GB1602747A - Creation of Inventions and Patents with Artificial Intelligence

GB1602747A – Methylthiobutyryl cyclohexene and cyclohexadiene derivatives
– Google Patents

GB1602747A – Methylthiobutyryl cyclohexene and cyclohexadiene derivatives
– Google Patents
Methylthiobutyryl cyclohexene and cyclohexadiene derivatives

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Publication number
GB1602747A

GB1602747A
GB8396/78A
GB839678A
GB1602747A
GB 1602747 A
GB1602747 A
GB 1602747A
GB 8396/78 A
GB8396/78 A
GB 8396/78A
GB 839678 A
GB839678 A
GB 839678A
GB 1602747 A
GB1602747 A
GB 1602747A
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United Kingdom
Prior art keywords
tobacco
composition
sulfur
carbon
containing compound
Prior art date
1977-03-03
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB8396/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

International Flavors and Fragrances Inc

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International Flavors and Fragrances Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1977-03-03
Filing date
1978-03-02
Publication date
1981-11-18

1978-03-02
Application filed by International Flavors and Fragrances Inc
filed
Critical
International Flavors and Fragrances Inc

1981-11-18
Publication of GB1602747A
publication
Critical
patent/GB1602747A/en

Status
Expired
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups

C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton

A—HUMAN NECESSITIES

A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS’ REQUISITES

A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF

A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form

A24B15/18—Treatment of tobacco products or tobacco substitutes

A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances

A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances

A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring

C—CHEMISTRY; METALLURGY

C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES

C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES

C11B9/00—Essential oils; Perfumes

C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring

C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2601/00—Systems containing only non-condensed rings

