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GB1589755A - 2-substituted-4,5-dialkyl- 3-thiazolines processes for producing same and organoleptic uses thereof - Google Patents

2-substituted-4,5-dialkyl- 3-thiazolines processes for producing same and organoleptic uses thereof Download PDF

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Publication number
GB1589755A
GB1589755A GB41064/77A GB4106477A GB1589755A GB 1589755 A GB1589755 A GB 1589755A GB 41064/77 A GB41064/77 A GB 41064/77A GB 4106477 A GB4106477 A GB 4106477A GB 1589755 A GB1589755 A GB 1589755A
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thiazoline
methyl
tobacco
composition
ethyl
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International Flavors and Fragrances Inc
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International Flavors and Fragrances Inc
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Priority claimed from US05/730,653 external-priority patent/US4040987A/en
Priority claimed from US05/730,157 external-priority patent/US4067344A/en
Application filed by International Flavors and Fragrances Inc filed Critical International Flavors and Fragrances Inc
Publication of GB1589755A publication Critical patent/GB1589755A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • 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
    • A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
    • A24B15/365—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having nitrogen and sulfur as hetero atoms in the same ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D227/00—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00
    • C07D227/02—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00 with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D227/06—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00 with only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D227/10—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/10—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0096—Heterocyclic compounds containing at least two different heteroatoms, at least one being nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Seasonings (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Cosmetics (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The organoleptic modifier contains, as active ingredient, at least one novel compound of the formula (1) <IMAGE> in which RA and RC are identical or different and denote hydrogen or methyl, and RB is alkyl or alkylthioalkyl. The compound of the formula 1 is prepared by the process defined in Patent Claim 2.

Description

(54) 2-SUB STITUTED-4,5-DIALKYL-A3-THIAZOLINES, PROCESSES FOR PRODUCING SAME AND ORGANOLEPTIC USES THEREOF (71) We, INTERNATIONAL FLAVORS & FRAGRANCES INC., a Corporation organised and existing under the laws of the State of New York, one of the 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:- The present invention provides novel compositions useful for augmenting or enhancing the aroma or taste of a material which is useful for human consumption, for example, foods, perfumes, perfumed articles (for example, soaps, detergents and cosmetics) and tobaccos and tobacco substitutes. The compositions contain 2 substituted-4,5-dialkyl.A3-thiazolines having the structure:
wherein RA and Rc are the same or different and each is methyl or hydrogen, and RB is alkyl or alkylthioalkyl. More particularly the compositions contain 2substituted-4,5-dialkyl-A3-thiazolines having two more specific generic structures, I and II, as follows:
(hereinafter referred to as "2-alkyl-substituted-4,5-dimethyl-A3-thiazolines") wherein one of R1, R2 and R3 is methyl and each of the other of R1, R2 and R3 is hydrogen or:
(hereinafter referred to as "2-alkylthioalkyl-4,5-dialkyl-A3-thiazolines") wherein R,l and R12 are the same or different and each is hydrogen or methyl. The present invention also relates to the above described thiazolines, per se, as well as the use of the above described thiazolines in organoleptic property-augmenting or enhancing quantities, with or without suitable adjuvants.
The 2-alkyl-substituted 4,5-dimethyl-A3-thiazolines of Formula I may be obtained by reacting an aldehyde or ketone with aqueous ammonia thereby forming the corresponding imine and reacting the thus-formed imine with 2mercapto-3-butanone according to the following reaction sequence:
wherein R R2 and R3 are the same or different and each represents hydrogen or methyl, details of which process are set forth hereinafter by way of example and are broadly set forth in the prior art, United States Patent Specification No. 2,879,273, United States Patent Specification No. 3,816,445, and German Auslegungschrift No. 1,095,284.
The 2-alkylthioalkyl-4,5-dialkyl-53-thiazolines of formula II may be prepared by first admixing an alkylthioalkanal with aqueous ammonia to form the corresponding imine and then reacting said imine with 3-mercapto-2-butanone or 3-mercapto-2-pentanone in order to produce the desired thiazoline. This reaction sequence is set forth as follows:
wherein R1l and R12 are the same or different and each of R11 and R,2 represents hydrogen or methyl. The reaction parameters are exemplified hereinbelow and are also exemplified and stated in United States Patent Specification No. 3,816,445, as well as United States Patent Specification No. 2,879,273 (wherein the substituent at the "2" position is alkyl rather than alkylthioalkyl).
Thus, according to one aspect of the present invention there is provided a process for producing a composition comprising a major quantity of a compound having the structure:
comprising the steps of (i) reacting NH3 with
to form
; and (ii) reacting
with
and (iii) separating from the reaction product a composition comprising a major quantity of a compound having the structure:
wherein RA and Rc are each the same or different and each represents hydrogen or methyl; and RB is alkyl or thioalkyl. The above described processes for preparing thiazolines of Formulae I and II are embodiments within this general process. The invention also relates to a thiazoline whenever prepared by a process according to the present invention.
Previously issued publications do not disclose the substance of our invention and our compounds are compositions represent an advance in the art over previously known subject matter. Thus, United States Patent Specification 3,816,445 discloses 2-substituted-53-thiazolines as flavorantes, which A3-thiazolines have the generic structure:
wherein R' may be C3-C11 alkyl, benzyl or 2-methylthioethyl. It is disclosed at column 2, lines 46-50 that generically speaking, these compounds have "interesting vegetable notes such as bean, tomato, pepperoni, asparagus as well as potato notes. Specifically disclosed are compounds having the structures:
Thus, for example, 2-isobutyl-53-thiazoline is indicated to have a "typical beanlike" fragrance with a "weak pepperoni note." The compounds are also disclosed in corresponding Swiss Patent Specification No. 565,515.
Compounds having the generic structure:
Wherein R;, R2, R3, R4 and R5 may be hydrogen or alkyl, are disclosed in United States Patent Specification No. 3,700,683 (as being intermediates for syntheses of penicillamine); in German Auslegungschrift 1,058,061; in German Auslegungschrift 1,063,602 and in German Auslegungschrift 1,095,284. The same generic structure is published by the same authors in United States Patent Specification No. 3,004,981. The compounds are not shown in this patent to have a utility as food flavorants, but rather as indicated at column 5, line 71 to: "exhibit considerable physiological action and may thus be used in the synthesis of therapeutic agents. They constitute valuable intermediates and final products for the pharmaceutical industry. Further, they may be used for many other purposes as, for example, as agents for combating pests, as preservatives for the preservation of wood, as weed killers and as protecting agents against rust and aging." Specifically, the compound 2,4,5-trimethyl-2-ethyl-A3-thiazoline is indicated to be produced according to Example I, and this compound has the structure:
2,4,5-trimethyl thiazoline having the structure:
has been identified in cooked beef, and it has been stated that it is a contributing factor to the flavor properties of cooked beef in a paper entitled "Identification and Flavor Properties of Some 3-oxazolines and 3-thiazolines Isolated from Cooked Beef," by Mussinan, Wilson, Katz, Hruza and Vock (Presented: Paper &num;22, Agricultural and Food Chemistry Division, 170th National Meeting, American Chemical Society, Chicago, Illinois, Aug. 26, 1975; In Press: Advances in Chemistry Series, American Chemical Society, Washington, D.C.).
Specific examples of 2-alkylthioalkyl-4,5-dialkyl-A3-thiazolines produced using the aforementioned process and their flavor properties are as follows (as set forth in Table 1, below): TABLE I Compound Structure Organoleptic Properties
2(2' Methylthioethyl)- A A sweet, meaty, meat 4,5-dimethyl-A3- / 1-h3- extract-like, beef broth-like, thiazoline S )~ / hydrolyzed vegetable S > 5t S protein-like, and bread crust-like aroma with bread crust-like, sweet, monosodium glutamate-like, meat extract-like, beef broth-like, hydrolyzed vegetable protein-like, salty, bloody and metallic taste and flavor nuances.
2(2 'Me thyIthiopropy I)- N A sweet, meaty, meat 4,5-dimethyl-A3- / \ | extract-like, beef broth-like, thiazoline S S hydrolyzed vegetable protein-like, potato-like aroma with sweet/meaty, meat extract-like, beef broth-like, hydrolyzed vegetable protein-like, metallic, salty and potato-like taste.' and flavor nuances.
2(2' Methylthioethyl- N A sulfury, roasted, roasted 4-methyl-5-ethyl-A3- ~Zo < / / meat-like, beef broth-like, thiazoline ~ so S vegetable and tomato-like aroma with sulfury, beef broth-like, vegetable, metallic and cooked tomato-like taste and flavor nuances.
Specific examples of 2-alkyl-substituted-4,5-dimethyl-A3-thiazolines and their food flavor properties are set forth in Table II below: TABLE II Compound Structure Flavor Property
2-(2'-methylpropyl)- N A sweet, roasted meat-like, 4,5-dimethyl-A3- 1 \ 1 roasted nut-like, dark thiazol ine S > chocolate-like, baked goods-like and vegetable green-like aroma with a sweet, roasted meat-like, roasted nut-like, chocolate like, vegetable green-like, hydrolyzed vegetable protein-like taste having hydrolyzed vegetable protein aftertaste and astringent and chocolate like notes.
2-(2' -n-butyl) 4,5- N A sweet, harbaceous, spicy, dimethyl-A3- chocolate-like, nutty, thiazoline S vegetable-like, hydrolyzed vegetable protein-like, roasted aroma with herbaceous, vegetable green-like, nutty, roasted, chocolate-like flavor and an astringent character.
2-n-propyl-2,4,5- sN A sweet, green bean-like, trimethyl-A3- cucumber-like, geranium-like thiazol inc S and spicy aroma with cucumber-like, green bean-like, spicy, watermelon like, black pepper-like flavor characteristics and an astringent character.
The distillate of hydrolyzed vegetable protein (as produced according to Example I, infra), appears to contain the following A3-thiazoline derivatives: 2,4-dimethyl-A3-thiazoline; 4,5-dimethyl-A3-thiazoline; 2,4,5-trimethyl-A3-thiazoline; 2-propyl-2,4,5-trimethyl-A3-thiazoline: 2-ethyl-2,4,5-trimethyl-A3-thiazoline; 2-(2'-butyl)-4-methyl-A3-thiazoline; 2-n-butyl-4,5-dimethyl-A3-thiazoline; 2-benzyl-4-methyl-A3-thiazoline; 2,5-dimethyl-2-benzyl-A3-thiazoline; 2-(2'-methyl-n-propyl)A,5-dimethyl-A3-thiazoline.
The presence of the foregoing materials in the distillate of refluxing hydrolyzed vegetable protein is indicated in various peaks in Figure 1. The presence of such compounds in hydrolyzed vegetable protein distillate is not considered to infer that these compounds can be used as foodstuff flavorants or in order to augment or enhance the flavor or aroma of a foodstuff.
When the 2-substituted-4,5-dialkyl-A3-thiazoline compound or compounds of our invention are used as food flavor adjuvants, or are used to augment or enhance the flavor or aroma characteristics of foodstuffs, the nature of the co-ingredients included with the said 2-substituted 4,5-dialkyl-A3-thiazolines in formulating the product composition will also serve to augment the organoleptic characteristics of the ultimate foodstuff treated therewith.
