Novel fragrance compositions containing 2,6,6 trimethyl-1-cyclohexen-1-yl acetaldehyde and phenyl C.sub.6 ketone

Abstract

Processes and compositions are described for the use in perfume aroma augmenting, modifying, altering and enhancing compositions and as perfume and perfumed article aroma imparting materials of mixtures of (i) 2,2,6-trimethyl-1-cyclohexen-1-ylacetaldehyde.BACKGROUND OF THE INVENTIONThe present invention relates to mixtures of (i) either or both of the phenyl C.sub.6 ketones, 2,5,-dimethyl-5-phenyl hexanone-4 (hereinafter referred to as "4-damascol") and 2,5,-dimethyl-5-phenyl hexen-1-one-3 (hereinafter termed "damascol") and(ii) 2,2,6-trimethyl-1-cyclohexen-1-ylacetaldehyde (hereinafter termed "beta-cyclohomocitral) produced by interalia, a novel process described and claimed in copending application for U.S. Pat. No. 507,414 on Sept. 19, 1974 now U.S. Pat. No. 3,956,393, issued on May 4, 1976, and copending application for U.S. Pat. No. 594,100 filed on July 8, 1975 and novel compositions using such mixtures of phenyl C.sub.6 ketone and beta-cyclohomocitral to alter, modify, enhance (or impart) aromas in (or to) perfumes, perfume compositions and/or perfumed articles.There has been considerable work performed relating to substances which can be used to impart (or alter, modify or enhance) fragrances to (or in) perfumed compositions, perfumes, or perfumed articles. These substances are used to diminish the use of natural materials, some of which may be in short supply and/or to provide more uniform properties in the finished product. Woody, rosey, camphoraceous, green and earthy notes are desirable in several types of perfume compositions, perfumes and perfumed articles.Arctander, "Perfume and Flavor Chemicals," 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "iso-cyclocitral", "alpha-cyclocitrylidene acetaldehyde" and "beta-cyclotrylidene acetaldehyde", thus:(I) "760: CYCLOCITRALAlpha-cyclocitral= (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde). Beta-cyclocitral= (2,2,6-trimethyl-6-cyclohexen-1-carboxaldehyde). Both isomers are known and have been produced separately. ##STR1## Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of many pieces of proof that isomers (alpha-beta) do often have different odors."(II) ("761: ISO-CYCLOCITRALA mixture of two chemicals: 3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta-cyclocitral). ##STR2## 2,4,6-TRIMETHYL-4-CYCLOHEXEN-1-CARBOXALDEHYDE (SYMMETRIC-ISO-CYCLOCITRAL). ##STR3## Powerful, and diffusive, foliage-green, "dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet-green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil.Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates for sweetness and lifts the topnote), with Ionones (freshness), Geranium and Galbanum (enhances the green and "vegetable" notes), etc. . . . "(iii) "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE ##STR4## Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogenated Ionones.Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. . . . " (iv) "763: beta-CYCLOCITRYLIDENE ACETALDEHYDE 2,6,6-trimethyl-1-cyclohexenyl-beta-acrolein. ##STR5## Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone.Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. . . . "(v) "896: DEHYDRO-beta-CYCLOCITRAL (Safranal) 2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ##STR6## Very powerful, sweet, green-floral and somewhat tobacco-herbaceous odor of good tenacity. In extreme dilution reminiscent of the odor of Safran (Saffron).Interesting material for fresh topnotes, as a modifier for aldehydic-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the aliphatic Aldehydes, with Oakmoss products and herbaceous oils. . . . "Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 11 (309) 1972. Beta-cyclocitral is disclosed as a component of Burley Tobacco flavor by Demole and Berthet, Helv. Chim. Acta. 55 Fasc-6, 1866 (1972).

Description

Claims

1. A mixture consisting essentially of (i) 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde having the structure: ##STR17## and (ii) a phenyl C.sub.6 ketone having the structure: ##STR18## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; the weight ratio of said 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde:phenyl C.sub.6 ketone being in the range of from about 1:1 up to about 1:5.

2. A fragrance modifying composition consisting essentially of (i) from 0.005% up to 10% by weight of said composition of a mixture consisting essentially of 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde having the structure: ##STR19## and at least one phenyl C.sub.6 ketone having the structure: ##STR20## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; and the remainder of said composition being (ii) an auxiliary perfume ingredient compatible with said 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde and said phenyl C.sub.6 ketone; the ratio of 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde:phenyl C.sub.6 ketone being in the range of from 1:1 up to 1:5.

3. A perfume composition consisting essentially of (i) from 0.005% up to 10% by weight of said composition of a mixture consisting essentially of 2,6,6-trimethyl-1-cyclohexen-1:ylacetaldehyde having the structure: ##STR21## and at least one phenyl C.sub.6 ketone having the structure: ##STR22## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; and (ii) the remainder of said composition being at least one compatible adjuvant, the ratio of 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde:phenyl C.sub.6 ketone being in the range of from 1:1 up to 1:5.

4. A cologne composition consisting essentially of (i) ethanol, (ii) water; and (iii) 2.5% of a mixture consisting essentially of 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde having the structure: ##STR23## and at least one phenyl C.sub.6 ketone having the structure: ##STR24## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; the ratio of 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde:phenyl C.sub.6 ketone being in the range of from 1:1 up to 1:5, the ratio of ethanol:water being 85:15.