Flavoring with 3-propylthio-4-heptanol
This application is a divisional of application for U.S. Pat. Ser. No. 730,537, filed on Oct. 7, 1976, now issued U.S. Pat. No. 4,044,164. 
    
    
     BACKGROUND OF THE INVENTION 
     The present invention relates to α-oxy(oxo) sulfides and ethers and novel compositions using such compounds to augment or enhance the flavor and/or aroma of foodstuffs. 
     There has been considerable work performed related to substances to (or in) various consumable materials including foodstuffs. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product. The following flavor and aroma notes are desirable, particularly in berry fruit flavored foodstuffs, vegetable flavored foodstuffs, spicey foodstuffs and citrus fruit flavored foodstuffs: 
     Aroma 
     Green/spicey, 
     Sweet, 
     Fruity, 
     Fresh/fruity, 
     Gooseberry-like, 
     Concord grape-like, 
     Grape-like, 
     Almond-like, 
     Nutty, 
     Cereal-like, 
     Lachrymatory onion-like, 
     Oniony, 
     Green onion-like, 
     Leek-like, 
     Broccoli-like, 
     Grapefruit-like, 
     Celery stalk-like, 
     Floral, 
     Rosey, 
     Woody, 
     Blackcurrant-like, 
     Buchu leaf oil-like, 
     Citronellal-like, 
     Neroli-like, Bergamot-like, 
     Violet leaves-like, 
     Jasmin-like, 
     Melon-like, 
     Cucumber-like, 
     Green, 
     Vegetable, 
     Sweet/floral. 
     Flavor 
     Spicey, 
     Sweet, 
     Fruity, 
     Milk caramel-like (dulce de leche-like), 
     Gooseberry-like, 
     Broccoli-like, 
     Nutty, 
     Cereal-like, 
     Oniony, 
     Grape-like, 
     Concord grape-like, 
     Citrusy, 
     Grapefruit-like, 
     Green fruit-like, 
     Mandarin-like, 
     Petitgrain-like, 
     Blackcurrant-like, 
     Minty, 
     Astringent, 
     Coriander-like, 
     Green, 
     Piney, 
     Citronellal-like, 
     Violet leaves-like, 
     Melon-like, 
     Cucumber-like, 
     Green, 
     Floral, 
     Floral/green, 
     Vegetable, 
     Garlic-like. 
     Prior to the this last decade it was the general opinion among those skilled in the art that compounds containing the mercapto or --SH moiety or substituted mercapto or --SR moiety (where R is an organic group such as alkyl or acetyl) were desirable for use in conjunction with foodstuff flavors only where alliaceous flavors were concerned, or where meaty flavors were concerned or where coffee-type flavors were concerned, and were not desirable for use in conjunction with other more delicate type flavors, e.g., blackcurrant, citrus and vegetable. However, within the last decade certain mercapto compounds have been ascertained to be useful, for example, in blackcurrant and buchu leaf oil-like flavors. In addition, within the last decade such compounds have been ascertained to be highly useful in perfumery also. 
     Thus, for example, British Pat. Nos. 1,423,914 and 1,423,915 issued on Feb. 4, 1976, teach that certain mercapto derivatives which are aliphatic or cycloaliphatic compounds having the formula: ##STR2## wherein X 1  represents a hydroxy group or an acyl-oxy group, and X 2  represents a hydrogen atom; R 1 , R 2 , R 3  and R 4  may be the same or different and each represents a hydrogen atom or a univalent aliphatic hydrocarbyl group; or R 1  and R 3  or R 4 , together with the intervening carbon atoms, constitute a cycloaliphatic ring, are useful as perfuming agents as exemplified by adding 3-methylthio-hexanol to a perfume base composition of the &#34;Fleuri&#34; type wherein the 3-methylthio-hexanol is said to give rise to a green, fruity aroma reminiscent of that of rhubarb. 