As used herein in regard to flavors, the term "augment" in its various forms means "supplying or imparting flavor character or note to otherwise bland, relatively tasteless substances or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste." As used herein regard to food flavors, 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, "enchancement" of a flavor or aroma means that the enhancement agent does not add any additional flavor note.
As used herein the term "foodstuff" includes both solids and liquids, and ingestible materials or chewable but no-ingestible materials such as chewing gum.
Such materials usually do, but need not, have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, gelatin desserts, diary products, candies, vegetables, cereals, soft drinks, snacks and the like.
Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. Apart from the requirements that any such materials be organoleptically compatible with the 2-substituted-4,5-dialkyl-A3-thiazolines, non-reactive with the 2-substituted-4,5-dialkyl-A3-thiazolines of our invention and "ingestibly" acceptable and thus non-toxic or otherwise non-deleterious, nothing particularly critical resides in the selection thereof. Accordingly, such materials which may in general be characterized as flavoring adjuvants or vehicles comprise broadly stabilizers, 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 hydrolyanisole (mixture of 2 and 3 tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene (2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like and sequestrants, e.g., citric acid.
Thickener compounds include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, e.g., agaragar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth; gelatin, proteinaceous materials; lipids; carbohydrates; starches, pectins and emulsifiers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup and the like.
Surface active agnets include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like.
Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like; colorants, e.g. carminic acid, cochineal, tumeric and curcuma and the like; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate; anzymes; yeast foods, e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.
Other flavorants and flavor intesifiers include vanillin, ethyl vanillin, diacetyl, phenethyl 2-furoate, maltol, neryl butyrate, dimethyl sulfide, linalool, acetic acid, methyl sulfide, acetaldehyde, isovaleraldehyde, isoamyl alcohol, acetic acid, lactones, isoamyl esters including the acetate, butyrate, and octanoate, pyrazine, methyl pyrazine, dimethyl pyrazine, 2-ethyl-3-methyl pyrazines, 2,3-diethyl-5methyl pyrazines, isobutyl phenyl alcohol, amyl octanoate, isoamyl-2-furan butyrate, benzoic acid, pyridine, phenylacetic acid, isobutyl phenethyl alcohol, cinnamyl esters such as the propionate, cinnamyl phenyl acetate, 4-phenyl-3 butene- -one, 3-phenyl-2-pentenal, 3-pentenal, 3-phenyl4-pentenal, 3-(2-methyl phenyl)4-pentenal, 3-phenyl-4-methyl-4-pentenal, 2-phenyl-4-pentenal, 2-phenyl-4pentenal dimethyl acetal, 2-isobutylthiazole, 2(secondary butyl) thiazole, cocoa extracts, cocoa distillates, cocoa bean particles, "bitterness principles" such as theobromin, caffein and naringin, "astringency principles" such as tannins, quebracho, and theotannates, and the like. These are combined in proportions requisite to obtain the desired effect as illustrated further hereinbelow.
The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, be capable of providing an tnvironment in which the 2-substituted-4,5-dialkyl-A3-thiazolines can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof, will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff to which the flavor and aroma are to be imparted. In contradistinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives.
As will be appreciated by those skilled in the art, the amount of 2-substituted 4,5-dialkyl-53-thiazolines employed in a particular instance can vary over a relatively wide range whereby to its desired organoleptic effects having reference to the nature of the product are achieved. Thus, correspondingly, greater amounts would be necessary in those instances wherein the ultimate food composition to be flavoured is relatively bland to the taste, whereas relatively minor quantities may suffice for purposes of enhancing the composition merely deficient in natural flavor or aroma. The primary requirement is that the amount selected be effective, i.e., sufficient to alter the organoleptic characteristics of the parent composition.
The use of insufficient quantities of 2-substituted-4,5-dialkyl-Q3-thiazolines will, of course, substantially vitiate any possibility of obtaining the desired results, while excess quantities prove needlessly costly and may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the terminology "effective amount" and "sufficient amount" is to be accorded a significance in the context of the present invention consistent with the obtention of desired flavoring effects.
Thus, and with respect to ultimate food compositions, it is found that quantities of 2-substituted-4,5-dialkyl-A3-thiazolines ranging from a small but effective amount, for example from 0.1 parts per million up to 50 parts per million by weight based on total composition (more preferably from 0.2 ppm up to 10 ppm) are suitable. Concentrations in excess of the maximum quantity stated are not normally recommended, since they fail to prove commensurate enhancement of organoleptic properties. In those instances, wherein the 2-substituted-4,5-dialkyl A3-thiazoline 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 thiazoline concentration in the foodstuff product.
Food flavoring compositions prepared in accordance with the present invention preferably contain the 2-substituted-4,5-dialkyl-A3-thiazoline in concentrations ranging from 0.1% up to 15% by weight based on the total weight of said flavoring composition.
The composition described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can be conveniently prepared by mixing the 2-substituted-4,5-dialkyl- 3- thiazoline with, for example, gum arabic, gum tragacanth, carageenan and the like, and thereafter spray-drying the resultant mixture whereby to obtain the particular solid product. Pre-prepared flavor mixes in powder form, for example fruit flavoured powder mix, are obtained by mixing the dried solid components, for example starch or sugar, and 2-substituted-4,5-dialkyl-A3-thiazoline in a dry blender until the requisite degree of uniformity is achieved.
It is presently preferred to combine with the 2-substituted-4,5-dialkyl-83- thiazoline, the following adjuvants: acetaldehyde; isobutyraldehyde; isovaleraldehyde; dimethyl sulfide; isobutyl acetate, isoamyl acetate: phenylethyl acetate; diacetyl; acetophenone; furfural; benzaldehyde; phenylacetaldehyde; isoamyl alcohol; phenylethyl alcohol; y-butyrolactone; 3-phenyl-4-pentenal; 3phenyl-3-pentenal; 3-phenyl-2-pentenal; 2-methyl pyrazine; 2,6-dimethyl pyrazine; 2,3,5,6-tetramethyl pyrazine; 2,3,5-trimethylpyrazine; 2-ethyl-3-methylpyrazine; 2ethyl-3,5-dimethylpyrazine; 2-ethyl-3,6-dimethylpyrazine; 2-ethyl-5methylpyrazine; 2(n-pentyl) thiazole; 2(i-butyl) thiazole; 2(i-propyl) thiazole; 2(npropyl) thiazole; 2-phenyl-4-pentenal; 2-phenyl-4-pentenaldimethylacetal; methional; 4-methylthiobutanal; 2-ethyl-3-acetylpyrazine; trans-2-hexenal; hydrolyzed vegetable protein; monosodium glutamate; black pepper oil; nutmeg oil; celery oil; lemon oil; and mustard oil.
Specific examples of the 2-alkyl-substituted-4,5-dimethyl-A3-thiazolines useful in perfumery and for use in perfumed articles, and their perfumery properties are set forth in Table III below: TABLE Ill Compound Structure Perfumery Property
2n-propyl-2,4, 5- FN A green, cucumber, dill trimethyl-A3- < ts aroma yielding, on dryout, thiazoline S floral, natural tuberose like, and orris-like nuances.
2(2'-methylpropyl)- cN An excellent fresh ground 4, 5-dimethy I-A3- 95zu coffee aroma with deep thiazoline green nuances.
One or more of the 2-alkyl-substituted-4,5-dimethyl- 3-thiazolines having the structure:
wherein R, and R3 are each the same or different and R1 and R3 are each one of hydrogen or methyl, is an olfactory agent and can be incorporated into a wide variety of compositions, each of which will be enhanced or augmented by its green, dill, coffee-like and/or floral, tuberose-like or orris-like nuances.
The 2-alkyl-substituted-4,5-A3-thiazolines can be added to perfume compositions as pure compounds or can be added to mixtures of materials in fragrance-imparting compositions to provide a desired fragrance character to a finished perfume material. The perfume and fragrance compositions obtained according to this invention are suitable in a wide variety of perfumed articles and can also be used to enhance, modify or reinforce natural fragrance materials. It will thus be appreciated that the 2-alkyl-substituted-4,5-dimethyl- 3-thiazoline(s) of our invention is (are) useful as olfactory agent(s) and fragrance(s).
The term "perfume composition" is used herein to mean a mixture of compounds, including, for example, natural oils, synthetic oils, alcohols, aldehydes, ketones, esters, lactones, nitriles and frequently hydrocarbons which are admixed so that the combined oders of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain (a) the main note or the "bouquet" or foundation-stone of the composition; (b) modifiers which roundoff 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) top-notes which are usually lowboiling, fresh-smelling materials. Such perfume compositions of our invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, and the like.
In perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus, one or more of the 2-alkyl-substituted-4,5-dimethyl- 3-thiazolines of our invention can be used to alter, augment, modify or enhance the aroma characteristics of a perfume composition or a perfumed article, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient of the composition.
The amount of one or more of the 2-alkyl-substituted-4,5-dimethyl- 3- thiazolines of our invention which will be effective in perfume compositions depends upon many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as much as 2% or as little as 0.005% by weight of the mixtures or compounds of this invention, or even less can be used to impart intense deep green and coffee-like aromas and floral aromas to soaps, cosmetics and other products The amount employed will depend upon considerations of cost, nature of the.end products, the effect desired in the finished product, and the particular fragrance sought.
One or more of the 2-alkyl-substituted-4,5-dimethyl- 3-thiazolines of our invention as disclosed herein can be used alone, in a fragrance modifying composition, or in a perfume composition as an olfactory component in detergents (an anionic detergents, cationic detergents, and nonionic detergents) and soaps; space deodorants; perfumes, colognes, bath preparations such as bath oil, bath salts; hair preparations such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun screens; powders such as talcs, dusting powders, face powders and the like. When one or more ot' the 2-alkyl-substituted-4,5-dimethyl-A3-thiazolines of our invention is used in perfumed articles such as the foregoing, it can be used in amounts of 0.01% or lower. Generally it is preferred not to use more than about 2% in the finished perfumed article, since the use of too much will tend to unbalance the total aroma and will nedlessly raise the cost of the article.
Specific examples of the compounds of our invention which have properties causing them to be useful for augmenting or enhancing the aroma or taste of tobacco or tobacco substitutes and their tobacco flavor properties prior to and on smoking are set forth in Table IV as follows: TABLE IV
Organoleptic Organoleptic Properties Properties Compound Name Compound Structure Prior to Smoking on Smoking 2-(2'-methyl-n- -N Chocolate-like, nutty, A sweeter, nutty, propyl)4,5-dimethyl- sweet \ | sweet bready, baked bready aroma with A3-thiazoline AS goods aroma and slightly green and taste. slight chocolate like nuances.
N 2-(2'-butyl)-4,5- green, nutty, bready Slightly cooling, dimethyl-Ag- A sweet, nutty, bready slightly bready thiazoline S \ aroma and flavor. nuances on smoking.
N 2-(2'-me thy I th N o-N < It has been found that the tobacco additives of our invention when incorporated into tobacco products impart a flavor and aroma both before and during smoking which many smokers consider to be desirable in smoking products.
However, it must be pointed out that the methods for defining or characterizing the quality of a flavor or aroma in the tobacco art are almost purely subjective and different smokers may define the same flavor quite differently. Also as indicated in the above table, the compounds included within the scope of this invention may impart different flavors or aromas depending upon the substituents therein. Thus, the compounds comprehended by this invention, by subjective tests, impart characteristic flavors which are desirable in tobacco products and the smoke therefrom even though the exact character thereof cannot be described on the basic of known standards.