C07C2601/12—Systems containing only non-condensed rings with a six-membered ring

C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Description

PATENT SPECIFICATION
( 11) 1 602 747 ( 21) Application No 8396/78 ( 31) Convention Application No.
( 22) Filed 2 Mar 1978 774055 ( 32) Filed 3 ( 33) United States of America (US) ( 44) Complete Specification Published 18 Nov 1981 ( 51) INT CL 3 C 07 C 149/26 A 23 L 1/226 A 61 K 7/46 C 11 D 3/50 9/44 ( 52) Index at Acceptance C 2 C 200 221 227 373 37 Y 463 771 803 80 Y A 2 B 303 401 411 A 2 C 20 HX A 5 B FD C 5 D 6 812 E 6 B 4 22 Y 464 AA 660 304 553 QU BCC ( 19) Mar 1977 in /, Y 351 355 612 625 665 ( 54) METHYLTHIOBUTYRYL CYCLOHEXANE AND CYCLOHEXADIENE DERIVATIVES ( 71) We INTERNATIONAL FLAVORS & FRAGRANCES INC, a corporation of the State of New York, United States of America of 521 West 57th Street, New York, N.Y 10019, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement:-
It has now been discovered that novel solid and liquid foodstuff, chewing gum, toothpaste and medicinal products and flavoring compositions having sweet, black tea-like, tobacco-like, “‘damascenone-like,” chocolate-like, dried fruit-like, rose petal-like and cocoa-like aroma characteristics as well as sweet, black tea-like, chocolate-like, “damascenone-like,” tobacco-like, dried fruit-like, rose petal-like and cocoa like flavor characteristics; novel perfume compositions having floral, natural rose oil-like and earthy aromas with potato top notes and minty, tomato vine, Brussel sprout-like and woody undertones; as well as novel tobacco and tobacco flavoring compositions having sweet, honeylike, rich, slightly fruity, dried fruit-like, hay tobacco-like cedarwood-like, raspberry-like, blackcurrent-like, Virginia tobacco-like and woody notes both prior to and on smoking may be provided by the utilization of 1-l 3-(methylthio)butyryll-2,6,6-trimethyl-cyclohexene and/or the corresponding 1 3-cyclohexadiene analog having the generic structure:
wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond in foodstuffs, chewing gums toothpastes medicinal products, perfume compositions, perfumed articles colognes and tobaccos as well as tobacco substitutes.
Sulfur-containing cycloaliphatic ketones for use in augmenting or enhancing the organoleptic properties of foodstuffs and perfumes are well known in the prior art U S.
2 1 602 747 2 Patent 3,979,422 discloses compounds having the structures:
0 SH and Alkylthio aliphatic ketones for use in augmenting or enhancing the organoleptic properties of foodstuffs are also well known in the prior art U S Patent 3,952,062 discloses such alkylthio aliphatic ketones, having the generic structure:
wherein R’ represents hydrogen or together with R 4 represents a C-C bond, R 2 represents hydrogen or together with R 6 represents a dimethylmethylene group, or, when R’ is isopropyl, together with R 5 represents a C-C bond, R 3 represents hydrogen or together with R represents a dimethylmethylene group, R 4 represents hydrogen or together with R 1 represents a C-C bond, R 5 represents hydrogen or when R signifies isopropyl together with R represents a C-C bond, R 6 represents isopropyl or together with R 2 or with R 3 represents a dimethylmethylene group, R 7 represents methyl, X represents a C-C double bond taking the place of a C-C single bond, m = 0 to 2, provided that when R 2, R 3 and Rs represent hydrogen, R 6 represents isopropyl, R 4 together with R’ represents a C-C bond.
m = 0 and R represents hydrogen or lower alkyl.
The methylthio derivatives of the present invention are not, however, disclosed or referred to implicitly or explicitly in U S Patent 3,952062.
It is noteworthy that at column 3, of U S Patent 3,952,062, the compounds having the structure:
are indicated to be useful in foodstuff flavors and aroma where cabbagelike or onion-like aromas are desired No such aromas are imparted or augmented or enhanced by the compounds of our invention.
1 602 747 3 1 602 747 3 Although the compounds of our invention having the generic structure:
wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond have been determined to be existing in black tobacco oil, the compounds of our invention do not have organoleptic qualities which are even remotely similar to the organoleptic qualities of black tobacco oil.
Accordingly, the 1-l 3-(methylthio)butyryll-2,6,6-trimethyl-cyclohexene and/or the corresponding analog of our invention having the generic structure:
0 5/CH 3 0 wherein the dashed line represents a carbon-carbon double bond or a carbon-carbon single bond, have properties which are unexpected, unobvious and advantageous when compared to black tobacco oil where these compounds are found, and when compared to the compounds of the prior art, specifically those of U S Patent 3,952,062 and U S Patent
3,979,422.
The compounds of the invention are prepared using ” 13-damascenone” or ” 3damascone” as starting materials or reactants Thus, 3-Damascenone is a compound having the structure:
Its organoleptic properties and preparation are set forth in Swiss Patent 520,479, issued on May 12, 1972.
3-damascone is a compound having the structure:
Its organoleptic properties and preparation are set forth in U S Patent 3, 927,107, issued on December 16, 1975.
The 1-l 3-(methylthio)butyryll-26,6-trimethyl-cyclohexene and/or the corresponding 1,3-cyclohexadiene analog useful as indicated, supra, may be produced preferably by a process which involves reacting methyl mercaptan (CH 3 SH) with ” 3damascone” or “p 3-damascenone” according to the reaction:
o O S CH 3 I ‘ + CH 3 SH 1 602 747 1 602 747 More specifically, the reactions carried out are as follows:
0 s 5 c + CH 35 H (beta-damascenone) 0 SO c H 3 + CH 35 H (beta-damascone) Our invention encompases the organoleptic uses of two compounds in particular having the structures and names as follows:
Structure Name 3-(methylthio)-1-( 2,6,6trimethyl-1,3-cyclohexadien-1-yl)-1-butanone or 1-l 3-(methylthio)butyryll2,6,6-trimethyl-1,3-cyclohexadiene CH 3 3-(methylthio)-1-( 2,6,6trimethyl-1-cyclohexen1-yl)-1-butanone.
or l A 1-l 3-(methylthio)butyrylllx 2,6,6-trimethylcyclohexene These compounds are preferably used in a substantially pure state having been produced synthetically.
These compounds have the following organoleptic properties:
Food Flavor Structure Properties Tobacco Flavor Properties Sweet, black-tea-like, tobacco-like, damascenone-like, chocolatelike, dried-fruit-like, rose-petal-like aroma characteristics with sweet, black-tea-like, chocolate-like, damascenone-like, tobaccolike, dried-fruit-like and rose-petal-like flavor characteristics.
Sweet, black-tea-like, cocoa-like and damascenone-like aroma characteristics with sweet, black-tea-like, cocoa-like and damascenone-like flavor characteristics.
Sweet-honey-like, rich, slightly-fruity haytobacco-like, woodylike flavor characteristics prior to and on smoking in the main stream and in the side stream with sweet, floral and fruity nuances.
Lingering rich, sweet, fruity, dried fruit-like, slightly floral, raspberrylike, blackcurrent-like aroma prior to and on smoking in both the main stream and side stream.
Floral and natural rose oil-like aroma nuances.
Earthy, potota-like top note, giving way to a minty, tomato vine/ Brussel sprout nuance, with woody undertone.
Perfumery Properties CH 3 1 602 747 The term “enhance” is used herein to mean the intensification of a flavor or aroma characteristic or note without the modification of the quality thereof Thus, “enhancement” of a flavor or aroma means that the enhancement agent does not add any additional flavor note or nuance.
Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known 5 in the art for such use, being extensively described in the relevant literature It is required that any such material be “ingestibly acceptable”, and thus non-toxic or otherwise non-deleterious, particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used does not cause the consumable material to have unacceptable aroma and taste nuances 10 It is a further requirement that such material be organoleptically compatible with the foodstuff with which it is used so that the flavor and aroma nuances of such material, taken together with the flavor and aroma nuances of the foodstuff (as a whole) give rise to a harmoniously aesthically pleasing aroma and taste profile Such material, in general, may be characterized as flavoring adjuvants or vehicles comprising broadly, stabilizers, 15 thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers.
