Perfume compositions – Perfume compositions – Ring containing active ingredient
Reexamination Certificate
2000-02-16
2001-07-03
Owens, Amelia (Department: 1625)
Perfume compositions
Perfume compositions
Ring containing active ingredient
C549S266000, C549S273000, C549S294000
Reexamination Certificate
active
06255276
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention provides odorant compositions containing macrocycles, namely 15 to 17-membered compounds of the formula
wherein the dotted line signifies an optional additional bond; one or both of X and Y are methylene or C
2-12
-polymethylene, optionally substituted with an additional methyl group; and A is hydrogen or methyl when the compounds are unsaturated and methyl when the compounds are saturated providing that the unsaturated compounds are in at least 80% cis form when A is hydrogen and are in at least 50% cis form when A is methyl with the exception of Z-oxacyclopentadec-6-en-2-one (15-membered ring), Z-oxacydoheptadec-8-en-2-one (17-membered ring) and Z-oxacycloheptadec-11-en-2-one (17-membered ring). The present invention also provides a process for the manufacture of the compounds of formula I.
The compounds I or the defined mixtures I with the substituents previously defined for formula I are novel with the exception of Z-oxacyclopentadec-3-(or 6-or 13-)en-2-one, Z-oxacyclohexadec-3-(or 6-, 11-, 12- or
13
)en-2-one and Z-oxacycloheptadec-8-(or 10-, 11-, 12-, 13- or 15-)en-2-one.
The compounds I thus embrace oxacyclopenta(or -hexa or -hepta)decen-2-ones and the respective corresponding decan-2-ones.
Formula I is intended to include all possible isomers. Thus, in the case of saturated and unsaturated compounds the racemates and the optically active compounds, that is to say the R- and S-forms, are included. In the case of the unsaturated compounds the cis/trans ratio is that according to the above definition. Further, diastereoisomeric forms are also possible with regard to multi-methyl substitutions.
Some derivatives of decan-2-ones and/or synthesis thereof have been described in articles, United States Patents and European Patents. Several of these references, as well as how the compounds described therein differ from the present invention, are discussed below.
In 1927 ambrettolide (Z-oxacycloheptadec-8-en-2-one) was isolated from ambrette seed oil (musk seed oil) (Ber. 60,902,(1927). In 1977 Z-oxacyclopentadec-6-en-2-one was isolated from the same oil (B. Maurer, A. Grieder, Helv. Chim. Acta, 60, 1155, (1977). The synthesis of E-oxacydoheptadec-10-en-2-one is the subject of U.S. Pat. No. 4,064,144.
The synthesis of a mixture of oxacydoheptadec-8-en-2-one, oxacyclo-heptadec-9-en-2-one, oxacycloheptadec-10-en-2-one and oxacycloheptadec-11-en-2-one, with the third compound being present in amounts up to 80% in the aforementioned mixture has been described in the literature. B. D. Mookherjee, R. W. Trenlde, R. R. Patel, J. Org. Chem. 37, 24, 3846, (1972). Although the stereochemistry of these compounds was not indicated, since the aforementioned synthesis is a pyrolysis of an ester, a selective formation of a cis-olefin would not be expected (see, Houben-Weyl, volume V/1b, 105, 1972).
A mixture of mainly E-oxacyclohexadec-12-en-2-one and E-oxacyclohexadec-13-en-2-one, with the Z-isomers being present only in a small percentage is the subject matter of European Patent No.0,424,787.
The use of oxacyclohexadec-11-en-2-one is the subject of U.S. Pat. No. 4,541,950. Although the use of the aforementioned compound is the subject of a U.S. patent, the cis/trans ratio of the product obtained is not given. However, since the product was obtained by metathesis, it is doubtful whether the trans content is higher than the cis content. (See, A. Fürstner, K. Langemann, J. Org. Chem. 61, 3942, 1996.)
The French company Mane et Fils in F-06620 Bar s/Loup sells a compound under the name cis-iso-ambrettolide which is Z-oxacycloheptadec-11-en-2-one (Parfums, Cosmétiques, Actualiées, No 128, avril/mai 63, 1996).
C. Collaud (Helv. Chim. Acta 25, 965, 1942) describes the production of a mixture of oxacycloheptadec-6-en-2-one and oxacydoheptadec-7-en-2-one without describing the stereochemistry of the products. However, since the aforementioned synthesis is a pyrolysis of an ester, a selective formation of a cis-olefin is not expected.
