Patent SU-786913-A3 (SU)
Inventor: PITTET ALAN OUEN
IPC: A23L27/00
Filed: 1976-10-22
Granted: 1980-12-07
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 unsubstituted 2,2,6-trimethyl-1-cyclohexen-1-vinyl alkanoates(hereinafter referred to as "enol esters") having the generic structure: (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: with a peracid having the formula: 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: (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: or                   with an alkanoic acid anhydride or an acyl halide having one of the formulae: or                     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: (a mixture of "cis" and "trans" isomers); or (3)  Reacting beta-cyclohomocitral having the formula: with a lower alkanoic acid anhydride having the formula: of an acyl halide having the formula: 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 under reflux conditions to form a mixture of "cis" and "trans" isomers. Addition of one or more of the enol esters having the formula: to consumable materials is indicated to produce: (a)  In foodstuffs, foodstuff flavorings, chewing gums, toothpastes and medicinal products, "damascenone-like" (damascenone has the structure: , 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, clovelike, 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, iononelike, "damascenone-like", rosey, woody, camphoraceous, violet, cedarwood-like, caryophyllenelike, 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, betaionone-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 f