Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-05-10
2001-02-06
Siegel, Alan (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S375000, C568S376000, C568S377000, C568S379000, C512S008000, C512S018000, C512S022000
Reexamination Certificate
active
06184419
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to new &agr;,&bgr;-unsaturated ketones exhibiting a green-galbanum, fresh (metallic, undecatriene type) and fruity-pineapple and/or fruity-cassis odor, and to the use of these new compounds as fragrance materials in different compositions.
BACKGROUND OF THE INVENTION
Inexpensive floral fruity and green fragrances with intense pineapple and galbanum undertones are highly desirable in the art of perfumery. However, many of the natural and commercially available compounds, e.g. galbanum oil, are expensive and show a lack of stability. Moderately weak galbanum type compounds became available in the mid seventies including allyl amyl glycolate (International Flavor and Fragrance Inc.) and CYCLOGALBANATE® (Dragocco S.A.). Another member of this family, the allyl cyclopentyl glycolate is described in Sprecker, U.S. Pat. No. 4,735,932. However, glycolates are generally not stable in alkali, acid or oxidizing media.
1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one is described by Morris, A. F.; Näf, F; Snowdon, R. L. in Perfumer & Flavorist 1991(16), 33 as an important compound for the perfumery. This compound possesses a powerful metallic odor reminiscent of galbanum with pineapple and hyacinth character that adds fresh, green, floral and fruity aspects to perfumes and perfumed products.
SUMMARY OF THE INVENTION
The present invention provides new compounds which have an intense and long lasting green galbanum type of odor accompanied by various fruity, mainly pineapple undertones.
One embodiment of the invention is a compound of formula I
wherein R is a residue A
or residue B
and R
1
, R
2
, R
3
, R
4
, and R
5
are independently hydrogen, methyl or ethyl, and further wherein R
1
, R
4
and R
5
are located at any position of the ring structure, n and m are independently 0, 1, 2, or 3 and the dotted lines represent in formula A an optional double bond and in formula B a double bond either in position 1 or 2.
DETAILED DESCRIPTION OF THE INVENTION
It has surprisingly been found that compounds of Formula I
wherein R is a residue A
or a residue B
and R
1
, R
2
, R
3
, R
4
and R
5
are independently hydrogen, methyl or ethyl, and R
1
, R
4
and R
5
are at any position of the ring structure, n and m are independently 0, 1, 2 or 3 and the dotted lines in formula A, if desired, stand for a double bond and the dotted lines in formula B stand, for a double bond either in position 1 or 2. These examples have an intense, very long lasting green-galbanum type of odor with fruity undertones. These characteristics make the new compounds well suited for difficult functional perfumery applications, as well as for imparting unique green galbanum and fruity notes to fine perfumery products.
The above formulas include all different possible stereo- and double-bond isomers.
New compounds of formula Ia are preferred:
wherein R
1
and R
2
are independently hydrogen or methyl and n stands for 0 or 1.
Further preferred compounds are:
2-cyclohexylhepta-1,6-dien-3-one;
(E)-and (Z)-3-cyclohexylocta-2,7-dien-4-one;
2-cyclopentylhepta-1,6-dien-3-one;
1-(3,4,4a,5,6,7,8,8a-octahydronaphth-2-yl)pent-4-en-1-one; and
1-(1,4,4a,5,6,7,8,8a-octahydronaphth-2-yl)pent-4-en-1-one.
In addition to the above excellent qualities, it has been found that the compounds of the invention show outstanding diffusion and/or high substantivity, the latter meaning persistence of odor. The high diffusion and substantivity is well perceived on fabrics washed with a detergent or treated with a softener containing one or more of the new &agr;,&bgr;-unsaturated ketones. The typical fresh green odor is already perceived very strongly on the wet fabric and later also on the dry material.
Due to the excellent odor and application qualities, the new compounds are excellent fragrances for use in any field of fine and functionary perfumery, such as perfumes, household products, laundry products, body care products, and cosmetics.
The new &agr;,&bgr;-unsaturated ketones of formula I, wherein R is a residue of formula A, may be prepared according to procedures known in the art as shown in Scheme 1.