     Furthermore, for example, Canadian Pat. No. 983,050 issued on Feb. 3, 1976, teaches that 3,7-dimethyl-octa-2,6-dienyl-mercaptan (thiogeraniol) of the formula: ##STR3## is used in making up a &#34;synthetic buchu leaf oil&#34; and imparts to a lavender type composition a greener and more herbal fragrance. USSR Pat. No. 345,677 teaches that para-menthane-8-thiol-3-one is useful as a synthetic black current flavoring for foodstuffs. This compound has the structure: ##STR4## German Offenlegungschrift Pat. No. 2,316,456, published on Oct. 11, 1973 discloses the use of certain thio alcohols or their corresponding esters in perfumery and in perfumed articles, such as detergents, cosmetics and waxes. Such mercapto alcohols having the generic structure:  wherein R 1  is a hydrocarbon moiety having from 1 up to 7 carbon atoms and R 2  is one of hydrogen, methyl or ethyl. 
     U.S. Pat. Nos. 3,950,429 issued on Apr. 13, 1976, and 3,952,062 issued on Apr. 20, 1976, disclose certain alkylthio-substituted oxo-terpenoids having 10 carbon atoms in the terpenoid skeleton as useful in perfumery and in flavors, particularly for providing vegetable notes. The generic structure of the compounds is as follows: ##STR5## wherein R 1  represents hydrogen or together with R 4  represents a C -- C bond, 
     R 2  represents hydrogen or together with R 6  represents a dimethylmethylene group, or, when R 6  is isopropyl, together with R 5  represents a C -- C bond, 
     R 3  represents hydrogen or together with R 6  represents a dimethylmethylene group, 
     R 4  represents hydrogen or together with R 1  represents a C -- C bond, 
     R 5  represents hydrogen or, when R 6  signifies isopropyl, together with R 2  represents a C-- C bond, 
     R 6  represents isopropyl or together with R 2  or with R 3  represents a dimethylmethylene group, 
     R 7  represents methyl, 
     X represents a C -- C double bond taking the place of a C -- C single bond, 
     m = 0 to 2, 
     Y represents oxo bound to a primary or secondary C-atom and Z represents mercapto or lower alkylthio located in the β-position to the carbonyl function, 
     provided that when R 2 , R 3  and R 5  represent hydrogen, R 6  represents isopropyl, R 4  together with R 1  represents a C -- C bond, Y is β to the carbon atom bearing the substituent R 7 , m=o, Z is α to the carbon atom bearing the substituent R 5  and β to the carbon atom bearing the substituent R 3 , then Z represents alkylthio. 
     However, none of the disclosure of the prior art contains a teaching to the effect that compounds having the generic structure: ##STR6## wherein X is one of: ##STR7## Z is one of sulfur or oxygen; when R 1  and R 2  are taken separately, R 1  is hydrogen or methyl, and R 2  is methyl; and when R 1  and R 2  are taken together, R 1  and R 2  form phenyl moieties; and Y is one of C 1  -C 4  alkyl, C 3  or C 4  alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl have the ability to create the following aroma and flavor notes in foodstuffs: 
     Aroma 
     Green/spicey, 
     Sweet, 
     Fruity, 
     Fresh/fruity, 
     Gooseberry-like, 
     Concord grape-like, 
     Grape-like, 
     Almond-like, 
     Nutty, 
     Cereal-like, 
     Lachrymatory onion-like, 
     Oniony, 
     Geen onion-like, 
     Leek-like, 
     Broccoli-like, 
     Grapefruit-like, 
     Celery stalk-like, 
     Floral, 
     Rosey, 
     Woody, 
     Blackcurrant-like, 
     Buchu leaf oil-like, 
     Citronellal-like, 
     Neroli-like, 
     Bergamot-like, 
     Violet leaves-like, 
     Jasmin-like, 
     Melon-like, 
     Cucumber-like, 
     Green, 
     Vegetable, 
     Sweet/floral. 
     Flavor 
     Spicey, 
     Sweet, 
     Fruity, 
     Milk caramel-like (dulce de leche-like), 
     Gooseberry-like, 
     Broccoli-like, 
     Nutty, 
     Cereal-like, 
     Oniony, 
     Grape-like, 
     Concord grape-like, 
     Citrusy, 
     Grapefruit-like, 
     Green fruit-like, 
     Mandarin-like, 
     Petitgrain-like, 
     Blackcurrant-like, 
     Minty, 
     Astringent, 
     Coriander-like, 
     Green, 
     Piney, 
     Citronellal-like, 
     Violet leaves-like, 
     Melon-like, 
     Cucumber-like, 
     Green, 
     Floral, 
     Floral/green, 
     Vegetable, 
     Garlic-like. 
