C - Chemistry – Metallurgy – 07 – C
Patent
C - Chemistry, Metallurgy
07
C
99/139, 167/153,
C07C 69/02 (2006.01) A23L 1/22 (2006.01) A24B 3/12 (2006.01) C11B 9/00 (2006.01)
Patent
CA 1053688
Abstract: Processes and compositions are described for the use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma, tobacco flavor and aroma and perfume aroma augmenting, modifying, enhancing and imparting compositions and as foodstuff, chewing gum, toothpaste, medicinal product, tobacco, perfume and perfumed article aroma imparting materials of one or more alkyl side chain methyl substituted or unsub- stituted 2,2,6-trimethyl-1-cyclohexen-1-vinyl alkanoates (hereinafter referred to as "enol esters") having the generic structure: Image (which structure is intended to cover both the "cis" and the "trans" isomers thereof) wherein R1 is C1-C11 alkyl and R4 is hydrogen or methyl, produced by one of the following processes: (1) A process which comprises the step of oxidizing beta-ionone or a beta-ionone homologue having the formula: Image with a peracid having the formula: Image wherein R1 is C1-C11 alkyl; R4 is hydrogen or methyl; and R2 is hydrogen, methyl, ethyl or metachlorophenyl and in the presence of a buffer and a solvent which is one of: methylene chloride; acetic acid; formic acid; propionic acid; benzene; cyclohexane; formamide; chloroform; or mixtures of two or more of the foregoing solvents and in the absence of substantial quantities of reactive solvents such as dimethyl aniline or, where a buffer is not present, dimethyl formamide, to form alkyl side chain substituted or unsubstituted 2,2,6-trimethyl-1-cyclohexen- 1-vinyl alkanoates (hereinafter referred to as "enol esters") having the formula: Image (which would be primarily the "trans" isomer when produced in this manner); (2) If desired reacting an enol acetate formed by the process (1) when R1 is CH3 and R4 is hydrogen) having the structure: Image or Image with an alkanoic acid anhydride or an acyl halide having one of the formulae: Image or Image wherein X is bromo or chloro, and wherein R3 is C2-C11 alkyl such as ethyl, n-propyl, isopropyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl- 2-propyl, n-heptyl, 2-methyl-1-nonyl, n-octyl and n-undecyl, in the presence of a catalyst such as paratoluene sulfonic acid or an alkali metal acetate to form a compound having the formula: Image (a mixture of "cis" and "trans" isomers); or (3) Reacting beta-cyclohomocitral having the formula: Image with a lower alkanoic acid anhydride having the formula: Image of an acyl halide having the formula: Image wherein X is bromo or chloro and wherein R1 is C1-C11 alkyl, in the presence of an alkali metal acetate under reflux conditions or in the presence of paratoluene sulfonic acid - 11 - under reflux conditions to form a mixture of "cis" and "trans" isomers. Addition of one or more of the enol esters having the formula: Image to consumable materials is indicated to produce: (a) In foodstuffs, foodstuff flavorings, chewing gums, toothpastes and medicinal products, "damascenone-like" (damascenone has the structure: Image , sweet, "cocoa like", "dried fruit-like", fruity, apple juice-like, sweet carrot juice, incense-like, ionone-like, spicey, woody, wood resin-like, winey, oriental/olibanum, clove- like, camphoraceous, rosey, raspberry, raspberry seed, grape, violet-like, caryophyllene-like, and/or floral aromas with fermented tea and tobacco nuances and sweet vegetable, tea, sweet carrot juice, sweet, fruity, dried fruit-like, apple juice, mimosa, raspberry, pear, ionone- like, "damascenone-like", rosey, woody, camphor- aceous, violet, cedarwood-like, caryophyllene- like, wood resin-like, winey, tobacco-like, hay-like, and raspberry kernel tastes (with sweet aftertastes); (b) In tobacco and tobacco flavorings, a sweet, floral, fruity, woody, ionone-like, spicey slightly fatty aromatic aroma prior to smoking and a sweet, tobacco-like characteristic in the mainstream on smoking; and (c) In perfumes, colognes and perfumed articles, sweet, fruity, acidic-fruity, dried fruit-like, floral, "damascenone-like", woody, green, beta- ionone-like notes with animal-tobacco nuances and fermented tea and tobacco topnotes and cognac, balsamic, tobacco undertones. The enol esters of our invention are also useful reaction intermediates for producing beta-cyclohomocitral which is valuable for its organoleptic properties. There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product. "Damascenone-like" (damascenone has the structure: Image sweet, "cocoa like", "dried fruit-like", fruity, apple juice- like, sweet carrot juice, incense-like, ionone-like, spicey, woody, wood resin-like, winey, oriental/olibanum, clove-like, camphoraceous, rosey, raspberry, raspberry seed, grape, violet- like caryophyllene-like, and/or floral aromas with fermented tea and tobacco nuances and sweet vegetable, tea, sweet carrot juice, sweet, fruity, dried fruit-like, apple juice, mimosa, raspberry, pear, ionone-like, "damascenone-like", rosey, woody, camphoraceous, violet, cedarwood-like, caryophyllene-like, wood resin-like, winey, tobacco-like, hay-like, and raspberry kernel tastes (with sweet aftertastes) are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors. Sweet, fruity, acidic-fruity, dried fruit-like, woody, green beta-ionone-like notes with animal-tobacco topnotes and cognac, balsamic, tobacco undertones are desirable in several types of perfume compositions, perfumed articles and colognes. Sweet, woody, floral, fruity, ionone-like, spicey, slightly fatty aromatic aromas prior to smoking and sweet, tobacco-like smoke aroma characteristics in the mainstream on smoking are desirable in tobaccos and in tobacco flavor- ing compositions. Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "isocyclocitral", "alpha-cyclo- citrylidene acetaldehyde" and "beta-cyclocitrylidene acetal- dehyde", thus: (i) "760" CYCLOCITRAL Alpha-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. Image Image Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of may pieces of proof that isomers (alpha-beta) do often have different odors." (ii) "761? iso-CYCLOCITRAL A mixture of two chemicals: 3,5,6-trimethyl-3-cyclohexen-1- carboxaldehyde (meta-cyclocitral). Image (corrected structure) 2,4,6-trimethyl-4-cyclohexen-1- carboxaldehyde (symmetric-iso-cylocitral). Image (corrected structure) 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 whereit 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 Image 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 avail- able 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. Image Sweet-woody, rather heavy odor, resembling that of
247541
Klaiber Erich M.
Pittet Alan O.
Shuster Edward J.
Vinals Joaquin
Vock Manfred H.
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