre olfactory directions interesting accords and perfumes can be synthesized around the compounds of formula (I). The compounds of formula (I), however, are outstandingly suitable for monolithic compounded perfumes of oriental-amber like olfactory directions. Further, new accentuated woody compositions such as, for example, of the “Féminit du Bois” (Shiseido 1992) type can be synthesized very advantageously with the compounds of formula (I).
In the present invention, use of the compounds of formula (I) is not limited to these types of perfume, or to special olfactory directions, odorant derivatives or classes of chemical substances. For example, classes of substances which harmonize especially well (i.e., may be combined) with the compounds of formula (I) include:
Ethereal oils and extracts, e.g.
bay oil, bergamot oil, cedarwood oil,
geranium oil, guaiac wood oil,
patchouli oil, petitgrain oil, rose oil,
rosewood oil, vetiver oil, ylang-ylang oil;
Alcohols, e.g.
citronellol, Dimetol ® ,
Ebanol ® , cis-3-hexenol,
geraniol, linalool, Peonile ® ,
phenoxanol, Rosalva ® , Rosaphen ® ,
Sandalore ® , cinnamic alcohol;
Aldehydes and ketones, e.g.
alpha-amylcinnamaldehyde,
Cashmeran ® , beta-damascenone,
Dupical ® , Florhydral ® ,
Frambinon ® , Givescone ® ,
Hedion ® , hydroxycitronellal, Lilial ® ,
vanillin;
Ethers and acetals, e.g.
Ambrox ® , Calone ® ,
Galaxolide ® , Magnolan ® ,
Rhubafuran ® , rose oxide,
Spirambrene ® ;
Esters and lactones, e.g.
Agrumex ® , benzyl acetate,
benzyl salicylate, citronellyl
acetate, delta- and gamma-
decalactone, gamma-undecalactone;
Macrocycles, e.g.
Ambrettolide ® , Ambretone ® ,
muscone, musk R-1,
Thibetolide ® , Trimofix O ® ;
Heterocycles, e.g.
indole, skatole.
The synthesis of the compounds of formula (I) may be effected on the one hand, as is set forth in more detail in Examples 1 and 11, by Diels-Alder reaction of the corresponding bis(methylene)cycloalkanes, ethylidenemethylenecycloalkanes or 1-vinylcycloalkenes, accessible, for example, according to J. W. van Straten, J. J. van Norden, T. A. M. van Schaik, G. T. Franke, W. H. de Wolf, F. Bickelhaupt [Recl. Trav. Chim. Pays-Bas 1978, 97, 105]
Frater Georg
Kraft Philip
Cave LLP Bryan
Givaudan Roure (International) S.A.
Haracz Stephan M.
Padmanabhan Sreeni
Waddell Mark E.
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