     Furthermore, other substituted mercaptans in the prior art which are shown to be useful in perfumery are indicated to have rhubarb-like, or berry, or other floral-type fragrances, e.g., ionone and irone derivatives having the structure: ##STR8## 
     Furthermore, certain α-mercaptoketones are disclosed in the prior art, but only in meat flavors. Thus, U.S. Pat. No. 3,773,524 issued on Nov. 20, 1973, discloses the use of α-ketothiols of the formula: ##STR9## wherein R 1  is methyl or ethyl; and R 2  and R 3  are hydrogen, methyl or ethyl to alter the meat flavor and aroma of foodstuffs. U.S. Pat. No. 3,892,878, issued on July 1, 1975, discloses the use of certain hydroxymercaptoalkanes to alter the flavor of foodstuffs, for example, 2-mercapto-3-butanol used in meat flavors. The genus disclosed by U.S. Pat. No. 3,892,878 is as follows: ##STR10## wherein X is oxygen or sulfur, n is 0 or 1, R 1  -R 7  are the same or different and each is hydrogen or lower alkyl of 1-4 carbon atoms, a and b are the same or different and each represents an integer of from 0 to 10 when n is 0 and when n is 1, a and b are the same or different and each represents an integer of from 1 to 10. 3-mercaptoheptanon-4 is disclosed per se in U.S. Pat. No. 2,888,487, issued on May 26, 1959. 3-mercapto-2,6-dimethyl-heptan-4-one is disclosed in Chem. Abstracts 6478 (d) Vol. 62, 1965 (abstract of Asinger, Diem and Schaefer, Monatsh. Chem. 95 (4-5), 1335-54 (1964). Beilstein E-IV-1 discloses 2-mercapto-2,4-dimethyl-pentan-3-on page 4039, 1-mercapto-octan-2-on at page 4040; and 1 -mercapto-nonan-2-on at 4052 and 1-mercapto-undecan-2-on at page 4060. 
     U.S. Pat. No. 3,922,366 issued on Nov. 25, 1975, discloses the enhancement of foodstuffs by addition of a small but effective flavor modifying amount of a compound of the general formula: ##STR11## wherein R 1  is hydrogen or alkyl and R 2  is alkyl or furfuryl. The flavor nuances which are enhanced or altered are those which are found in coffee flavors and aromas. 
     THE INVENTION 
     The invention comprises novel compositions, and foodstuffs containing α-oxy(oxo) sulfides and ethers having the structure: ##STR12## wherein X is one of: ##STR13## Z is one of sulfur or oxygen; when R 1  and R 2  are taken separately, R 1  is hydrogen or methyl, and R 2  is methyl; and when R 1  and R 2  are taken together, R 1  and R 2  form phenyl moieties, and Y is one of C 1  -C 4  alkyl, C 3  or C 4  alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl the specific embodiments of which are described hereinafter by way of example and in accordance with which it is now preferred to practice the invention. 
     Such α-oxy(oxo) sulfides and ethers are obtained by reacting an alkanone with SO 2  Cl 2  to form an α-chloro-alkanone; reacting the α-chloro-alkanone with either an alkali metal mercaptide or an alkali metal alkoxide (depending on whether Z is sulfur or oxygen) to form either an α-oxo sulfide or an α-oxo ether which can be used for its food flavor properties; or, if desired, reacting the resulting α-oxo sulfide or α-oxo ether with a reducing agent such as an alkali metal borohydride in order to obtain an α-oxy sulfide or an α-oxy ether. Thus, the aforementioned reaction sequence is illustrated as follows: ##STR14## wherein X is one of: ##STR15## Z is one of sulfur or oxygen; when R 1  and R 2  are taken separately, R 1  is hydrogen or methyl, and R 2  is methyl; and when R 1  and R 2  are taken together, R 1  and R 2  form phenyl moieties, and Y is one of C 1  -C 4  alkyl, C 3  or C 4  alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl. 