Stabilizer compounds include preservatives, e g, sodium chloride; antioxidants, e g, calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2 and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene ( 2,6-ditertiary-butyl-4methyl phenol) or propyl gallate and sequestrangs, e g, citric acid 20 With respect to ultimate food compositions it is found that quantities of 1-l 3(methylthio)butyryll-2,6,6-trimethyl-cyclohexene and/or its corresponding 1,3cyclohexadiene analog ranging from a small but effective amount, e g, 0 5 parts per million up to about 20 parts per million by weight based on total composition are suitable.
Concentrations in excess of the maximum quantity stated are not normally recommended, 25 since they fail to prove commensurate enhancement of organoleptic properties In those instances, wherein the 1-l 3-(methylthio)butyryll-2,6,6-trimethylcyclohexene and/or its corresponding 1, 3-cyclohexadiene analog is added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total quantity of flavoring composition employed be sufficient to yield an effective 1-l 3 30 (methylthio)butyryll-2,66-trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexene analog concentration in the foodstuff product.
Food flavoring compositions prepared in accordance with the present invention preferably contain the 1-l 3-(methylthio)butyryll-2,6,6-trimethylcyclohexene and/or its corresponding 1 3-cyclohexadiene analog in concentrations ranging from about 0 1 % up to 35 about 15 % by weight based on the total weight of said flavoring composition.
It is presently preferred to combine with the 1-l 3-(methylthio)butyryll2,6,6-trimethylcyclohexene and/or its corresponding 1,3-cyclohexadiene analog the following adjuvants:
p-hydroxybenayl acetone: geraniol; acetaldehyde; maltol; ethyl methyl phenyl glycidate; benzyl acetate: dimethyl sulfide: vanillin; methyl cinnamate; ethyl pelargonate; methyl 40 anthranilate: isoamyl acetate: isobutyl acetate: alpha ionone; ethyl butyrate; acetic acid; gamma-undecalactone: naphthyl ethyl ether: diacetyl; ethyl acetate; anethole; isoamyl butyrate: cis-3-hexenol-1: 2-methyl-2-pentenoic acid: elemecine ( 4-allyl1,2,6-trimethoxybenzene): isoelemecine ( 4-propenyl-12, 6-trimethoxy benzene): and 2-( 4hydroxy-4methylpentyl) norbornadiene 45 This invention further provides improved smoking tobacco additives and methods whereby various desirable sweet honey-like, rich, slightly fruity, dried fruit-like, raspberrylike, blackcurrent-like Virginia tobacco-like damascenone-like, hay tobacco-like, woody and cedarwood flavor and aroma characteristics may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavoring 50 characteristics.
In carrying out this aspect of our invention, we add to smoking tobacco materials or a suitable substitute therefor (e g dried lettuce leaves) an aroma and flavor additive containing as an active ingredient 1-l 3-(methylthio)butyryll-266trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog 55 In addition to the 1-l 3-(methylthio)butyryll-266-trimethyl-cyclohexene and/or its corresponding 1 3-cyclohexadiene analog of our invention, other flavoring and aroma additives may be added to the smoking tobacco material or substitute therefor either separately or in mixture with the 1-l 3-(methylthio)butyryll-2,6,6trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog as well known in the art 60 An aroma and flavoring concentrate containing 1-l 3-(methylthio)butyryll2,6,6trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog and, if desired.
one or more of the above indicated additional flavoring additives may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper The smoking tobacco material may be shredded, cured, cased and blended tobacco material or 65 1 602 747 reconstituted tobacco material or tobacco substitutes (e g, lettuce leaves) or mixtures thereof The proportions of flavoring additives may be varied in accordance with taste but insofar as the augmentation, or the enhancement or the imparting of the sweet, honey-like, fruity, woody, cedarwood, dried fruit-like, raspberry-like, blackcurrentlike, Virginia tobacco-like notes are concerned, we have found that satisfactory results are obtained if the 5 proportion by weight of the sum total 1-l 3-(methylthio)butyryll-2,6,6trimethylcyclohexene and/or its corresponding 1,3-cyclohexadiene analog to smoking tobacco material is between 250 ppm and 1 500 ppm ( 025 %-1 5 %) of the active ingredients to the smoking tobacco material We have further found that satisfactory results are obtained if the proportion by weight of the sum total of 1-l 3-(methylthio)butyryll-2, 6,6-trimethyl 10 cyclohexene and/or its corresponding 1,3-cyclohexadiene analog used to flavoring material is between 2,500 and 10000 ppm.
Any convenient method for incorporating the 1-l 3-(methylthio)butyryll-2, 6,6-trimethylcyclohexene and/or its corresponding 1,3-cyclohexadiene analog in the tobacco product may be employed Thus, the 1-l 3-(methylthio)butyryll-2,6,6-trimethylcyclohexene and/or 15 its corresponding 1,3-cyclohexadiene analog taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, npentane, diethyl ether and/or other volatile organic solvents and the resulting solution may either be sprayed on the cured, cased and blended tobacco material or the tobacco material may be dipped into such solution Under certain circumstances, a solution of the 1-l 3(methylthio)butyryll 20 2,6,6-trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog taken along or taken further together with other flavoring additives as set forth above, may be applied by means of a suitable applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be applied to the filter by either spraying or dipping or coating 25 Furthermore, it will be apparent that only a portion of the tobacco or substitute therefor need be treated and the thus treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed In such cases, the tobacco treated may have the 1-l 3-(methylthio)butyryll-266-trimethyl-cyclohexene and/or its corresponding 1,3cyclohexadiene analog in excess of the amount or concentrations above indicated so that 30 when blended with other tobaccos, the final product will have the percentage within the indicated range.
In accordance with one specific example of our invention, an aged, cured and shredded domestic burley tobacco is spread with a 20 % ethyl alcohol solution of 1l 3-(methylthio) butyryll-2,66-trimethyl-cyclohexene and/or its corresponding 1,3cyclohexadiene in an 35 amount to provide a tobacco composition containing 800 ppm by weight of 1l 3(methylthio)butyryll-2,6 6-trimethyl-cycohexene and/or its corresponding 1,3cyclohexadiene analog on a dry basis Thereafter, the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques The cigarette when treated as indicated has a desired and pleasing aroma which is detectable in the main and 40 side streams when the cigarette is smoked This aroma is described as being sweet, rich, floral, fruity hay tobacco-like, honey-like, cedarwood-like and Virginia tobacco-like.
While our invention is particularly useful in the manufacture of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fines may also be used Likewise, the 1-l 3(methylthio)butyryll 45 2,6,6-trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog of our invention can be incorporated with materials such as filter tip materials, seam paste and packaging materials which are used along with tobacco to form a product adapted for smoking Furthermore, the 1-l 3-(methylthio)butyryll-2,6,6-trimethylcyclohexene and/or its corresponding 1, 3-cyclohexadiene analog can be added to certain tobacco substitutes of 50 natural or synthetic origin (e g, dried lettuce leaves) and, accordingly, by the term “tobacco” as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substitute materials or both.
The 1-l 3-(methylthio)butyryll-26,6-trimethyl-cyclohexene and/or its corresponding 1,3 55 cyclohexadiene analog and one or more auxiliary perfume ingredients, including, for example, alcohols aldehydes nitriles, esters, other ketones, cyclic esters, synthetic essential oils, and natural essential oils may be admixed so that the combined odor of the individual components produce a pleasant and desired fragrance, particularly and preferably in floral fragrances Such perfume compositions usually contain (a) the main 60 note or the “bouquet’ or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) topnotes which are usually low boiling fresh smelling materials 65 8 1 602 747 8 The amount of 1-l 3-(methylthio)butyryll-2,6,6-trimethylcyclohexene and/or its corresponding 1,3-cyclohexadiene analog of our invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired It has been found that perfume compositions containing as little as 0 1 % of 1-l 3-(methylthio)butyryll-2,6,6-trimethyl-cyclohexene and/or its corres 5 ponding 1,3-cyclohexadiene analog (e g, 0 05 %) can be used to impart floral and natural rose oil-like odor to soaps, cosmetics or other products The amount employed can range up to 10 % of the fragrance components and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought 10 The 1-l 3-(methylthio)butyryll-2,6,6-trimethyl-cyclohexene and/or its corresponding 1,3cyclohexadiene analog is useful, taken alone or in perfume compositions as an olfactory component in detergents and soaps, space odorants and deodorants, perfumes, colognes, toilet water, bath preparations, such as bath oils, and bath solids; hair preparations, such as lacquers, brilliantines, pomades and shampoos; cosmetics preparations, such as creams, 15 deodorants, hand lotions and sun screens; powders, such as talcs, dusting powders and face powders When used as an olfactory component, as little as 1 % of the 1-l 3(methylthio)butyryll-2,6,6-trimethyl-cyclohexene and/or its corresponding 1,3cyclohexadiene analog will suffice to impart a natural rose oil-like or earthy and woody note(s) to floral formulations Generally, no more than 3 % of 1-l 3(methylthio)butyryll 20 2,6,6-trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog based on the ultimate end product is required in the perfume composition.