In accordance with one aspect of this invention, one or more of the thiazolines of our invention or mixtures thereof is added to tobacco or applied to a smoking article or its components parts in amounts in the range of from 50 to 5,000 parts per million (ppm) based on dry weight of the tobacco product. Preferably, the amount of additive is in the range of from 100 to 500 ppm by weight in order to provide a tobacco product having a desired flavor and aroma. However, the amount used will depend upon the amount of flavor and aroma desired and the particular thiazoline compound or mixture thereof that is used.
The additive may be incorporated at any step in the treatment of the tobaco, but is preferably added after aging, curing and shredding and before the tobacco is formed into cigarettes. Likewise it will be apparent that only a portion of the tobacco need be treated and the thus-treated tobacco may be blended with other tobaccos before the cigarettes or other smoking articles are formed. In such case the tobacco treated may have the additive . in excess of the amounts above indicated so that when blended with other tobaccos, the final product will have the percentage within the indicated range.
In accordance with one specific embodiment of this invention an aged, fluecured and shredded tobacco is sprayed with a 1% ethyl alcohol solution of a 40:40:20 (weight:weight:weight) mixture of 2-(2'-methyl-n-prdpyl)-4,5-dimethyl-A3- thiazoline: 2-(2'-n-butyl)-4,5-dimethyl-A3-thiazoline: 2-(2 '-methylthioethyl)-4,5dimethyl-A3-thiazoline in an amount to provide a tobacco containing 100 ppm by weight of the mixture of thiazoline additives on a dry basis. Thereafter, the alcohol is removed by evaporation, and the tobacco is manufactured into cigarettes by the usual techniques. It has been found that this cigarette, when prepared as indicated has a desired and pleasing flavor, an aroma to which some people is described as "nutty-bready" and is very much akin to a "bright" tobacco, and is detectable and pleasing in the main and side smoke streams when the cigarette is smoked.
The additives falling within the scope of this invention may be applied to the tobacco by spraying, dipping or otherwise, utilizing suitable suspensions or solutions of the thiazoline additive. Thus, water or volatile organic solvents, such as alcohol, ether, acetone, volatile hydrocarbons and the like, may be used as the carrying medium for the additive while it is being applied to the tobacco. Also, other flavor and aroma producing additives such as: (a) Esters, for example, ethyl butyrate; ethyl acetate; ethyl valerate; amyl acetate; phenyl ethyl isovalerate, and methyl heptyl carbonate; (b) Aldehydes, for example, 3-phenyl-2-pentenal; 3 phenyl-3-pentenal; phenyl ~ acetåldehyde; cinn mwaldehyde; and; - beta-ethyl- cinnamaldehyde; (c) Ketones, for example, benzylidene acetone; acetophenone; maltol; and ethyl maltol; (d) Acetals, for example, 3-phenyl-4-pentenal dimethyl acetal; and 3-phenyl-4-pentenal diethyl acetal (described in United States Patent No. 3,922,237; (e) Natural Oils and Extracts, for example, vanilla; coffee extract, origanum oil; cocoa extract; oil of cloves; nutmeg oil; celery seed oil; bergamot oil; and ylang-ylang oil; (f) Lactones, for example, delta-decalactone; deltaundecalactone; delta-dodecalactone; gamma-undecalactone; and coumarin; (g) Ethers, for example, dibenzyl ether; vanillin; and eugenol; (h) Pyrazines, for example, 2-acetyl pyrazine; 2-acetyl-6-methyl pyrazine; 2-ethyl pyrazine; 2,3dimethyl pyrazine; 2,5-dimethyl pyrazine; and 2-ethyl-5-methyl pyrazine; (i) Pyrroles, for example, N-cyclopropyl pyrrole; and N-cyclooctyl pyrrole; as well as those additives disclosed in United States Patent Specifications Nos. 2,776,145; 2,905,575; 2,905,576; 2,978,365; 3,041,211; 2,776,149; 2,776,150; 3,589,372; 3,228,146; 3,402,051; and 3,380,457 as well as Australian Patent Specification Nos.
444,545; 444,507 and 444,389, may be incorporated into the tobacco with the additives of this invention.
While this invention is principally useful in the manufacture of cigarette tobacco, it is also suitable for use in connection with the manufacture of pipe tobacco, cigars or other tobacco products. Furthermore, the compounds may be added to certain tobacco substitutes of natural or synthetic origin and by the term "lobacco" as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substituted materials or both for example dried lettuce leaves and cabbage leaves).
Also, the invention has been particularly described with reference to the addition of the compounds directly to tobacco. However, it will be apparent that the compound may be applied to the paper of the cigarette or to the wrapper of a cigar. Also, it may be incorporated into the filter tip, the packaging material or the seam paste employed for gluing the cigarette paper. Thus, a tobacco product is provided which includes the specified additives and tobacco although in every instance the compound need not be admixed with the tobacco as above specifically described.
The following Examples are given to illustrate embodiments of the invention as it is presently preferred to practice it. It will be understood that these Examples are illustrative and that the invention is not to be considered as restricted thereto except as indicated in the appended claims.
EXAMPLE I.
Preparation of reflux distillate of hydrolyzed vegetable protein Into a 22-liter, round-bottom flask equipped with heating mantle, air-driven stirrer, 4 cm x 57 cm jacketed column packed with 1/8 inch glass helices, magnetically controlled reflux takeoff head and one liter addition funnel, is placed 5 kg Nestle 4BE hydrolyzed vegetable protein and 10 liters distilled water. The reaction mixture is heated to reflux, and reflux is commenced with a "take-off" at a rate of 20%. Two liters of distillate are collected, and the distillate is extracted with diethyl ether. The diethyl ether extract is concentrated to 100 ml and fractionated into acidic, phenolic, basic and neutral components. Each of the fractions is analyzed using GLC, NMR, mass spectral and IR analyses. The following thiazolines are determined by means of the foregoing analyses in the basic fraction: 2,4-dimethyl-A3-thiazoline; 4,5-dimethyl-A3-thiazoline; 2,4,5-trimethyl-53-thiazoline; 2-propyl-2,4,5-trimethyl-A3-thiazoline 2-ethyl-2,4,5-trimethyl-A3-thiazoline; 2-(2'-butylj-4-methyl-A3-thiazoline 2-n-butyl-4,5-dimethyl-A3-thiazolir.e; 2-benzyl-4-methyl-A3-thiazoline; 2,5-dimethyl-2-benzyl-A3-thiazoline; 2-(2'-methyl-n-propyl)-4,5-dimethyl-A3-thiazoline.
The GLC spectrum for the basic fraction is set forth in Figure 1. The MS profile for 2(2-methyl-n-propyl)-4,5-dimethyl-A3-thiazoline present in the basic spectrum is set forth in Figure 2 (isomer I) and Figure 3 (isomer II).
The MS profile for 2-(2'-butyl)-4,5-dimethyl-A3-thiazoline is set forth in Figure 4 (isomer I) and Figure 5 (isomer II).
EXAMPLE II.
Preparation of 2-(2-methyl-n-propyl)-4,5-dimethyl-53-thiazoline Reaction:
Into a 500 ml, three-necked, round-bottom flask equipped with stirrer, 250 ml addition funnel, ice bath and Fredericks condenser, is placed 45 ml water and 45 ml 58% aqueous NH3. With stirring, 43 grams of isobutyraldehyde is added dropwise.
104 Grams of a 50% ethanolic solution of 3-mercapto-2-butanone is then added dropwise over a period of one hour. The reaction mass is then allowed to stir for one hour at room temperature.
The resulting product is extracted with three 100 ml portions of diethyl ether.
The ether extracts are combined and dried over anhydrous sodium sulfate and then evaporated on a rotary evaporator. The resulting product is then distilled on a 12" Vigreux column at 4 mm Hg pressure and 70"C vapor temperature yielding a product containing 97% 2-(2'-methyl-n-propyl)-4,5-dimethyl-A3-thiazoline.
The MS profiles show that two isomers exist; an "endo" and an "exo" isomer.
The MS profile for isomer I is set forth in Figure 6. The MS profile for isomer II is set forth in Figure 7.
The NMR spectrum for the resulting product is set forth in Figure 8.
The infrared spectrum for the resulting product is set forth in Figure 9.
The NMR analysis is as follows: Chemical Shift Assignment Protons 1.00 ppm (doublet "Isopropyl" methyl of doublets) protons 6H
1.50 (dbublet CH3-C-S 3H of doublets) C=N 2.10 (d,J=2Hz) CH3-C=N- 3H 2.00-1.60(m) CH2+ HC 3H I 4.25 (m) HC-S 1H I C=N 5.55 (m) HC-N=C= lH 1H S The IR analysis is as follows: 940 cm-', 1160, 1200, 1370, 1380, 1430, 1440, 1470, 1670, 2880, 2940, 2960.
The mass spectral analysis is as follows: M/E Relative Intensity 41 15 42 19 55 17 68 542 71 365 87 433 101 19 114 100' 138 308 M 171 404 EXAMPLE Ill.
Preparation of 2-(2 '-n-butyl)-4,5-dimethylA3-thiazoline Reaction:
Into a 500 ml, three-necked, round-bottom flask equipped with mechanical stirrer, 250 ml addition funnel, thermometer, Friedrich's condenser, and ice bath, is placed 87.4 ml 30% aqueous ammonia and 45 ml distilled water. 43 Grams 2-methyl butanal is then added dropwise to the reaction mass while maintaining the reaction mass at room temperature. After completion of the addition of the 2-methyl butanal, 104 grams of a 50% (in 95% ethanol) solution of 3-mercapto-2-butanone is added dropwise over a period of one hour. The reaction mass is then extracted with 300 ml diethyl ether in 3 portions. The ether extracts are combined and dried over anhydrous sodium sulfate, and then evaporated on a Rotovap. The resulting product is then distilled at a vapor temperature of 105--107"C and a vacuum of 20 mm Hg yielding a product containing 98% 2-(2'-n-butyl)-4,5-dimethyl-A3- thiazoline. The distillation is carried out on a 12" Vigreux column. In order to purify the resulting product, it is redistilled at 60-610C at a pressure of 3 mm Hg.
The resulting material exists in two isomeric forms, an "endo" and an "exo" form. The MS profile for the first isomer is set forth in Figure 10. The MS profile for the second isomer is set forth in Figure 11.
The NMR spectrum is set forth in Figure 12.
The infrared spectrum for the resulting material is set forth in Figure 13.
The NMR analysis is as follows: Chemical Shift Assignment Protons 1.010.80 ppm methyl proton 6H
1.46 C H 3-C-S- 3H C=N 2.08 CH,--C=NN- 3H 1.96-I. 18 methylene methine protons 3H 4.20 C--C 111 H-C-S I 5.54 H-C-S- 1H N=C The IR analysis is as follows: 910 cm-', 1250, 1370, 1430,1450, 1460, 1670, 2880, 2940, 2960.
The mass spectral analysis is as follows: M/E Relative Intensity 41 9 42 8 55 8 71 7 82 144 87 222 100 9G 114 100l 115 96 M 171 173 EXAMPLE IV.