     The reaction between the SO 2  Cl 2  and the ketone preferably takes place in the absence of a solvent at a temperature of between 15° C and 40° C. The SO 2  Cl 2  is preferably added to the ketone. At the end of the reaction, the reaction mass is worked up, the chlorinated ketone being distilled in vacuo. 
     The resulting chlorinated ketone is then reacted with either an alkali metal mercaptide or an alkali metal alkoxide. Preferably the alkali metal mercaptide is sodium mercaptide, preferably which is prepared by reaction of sodium methylate with an appropriate mercaptan in methanol. Preferably the alkali metal alkoxide is sodium methoxide. The chlorinated ketone is preferably contained in an inert solvent, e.g., in methanolic solution. Preferably the methanolic solution of chlorinated ketone is slowly added to the pre-prepared alkali metal mercaptide or alkali metal alkoxide at a temperature of between 0° C and 30° C; preferably between 15° C and 30° C. The reaction mass is then extracted with a solvent such as methylene chloride, and the resulting extract is then worked up using evaporation and distillation techniques or GLC trapping whereby the α-oxo sulfide or α-oxo ether (as the case may be) is recovered. The resulting α-oxo sulfide or ether is then used (&#34;as is&#34;) for its flavor properties; or it may be further reacted with a reducing agent such as an alkali metal borohydride, conveniently sodium borohydride. The reaction with sodium borohydride takes place in an inert solvent such as anhydrous ethanol at a temperature of between 20° C and 35° C. A solution in anhydrous ethanol of the α-oxo sulfide or ether is added to a solution in anhydrous ethanol of the alkali metal borohydride. The reaction is carried out over a period of time of between two and ten hours. At the end of the reaction, the reaction mass is concentrated and is then admixed with water. The resulting mixture is then acidified to a pH of between 2 and 3 and then extracted with an inert extraction solvent such as methylene chloride. The methylene chloride extract is then dried, evaporated, and the resulting α-oxy sulfide or ether is distilled in vacuo or isolated by GLC trapping. 
     Alternatively, the α-chloro ketone may be reacted with an alkali metal hydrosulfide such as sodium hydrosulfide or an alkali metal hydroxide such as sodium hydroxide to form the corresponding α-mercapto ketone or α-hydroxy ketone. The α-mercapto ketone or α-hydroxy ketone may then be reacted with base (e.g., sodium methoxide) to form the alkali metal salt. The alkali metal salt of the α-mercapto ketone or α-hydroxy ketone is then reacted with an alkyl or alkenal halide (e.g., methallyl chloride) thereby forming the desired α-oxo sulfide or α-oxo ether which may then, if desired, be used as such for its organoleptic properties, or it can be reduced with an alkali metal borohydride (e.g., sodium borohydride) to the corresponding α-oxy sulfide or α-oxy ether. This reaction sequence is illustrated as follows: ##STR16## Specific examples of α-oxy(oxo) sulfides and ethers produced using the afore-mentioned processes and their food flavor properties are as follows (as set forth in Table I below): 
     
                       TABLE I                                                     
______________________________________                                    
COMPOUND  STRUCTURE      FLAVOR PROPERTY                                  
______________________________________                                    
3-methylthio-4- heptanone                                                 
           ##STR17##     Green, piney, necroli- like, fruity, blackcurrant
                         ,bucchu- like and concord grape aroma            
                         characteristic and sweet, fruity, blackcurrant,  
                         concord grape-like, minty and astringent flavor  
                         characteristics at 1.0 ppm.                      
3-propylthio-4- heptanol                                                  
           ##STR18##     &#34;Violet leaves,&#34; melon, cucumber, green, fruity, 
                         egetable and floral aroma characteristics with   
                         violet leaves melon, cucumber, green, citrus,    
                         vegetable, garlic flavor character- istics with  
                         a lasting mouthfeel at 5 ppm.                    