In addition, the perfume composition or fragrance composition of our invention can contain a vehicle, or carrier for the 1-l 3-(methylthio)butyryll-2,6,6trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog The vehicle can be a liquid such as a 25 non-toxic alcohol or a non-toxic glycol The carrier can also be an absorbent solid, such as a gum (e g, gum arabic) or components for encapsulating the composition (such as gelatin).
It will be apparent that 1-l 3-(methylthio)butyryll-2,6,6-trimethylcyclohexene and/or its corresponding 1,3-cvclohexadiene analog can be utilized to alter the sensory properties, particularly organoleptic properties, such as flavors and/or fragrances of a wide variety of 30 consumable materials.
The following examples are illustrative and the invention is to be considered to be restricted thereto only as indicated in the appended claims These examples serve to illustrate processes for producing the 1-l 3-(methylthio)butyryll-2,6,6trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog useful in our invention and processes 35 for using the 1-l 3-(methylthio)butyryll-2,6,6-trimethyl-cyclohexene and/or its corresponding 1,3-cyclohexadiene analog of our invention for their organoleptic properties.
All parts and percentages given herein are by weight unless otherwise specified.
The words “Carbowax” “Cab-O-Sil”, “Hobart” and “Rocoat” are Trade Marks.
40 EXAMPLE I
Extraction of 1-l 3-(minethyvlthio)butyrvll-2,6,6-trimtnethyl-cyclohexene and its corresponding 1,3-cyclohexadiene analog from black tobacco 560 lbs of black tobacco lamina obtained from the Dominican Republic is ground and subjected to steam distillation under atmospheric pressure The distillate is extracted with 45 methylene chloride The extract is then dried, partially concentrated, and separated into acidic (phenolic), basic and neutral fractions by back extraction with 0 1 N Na OH and 0 1 N HCI respectively When these fractions are concentrated, the acidic (phenolic) fraction totals 12 grams, the basic fraction totals 250 grams and the neutral fraction totals 100 grams.
The neutral oil is treated with Girard-T reagent to concentrate carbonyls This fraction 50 totals 4 grams of oil The “carbonyl-poor” fraction, which totals 89 grams, is subjected to adsorption chromatography on activity grade II silica gel in isopentane and fractions are eluted with increasing proportions of ether:isopentane Fraction # 14 which is eluted with 4 % ether in isopentane totals 0 74 grams of oil and is subjected to GLC/MS analysis on a 400 ‘ x 0 032 ” glass capillary column coated with SE-30 liquid phase Figure 1 sets forth a 55 portion of the GLC profile in the vicinity of two peaks, “B” and “A” subsequently identified as consisting of the 1-l 3-(methylthio)butyryll-2,6,6trimethyl-cyclohexene and its 1,3-cyclohexadiene analog, respectively, of our invention The scan of Figure 2 is obtained on peak “A” and the scan of Figure 3 on peak “B” The GLC retention times of these two peaks are determined relative to a series of ethyl esters of the normal alkanoic acids, 60 Cl-Cl,, C 12, C 14 and C 16 Peak “A” has a relative retention time (IE) of 13 00 and the IE of peak “B” is calculated to be 13 25 The parent ion of peak “A” is 238 and that of peak “B”, is 240 In each case the M+ 2 ion suggests the presence of one S atom in each molecule and the M-47 fragmentation of each is consistent with the loss of a CH 3-S group The major fragments of 121 and 149 for peak “A” and 123/151 for peak “B” are suggestive of 65 1 602 747 fragmentation a to the carbonyl group in the P-damascenone/f-damascone series.
The methylthio additives of 3-damascenone and 3-damascone are synthezied according to the procedures given in Examples II and III respectively The mass spectra and GLC retention times of the synthetic products are superimposable on those of peaks “A” and “B” respectively and the NMR data for each of the synthetic materials indicate the absence of allylic protons, therefore peaks “A” and “B” are assigned the structures:
0 SCH 3 0 SCH 3 and The NMR (nuclear magnetic resonance) analysis for peak “A” which consists of the compound 1-l 3-(methylthio)butyryll-2,6,6-trimethyl-1,3-cyclohexadiene having the structure:
CH 3 is as follows:
1.09 ppm (s) 1.34 (d) 1.74 (s) 2.14 (s) gem dimethyl protons CH 3-C-S=C-CH 3 CH 3-S2.12 (m) 2.82 (m) 3.28 (m) ) ) ) S O III -C-CH 2-CH-C-Solefinic protons 6 H 3 H 3 H H 2 H 1 H 5.81 (broad s) 2 H 1 602 747 The mass spectral analysis for 1-l 3-(methylthio)butyryll-2,6,6-trimethyl1,3cyclohexadiene is as follows:
relative intensity The NMR analysis for 1-l 3-(methylthio)butyryll-26,6-trimethylcyclohexene is as follows:
1.70 ppm (s) 1.34 (d) 1.59 (s) 1.78-1 42 (m) 1.93 (m) 2.12 (s) 2.80 (m) gem dimethyl protons CH 3-C-S) ) =C-CH 3) ) -CH 2) =C-CH 2CH 3-SI -CH,-C=O HC-Sm/e 117 121 133 149 223 238 p 6 H H 2 H 3 H 2 H 1 H 3.26 1 602 747 The mass spectral analysis for 1-l 3-(methylthio)butyryll-2,6,6-trimethylcyclohexene is as follows:
m/e relative intensity 123 151 177 193 225 240 p EXAMPLE II
Preparation of 3-(methlylthio)-l-( 2,6,6-trimethyl-1,3-cyclohexadien-l-yl) – 11-butanone o CH 3 + CH 35 H In a 50-mi three-necked, round-bottom flask equipped with a magnetic stirring assembly, a tube submerged for the introduction of gas, an immersion thermometer and a dry ice isopropanol condenser, the outlet of which leads through a 50 % alkali trap to the hood sink, is placed 8 3 grams of beta-damascenone and approximately 1 gram of triethylamine Gaseous methyl mercaptan is introduced into the stirred reaction mixture which is maintained at 10 C Addition is continued for approximately one hour and then stopped The stirred reaction mix is allowed to attain room temperature, and the reaction mix is stirred overnight at room temperature The next morning the light yellow reaction mix is transferred to 50 ml of ether in a separatory funnel and washed twice with dilute sulfuric acid twice with saturated sodium bicarbonate solution, and then with saturated saline solution until the wash is neutral The dried ether layer is stripped of solvent on a rotovap’ and GLC of the residue on an 1/8 ” x 10 ‘ stainless steel 5 % Carbowax 20 M column isothermally at 190 C shows one major late eluting peak which is trapped for infra-red and nuclear magnetic resonance/mass spectral analyses Infra-red analysis suggests that the cyclohexadienyl ring structure is intact and in conjugation with the side chain ketone which is however, now out of cross conjugation Therefore, reaction appears to have occurred at the side chain olefinic site Mass spectral analysis shows a molecular weight of 238, and the proper fragmentation for the proposed structure The mass spectral analysis also is a satisfactory match with the scan for peak “A” as set forth in Example I.
This peak has an IF on SE-30 of 13 00 A trap of the synthetic material is run for IE and the IF on SE-30 is 13 08.
Reaction:
12 1 602 747 12 They are thus considered to be the same compound, nuclear magnetic resonance showing the absence of allylic protons The structure is then deduced to be:
O 5 10 The product is subjected to vacuum fractional distillation at 2 95 mm Hg Six fractions plus residue are obtained, the highest purity of which is 87 8 % All fractions still smell strongly of CH 3 SH as if a small amount has formed during the distillation To permit the evaluation of pure material, it is subjected to preparative gas liquid chromatography on a 15 ‘ x 1/4 ” Carbowax 20 M column.
The NMR analysis is the same as that set forth in Example I for 3(methylthio)-1-2,6,6trimethyl-1,3-cyclohexadiene-1-yl)-1-butanone.
The mass spectral analysis is as follows:
20 m/e relative intensity 39 27 25 41 86 43 38 30 21 69 58 75 100 35 34 91 29 40 48 117 29 121 61 45 133 19 149 43 50 3 2 223 12 55 238 p 1 602 747 EXAMPLE III