Preparation of 2,4,5-trimethyl-2-n-propyl-A3-thiazoline Reaction:
Into a 500 ml, three-necked, round-bottom flask equipped with mechanical stirrer, 250 ml addition funnel, thermometer, Friedrich's condenser and ice bath is placed 45.2 ml of a 58% aqueous NH3 solution and 45 ml distilled water. 43.05 Grams of 2-pentanone is then added dropwise from the addition funnel with stirring while maintaining the reaction mass at a temperature of between 25 and 28 C. At the completion of the addition of the 2-pentanone, 104 grams of a 50% (in 95% ethanol) solution of 3-mercapto-2-butanone is then added to the reaction mass over a period of one hour with stirring while maintaining the reaction mass at room temperature.
The reaction'mass is then extracted with three 100 ml portions of diethyl ether, and the diethyl ether extracts are combined. The ether extracts are then washed with two 100 ml portions of water, and the ether extracts are dried over anhydrous sodium sulfate and evaporated on a rotary evaporator. The resulting product is then distilled at a vapor temperature of 104"C and a pressure of 31 mm Hg.
The MS profile of the resulting material is set forth in Figure 14.
The NMR spectrum of the resulting material is set forth in Figure 15.
The infrared spectrum of the resulting material is set forth in Figure 16.
The NMR spectrum analysis is set forth as follows: Chemical Shift (ppm) Assignment Quantification
0.90 C11- 3H 1.48 C113-C-S 1.58 CH,-C-N- 10H 1.84-1.11 -CH2 2.02 C112-C=N- 3H 4.26 CH3-C11-S- 1H The infrared analysis is as follows: 840 cm-', 895, 1130, 1180, 1250, 1370, 1450, 1670, 2880, 2940, 2960.
The mass spectral analysis is as follows: M/E Relative Intensity 42 318 69 24 82 345 87 442 96 22 110 344 III 22 128 100 138 25 M 171 403 EXAMPLE V.
A commercial cocoa mix is used to prepare two different batches of beverage.
The first batch is evaluated without any further additive, while 2-(2'-methyl-n propyl)-4,5-dimethyl-A'-thiazoline prepared according to Example II is added to the second barch in the ratio of 40 mg of said 2-(2'-methyl-n-propyl)-4,5-dimethyl A3-thiazoline to each kilogram of cocoa beverage. The beverage without 2-(2' methyl-n-prnpyl)-4,5-dimethyl-A'-thiazoline gives a rather harsh flavor impression, while the beverage containing 2-(2'-methyl-n-propyl)-4,5-dimethyl-A3-thiazoline according to the present invention has a fuller, richer sweet milk chocolate flavor.
EXAMPLE Vl.
A basic chocolate flavor composition is prepared by admixing the following ingredients: Compound Amount (grams) Dimethyl sulfide 1.0 Isobutyl acetate 1.0 Isoamyl acetate 1.0 Phenylethyl acetate 0.5 Compound Amount (grams) Diacetyl (10% in 95% food-grade ethyl alcohol) 0.5 Furfural (50% in propylene glycol 0.5 Isoamyl alcohol 1.0 y-Butyrolactone 5.0 Acetophenone 0.5 Benzaldehyde 1.0 Phenyl acetic acid 2.0 Maltol 3.0 Acetaldehyde 2.0 Isobutyraldehyde 8.0 Isovaleraldehyde 15.0 Phenylethyl alcohol 8.0 Vanillin 15.0 Propylene glycol 40.0 The flavour is divided into two portions. To a first portion 2-(2'-methyl-npropyl)-4,5-dimethyl-A3-thiazoline is added at a rate of 2%. To a second portion no thiazoline derivative is added. The two portions of flavor formulation are compared at a rate of 5 ppm in water and evaluated by a bench panel. It was found that the flavor containing the 2-(2'-methyl-n-propyl)-4,5-dimethyl-A3-thiazoline has a more characteristic cocoa powder note, both in aroma and taste, and is therefore preferred.
EXAMPLE VII.
The following basic walnut formulation is prepared: Ingredient Parts by Weight Cyclotene 4 Vanillin 2 Butylisovalerate 0.5 Cuminaldehyde (10% in food-grade 95% ethyl alcohol) 0.5 2,6-dimethoxyphenol (10% in food-grade 95% ethyl alcohol) 0.5 Benzaldehyde 8 2,3-diethyl pyrazine 2 Ethyl-2-methyl butyrate 0.5 Gamma-butyrolactone 20 Gamma-hexalactone 12 Benzyl alcohol 15 Propylene glycol 35 The basic walnut flavor formulation is divided into two portions. To a first portion at the rate of 8% is added 2-(2'-methyl-l-propyl)-4,5-dimethyl-A3- thiazoline. Nothing additional is added to the second portion of the basic walnut flavor formulation. The two formulations, both with and without the thiazoline derivative, are compared at the rate of 8 ppm by a bench panel. All members stated that the flavor containing the thiazoline derivative has a more characteristic walnut kernel characteristic with its walnut skin astringent notes. Therefore the flavor containing the said thiazoline derivative is preferred.
A comparison with and without the same thiazoline derivative was conducted using a commercial vanilla ice cream to which the two walnut flavors have been added at the rate of 15 ppm. The ice cream with the walnut flavor containing the thiazoline derivative is preferred as being more walnut kernel-like.
EXAMPLE VIII.
A flavor composition according to this invention is prepared by combining the following materials as shown: Compound Amount (grams) 2-Methyl pyrazine 6 2,6-Dimethyl pyrazine 15 2,3,5,6-Tetramethyl pyrazine 12 3-Phenyl-4-pentenal 50/50 (w/w) mixture of 2-(2'methyl-n-propyl)-4,5 dimethyl-A3-thiazoline and 2-n-propyl-2,4,5-trimethyl A3-thiazoline 4 This composition is added to a chocolate/milk having a bland, thin cocoa flavor.
Adding 30 mg/kg increases the sweet milk chocolate and nut-like notes and supplemental addition of 40 mg/kg of the basic cocoa flavor material as described in Example VI gives the chocolate milk an excellent cocoa flavor and aroma note.
EXAMPLE IX.
To a portion of essentially flavorless salad dressing, 2-(2'-n-butyl)-4,5-dimethyl thiazoline is added at a rate of 0.10 ppm. The resulting mixture has a characteristic cucumber, spiced pickle note. The salad dressing is a mixture of the following: Ingredient Parts Black pepper oil 3 Nutmeg oil 3 Celery oil 3 Lemon oil 3 Mustard oil 1 Vinegar-citric acid (50:50 mixture) 120 Starch paste prepared from tapioca flour-water (50:50 mixture) 300 Liquid egg yolks 210 Sodium chloride 7 Sucrose 10 Mustard 20 Locust Bean gum 6 EXAMPLE X.
Preparation of 2(2'methylthioethyl)-4, 5-dimethyl-n3-thiazoline Rer.tinn
Into a 500 ml, three-necked, round-bottom flask, equipped with mechanical stirrer, 250 ml addition funnel, thermometer, Friedrichs condenser and ice-bath is placed 45.2 ml of a 58% aqueous ammonia solution and 45 ml distilled water.
Dropwise with stirring, while maintaining the temperature at 25-280C, 52 gms of methional is added to the ammonia solution. After the methional is added, dropwise, with stirring, over a period of one hour, 104 gms of a 50% solution of 3mercapto-2-butanone in 95% ethanol is added. The resulting reaction mass is kept at room temperature with stirring during the addition of the 3-mercapto-2butanone. The reaction mass is then extracted with two 100 ml portions of diethyl ether. The diethyl ether extracts are combined and washed with three 100 ml portions of distilled water and then dried over anhydrous sodium sulfate. The dried extracts are then evaporated on a rotary evaporator and the resulting oil is distilled on a 6" Vigreux column at a vapor temperature of 97--103"C, a liquid temperature of 129--140"C and a pressure of 2 mm Hg.
The mass spectrum is set forth in Figure 17. The NMR spectrum is set forth in Figure 18. The infra-red spectrum is set forth in Figure 19.
The NMR analysis is as follows:
1.50 ppm C=C (doublet of I 3H doublets) C113-C-S 2.08 (d,J=2Hz) C112-C=N 2.13 (s) C112-S- 1 8H 2.46-1.86(m) methylene methine 2.66 (t) -C112-S- 2H 4.28 (m) HC-S 111 C=C= 5.62 (m) HC--N=C 1H S The infra-red analysis is as follows: 880 cm-', 940, 1160, 1220, 1240, 1280,1370, 1430, 1660, 2920, 2960.
The Mass Spectral analysis is as follows: M/E Relative Intensity 55 13 61 19 68 18 87 304 100 215 114 323 126 216 128 16 174 100' M 189 442 EXAMPLE Xl.
Preparation of 2(2'-methylthiopropyl)-4,5-dimethyl-A3-thiazoline Reaction:
Into a 500 ml, three-necked, round bottom-flask, equipped with mechanical stirrer, thermometer, Friedrichs condenser, 250 ml addition funnel and cooling bath, is placed 87 ml of a 30% aqueous ammonia solution. The ammonia solution is cooled to a temperature of between 13 and 17"C and, drop-wise, with stirring, 59.1 gms of 3-methylmethional is added. The reaction mass is stirred for a period of 90 minutes, after which time 106 gms of a 50% solution (in 95% ethanol) of 3mercapto-2-butanone is added over a 30 minute period, dropwise. The reaction mass is maintained during the addition at a temperature of between 11 and 16"C.
After the addition, the reaction mass is permitted to warm up to 250C and is stirred for an additional 2.5 hours. The reaction mass is then transferred to a separatory funnel and is observed to exist in two phases; an oil phase and an aqueous phase.
The oil phase is drawn off and the aqueous phase is extracted with three 100 ml portions of diethyl ether. The ether extracts and the oil phase are then combined and dried over anhydrous sodium sulfate and then stripped of solvent on a rotary evaporator. The product is then distilled on a 8" Vigreux column at a vapour temperature of 100--104"C and a pressure of 2 mm Hg.
The resulting material is confirmed by GLC, NMR, IR and Mass Spectral analyses to have the structure:
The mass spectrum is set forth in Figure 20. The NMR spectrum is set forth in Figure 21. The infra-red spectrum is set forth in Figure 22.
The NMR analysis is as follows:
1.34 ppm CH,-C-S 3H (doublet of doublets) 1.50(d) CH,-C-C=N I S 3H 2.45--1.55 (m) -CH,- 2H 2.53 (m) CH,CH-S- 1H 4.25 (m) CH,--CHH--S IH C--N 5.90 (m) HC-N=C 111 S The infra-red analysis is as follows: 940 cm-', 1245, 1370, 1430, 1440, 1660, 2920, 2960.
The Mass Spectral analysis is as follows: M/E Relative Intensity 55 20 75 474 87 40 89 20 100 22 114 458 122 476 140 613 188 100' M203 662 EXAMPLE XII.