3-isobutylthio-4- heptanone                                               
           ##STR19##     Sweet/floral, citrus, fruity, necroli, bergamot, 
                         asmin aroma character- istic with a              
                         green/floral, minty, petitgrain, fruity, citrus, 
                         sulfury flavor character- istic at 2 ppm.        
3-propylthio-4- heptanone                                                 
           ##STR20##     Sweet, floral, jasmin and  berry-like aroma      
                         characteristic with sweet/floral, jasmin,        
                         grapefruit and black- currant flavor character-  
                         istic at 2 ppm.                                  
3-(methallyl- thio)-2,6- dimethyl-4- heptanone                            
           ##STR21##     Citrus, grapefruit, floral, celery stalk-like,   
                         rosey aroma characteristic with citrus,          
                         grapefruit, floral,spicey,green/ fruity,         
                         astringent flavor  characteristics at 2 ppm.     
3-crotylthio-2,6- dimethyl-4- heptanone                                   
           ##STR22##     Floral, citronellal-like, citrus, grapefruit,    
                         woody aroma character- istic and a citrus        
                         grapefruit, coriander- like flavor character-    
                         istic at 3 ppm.                                  
3-allythio-2,6- dimethyl-4- heptanone                                     
           ##STR23##     A sweet, grapefruit, floral, citrus, green/      
                         spicey,necroli-like aroma characteristic with a  
                         sweet, citrus, floral/  green,citronellal-like,  
                         &#34;ecaying fruit-&#34; like flavor characteristic at 4 
                         ppm.                                             
3 (methoxycar- bonyl)-methyl- thio!-4- heptanone                          
           ##STR24##     At 10 ppm, a sweet, sulfury, nutty, meaty,       
                         cereal aroma character and a sweet,meaty, nutty, 
                         cereal flavor characteristic with an outstanding 
                         mouthfeel effect.                                
3-methoxy-4- heptanone                                                    
           ##STR25##     At 3 ppm, a sweet, fruity, gooseberry-like,      
                         grape, almond aroma character with a sweet,      
                         fruity, gooseberry-like, nutty, grape flavor     
                         character.                                       
1-propylthio-1,3- diphenyl-2- propanone                                   
           ##STR26##     At 0.5 ppm, a green onion aroma with             
                         a lachrymating onion and biting effect and a     
                         sweet, rubbery, meaty flavor characteristic; at  
                         2 ppm the garlic aroma dominates alongwith  the  
                         fresh onion notes.                               
(1,3-diethylace- tonyl) (1,3-di- isopropylace- tonyl) sulfide             
           ##STR27##     At 10 ppm, a grapefruit, floral and woody aroma  
                         character with a sweet, sulfury,                 
                         grapefruit-like, mandarin flavor character-      
                         istic and bitter nuances.                        
3-acetylthio-4- heptanone                                                 
           ##STR28##     At 1 ppm a fresh fruity, blackcurrant-like,      
                         buchu leaf oil-like, aroma with meaty and        
                         sulfury nuances and a fresh fruit, black-        
                         currant-like flavor characteristic with an       
                         oniony aftertaste.                               
______________________________________                                    
 
    
     When the α-oxy(oxo) sulfide and ether 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 α-oxy(oxo) sulfides and ethers 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 &#34;augment&#34; in its various forms means &#34;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.&#34; 
     As used herein in regard to food flavors, the term &#34;enhance&#34; is used herein to mean the intensification of a flavor or aroma characteristic or note without the modification of the quality thereof. Thus, &#34;enhancement&#34; of a flavor or aroma means that the enhancement agent does not add any additional flavor note. 