Preparation of 1-l 3-(methylthio)butyryll-2,2,6-trimethyl-cyclohexene-1 Reaction:
5 0 O S CH 3 + CH 3 SH 10 In the same reaction apparatus used for Example II is placed 13-damascone weighing approximately 6 grams Approximately 1 gram of triethyl amine is added, and the stirred mix is treated with gaseous CH 3 SH for approximately 2 hours at room temperature 15Addition of CH 3 SH is stopped and the reaction mix is stirred overnight and then worked up in the same manner as the product of Example II GLC of the residue on Carbowax 20 M shows that all of the P-damascone has reacted A trap of the major peak is submitted for mass spectral analysis, and the proper molecular weight ( 240) and fragmentation for the following structure is observed: 20 25 The scan for peak B of Figure 3 matches the mass spectrum of the synthetic material The IE of the synthetic material on SE-30 is 13 20 and that of the peak corresponding to the above scan is 13 29 30 The NMR analysis is the same as that set forth in Example I for 1-l 3(methylthio)butyryl l-2,2,6-trimethyl-cyclohexene 1.
The mass spectral analysis is as follows:
relative intensity 35 m/e 17 41 11 40 43 18 69 33 75 45 26 81 47 89 47 50 123 151 6 177 55 7 193 225 32 60 240 p 14 1 602 747 14 EXAMPLE IV
Basic raspberry formulation containing 3-(methylthio)-1-( 2, 6, 6trimethyl-1,3-cvclohexadienl-yl)-l-butanone The following basic raspberry formulation is prepared:
5 Ingredients Parts by Weight Vanillin 2 10 Maltol 4 Para-Hydroxybenzylacetone 5 15 ca-Ionone ( 10 % in propylene glycol) 2 Ethyl butyrate 6 Ethyl acetate 16 20 Dimethylsulfide 1 Isobutylacetate 14 25 Acetic acid 10 Acetaldehyde 10 Propylene glycol 930 30 The basic raspberry formulation is divided into two parts To the first part 0 1 % by weight of 3-(methylthio)-1-( 2 66-trimethyl-1 3-cyclohexadien-1-yl)-1butanone prepared according to Example II is added Both flavors with and without the additional material are 35 compared at the rate of 100 parts per million in water by a bench panel consisting of four people The raspberry flavor with the addition of 3-(methylthio)-1-( 2,6,6trimethyl-13cyclohexadien-l-yl)-1-butanone is considered not only stronger but as having a more raspberry juice-like character and having more of the desired raspberry seed or kernel note.
The taste is closer to the ripe raspberry with pleasant tea and raspberry kernel notes 40 Therefore all panel members prefer the flavor with the addition of this flavor chemical.
1 602 747 15 EXAMPLE V
Basic raspberry flavor formulation containing 3-(methylthio)-1-( 2,6,6trimethyl-1cyclohexen-l-yl) -1 -butanone The following basic raspberry formulation is prepared:
5 Ingredients Parts by Weight Vanillin 2 10 Maltol 4 Para-Hydroxybenzylacetone 5 15 ta-lonone ( 10 % in propyleneglycol) 2 Ethylbutyrate 6 Ethyl acetate 16 20 Dimethylsulfide 1 Isobutylacetate 14 25 Acetic acid 10 Acetaldehyde 10 Propylene glycol 930 30 The formulation is divided into two parts To one of the parts 0 1 % by weight of 3-(methylthio)-1-( 2,6 6-trimethyl-l-cyclohexen-1 l-yl)-1-butanone prepared according to Example III is added To the second part of the basic raspberry formulation nothing else is 35 added Both formulations with and without the additional material are compared at the rate of 100 ppm (parts per million) in water by a bench panel All members of the bench panel prefer the raspberry flavor with the addition of ( 3-methylthio)-1-( 2,6, 6-trimethyl-1cyclohexen-l-yl)-l-butanone The aroma is sweeter and more raspberry syruplike, and the taste has a more raspberry distillate, black tea-like character and a raspberry kernel note 40 J 1 602 747 EXAMPLE VI
Perfume formulation containing 2,2,6-trimethyl-1-l 3-(methylthio butyryll1,3cvclohexadiene The following floral perfume formulation is prepared:
5 Ingredients Parts by Weight Phenylethyl alcohol 25 10 Rhodinol 22 Hydroxycitronellal 6 15 Linalool 5 Cinnamic alcohol 3 Alpha ionone 15 20 Amyl acetate ( 1 % in diethylphthalate) 6 Vetiverol 2 25 Ylang-ylang oil 3 Nerol 2 Musk ketone 3 30 Vanillin ( 10 % in diethylphthalate) 2 Styrax essence 1 35 2,2, 6-trimethyl 1 -l 3-(methylthio) butyryll 1 3-cyclohexadiene (produced according to Example II) 5 40 The product of Example II itself has a sweet, rosey, floral, cured tobacco note It gives lift and a more natural floralcy to the fragrance in which it is incorporated Although it was incorporated above at a level of 5 % by weight it may be effectively used at from O 1 to 10 % by weight in such floral formulations For special effects it may be used as high as 50 % by weight Addition of the product of Example II to the instant fragrance, greatly increases its 45 esthetic qualities and gives the olfactory illusion of the presence of natural rose oil.
1 602 747 EXAMPLE VII
Tobacco formulation A tobacco mixture is produced by admixing the following ingredients:
Parts by Weight Stem (flue-cured) Cigarettes are prepared from this tobacco.
The following flavor formulation is prepared:
Ingredients Parts by Weight Ethyl butyrate Ethyl valerate Maltol Cocoa extract Coffee extract Ethyl alcohol Water 2.00 26.00 10.00 20.00 41.90 The above-stated tobacco flavor formulation is applied at the rate of 0 1 % to all of the cigarettes produced using the above tobacco formulation Half of the cigarettes are then treated with 500 or 1000 (( ppm of 3-(methylthio)-1-( 2,6,6-trimethyl-1,3cyclohexadien-1-yl)1-butanone produced according to the process of Example II The control cigarettes not containing the 3-(methylthio)-1-( 2 6 6-trimethyl 1,3-cyclohexadien 1-yl) 1 -butanone produced according to the process of Example II and the experimental cigarettes which contain the 3-(methylthio) 1 -( 2,66-trimethyl 1 3-cyclohexadien-1-yl)-1-butanone produced according to the process of of Example II are evaluated by paired comparison and the results are as follows:
The experimental cigarettes are found to have more body and to be, on smoking, more tobacco-like, more aromatic, sweet, fruity hay-like and Virginia tobaccolike, with sweet, rich, honey-like and cedarwood-like nuances.
The tobacco of the experimental cigarettes prior to smoking has a sweet, rich, honey-like, slightly fruity, hay tobacco-like, woody and cedarwood-like aroma nuances The product of Example II produced according to the process of Example II enhances the tobacco-like taste and aroma of the blend cigarette imparting to it honey-like tobacco notes.
Ingredients Bright Burley 40.1 Maryland Turkish 24.9 1.1 11.6 Glycerine Water 14.2 2.8 5.3 1 602 747 EXAMPLE VIII
Perfumed liquid detergent Concentrated liquid detergents with floral and rose-oil like aromas are prepared containing 0 10 %, 0 15 % and 0 20 % of 3-(methylthio)-1-( 2,6,6trimethyl-1,3cyclohexadien-1-yl)-1-butanone prepared according to Example II They are prepared by 5 adding and homogeneously mixing the appropriate quantity of 3-(methylthio) -1-( 2,6,6trimethyl-1,3-cyclohexadien-1-yl)-1-butanone in the liquid detergents The detergents all possess a floral, and rose-oil like fragrance, the intensity increasing with greater concentrations of 3-(methylthio)-1-( 2,6,6-trimethyl-1,3-cyclohexadien-1yl)-1-butanone.
10 EXAMPLE IX
Preparation of a cologne and handkerchief perfume 3-(Methylthio)-1-( 2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone prepared according to the process of Example II is incorporated in a cologne at a concentration of 2 5 % in 85 % aqueous ethanol; and into a handkerchief perfume at a concentration of 20 % (in 95 % 15 aqueous ethanol) A distinct and definite floral and rose-oil like aroma is imparted to the cologne and to the handkerchief perfume.
EXAMPLE X
Preparation of a cologne and handkerchief perfume -20 The composition of Example VI is incorporated in a cologne at a concentration of 2 5 % in 85 % aqueous ethanol, and into a handkerchief perfume at a concentration of 20 % (in % aqueous ethanol) The use of the 2,2,6-trimethyl-1-l 3-(methylthio) butyryll-1,3cyclohexadiene in the composition of Example VI affords a distinct and definite strong floral, rose oil-like aroma to the handkerchief perfume and to the cologne 25 EXAMPLE XI
Preparation of soap composition One hundred grams of soap chips are mixed with one gram of 3-(methylthio)1-( 2,6,6trimethyl-1,3-cyclohexadien-l-yl)-l-butanone produced according to the process of Example 30 II until a substantially homogeneous composition is obtained The perfumed soap composition manifests an excellent floral and rose oil-like aroma.
EXAMPLE Xl I
Preparation of a detergent composition 35 A total of 100 g of a detergent powder is mixed with O 15 g of the 3(methylthio)-1-( 2,6,6trimethyl-1,3-cyclohexadien-l-yl)-1-butanone of Example II until a substantially homogeneous composition is obtained This composition has an excellentfloral, rose oil-like aroma.
40 EXAMPLE XIII