Preparation of 2(2'-methylthioethyl)-4-methyl-5-ethyl-A3-thiazoline Reaction:
Into a I-liter reaction flask, equipped with mechanical stirrer, Friedrichs condenser, thermometer, isopropanol/dry-ice bath, and 250 ml addition funnel is placed 145.8 ml of a 30% aqueous ammonia solution. The solution is maintained at 5-150C and over a period of 45 minutes, dropwise, with stirring, is added 105.5 gms of methional. After the methional is added, 253.9 gms of a 50% 3-mercapto-2pentanone solution (in 95% aqueous ethanol) is added to the reaction mass over a period of two hours while maintaining the reaction mass at 1015 C. After the addition of the 3-mercapto-2-pentanone, the temperature of the reaction mass is permitted to rise to 250C and is maintained at 250C for a period of 1.5 hours with stirring. The reaction mass is then transferred to a separatory funnel and 100 ml of a saturated aqueous sodium chloride solution is added thereto. The reaction phase now exists in two phases: an oil phase and an aqueous phase. The oil phase is separated from the aqueous phase and the aqueous phase is extracted with three 100 ml portions of diethyl ether. The ether extracts and the oil phase are then combined and washed with two 100 ml portions of saturated aqueous sodium chloride solution. The resulting organic phase is then dried over anhydrous sodium sulfate, stripped of ether on a rotary evaporator and distilled on a 12" Vigreux column at 1740C and 22 mm Hg pressure.
GLC, NMR, IR and Mass Spectral analyses confirm that the compound has the structure.
This material has a threshold level of 0.005 ppm and a use level at a concentration of 0.01 ppm and at this use level yields a sulfury, roasted, roasted meat-like, beef broth-like, vegetable and tomato aroma with a sulfury beef broth-like, vegetable, metallic and cooked tomato-like flavor character.
The Mass spectrum is set forth in Figure 23. The NMR spectrum is set forth in Figure 24. The infra-red spectrum is set forth in Figure 25.
The NMR analysis is as follows:
0.94 CH3 3H 2.02 CH3-C--N 2.06 CH3-S 1211 2.36-2.00 -CH2 4.24 C= HC-S 1H 5.52 -S-HC-N-- 111 The infra-red analysis is as follows: 945 cm-, 1230, 1260, 1370, 1430, 1660, 2920, 2960.
EXAMPLE XIII.
A walnut flavor formulation is prepared by blending the following ingredients: Ingredients Parts by Weight Vanillin 4.0 Ethyl-2-methylbutyl 1.0 Butyl isovalerate 4.0 2,3-Diethyl pyrazine 0.5 Methyl cyclopentenolone 8.0 a-Hydroxy-pmethyl-A, a"B-y-hexenolactone 2.0 Benzaldehyde 6.0 Valerian oil Indonesian (0.1% solution in propylene glycol) 0.5 Propylene glycol 74.0 This walnut flavor is compared in water at the rate of 10 ppm with the identical flavor to which 0.5 parts of 2(2'methylthioethyl)-4-methyl-5-ethyl-A3-thiazoline prepared according to Example XII is added. The flavor containing 2(2'methylthioethyl)-4-methyl-5-ethyl-A3-thiazoline has a fuller, more natural walnut kernel-like taste because of the addition to the formulation of said thiazoline compound.
EXAMPLE XIV.
A walnut flavor is prepared by blending the following ingredients: Ingredients Parts by Weight Vanillin 4.0 Ethyl-2-methylbutyrate 1.0 Butyl isovalerate 4.0 2,3-diethyl pyrazine 0.5 Methyl cyclopentenolone 8.0 a-Hydroxy-p-methyl-A-a -hexenolactone 2.0 Benzaldehyde 6.0 Valerian Oil Indonesian (0.1% solution in propylene glycol) 0.5 Propylene glycol 74.0 This walnut flavor is compared in water at the rate of 10 ppm with the same flavor to which 2% 2(2'methylthioethyl)-4,5-dimethyl-A3-thiazoline prepared according to Example X is added. The flavor containing the 2(2'methylthioethyl) 4,5-dimethyl-A3-thiaz6line has a sweeter, more walnut kernel and rounded taste and is therefore improved.
EXAMPLE XV.
Vegetable flavor formulation 2(2 Methylthioethyl)-4-methyl-5-ethyl-A3-thiazoline prepared according to Example XII is added directly to a food product prior to processing and canning.
The following illustrates the beneficial flavor effect when 2(2'methylthioethyl)-4methyl-5-ethyl-A3-thiazoline prepared according to Example XII is added to several food products just prior to their consumption: (i) In blended vegetable sauce at approximately 30 ppm: Brings out the cooked vegetable note with tomato nuances.
(ii) In vegetable soup at 40 ppm: Imparts a cooked vegetable flavor. The cooked notes give the entire vegetable flavor a fuller body.
(iii) In bean tomato sauce at approximately 20 ppm: Modifies the flavor by reducing the harsh character of the tomato spice mixture while at standard commercial mashed potato when the formulation is added thereto at the rate of 5 ppm (rate of A3-thiazoline: 0.15 ppm).
EXAMPLE XVIII.
Narcisse perfume formulation The following formulation is prepared: Ingredients Parts by Weight 2-(2'-methylpropyl)-4,5 dimethyl-A3-thiazoline (prepared according to Example II) 3 Heliotropine 30 Para cresyl phenyl acetate 15 Oxyphenylon I Para cresol 2 Acetyl isoeugenol 20 Isoeugenol 15 Ylang extra 5 Nerol 50 Geraniol 40 Terpinenol 4 5 a-terpinineol 35 Linalool (synthetic) 50 Benzyl alcohol 80 Benzyl acetate 10 Para cresyl salicylate 50 The 2-(2'-methylpropyl)-4,5-dimethyl-53-thiazoline imparts a deep green, coffeelike note so necessary for the Narcisse formulation.
EXAMPLE XIX.
Preparation of a soap composition 100 Grams of soap chips are mixed with one gram of the composition produced according to Example XVIII until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent Narcisse aroma having deep green and coffee-like nuances.
EXAMPLE XX.
Preparation of a detergent composition A total of 100 grams of a detergent powder prepared according to Example I of Canadian Patent Specification No. 985,597 is intimately admixed with 0.15 grams of the perfume composition prepared according to Example XVIII until a substantially homogeneous composition is obtained. This composition has an excellent Narcisse aroma with deep green and coffee-like nuances.
EXAMPLE XXI.
Preparation of cosmetic powder composition A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder with 0.25 grams of the Narcisse formulation prepared according to Example XVI II. The resulting powder has an excellent Narcisse aroma having, in addition, deep green and coffee-like nuances.
EXAMPLE XXII.
Perfumed liquid detergent Concentrated liquid detergents with rich, pleasant, Narcisse aromas are prepared containing 0.10%, 0.15% and 0.20% of the Narcisse formulation of Example XVIII. They are prepared by adding and homogeneously admixing the appropriate quantity of the product of Example XVI II in the liquid detergent. The liquid detergents are all produced using anionic detergents containing a 50:50 mixture of sodium lauroyl sarcosinate and potassium N-methyl lauroyl tauride. The detergents all possess a pleasant fragrance which can be described as Narcisse having deep green and coffee-like nuances.
EXAMPLE XXIII.
Cologne and handkerchief perfume The composition of Example XVIII is incorporated into a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 25% (in 95% aqueous ethanol). A distinct and definite strong Narcisse fragrance is imparted to the cologne and to the handkerchief perfume, and these fragrances have intense and pleasant underlying deep green and coffee like nuances.
EXAMPLE XXIV.
Colgne and handkerchief perfume 2-n-propyl-2,4,5-trimethyl-A3-thiazoline produced according to Example IV is incorporated into a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). A distinct and definite strong green, floral fragrance having tuberose-like and orris-like nuances is imparted to the cologne and to the handkerchief perfume.
EXAMPLE XXV.
Cologne and handkerchief perfume 2(2'-methylpropyl)-4,5-dimethyl-å3-thiazoline produced according to Example II is incorporated into a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). A distinct and definite strong coffee-like fragrance with excellent green nuances is imparted to the cologne and to the handkerchief perfume.
EXAMPLE XXVI.
Tobacco use of 2-(2'-methylthioethyl)-4,5-dimethyl-å3-thiazoline The following tobacco Formulation (A) is prepared: Ingredients Parts Ethyl Butyrate 0.05 Ethyl Valerate 0.05 Maltol 2.00 Cocoa Extract 26.00 Coffee Extract 10.00 Ethanol (95% aqueous) 20.00 Water 41.90 The following tobacco Formulation (B) is prepared: Ingredients Parts Bright Tobacco 40.1 Burley Tobacco 24.9 Maryland Tobacco 1.1 Turkish Tobacco 11.6 Stem (Flue-cured) Tobacco 14.2 Glycerine 2.8 Water 5.3 The flavor Formulation (A) is added to a portion of the smoking tobacco Formulation (B) at the rate of 0.1% by weight of the tobacco. The flavored and non-flavored tobacco formulations are then formulated into cigarettes by the usual manufacturing procedure: At the rate of 100 ppm to half of the cigarettes in each group is added 2-(2' methylthioethyl)-4,5-dimethyl-å3-thiazoline prepared according to Example X. The use of the 2-(2'-methylthioethyl)-4,5-dimethyl-å3-thiazoline in the cigarettes causes the cigarettes, prior to smoking, to have a burnt aroma with a pleasant, slightly fatty nuance. In smoke flavor these notes are still found, and the tobacco flavor on smoking is more aromatic and renders the tobacco more "bright-" like whether or not the other flavor ingredients of Formulation (A) are present.
EXAMPLE XXVII.
Tobacco use of 2-(2'-methyl-n-propyl)-4,5-dimethyl-å3-thiazoline The following tobacco flavor Formulation (A) is prepared: Ingredients Parts Ethyl Butyrate 0.05 Ethyl Valerate 0.05 Maltol 2.00 Cocoa Extract 26.00 Coffee Extract 10.00 Ethanol (95% aqueous) 20.00 Water 41 90 The following tobacco Formulation (B) is prepared: Ingredients Parts Bright Tobacco 40.1 Burley Tobacco 24.9 Maryland Tobacco 1.1 Turkish Tobacco 11.6 Stem (Flue-cured) Tobacco 14.2 Glycerine 2.8 Water 5.3 The flavor Formulation (A) is added to a portion of the smoking tobacco Formulation (B) at the rate of 0.1% by weight of tobacco. The flavored and nonflavored tobacco formulations are then formulated into cigarettes by the usual manufacturing procedure: At the rate of 100 ppm to half of the cigarettes in each group is added 2-(2' methyl-n-propyl)-4,5-dimethyl-å3-thiazoline produced according to Example II. The use of the 2-(2'-methyl-n-propyl)-4,5-dimethyl-å3-thiazoline in the cigarettes causes the cigarettes, prior to smoking, to have a chocolate-like, nutty, sweet, bready, baked goods aroma and taste. In smoke flavor these notes are still found, and the tobacco flavor on smoking has a sweeter, nutty, bready aroma with slight green and slight chocolate-like nuances causing it to be very closely akin to "bright" tobacco whether or not the other flavor ingredients of Formulation (A) are present.
EXAMPLE XXVIII.