     As used herein the term &#34;foodstuff&#34; includes both solids and liquids, and ingestible materials or chewable but non-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, dairy 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 α-oxo-substituted chalcogenalkanes, non-reactive with the α-oxo-substituted chalcogenalkanes of our invention and &#34;ingestibly&#34; 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 hydroxyanisole (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., agar agar, 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 agents 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 acid, 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 cid, lactic acid, vinegar and the like; colorants, e.g., carminic acid, cochineal, tumeric, curcumin 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; enzymes; 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 intensifiers include organic acids, e.g., acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, alpha-methyl-butyric acid, propionic acid, valeric acid, 2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones and aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, beta, beta-dimethyl-acrolein, n-hexanal, 2-hexenal, cis-3-hexenal, 2-heptanal, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone, 2-methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols such as 1-butanal, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol, geraniol. 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, fenchyl alcohol, isofenchyl alcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyl alpha-methylbutyrate, ethyl propionate, ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, alpha-methylbutyrate, propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutyl cinnamate and terpenyl acetate; absolutes, such as jasmine absolute, rose absolute, orris absolute, and essential oils such as orange oil, lemon oil, Bulgarian rose oil and natural vanilla; lactones; sulfides, e.g., dimethyl sulfide and other materials such as maltol, pulegone mercaptan, α-phellandrene, ethyl maltol, 2,2,4,4,6,6-hexamethyl-S-trithiane, acetoin and acetals, (e.g., 1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane.) 
     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 environment in which the α-oxy(oxo) sulfides and ethers 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 α-oxy(oxo) sulfide and ether employed in a paticular 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 flavored 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, whether foodstuff per se or flavoring composition. 
     The use of insufficient quantities of α-oxy(oxo) sulfides and ethers will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantities prove needlessly costly and in extreme cases, may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the terminology &#34;effective amount&#34; and &#34;sufficient amount&#34; 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 α-oxy(oxo) sulfides and ethers ranging from a small but effective amount, e.g., about 0.1 parts per million up to about 50 parts per million by weight based on total composition (more preferably from about 0.2 ppm up to about 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 α-oxy(oxo) sulfides and ethers are 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 α-oxy(oxo) sulfide and ether concentration in the foodstuff product. 
     Food flavoring compositions prepared in accordance with the present invention preferably contain the α-oxy(oxo) sulfide and ether in concentrations ranging from about 0.1% up to about 15% by weight based on the total weight of said flavoring composition. 
     The compositions 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 particlate solids can be conveniently prepared by mixing the α-oxy(oxo) sulfide and ether with, for example, gum arabic, gum tragacanth, carrageenan and the like, and thereafter spray-drying the resultant mixture whereby to obtain the particulate solid product. Pre-prepared flavor mixed in powder form, e.g., a fruit-flavored powder mix are obtained by mixing the dried solid components, e.g., starch, sugar and the like and α-oxy(oxo) sulfide and ether in a dry blender until the requisite degree of uniformity is achieved. 
     It is presently preferred to combine with the α-oxy(oxo) sulfides and ethers the following adjuvants: 
     p-Hydroxybenzyl acetone; 
     Geraniol; 
     Acetaldehyde; 
     Maltol; 
     Ethyl methyl phenyl glycidate; 
     Benzyl acetate; 
     Dimethyl sulfide; 
     Vanillin; 
     Methyl cinnamate; 
     Ethyl pelargonate; 
     Methyl anthranilate; 
     Isoamyl acetate; 
     Isobutyl acetate; 
     Alpha ionone; 
     Ethyl butyrate; 
     Acetic acid; 
     Gamma-undecalactone; 
     Naphthyl ethyl ether; 
     Diacetyl; 
     Ethyl acetate; 
     Anethole; 
     Isoamyl butyrate; 
     Cis-3-hexenol-1; 
     2-Methyl-2-pentenoic acid; 
     Elemecine (4-allyl-1,2,6-trimethoxy benzene); 
     Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene); 
     2-(4-hydroxy-4-methylpentyl) norbornadiene prepared according to U.S. Application for Letters Patent Ser. No. 461,703 filed on Apr. 17, 1974; 
     Natural blackcurrent juice; 
     Buchu leaf oil; 
     α-phellandrene; 
     Cis-3-hexen-1-ol; 
     Terpinenol-4; 
     Ethyl maltol; 
     Methyl benzoate; 
     Benzaldehyde; 
     Coriander oil; 
     α-ionone; 
     Ethyl heptanoate; 
     Methyl anthranilate; 
     Ethyl anthranilate; 
     Cinnamic alcohol; 
     Amyl valerinate; 
     Cinnamyl propionate; 
     Rhodinyl acetate; 
     Methyl β-hydroxy butyrate; 
     Ethyl β-hydroxy butyrate; 
     2-phenyl-3-carboethoxyfuran; 
     Cyclohexyl disulfide; 
     Grapefruit oil; 
     Nootkatone; 
     Bergamot oil; 
     Citral; 
     Amyl alcohol; 
     5-phenyl-4-pentenal; 
     5-phenyl-2-pentenal; 
     Allyl caproate; 
     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; 
     Tetramethyl pyrazine; 
     2-methyl pyrazine; 
     trans-2-hexenal; 
     Hydrolyzed vegetable protein; 
     Monosodium glutamate; 
     Dimethyl disulfide; 
     Methyl propyl disulfide; 
     Methyl propenyl disulfide; 
     Methyl allyl disulfide; 
     Allyl propyl disulfide; 
     Propyl propenyl disulfide; 
     Dipropyl disulfide; 
     Diallyl disulfide; 
     Propyl propenyl trisulfide; 
     Thiopropanal-S-oxide; 
     Thiobutanal-S-oxide; 
     Thioethanol-S-oxide; 
     Thiohexanal-S-oxide; and 
     Propyl propene thiosulfonate. 