A Powder flavor composition () Grams of the flavor composition of Example IV containing 3-(methylthio) -1-( 2,6,6trimethyl-1,3-cyclohexadien-1-yl)-1-butanone is emulsified in a solution containing 300 gm gum acacia and 700 gm water The emulsion is spray-dried with a Bowen Lab Model Drier 45 utilizing 260 c f m of air with an inlet temperature of 500 F, an outlet temperature of W F and a wheel speed of 50,000 r p m.
1 602 747 B Sustained release flavor The following mixture is prepared:
Ingredient Parts by Weight S Liquid Raspberry Flavor) 20 composition of Example IV) containing 3-(methylthio)) 10 1-( 2,6,6-trimethyl-1,3) cyclohexadiene 1-yl)-1-butanone) Propylene glycol 9 15 Cab-O-Sil M-5 (Brand of Silica) 5 00 produced by the Cabot Corporation) of 125 High Street, Boston, Mass) 02110, Physical Properties:) 20) 20 Sulface area: 200 m 2/gm) Nominal particle size: 0 012 microns) Density: 2 3 lbs/cu ft)) The Cab-O-Sil is dispersed in the liquid raspberry flavor composition of Example IV with 25 vigorous stirring, thereby resulting in a viscous liquid 71 Parts by weight of the powder flavor composition of Part A, supra is then blended into the said viscous liquid, with stirring at 25 C for a period of 30 minutes resulting in a dry, free flowing sustained release flavor powder.
30 EXAMPLE XIV
Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150 F The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120 F 20 Parts by weight of the liquid flavor composition of Example IV containing 3-(methylthio)-1-( 2,6,6-trimethyl-1,3cyclohexadien-1-yl)-1 35 butanone is added to the solution which is then homogenized to form an emulsion having particle size typically in the range of 2-5 microns This material is kept at 120 F under which conditions the gelatin will not gel.
Coascervation is induced by adding slowly and uniformly 40 parts by weight of a 20 % aqueous solution of sodium sulphate During coascervation, the gelatin molecules are 40 deposited uniformly about each oil droplet as a nucleus.
Gelation is effected by pouring the heated coascervate mixture into 1,000 parts by weight of 7 % aqueous solution of sodium sulphate at 65 F The resulting gelled coascervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt 45 Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37 %c solution of formaldehyde in water The cake is then washed to remove residual formaldehyde.
EXAMPLE XV 50
Chewing gun parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XIII 300 parts of sucrose and 100 parts of corn syrup are added.
Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co 55 The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0 1 inches in thickness The strips are cut into lengths of 3 inches each On chewing, the chewing gum has a pleasant long lasting raspberry flavor.
EXAMPLE XVI 60 Chewing glnum parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example XIV 300 parts of sucrose and 100 parts of corn syrup are then added Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co 65 1 602 747 The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0 1 inches in thickness The strips are cut into lengths of 3 inches each On chewing, the chewing gum has a pleasant long lasting raspberry flavor.
EXAMPLE XVII 5 Toothpaste formulation The following separate groups of ingredients are prepared:
Parts by Weight Ingredient 10 Group “A” 30 200 Glycerin 15 15.325 Distilled Water ( Sodium Benzoate Saccharin Sodium 400 Stannous Fluoride 20 Group “B” 12.500 Calcium Carbonate 37 200 Dicalcium Phosphate (Dihydrate) 25 Group “C” 2 000 Sodium N-Lauroyl Sarcosinate (foaming agent) 30 Group “D” 1 200 Flavor Material of Example XIII 35 O () (Total) 40 Procedure 1 The ingredients in Group “A” are stirred and heated in a steam jacketed kettle to 1600 F.
45 2 Stirring is continued for an additional three to five minutes to form a homogenous gel.
3 The powders of Group “B” 3 are added to the gel, while mixing until a homogenous paste is formed 50 4 With stirring, the flavor of -D” is added and lastly the sodium nlauroyl sarcosinate.
5 The resultant slurry is then blended for one hour The completed paste is 55 then transferred to a three roller mill and then homogenized, and finally tubed.
The resulting toothpaste when used in a normal toothbrushing procedure yields 60 a pleasant raspberry flavor, of constant strong intensity throughout said procedure ( 1-1 5 minutes).
1 602 747 EXAMPLE XVIII
Chewable vitamin tablets The flavor material produced according to the process of Example XIV is added to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kg which Chewable Vitamin Tablet Formulation is prepared as follows: 5 In a Hobart Mixer, the following materials are blended to homogeneity:
Gms/1000 tablets 10 Vitamin C (ascorbic acid) as ascorbic acid-sodium ascorbate mixture 1:1 70 0 15 Vitamin B, (thiamine mononitrate) as Rocoat thiamine mononitrate 33-% (Hoffman La Roche) 4 0 Vitamin B 2 (riboflavin) 20 as Rocoat riboflavin 33 % 5 O Vitamin B 6 (pyridoxine hydrochloride) as Rocoat pyridoxine hydrochloride 33 % 4 0 25 Niacinamide as Rocoat niacinamide 33 % 33 0 Calcium pantothenate 11 5 30 Vitamin B 12 (cyanocobalamin) as Merck O 1 %c in gelatin 3 5 Vitamin E (dl-alpha tocopheryl acetate) as dry Vitamin E acetate 33 % Roche 6 6 35 d-Biotin 0 044 Certified lake color 5 O 40 Flavor of Example XIV (as indicated above) Sweetener sodium saccharin 1 0 Magnesium stearate lubricant 10 O 45 Mannitol q s to make 500 0 Preliminary tablets are prepared by slugging with flat-faced punches and grinding the 50 slugs to 14 mesh 13 5 g drv Vitamin A Acetate and 0 6 g Vitamin D are then added as beadlets The entire blend is then compressed using concave punches at 0 5 g each.
Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong raspberry flavor for a period of 12 minutes.
1 602 747 EXAMPLE XIX
Chewing tobacco Onto 100 pounds of tobacco for chewing ( 85 % Wisconsin leaf and 15 % Pennsylvania leaf) the following casing is sprayed at a rate of 30 %:
Ingredients Parts by Weight Corn syrup Licorice Glycerine Fig juice Prune juice Flavor material of Example XIII 4.6 0.4 The resultant product is redried to a moisture content of 20 % On chewing, this tobacco has an excellent substantially consistent, long-lasting raspberry ( 20 minutes) nuance in conjunction with the main fruity tobacco note.
EXAMPLE XX
Tobacco formulation A tobacco mixture is produced by admixing the following ingredients:
Ingredient Parts by Weight Bright 40.1 Burley Maryland 24.9 1.1 Turkish 11.6 Stem (flue-cured) Glycerine 14.2 2.8 Water 5.3 Cigarettes are prepared from this tobacco.
23 1 602 747 23 The following flavor formulation is prepared:
Ingredient Parts by Weight 5 Ethyl butyrate 05 Ethyl valerate 05 10 Maltol 2 00 Cocoa extract 26 00 Coffee extract 10 00 15 Ethyl alcohol 20 00 Water 41 90 20 The above-stated tobacco flavor formulation is applied at the rate of 0 1 % to all of the cigarettes produced using the above tobacco formulation Half of the cigarettes are then treated with 500 or 100 ()0 ppm of 1-l 3-(methylthio)butyryll-2,6,6trimethyl-cyclohexene produced according to the process of Example III The control cigarettes not containing the 25 1-l 3-(methylthio)butyryll-2,6,6-trimethyl-cyclohexene produced according to the process of Example III and the experimental cigarettes which contain the 1-l 3(methylthio)butyryll2,6,6-trimethyl-cyclohexene produced according to the process of Example III are evaluated by paired comparison and the results are as follows:
The experimental cigarettes prior to smoking are found to have a rich sweet flavor effect 30 with lingering sweetness with fruity, blackcurrant-like, raspberry-like, dried fruit-like, and damascenone-like notes, and to have, on smoking, more tobacco-like, sweet fruity and damascenone-like notes and to have more body than the control cigarettes.
The tobacco of the experimental cigarettes prior to smoking, has sweet, floral, fruity, earthy and green notes All cigarettes are evaluated for smoke flavor with a 20 mm cellulose 35 acetate filter.
The 1-l 3-(methylthio)butyryll-2 6 6-trimethyl-cyclohexene produced according to the process of Example II enhances the sweet tobacco-like, fruity aromatic taste and aroma of the blended cigarette imparting to it.
40 Brief description of the drawings
Figure 1 is the GLC profile of that portion of extract of black tobacco leaf which includes the compounds of the present invention.
Figure 2 is the mass spectral scan of peak A of the GLC profile of the extract of black tobacco leaf which consists of the compound 3-(methylthio)-1-( 2,2,6trimethyl-1,3 45 cyclohexadien l -yl)-1-butanone.
Figure 3 is the mass spectral scan of peak B of the GLC profile of the extract of black tobacco leaf produced according to Example I which consists essentially of the compound 1-l 3-(methvlthio)-butyrylj-2 66-trimethvl-cyclohexene-1.