The starting materials of formula (a) in Scheme 1 may be prepared by oxidation of the corresponding alcohols. By methylenation with formaldehyde (Mannich reaction), aldehydes of formula (b) wherein R
2
and R
3
are hydrogen are obtained.
The &agr;,&bgr;-unsaturated aldehydes corresponding to compounds of Formula I wherein R is a residue of formula A and R
2
and/or R
3
are not hydrogen may be prepared, for example, via cross-aldol condensation using Mukaiyama conditions followed by dehydration (T. Mukaiyama, K. Banno, K. Narasaka: J. Amer. Chem. Soc. 1974 (96), 7503).
Alternatively, the Grignard reaction may be carried out using appropriately substituted nitrites. This “one pot reaction” gives good yields of &agr;,&bgr;-unsaturated ketones. 2-substituted-3-trimethylsilyloxypropionitriles are especially well suited for this transformation. The latter can be prepared, for example, from the respective cyclic ketones and ethyl cyanoacetate (according to J. A. Marshall, R. D. Carroll: J. Org. Chem. 1965 (30), 2748) followed by protection of the hydroxy-group with trimethylchlorosilane.
Another possible preparation of the &agr;,&bgr;-unsaturated ketones of Formula I in which R is a residue A proceeds via Claisen transposition of the corresponding vinyl ether (See. e.g., T. Masso, A. Portella, E. Rus: Perfumer & Flavorist 1990 (15), 39) starting with the suitably substituted 3-butene-2-ones (prepared, e.g., according to R. A. Cormier, W. L. Schreiber, W. C. Agosta: J. Amer. Chem. Soc. 1973 (95), 4873).
The new &agr;,&bgr;-unsaturated ketones of Formula I wherein R is a residue of formula B can be prepared from the corresponding bicyclic ketones according to the process illustrated in Scheme 2.
The starting ketones are either commercially available, or can be synthesized by Robinson annullation from the corresponding ketones with substituted or unsubstituted methyl vinyl ketones, followed by selective hydrogenation with Pd/C (see e.g., G. Stork, A. Brizzolara, H. Landesman, J. Szmuskovicz, R. Terrell: J. Amer. Chem. Soc 1963 (85), 207).
The &agr;,&bgr;-unsaturated ketones wherein R is a residue of formula B, are generally obtained as mixtures of cis-/trans-isomers. The double bond is either in position 1 or 2. The odors of the different isomers are all of the same “green” type, however the GC thresholds may vary within broad ranges. A preferred compound is cis-1-(1,4,4a,5,6,7,8,8a-octahydronaphth-2-yl)pent-4-ene-1-one (n═m=1, and R
4
═R
5
=H), wherein the most powerful isomer has a GC-threshold of only 10 pg/l.
The new odorants may be combined with numerous odorant ingredients of natural and/or synthetic origin. The range of the natural odorants includes, in addition to readily volatile, also moderately and only slightly volatile components. The synthetic odorants embrace representatives from practically all classes of odorant substances. The following list comprises examples of known odorants which may be combined with the compounds of the invention:
natural products: tree moss absolute, basil oil, tropical fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, lavender oil, rose oil, jasmine oil, ylang-ylang oil, etc.;
alcohols: farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, (Z)-hex-3-en-1-ol, menthol, a-terpineol, etc.;
aldehydes: citral, &agr;-hexyl cinnamaldehyde, Lilial, methylionone, verbenone, nootkatone, geranylacetone, etc.;
esters: allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, cis-3-hexenyl isobutyrate, cis-3-hexenyl salicylate, linalyl acetate, methyl dihydrojasmonate, styralyl propionate, vetiveryl acetate, benzyl acetate, geranyl acetate, etc.;
lactones: &ggr;-undecalactone, &dgr;-decalactone, pentad
Bajgrowiecz Jerzy A.
Berg-Schultz Katja
Bryan Cave LLP
Givaudan Roure ( International ) SA
Haracz Stephen M.
Siegel Alan
Waddell Mark E.
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