Tobacco use of 2-(2'-n-butyl)-4,5-dimethyl-A3-thiazoline The following tobacco flavor Formulation (A) is prepared: Ingredients Parts Ethyl Butyrate 0.05 Ethyl Valerate 0.05 Maltol 2.00 Cocoa Extract 26.00 Coffee Extract 10.00 Ethanol (95% aqueous) 20.00 Water 41.90 The following tobacco Formulation (B) is prepared: Ingredients Parts Bright Tobacco 40.1 Burley Tobacco 24.0 Maryland Tobacco 1.1 Turkish Tobacco 11.6 Stem (Flue-cured) Tobacco 14.2 Glycerine 2.8 Water 5.3 The flavor Formulation (A) is added to a portion of the smoking tobacco Formulation (B) at the rate of 0.1% by weight of the tobacco. The flavored and non-flavored tobacco formulations are then formulated into cigarettes by the usual manufacturing procedure: At the rate of 100 ppm to half of the cigarettes in each group is added 2-(2'-n butyl)-4,5-dimethyl-å3-thiazoline prepared according to Example III. The use of the 2-(2'-n-butyl)-4,5-dimethyl-å3-thiazole in the cigarettes causes the cigarettes, prior to smoking, to have a sweet, slightly green, nutty, bready aroma and flavor. In smoke flavor, these notes are still found, and the tobacco flavor on smoking has a noticeable cooling characteristic with slightly bready nuances causing it to be very closely akin to "bright" tobacco, whether or not other flavor ingredients of Formulation (A) are present.
EXAMPLE XXIX.
Tobacco flavor formulation A tobacco flavoring formulation is prepared by admixing the following ingredients: Ingredients Parts Bergamot Oil, Italy 5.00 Ylang-ylang oil 1.20 2-(2'-methyl-n-propyl)-4,5-dimethyl- å3-thiazoline prepared according to Example II 1.40 Acetophenone 1.20 Phenyl acetaldehyde 0.50 Phenyl ethyl isovalerate 1.00 Methyl heptyl carbonate 0.50 3-Phenyl-4-pentenal diethyl acetal prepared according to the process disclosed in United States Patent Specification 3,992,237 20.00 95% Aqueous Ethanol 69.40 The foregoing flavor is added to smoking tobacco at the rates of 0.10%, 0.20% and 0.30% based on the weight of dry tobacco. The tobacco is then manufactured into cigarettes according to standard manufacturing practice. The purpose of the 3phenyl-4-pentenal diethyl acetal is to cause the tobacco on smoking to have a hay, clover-like flavor with fruity notes. The 2-(2'-methyl-n-propyl)-4,5-dimethyl-å3- thiazoline (at concentrations, based on the dry weight of tobacco, of 200 ppm) acts as an excellent additive to supply a strong, intense, long-lasting "bright" note to this previously bland tobacco flavor formulation. This is due to the bready, nutty taste nuances imparted by said thiazoline derivative.
BRIEF DESCRIPTION OF THE DRAWINGS Figure I represents that portion of the GLC spectrum setting forth the peaks for 2-substituted-4,5-dimethyl-A3-thiazoiines obtained from the distillate of hydrolyzed vegetable protein.
Figure 2 represents the MS profile for an isomeric form of 2-(2'-methyl-n propyl)-4,5-dimethyl-å3-thiazoline produced according to Example I.
Figure 3 represents the GC-MS profile for 2-(2'-methyl-n-propyl)-4,5 dimethyl-å3thiazoline (isomer II) produced according to Example I.
Figure 4 represents the MS profile for 2-(2'-n-butyl)-4,5-dimethyl-å3-thiazoline extracted from hydrolyzed vegetable protein and produced according to Example I.
Figure 5 represents the MS profile for a second isomer of 2-(2'-n-butyl)-4,5 dimethyl-å3-thiazoline extracted from hydrolyzed vegetable protein and produced according to Example I.
-Figure 6 represents the MS profile for a first isomer of 2-(2'-methyl-n-propyl) 4,5-dimethyl-å3-thiazoline produced according to Example II.
Figure 7 represents the MS profile of a second isomer of 2-(2'-methyl-n propyl)-4,5-dimethyl-å3-thiazoline produced according to Example II.
Figure 8 represents the NMR spectrum for 2-(2'-methyl-n-propyl)-4,5 dimethyl-å3-thiazoline produced according to Example II.
Figure 9 represents the infrared spectrum for 2-(2'-methyl-n-propyl)-4,5 dimethyl-å3-thiazoline produced according to Example II.
Figure 10 represents the MS profile for a first isomer of 2-(2'-n-butyl)-4,5 dimethyl-å3-thiazoline produced according to Example III.
Figure 11 represents the MS profile for a second isomer of 2-(2'-n-butyl)-4,5 dimethyl-A3-thiazoline produced according to Example III.
Figure 12 represents the NMR spectrum for 2-(2'-n-butyl)-4,5-dimethyl-å3- thiazoline produced according to Example III.
Figure 13 represents the infrared spectrum for 2-(2'-n-butyl)-4,5-dimethyl-A3thiazoline produced according to Example III.
Figure 14 represents the MS profile for 2-n-propyl-2;4,5-trimethyl-h3-thiazol- ine produced according to Example IV.
Figure 15 represents the NMR spectrum for 2-n-propyl-2,4,5-trimethyl-A3- thiazoline produced according to Example IV.
Figure 16 represents the infrared spectrum for 2-n-propyl-2,4,5-trimethyl-å3- thiazoline produced according to Example 1V.
Figure 17 represents the Mass spectrum for 2(2'-methyl-thioethyl)-4,5 dimethyl-å3-thiazoline produced according to Example X.
Figure 18 represents the NMR spectrum for 2-(2'-methyl-thioethyl)-4,5 dimethyl-å3-thiazoline produced according to Example X.
Figure 19 represents the infrared spectrum for 2-(2'-methylthioethyl)-4,5 dimethyl-å3-thiazoline produced according to Example X.
Figure 20 represents the Mass spectrum for 2-(2'-methyl-thiopropyl)-4,5 dimethyl-å3-thiazoline produced according to Example XI.
Figure 21 represents the NMR spectrum for 2-(2'-methyl-thiopropyl)-4,5 dimethyl-å3-thiazoline produced according to Example XI.
Figure 22 represents the infrared spectrum for 2-(2'-methylthiopropyl)-4,5 dimethyl-å3-thiazoline produced according to Example XI.
Figure 23 represents the mass spectrum for 2-(2'-methylthioethyl)-4-methyl-5- ethyl-å3-thiazoline produced according to Example XII.
Figure 24 represents the NMR spectrum for 2-(2'-methylthioethyl)-4-methyl-5 ethyl-å3-thiazoline produced according to Example XII.
Figure 25 represents the infrared spectrum for 2-(2'-methylthioethyl)-4-methyl 5-ethyl-å3-thiazoline produced according to Example XII.
WHAT WE CLAIM IS: .1. At least one 2-substituted-å3-4,5-dialkyl-thiazoline compound having the structure:
wherein RA and Rc are the same or different and are hydrogen or methyl, and R8 is alkyl or alkylthioalkyl.
2. A 2-substituted-4,5-dialkyl-å3-thiazoline according to Claim 1, having the structure:
wherein one of R1, R2 or R3 is methyl, and each of the other of R1, R2 and R3 is hydrogen.
3. A thiazoline according to Claim 2, wherein R, is methyl and R2 and R3 are each hydrogen.
4. A thiazoline according to Claim 2 wherein R2 is methyl and R1 and R3 are each hydrogen.
5. A thiazoline according to Claim 2, wherein R3 is methyl and R1 and R2 are each hydrogen.
6. A 2-substituted-4,5-dialkyl-A3-thiazoline having the structure:
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (76)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    Figure 12 represents the NMR spectrum for 2-(2'-n-butyl)-4,5-dimethyl-å3- thiazoline produced according to Example III.
    Figure 13 represents the infrared spectrum for 2-(2'-n-butyl)-4,5-dimethyl-A3thiazoline produced according to Example III.
    Figure 14 represents the MS profile for 2-n-propyl-2;4,5-trimethyl-h3-thiazol- ine produced according to Example IV.
    Figure 15 represents the NMR spectrum for 2-n-propyl-2,4,5-trimethyl-A3- thiazoline produced according to Example IV.
    Figure 16 represents the infrared spectrum for 2-n-propyl-2,4,5-trimethyl-å3- thiazoline produced according to Example 1V.
    Figure 17 represents the Mass spectrum for 2(2'-methyl-thioethyl)-4,5 dimethyl-å3-thiazoline produced according to Example X.
    Figure 18 represents the NMR spectrum for 2-(2'-methyl-thioethyl)-4,5 dimethyl-å3-thiazoline produced according to Example X.
    Figure 19 represents the infrared spectrum for 2-(2'-methylthioethyl)-4,5 dimethyl-å3-thiazoline produced according to Example X.
    Figure 20 represents the Mass spectrum for 2-(2'-methyl-thiopropyl)-4,5 dimethyl-å3-thiazoline produced according to Example XI.
    Figure 21 represents the NMR spectrum for 2-(2'-methyl-thiopropyl)-4,5 dimethyl-å3-thiazoline produced according to Example XI.
    Figure 22 represents the infrared spectrum for 2-(2'-methylthiopropyl)-4,5 dimethyl-å3-thiazoline produced according to Example XI.
    Figure 23 represents the mass spectrum for 2-(2'-methylthioethyl)-4-methyl-5- ethyl-å3-thiazoline produced according to Example XII.
    Figure 24 represents the NMR spectrum for 2-(2'-methylthioethyl)-4-methyl-5 ethyl-å3-thiazoline produced according to Example XII.
    Figure 25 represents the infrared spectrum for 2-(2'-methylthioethyl)-4-methyl 5-ethyl-å3-thiazoline produced according to Example XII.
    WHAT WE CLAIM IS: .1. At least one 2-substituted-å3-4,5-dialkyl-thiazoline compound having the structure:
    wherein RA and Rc are the same or different and are hydrogen or methyl, and R8 is alkyl or alkylthioalkyl.
  2. 2. A 2-substituted-4,5-dialkyl-å3-thiazoline according to Claim 1, having the structure:
    wherein one of R1, R2 or R3 is methyl, and each of the other of R1, R2 and R3 is hydrogen.
  3. 3. A thiazoline according to Claim 2, wherein R, is methyl and R2 and R3 are each hydrogen.
  4. 4. A thiazoline according to Claim 2 wherein R2 is methyl and R1 and R3 are each hydrogen.
  5. 5. A thiazoline according to Claim 2, wherein R3 is methyl and R1 and R2 are each hydrogen.
  6. 6. A 2-substituted-4,5-dialkyl-A3-thiazoline having the structure:
    wherein R1, is one of hydrogen or methyl, and R,2 is one of hydrogen or methyl.
  7. 7. A thiazoline according to Claim 6, wherein R" is methyl and R,2 is hydrogen.
  8. 8. A thiazoline according to Claim 6, wherein R12 is methyl and R11 is hydrogen.
  9. 9. A thiazoline
  10. 10. A thiazoline according to Claim 6, wherein R11 and R12 are each methyl.
  11. II. A process for augmenting or enhancing the organoleptic properties of a consumable material which is a foodstuff, a tobacco, a substitute tobacco, a perfume, a cologne or a perfumed article, which process comprises admixing the said consumable material an organoleptic property-augmenting or enhancing quantity of a 2-substituted-4,5-dialkyl-å3-thiazoline in accordance with Claim 1.
  12. 12. A composition useful for augmenting or enhancing one or more organoleptic properties of a consumable material which is a foodstuff, a tobacco, a substitute tobacco, a perfume, a cologne or a perfumed article, which composition comprises (i) an organoleptic property-augmenting or enhancing quantity of a 2 substituted-4,5-dialkyl-83-thiazoline in accordance with Claim 1 and (ii) the remainder of the composition is at least one non-reactive and organoleptically compatible adjuvant for the 2-substituted-4,5-dialkyl-å3-thiazoline.