Claims (1)

WHAT WE CLAIM IS: 50
1 A sulfur-containing compound which is 1-l 3-(methylthio)butyryll-2,6,6trimethylcvclohexene or the 1,3-cyclohexadiene analog defined by the structure:
O $/CH 3 55 l 60 wherein the dashed line is a carbon-carbon single bond or a carbon-carbon double bond.
2 A substantially pure, synthetically produced compound in accordance with Claim 1.
3 The sulfur-containing compound of claim 1 or 2 wherein the dashed line is a carbon-carbon double bond 65 24 1 602 747 24 4 The sulfur-containing compound of claim 1 or 2 wherein the dashed line is a carbon-carbon single bond.
A process for augmenting or enhancing the organoleptic properties of a consumable material which is, in the alternative, one of a perfume composition, a perfumed article, a food flavoring composition, a foodstuff, a chewing gum, a chewing gum flavoring S composition, a chewing tobacco, a medicinal product, a toothpaste, a flavoring composition for a chewing tobacco, a flavoring composition for a medicinal product, a flavoring composition for a toothpaste a smoking tobacco flavoring composition, or a smoking tobacco, which comprises adding thereto a small but organoleptically effective amount of a composition comprising at least one of the sulfur-containing compounds defined according 10 to claim 1 or 2.
6 The process of claim 5 wherein, in the sulfur-containing compound, the dashed line represents a carbon-carbon double bond.
7 The process of claim 5 wherein, in the sulfur-containing compound, the dashed line represents a carbon-carbon single bond 15 8 The process of claim 5, 6 or 7, wherein the consumable material is a foodstuff.
9 The process of claim 8, wherein the amount of said sulfur-containing compound added is in the range of from 0 5 ppm to 20 ppm by weight based on the total composition.
The process of claim 5 6 or 7 wherein the consumable material is a chewing gum.
11 The process of claim 5, 6 or 7 wherein the consumable material is a perfumed article 20 which is, in the alternative, a soap, a detergent or a cosmetic powder.
12 The process of claim 5 6 or 7 wherein the consumable material is a perfume composition.
13 The process of claim 5, 6 or 7, wherein the consumable material is a smoking tobacco or a tobacco flavoring composition 25 14 The process of claim 5 6 or 7 wherein the consumable material is a foodstuff flavor.
A flavor modifying composition comprising (i) at least one sulfurcontaining compound defined according to claim 1 or 2 and (ii) the remainder of said composition being a flavor adjuvant which is non-reactive and organoleptically compatible with said sulfur-containing compound 30 16 The flavor modifying composition of claim 15 comprising the sulfurcontaining compound defined according to claim 1 or 2 and, as a flavor adjuvant, at least one compound which is in the alternative, one of p-hydroxybenzyl acetone, maltol, benzyl acetate, methyl cinnamate geraniol, ethyl methyl phenyl glycidate, vanillin, methyl anthranilate, alpha-ionone gamma undecalactone ethyl pelargonate, isoamyl acetate, 35 acetaldehyde, dimethyl sulfide isobutyl acetate, acetic acid, ethyl butyrate, diacetyl, anethole, cis-3-hexenol-1 naphthyl ethyl ether, ethyl acetate, isoamyl butyrate, 2-methyl-2pentenoic acid 2 ( 4-hydroxy-4-methylphenyl)norbornadiene 4-allyl-1,2,6trimethoxy benzene and 4-propenyl-12,6-trimethoxy benzene.
17 A fragrance modifying composition comprising at least one sulfurcontaining 40 compound defined according to claim 1 or 2 and an auxiliary perfume ingredient compatible with said sulfur-containing compound.
18 A perfume composition comprising at least one sulfur-containing compound defined according to claim 1 or 2 and at least one adjuvant organoleptically compatible with said sulfur-containing compound and non-reactive with said sulfurcontaining compound 45 which is in the alternative, a natural perfume oil, a synthetic perfume oil, a nitrile, an alcohol, an aldehyde a ketone other than said sulfur-containing compound, an ester or a lactone.
19 A perfumed article comprising at least one sulfur-containing compound defined according to claim 1 or 2 and, in the alternative, a detergent, a soap, a cosmetic 50 preparation, or a powder.
A tobacco flavoring composition comprising at least one sulfur-containing compound defined according to claim I or 2 and an adjuvant therefor which, on smoking and prior to smoking is organoleptically compatible with said sulfurcontaining compound.
21 A tobacco flavoring composition comprising at least one sulfurcontaining 55 compound defined according to claim 1 or 2 and a flavor adjuvant organoleptically compatible with said tobacco flavoring composition which is, in the alternative, ethyl butyrate ethyl valerate or maltol.
22 A smoking article comprising a smoking tobacco and an outer wrapper causing said smoking tobacco to be maintained in a substantially cylindrical shape and, optionally a 60 filter for smoke, which smoke is produced by burning said smoking tobacco and said outer wrapper while smoking, and having admixed with said smoking tobacco or said outer wrapper or said filter or a combination of two or three of said smoking tobacco, said wrapper and said filter, at least one sulfur-containing compound defined according to claim 1 or 2 65 1 602 747 23 A smoking article comprising a smoking tobacco and intimately admixed therewith a composition consisting essentially of at least one sulfur-containing compound defined according to claim 1 or 2.
24 A process for producing a sulfur-containing compound having the structure:
5 0 T’CH 3 10 wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond, comprising the step of reacting methyl mercaptan with a ketone having the structure: 15 20 25 The process of claim 24 wherein the dashed line is a carbon-carbon single bond 25 26 The process of claim 24 wherein the dashed line is a carbon-carbon double bond.
27 The process of claim 24 wherein, in the process a triethyl amine catalyst is used.
28 The process of claim 25 wherein, in the process a triethyl amine catalyst is used.
29 The process of claim 26 wherein, in the process, a triethyl amine catalyst is used.
30 The product produced according to the process of claim 24 30 31 The product produced according to the process of claim 25.
32 The product produced according to the process of claim 26.
33 The product produced according to the process of claim 27.
34 The product produced according to the process of claim 28.
35 The product produced according to the process of claim 29 35 38 The process of claim 20 substantially as herein described with reference to either of Examples 11 or Ill.
39 The process of claim 21 substantially as herein described with reference to Example ill.
38 The process of claim 22 substantially as herein described with reference to Example 40 39 The process for producing a sulfur-containing compound defined according to claim 1 substantially as herein described with reference to Example 1.
The flavor modifying composition of claim 15 substantially as herein described with reference to any one of Examples IV V XIII or XIV 45 41 The process for augmenting or enhancing the organoleptic properties of a consumable material defined according to claim 5 substantially as herein described with reference to any one of Examples VI VII VIII, IX X, XI, XII XV, XVI XVII, XVIII, XIX or XX.
1 602 747 42 The process defined according to claim 8 substantially as herein described with reference to Example XV or Example XVI.
43 The process defined according to claim 13 substantially as herein described with reference to Example VII or Example XX.
44 The composition defined according to either of claims 17 or 18 substantially as 5 herein described with reference to any one of Examples VI, IX or X.
The process of claim 11 substantially as herein described with reference to any one of Examples VIII, XI or XII.
46 The perfumed article of claim 19 substantially as herein described with reference to any one of Examples VIII, XII or XI 10 FORRESTER, KETLEY & CO, Chartered Patent Agents, Forrester House, 52 Bounds Green Road 15 London Nil 2 EY.
-and also atRutland House, 148 Edmund St, Birmingham B 3 2 LD 20 -andScottish Provident Building, 29 St Vincent Place, Glasgow G 1 2 DT.
Agents for the Applicants 25 Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1981.
Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