Unlike the aforementioned compounds, compounds of formula I have extremely low threshold values and very good adhesion properties. All compounds of formula I have intensive musk notes, which are often accompanied by powdery, fruity, flowery side-notes. In addition, compounds of formula I also have amber-like, earthy notes similar to the scent of ambrette seeds. Z-13-methyl-oxacyclopentadec-10-en-2-one in particular has an especially fine perfumistic effect with a dominant musk note. This musk note is rounded off by a powdery, fruity component.
SUMMARY OF THE INVENTION
The present invention provides odorant compositions having extremely low threshold values and very good adhesion properties. These compositions also have intensive musk notes, which are often accompanied by powdery, fruity, amber-like, earthy notes and flowery side-notes. The compositions also have amber-like, earthy notes similar to the scent associated with ambrette seeds.
The odorant compositions containing macrocycles, namely 15 to 17-membered compounds have the formula:
wherein the dotted line signifies an optional additional bond; X and Y is methylene or C
2-12
-polymethylene, optionally substituted with an additional methyl group;
and A is hydrogen or methyl when the compounds are unsaturated and methyl when the compounds are saturated providing that the unsaturated compounds are present in at least 80% cis form when A is hydrogen and are present in at least 50% cis form when A is methyl
with the exception of Z-oxacydopentadec-6-en-2-one (15-membered ring), Z-oxacycloheptadec-8-en-2-one (17-membered ring) and Z-oxacycloheptadec-11-en2-one (17-membered ring). The present invention also provides a process for the manufacture of the compounds of formula I.
Another embodiment of the present invention is an odorant composition, which contains at least one 15-17 membered lactone compound of the formula:
wherein the dotted line signifies an optional additional bond but which in case of a 16-membered lactone compound is not placed at position 11, 12 or 13; one or both of X and Y is methylene or C
2-12
-polymethylene, optionally substituted with an additional methyl group with the proviso that the sum of carbon atoms of X and Y is 11, 12 or 13, and A is hydrogen or methyl when the compound is unsaturated and methyl when the compound is saturated providing that the unsaturated compounds are in at least 80% of cis form when A is hydrogen and are in at least 50% of cis form when A is methyl, with the exception of Z-oxacyclopentadec-6-en-2-one, Z-oxacycloheptadec-8-en-2-one and Z-oxacycloheptadec-11-en-2-one.
The odorant composition set forth above may contain at least one compound selected from the following group: Z-oxacycloheptadec-12-en-2-one, Z-oxacylohexadec-5-en-2-one, Z-oxacycloheptadec-7-en-2-one, Z-oxacycloheptadec-13-en-2-one, Z-oxacycloheptadec-10-en-2-one, Z-oxacycloheptadec-8-en-2-one, and Z-4-methyl-oxacyclohexadec-6-en-2-one.
The odorant composition set forth above may also contain at least one compound selected from the following group: oxacycloheptadec-12-en-2-one, oxacycloheptadec-9-en-2-one, oxacycloheptadec-7-en-2-one, oxacycloheptadec-13-en-2-one, oxacycloheptadec-10-en-2-one, oxacycloheptadec-14-en-2-one, 15-methyl-oxacycloheptadec-12-en-2-one, 13-methyl-oxacyclopentadec-10-en-2-one, oxacyclohexadec-5-en-2-one, 10-methyl-oxacyclopentadec-9-en-2-one, 10-methyl-oxacyclopentadecan-2-one, 8-methyl-oxacyclopentadec-7-en-2-one, 8-methyl-oxacyclopentadecan-2-one, 9,13-dimethyl-oxacyclopentadec-8-en-2-one, 7-methyl-oxacyclohexadec-6-en-2-one, 4-methyl-oxacyclohexadecan-2-one, 7-methyl-oxacyclohexadecan-2-one, and 8,15-dimethyl-oxacyclopentadec-7-en-2-one.
The odorant composition is preferably 13-methyl-oxacyclopentadec-10-en-2-one, 13-methyl-oxacyclopentadec-10-en-2-one having the Z-(13S)-configuration, or 13-methyl-oxacyclopentadec-10-en-2-one having the Z-(13R)-configuration.
Another embodiment of the present invention provides compounds of the formula:
wherein the dotted line signifies an optional additional bond but which in case of a 16-me
Frater Georg
Helmlinger Daniel
Muller Urs
Bryan Cave LLP
Givauden Roure (International) S.A.
Haracz Stephen M.
Owens Amelia
Waddell Mark E.
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