  13. 13. A process according to Claim 11, wherein the consumable material is a foodstuff.
  14. 14. A process according to Claim 11, wherein the consumable material is a tobacco, a substitute tobacco, a tobacco article or a substitute tobacco article.
  15. 15. A process according to Claim 11, wherein the consumable material is a perfume or cologne.
  16. 16. A process according to Claim 11, wherein the consumable material is a perfumed article.
  17. 17. A composition according to Claim 12, wherein the consumable material is a foodstuff.
  18. 18. A composition according to Claim 12, wherein the consumable material is a tobacco, a substitute tobacco, a tobacco article or a substitute tobacco article.
  19. 19. A composition according to Claim 12, wherein the consumable material is a perfume or cologne.
  20. 20. The composition according to Claim 12, wherein the consumable material is a perfumed article.
  21. 21. A process for augmenting or enhancing the aroma or taste of a foodstuff which process comprises adding to the foodstuff an organoleptic propertyaugmenting or enhancing quantity in the range of from 0.1 parts per million to 50 parts per million by weight based on total composition of a compound in accordance with Claim 2.
  22. 22. A process according to Claim 21, wherein the compound added is in accordance with Claim 3.
  23. 23. A process according to Claim 21, wherein the compound added is in accordance with Claim 4.
  24. 24. A process according to Claim 21, wherein the compound added is in accordance with Claim 5.
  25. 25. A flavor augmenting or enhancing composition useful for augmenting or enhancing one or more organoleptic properties of a foodstuff, which composition comprises an organoleptic property-augmenting or enhancing quantity in the range of from 0.1% to 15% by weight based on total weight of the composition of at least one compound in accordance with Claim 2, and the remainder of the composition is at least one adjuvant therefor which is one of: Acetaldehyde; Isobutyraldehyde; Isovaleraldehyde; Dimethyl sulfide; Isobutyl acetate; Isoamyl acetate; Phenylethyl acetate; Diacetyl; Acetophenone; Furfural: Benzaldehyde; Phenylacetaldehyde; Isoamyl alcohol; Phenylethyl alcohol; y-Butyrolactone; 3-Phenyl-4-pentenal; 3-Phenyl-3-pentenal; 3-Phenyl-2-pentenal; 2-Methyl pyrazine; 2,6-Dimethyl pyrazine; 2,3,5,6-Tetramethyl pyrazine; 2,3,5-Trimethylpyrazine; 2-Ethyl-3-methylpyrazine; 2-Ethyl-3,5-dimethylpyrazine; 2-Ethyl-5-methylpyrazine; 2(n-pentyl) thiazole; 2(i-butyl) thiazole; 2(i-propyl) thiazole; 2(n-propyl) thiazole; Z-Phenyl-4-pentenal; 2-Phenyl-4-pentenaldimethylacetal; Methional; 4-Methylthiobutanal; 2-Ethyl-3-acetylpyrazine; Trans-2-hexenal; Hydrolyzed vegetable protein; Monosodium glutamate; Black pepper oil; Nutmeg oil; Celery oil; Lemon oil; or Mustard oil.
  26. 26. A flavor augmenting or enhancing composition useful for augmenting or enhancing one or more organoleptic properties of a foostuff, which composition comprises an organoleptic property-augmenting or enhancing quantity in the range of from 0. 1% to 15% by weight based on total weight of the composition of at least one compound in accordance with Claim 3, and the remainder of the composition is at least one adjuvant therefor which is one of: Acetaldehyde; Isobutyraldehyde; isovaleraldehyde; Dimethyl sulfide; Isobutyl acetate; Isoamyl acetate; Phenylethyl acetate; Diacetyl; Acetophenone; Furfural; Benzaldehyde; Phenylacetaldehyde; Isoamyl alcohol; Phenylethyl alcohol; y-Butyrolactone; 3-Phenyl-4-pentenal; 3-Phenyl-3-pentenal; 3-Phenyl-2-pentenal; 2-Methyl pyrazine; 2,6-Dimethyl pyrazine; 2,3,5,6-Tetramethyl pyrazine; 2,3,5-Trimethylpyrazine; 2-Ethyl-3-methylpyrazine; 3-Ethyl-3,5-dimethylpyrazine; 2-Ethyl-3,6-dimethylpyrazine; 2-Ethyl-5-methylpyrazine; 2(n-pentyl) thiazole; 2(i-butyl) thiazole; 2(i-propyl) thiazole; 2(n-propyl) thiazole; 2-Phenyl-4-pentenal; 2-Phenyl-4-pentenaldimethylacetal; Methional; 4-Methylthiobutanal; 2-Ethyl-3-acetylpyrazine; Trans-2-hexenal; Hydrolyzed vegetable protein; Monosodium glutamate; Black pepper oil; Nutmeg oil; Celery oil; Lemon oil; or Mustard oil.
  27. 27. A flavor augmenting or enhancing composition useful for augmenting or enhancing one or more organoleptic properties of a foodstuff, which composition comprises an organoleptic property-augmenting or enhancing quantity in the range of from 0.1% to 15% by weight based on total weight of the composition of at least one compound in accordance with Claim 4, and the remainder of the composition is at least one adjuvant therefor which is one of: Acetaldehyde; Isobutyraldehyde; Isovaleraldehyde; Dimethyl sulfide; Isobutyl acetate; Isoamyl acetate; Phenylethyl acetate; Diacetyl; Acetophenone; Furfura; B enzaldehyde; Phenylacetaldehyde; Isoamyl alcohol; Phenylethyl alcohol; y-Butyrolactone; 3-Phenyl-4-pentenal; 3-Phenyl-3-pentenal; 3-Phenyl-2-pentenal; 2-Methyl pyrazine; 2,6-Dimethyl pyrazine; 2,3,5,6-Tetramethyl pyrazine; 2,3,5-Trimethylpyrazine; 2-Ethyl-3-methylpyrazine; 2-Ethyl-3,5-dimethylpyrazine; 2-Ethyl-3,6-dimethylpyrazine; 2-Ethyl-5-methylpyrazine; 2(n-pentyl) thiazole; 2(i-butyl) thiazole; 2(i-propyl) thiazole; 2(n-propyl) thiazole; 2-phenyl-4-pentenal; 2-phenyl-4-pentenaldimethylacetal; Methional; 4-methylthiobutanal; 2-ethyl-3-acetylpyrazine; trans-2-hexenal; Hydrolyzed vegetable protein; Monosodium glutamate; Black pepper oil; Nutmeg oil; Celery oil; Lemon oil; or Mustard oil.
  28. 28. A flavor augmenting or enhancing composition useful for augmenting or enhancing one or more organoleptic properties of foodstuff, which composition comprises an organoleptic property augmenting or enhancing quantity in the range of from 0.1% to 15% by weight based on total weight of the composition of at least one compound in accordance with Claim 5, and the remainder of the composition is at least one adjuvant therefor which is one of: Acetaldehyde; Isobutyraldehyde; Isovaleraldehyde; Dimethyl sulfide; Isobutyl acetate; Isoamyl acetate; Phenylethyl acetate; Diacetyl; Acetophenone; Furfural; Benzaldehyde; Phenylacetaldehyde; Isoamyl alcohol; Phenylethyl alcohol; -Butyrolactone; 3-Phenyl-4-pentenal; 3-Phenyl-3-pentenal; 3-Phenyl-2-pentenal; 2-Methyl pyrazine; 2,6-Dimethyl pyrazine; 2,3,5,6-Tetramethyl pyrazine; 2,3,5-Trimethylpyrazine; 2-Ethyl-3-methylpyrazine; 2-Ethyl-3,5-dimethylpyrazine; 2-Ethyl-3,6-dimethylpyrazine; 2-Ethyl-5-methylpyrazine; 2(n-pentyl) thiazole; 2(i-butyl) thiazole; 2(i-propyl) thiazole; ,2(n-propyl) thiazole; 2-phenyl-4-pentenal; 2-phenyl-4-pentenaldimethylacetal; Methional; 4-methylthiobutanal; 2-ethyl-3-acetylpyrazine trans-2-hexenal; Hydrolyzed vegetable protein; Monosodium glutamate; Black pepper oil; Nutmeg oil; Celery oil; Lemon oil; or Mustard oil.
  29. 29. A process for augmenting or enhancing the nutty, bready, or vegetable flavor or aroma of a foodstuff, which process comprises adding thereto an organoleptic property-augmenting or enhancing quantity of a 2-alkylthioalkyl-4,5dialkyl-53-thiazotine in accordance with Claim 6 having the structure:
    wherein R" and R,2 are the same or different, and each of R,1 and R,2 are one of methyl or hydrogen.
  30. 30. A process according to Claim 29, wherein, in the thiazoline, R" is methyl and R12 is hydrogen.
  31. 31. A process according to Claim 29, wherein, in the thiazoline R12 is methyl and R" is hydrogen.
  32. 32. A process according to Claim 29, wherein, in the thiazoline R" and R,2 are each hydrogen.
  33. 33. A composition adapted to augment or enhance the nutty, bready or vegetable flavor or aroma of a foodstuff which comprises (i) an organoleptic property augmenting or enhancing quantity of a 2-alkylthioalkyl-4,5-dialkyl-A3- thiazoline in accordance with Claim 6 having the structure:
    wherein R" and R,2 are the same or different and each of R" and R,2 are one of hydrogen or methyl; and (ii) the remainder of the composition being an adjuvant material organoleptically compatible and non-reactive with the 2-alkylthioalkyl 4,5-dialkyl-A3-thiazoline which is one of: Bergamot oil; Citral; Amyl aclohol; 5-Phenyl-2-pentenal; 5-Phenyl-4-pentenal; n-Octanal; n-Decanal; Limonene; Geraniol; Cadinene; Dimethylanthranilate; Amyl butyrate; 2(n-Pentyl)thiazole; 2(i-Propyl)thiazole; 2(n-Propyl)thiazole; 4-Methylthiobutanal; 2-Ethyl-3-acetyl pyrazine; Tetramethyl pyrazine; 2-Methyl pyrazine; 2-Trans hexenal; Maltol; 2-Phenyl-4-pentenal; 2-Phenyl-4-pentenal dimethyl acetal; 2-Phenyl-4-pentenal diethyl acetal; 2(,i-hydroxyethyl)thiazole; 2-Methyl butanethiol; 4-Mercapto-2-butanone; 3-Mercapto-4-pentanone; 1 -Mercapto-2-propanone; Furfural; Furfuryl alcohol; 2-Mercapto propionic acid; 2-Ethyl-3-methyl pyrazine; Tetramethyl pyrazine; Polysulfides; Dipropyl disulfide; Methyl benzyl disulfide; 2-Butyl thiophene; 2,3-Dimethyl thiophene; 5-Methyl furfural; 2-Acetyl furan; 2,5-Dimethyl-3-acetyl furan; 2,4-Decadienal; Guaiacol; Phenyl acetaldehyde; b-Decalactone; d-Limonene; Acetoin; Amyl acetate; Ethyl butyrate; Levulinic acid; Piperonal; Ethyl acetate; n-Pentanal; Hexanal; Diacetyl; Monosodium glutamate; Cysteine; Hydrolyzed vegetable protein; Hydrolyzed fish protein; Vanillin; Methyl furoate; Methyl cyclopentenolone; Pyruvic acid; Isoamyl levulinate; Ethyl anthranilate; Orange oil; Ethyl heptanoate; Acetoin; Butyl butyryl lactate; Ethyl vanillin; Ethyl butyrate; Rose oil; Benzyl acetate; Tolyl aldehyde; cu-ionone; Para-tolylacetaldehyde; Heliotropin; Butyric acid; Acetylmethylcarbinol; Methional 2-(2-methylthioethyl)-A3-thiazoline; Alcohol; Acetaldehyde; i-Valeric acid; Caprylic acid; Benzaldehyde; i-Valeraldehyde; Butyric acid; Propionic acid; Phenylacetaldehyde; Linanool; Dimethylsulphide; Terpinylbutyrate: Cis-3-hexenol; Phenylacetic acid guaiacyl ester; Methylheptenone; Caproaldehyde; 2-Isobutyl thiazole; or 2-n-Butyl thiazole.