GB8396/78A
1977-03-03
1978-03-02
Methylthiobutyryl cyclohexene and cyclohexadiene derivatives

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1-[3-(Methylthio)butyryl]-2,6,6-trimethyl-cyclohexene and the 1,3-cyclohexadiene analog

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WO2003049666A2
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2001-12-13
2003-06-19
Firmenich Sa
Compounds for a controlled release of active molecules

WO2004105713A1
(en)

2003-06-02
2004-12-09
Firmenich Sa
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Assignee
Title

US4162335A
(en)

1977-03-03
1979-07-24
Int Flavors & Fragrances Inc
Flavoring with 1-{8 3-(methylthio)butyryl{9 -2,6,6-trimethyl-cyclohexene and the 1,3-cyclohexadiene analog

US4209025A
(en)

1977-03-03
1980-06-24
International Flavors & Fragrances Inc.
Process for augmenting or enhancing the flavor of tobacco using 1-(3-methylthio)butyryl)-2,6,6-trimethyl-cyclohexene and the 1,3-cyclohexadiene analog thereof

US4107209A
(en)

1977-03-03
1978-08-15
International Flavors & Fragrances Inc.
1-[3-(Methylthio)butyryl]-2,6,6-trimethyl-cyclohexene and the 1,3-cyclohexadiene analog

US4115431A
(en)

1977-05-26
1978-09-19
International Flavors & Fragrances Inc.
Substituted dimethyl dihydroxy benzene and cyclohexadiene compounds and uses thereof for augmenting or enhancing the taste and/or aroma of consumable materials including tobaccos, perfumes and perfumed articles

US4284654A
(en)

1979-10-26
1981-08-18
International Flavors & Fragrances Inc.
Use of 1-hydroxy-1-ethynyl-2,2,6-trimethyl cyclohexane in augmenting or enhancing the aroma or taste of foodstuffs

JPS5893840A
(en)

1981-11-30
1983-06-03
Toyota Motor Corp
Combination of member

JPS5893841A
(en)

1981-11-30
1983-06-03
Toyota Motor Corp
Fiber reinforced metal type composite material

JPS5893839A
(en)

1981-11-30
1983-06-03
Toyota Motor Corp
Combination of member

DE3228289A1
(en)

1982-07-29
1984-02-09
Dragoco Gerberding & Co Gmbh, 3450 Holzminden

1- (1-METHYLTHIO-3-OXO-BUTYL) -2,6,6-TRIMETHYL-CYCLOHEXENES AND THE USE THEREOF AS A SMELLING AND FLAVORING SUBSTANCE

DE3307869A1
(en)

1983-03-05
1984-09-06
Dragoco Gerberding & Co Gmbh, 3450 Holzminden

METHYL-SUBSTITUTED 1 – ((3-METHYLTHIO) -1-OXO-BUTYL) -CYCLOHEX-2-ENE, METHOD FOR THE PRODUCTION AND USE THEREOF AS A SMELLING AND FLAVORING SUBSTANCE

JPS62227106A
(en)

1986-03-28
1987-10-06
Nippon Telegr & Teleph Corp
Assembling method for optical connector

JPS62227107A
(en)

1986-03-28
1987-10-06
Nippon Telegr & Teleph Corp
Assembling method for optical connector

JPS62286464A
(en)

1986-06-05
1987-12-12
積水化学工業株式会社
Deodorant

JPS63165522A
(en)

1986-12-27
1988-07-08
Nippon Steel Corp
Production of alumina fiber

JPS646121A
(en)

1987-06-23
1989-01-10
Toshiba Monofrax
High-strength ceramic fiber and production thereof

US5076960A
(en)

1989-10-23
1991-12-31
The Drackett Company
Deodorizing and cleaning compositions and method

JPH03115180A
(en)

1990-06-14
1991-05-16
Toshiba Monofrax Co Ltd
Production of heat insulation structure for high temperature

US6509054B1
(en)

2000-05-05
2003-01-21
American Fruits And Flavors
Food additives having enlarged concentration of phenolics extracted from fruits, and process of obtaining the same

US6620452B1
(en)

2000-05-05
2003-09-16
American Fruit And Flavors
Food additives having enlarged concentration of phenolics extracted from fruits and vegetables and process of obtaining the same

KR101425260B1
(en)

2008-08-19
2014-08-01
다우 아그로사이언시즈 엘엘씨
Improved process for the addition of thiolates to alfa,beta-unsaturated carbonyl or sulfonyl compounds

CN104394718A
(en)

2012-07-02
2015-03-04
西姆莱斯股份公司
A method of flavouring a smoking product

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1969-09-10
1977-06-28
Givaudan Corporation
Perfume compositions containing p-menthane-8-thiol-3-one

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1969-09-10
1976-04-20
Givaudan Corporation
Mercapto- or alkylthio-substituted menthenones

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(en)

1971-11-26
1975-05-13
Givaudan Corp
Novel mercaptoderivatives of ionones and irones

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(en)

1972-10-17
1976-01-15
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1974-03-04
1977-04-26
Sagami Chemical Research Center
Cyclic ketone mercaptal S-oxides

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(en)

1974-11-29
1977-06-21
International Flavors & Fragrances Inc.
Altering perfume green notes using trithioacetone

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(en)

1976-09-15
1977-12-27
International Flavors & Fragrances Inc.
α-Oxy(oxo) sulfide perfume and cologne compositions

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(en)

1976-09-15
1977-05-17
International Flavors & Fragrances Inc.
Flavoring with α-oxy(oxo)mercaptans

US4076853A
(en)

1977-02-04
1978-02-28
International Flavors & Fragrances Inc.
Flavoring with substituted norbornane derivatives

US4107209A
(en)

1977-03-03
1978-08-15
International Flavors & Fragrances Inc.
1-[3-(Methylthio)butyryl]-2,6,6-trimethyl-cyclohexene and the 1,3-cyclohexadiene analog

1977

1977-03-03
US
US05/774,055
patent/US4107209A/en
not_active
Expired – Lifetime

1978

1978-03-01
DE
DE2808710A
patent/DE2808710C3/en
not_active
Expired

1978-03-02
JP
JP2403278A
patent/JPS53109959A/en
active
Granted

1978-03-02
GB
GB8396/78A
patent/GB1602747A/en
not_active
Expired

1978-06-21
US
US05/917,662
patent/US4154693A/en
not_active
Expired – Lifetime

1978-06-21
US
US05/917,661
patent/US4156662A/en
not_active
Expired – Lifetime

1979

1979-06-29
JP
JP8337479A
patent/JPS5527176A/en
active
Granted

1979-06-29
JP
JP8337379A
patent/JPS5526888A/en
active
Granted

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Assignee
Title

WO2003049666A2
(en)

2001-12-13
2003-06-19
Firmenich Sa
Compounds for a controlled release of active molecules

WO2003049666A3
(en)

2001-12-13
2004-07-15
Firmenich & Cie
Compounds for a controlled release of active molecules

AU2002348801B2
(en)

2001-12-13
2007-11-22
Firmenich Sa
Compounds for a controlled release of active molecules

US7723286B2
(en)

2001-12-13
2010-05-25
Firmenich Sa
Compounds for a controlled release of active molecules

US7935669B2
(en)

2001-12-13
2011-05-03
Firmenich Sa
Compounds for a controlled release of active molecules

US8354369B2
(en)

2003-05-07
2013-01-15
Firmenich Sa
Sprayable perfume with an improved tenacity

WO2004105713A1
(en)

2003-06-02
2004-12-09
Firmenich Sa
Compounds for a controlled release of active molecules

US7589055B2
(en)

2003-06-02
2009-09-15
Firmenich Sa
Compounds for a controlled release of active molecules

Also Published As

Publication number
Publication date

US4154693A
(en)

1979-05-15

JPS552265B2
(en)

1980-01-19

US4156662A
(en)

1979-05-29

JPS6133005B2
(en)

1986-07-31

JPS5618189B2
(en)

1981-04-27

JPS53109959A
(en)

1978-09-26

DE2808710A1
(en)

1978-09-14

DE2808710B2
(en)

1980-01-17

US4107209A
(en)

1978-08-15

DE2808710C3
(en)

1980-09-18

JPS5526888A
(en)

1980-02-26

JPS5527176A
(en)

1980-02-27

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