  34. 34. A composition according to Claim 33, wherein, in the thiazoline, R1, and R12 are each hydrogen.
  35. 35. A composition according to Claim 33, wherein, in the thiazoline, R11 is methyl and R12 is hydrogen.
  36. 36. A composition according to Claim 33, wherein, in the thiazoline, R12 is methyl and R11 is hydrogen.
  37. 37. A composition according to Claim 33, wherein, in the thiazoline, R11 is methyl and R,2 is methyl.
  38. 38. A perfume composition, which comprises a perfuming quantity of a 2 alkyl-substituted-4,5-dimethyl-A3.thiazoline having the structure:
    wherein R1 and R3 are the same or different an each of R1 and R3 are one of hydrogen or methyl, and at least one adjuvant which is a natural perfume oil, a synthetic perfume oil, an alcohol, an aldehyde, a ketone, a nitrile, an ester or a lactone.
  39. 39. A cologne which comprises ethanol, water and an organolepticaugmenting or enhancing quantity 2-alkyl-substituted-4,5-dimethyl- 3-thiazoline having the structure:
    wherein R, and R3 are the same or different and each of R, and R3 are one of methyl or hydrogen.
  40. 40. A composition according to Claim 38, wherein, in the thiazoline, R, is hydrogen and R3 is methyl.
  41. 41. A composition according to Claim 38, wherein, in the thiazoline, R, is methyl and R3 is hydrogen.
  42. 42. A cologne according to Claim 39, wherein, in the thiazoline, R, is hydrogen and R3 is methyl.
  43. 43. A cologne according to Claim 39, wherein, in the thiazoline, R, is methyl and R3 is hydrogen.
  44. 44. A perfumed article which comprises an organoleptic-augmenting or enhancing quantity of at least one 2-alkyl-substituted-4,5-dimethyl- 3-thiazoline having the structure:
    wherein R, and Rl are the same or different and each of Rl and R3 are one of methyl or hydrogen, and a detergent, soap, bath preparation, hair preparation, cosmetic preparation or powder.
  45. 45. A tobacco product or substituted tobacco product having added thereto an amount sufficient to augment or enhance the flavor or aroma of the tobacco product an organoleptic augmenting or enhancing quantity of one or more thiazolines having the formula:
    wherein X is one of:
    and wherein Rl and R2 are each one of hydrogen or methyl, R, and R2 being different.
  46. 46. A tobacco product or substituted tobacco product in accordance with Claim 45, wherein, in the thiazoline, X is:
    and R1 is methyl and R2 is hydrogen.
  47. 47. A tobacco product or substituted tobacco product according to Claim 45, wherein, in the thiazoline, X is:
    and R, is hydrogen and R2 is methyl.
  48. 48. A tobacco product or substituted tobacco product according to Claim 45, wherein, in the thiazoline, X is:
  49. 49. A tobacco product or substituted tobacco product according to any one of Claims 45 to 48, wherein the concentration of thiazoline in the tobacco product or substituted tobacco product is in the range of 50 to 5,000 parts per million (ppm) based on the total weight of tobacco or substituted tobacco on a dry basis.
  50. 50. A tobacco product or substituted tobacco product according to Claim 49, wherein the concentration of thiazoline in the tobacco product or substituted tobacco product is in the range of from 100 to 500 parts per million (ppm) based on the total weight of tobacco or substituted tobacco on a dry basis.
  51. 51. A tobacco flavoring composition or substituted tobacco flavoring composition, which comprises (i) an organoleptic augmenting or enhancing quantity of one or more thiazolines having the structure:
    wherein X is one of:
    and R, and R2 are each different and each of R, and R2 are one of hydrogen or methyl; and (ii) at least one of tobacco flavoring additives, being, one or more of: Esters; Aldehydes; Ketones; Acetals; Natural oils and extracts; Lactones; Ethers; Pyrazines; or Pyrroles.
  52. 52. A tobacco or substitute tobacco flavoring composition according to Claim 51, wherein, in the thiazoline X is:
    and R, is methyl and R2 is hydrogen.
  53. 53. A tobacco or substitute tobacco flavoring composition according to Claim 51, wherein, in the thiazoline X has the structure:
    and R2 is methyl and R, is hydrogen.
  54. 54. A tobacco flavoring or substitute tobacco flavoring composition according to Claim 51, wherein, in the thiazoline, X has the structure:
  55. 55. A process for producing a composition comprising a major quantity of a compound having the structure:
    comprising the steps of (i) reacting NH3 with
    to form
    and (ii) reacting
    with
    and (iii) separating from the reaction product a composition comprising a major quantity of a compound having the structure:
    wherein RA and Rc are each the same or different and each represents hydrogen or methyl; and RB is alkyl or thiaolkyl.
  56. 56. A process according to Claim 55, limited according to the reaction:
    wherein R1, R2 and R3 are the same or different and each represents hydrogen or methyl.
  57. 57. A process according to Claim 55. limited according to the reaction:
    wherein R" and R,2 are the same or different and each of R" and R,2 represents hydrogen or methyl.
  58. 58. A product whenever produced by a process in accordance with Claim 55.
  59. 59. A product whenever produced by a process in accordance with Claim 56.
  60. 60. A product whenever produced by a process in accordance with Claim 57.
  61. 61. A compound according to Claim 1, whenever produced according to Example I.
  62. 62. A compound according to Claim 1, whenever produced according to any one of Examples II, III, IV, X, XI and XII.
  63. 63. A process in accordance with Claim 11 for augmenting or enhancing the organoleptic properties of a consumable material, substantially as described in any one of foregoing Examples V, VI, VII, VIII, IX, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII and XXIX.
  64. 64. A process in accordance with any one of Claims 21, 22, 23 and 24 for augmenting or enhancing the aroma or taste of a foodstuff, substantially as described in any one of foregoing Examples, V, VI, VII, VIII and IX.
  65. 65. A process in accordance with any one of Claims 29, 30, 31 and 32 for augmenting or enhancing the aroma or taste of a foodstuff, substantially as described in any one of foregoing Examples XIII, XIV, XV, XVI and XVII.
  66. 66. A composition in accordance with Claim 12 useful for augmenting or enhancing one or more organoleptic properties of a consumable material, substantially as described in any one of foregoing Examples V, VI, VII, VII I, IX, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXI II, XXIV, XXV, XXVI, XXVII, XXVIII and XXIX.
  67. 67. A composition in accordance with any one of Claims 25, 26, 27 and 28 useful for augmenting or enhancing the aroma or taste of a foodstuff, substantially as described in any one of foregoing Examples V, VI, VII, VIII and IX.
  68. 68. A composition in accordance with any one of Claims 33, 34, 35, 36 and 37 useful for augmenting or enhancing the aroma or taste of a foodstuff, substantially as described in any one of foregoing Examples XIII, XIV, XV, XVI and XVII.
  69. 69. A perfume composition in accordance with any one of Claims 12, 19, 38, 40 and 41, substantially as described in any one of foregoing Examples XVIII, XXIII, XXIV and XXV.
  70. 70. A cologne in accordance with any one of Claims 12, 19, 39, 42 or 43, substantially as described in any one of foregoing Examples XXIII, XXIV and XXV.
  71. 71. A perfumed article in accordance with any one of Claims 12, 20 or 44, substantially as described in any one of foregoing Examples XIX, XX, XXI and XXII.
  72. 72. A tobacco product or substituted tobacco product in accordance with any one of Claims 45, 46, 47, 48, 49 and 50, substantially as described in any one of foregoing Examples XXVI, XXVII, XXVIII and XXIX.
  73. 73. A tobacco or substituted tobacco flavor composition in accordance with any one of Claims 12, 18, 51, 52, 53 and 54, substantially as described in any one of foregoing Examples XXVI, XXVII, XXVIII and XXIX.
  74. 74. A process in accordance with any one of Claims 55, 56 and 57, substantially as described in any one of foregoing Examples II, III, IV, X, XI and XII.
  75. 75. A process in accordance with Claim 56, substantially as described in any one of foregoing Examples II, III and IV.
  76. 76. A process in accordance with Claim 57, substantially as described in any one of foregoing Examples X, XI and XII.
GB41064/77A 1976-10-07 1977-10-03 2-substituted-4,5-dialkyl- 3-thiazolines processes for producing same and organoleptic uses thereof Expired GB1589755A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US73053676A 1976-10-07 1976-10-07
US73015676A 1976-10-07 1976-10-07
US05/730,653 US4040987A (en) 1976-10-07 1976-10-07 2-Alkyl-substituted-4,5-dimethyl thiazoline perfume and cologne compositions
US05/730,157 US4067344A (en) 1976-10-07 1976-10-07 Novel tobacco product comprising one or more thiazolines and process

Publications (1)

Publication Number Publication Date
GB1589755A true GB1589755A (en) 1981-05-20

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Country Link
JP (1) JPS5347543A (en)
CH (1) CH630512A5 (en)
DE (1) DE2742391C3 (en)
FR (1) FR2367071A1 (en)
GB (1) GB1589755A (en)
IT (1) IT1143703B (en)
NL (1) NL7710519A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015171738A3 (en) * 2014-05-06 2015-12-30 The Procter & Gamble Company Fragrance compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5261185B2 (en) * 2006-10-19 2013-08-14 小川香料株式会社 3-mercapto-2-alkanone and perfume composition containing said compound
DE102015217868A1 (en) * 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Perfume composition with odor modulator compounds to increase fragrance intensity

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015171738A3 (en) * 2014-05-06 2015-12-30 The Procter & Gamble Company Fragrance compositions
US9708568B2 (en) 2014-05-06 2017-07-18 The Procter & Gamble Company Fragrance compositions
US11365370B2 (en) 2014-05-06 2022-06-21 The Procter & Gamble Company Fragrance compositions

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Publication number Publication date
IT1143703B (en) 1986-10-22
DE2742391A1 (en) 1978-04-13
CH630512A5 (en) 1982-06-30
FR2367071A1 (en) 1978-05-05
FR2367071B1 (en) 1980-08-01
DE2742391C3 (en) 1980-02-28
JPS5347543A (en) 1978-04-28
NL7710519A (en) 1978-04-11
DE2742391B2 (en) 1979-06-28

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