     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. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is the NMR spectrum for the product of Example I(B) wherein 3-thioacetyl-4-heptanone is produced. 
     FIG. 2 is the IR spectrum for the product of Example I(B) wherein 3-thioacetyl-4-heptanone is produced. 
     FIG. 3 is the NMR spectrum for the product of Example I(C) wherein 3-thiomethyl-4-heptanone is produced. 
     FIG. 4 is the IR spectrum for the product of Example I(C) wherein 3-thiomethyl-4-heptanone is produced. 
     FIG. 5 is the NMR spectrum for the product of Example I(D) wherein 3-thiomethyl-4-heptanol is produced. 
     FIG. 6 is the IR spectrum for the product of Example I(D) wherein 3-thiomethyl-4-heptanol is produced. 
     FIG. 7 is the NMR spectrum for the product of Example II(C) werein 3-methallylthio-2,6-dimethyl-4-heptanone is produced. 
     FIG. 8 is the IR spectrum for the product of Example II(C) wherein 3-methallylthio-2,6-dimethyl-4-heptanone is produced. 
     FIG. 9 is the NMR spectrum for the product of Example II(D) wherein 3-crotylthio-2,6-dimethyl-4-heptanone is produced. 
     FIG. 10 is the IR spectrum for the product of Example II(D) wherein 3-crotylthio-2,6-dimethyl-4-heptanone is produced. 
     FIG. 11 is the NMR spectrum for the product of Example II(E) wherein 3-allylthio-2,6-dimethyl-4-heptanone is produced. 
     FIG. 12 is the IR spectrum for the product of Example II(E) wherein 3-allylthio-2,6-dimethyl-4-heptanone is produced. 
     FIG. 13 is the NMR spectrum for the product of Example II(F) wherein (1,3-diethylacetonyl) (1,3-diisopropylacetonyl)sulfide is produced. 
     FIG. 14 is the IR spectrum for the product of Example II(F) wherein (1,3-diethylacetonyl) (1,3-diisoproylacetonyl)sulfide is produced. 
     FIG. 14(A) is the NMR spectrum for the product of Example II(G) wherein 3- (methoxycarbonyl)methylthiol!-2,6-dimethyl-4-heptanone is produced. 
     FIG. 14(B) is the IR spectrum for the product of Example II(B) wherein 3- (methoxycarbonyl)methylthio!-2,6-dimethyl-4-heptanone is produced. 
     FIG. 15 is the NMR spectrum for the product of Example II(H) wherein 3- (methoxycarbonyl)methylthio!-4-heptanone is produced. 
     FIG. 16 is the IR spectrum for the product of Example II(H) wherein 3- (methoxycarbonyl)methylthio!-4-heptanone is produced. 
     FIG. 17 is the NMR spectrum for the product of Example III(A) wherein 3-n-propylthio-4-heptanone is produced. 
     FIG. 18 is the IR spectrum for the product of Example III(A) wherein 3-n-propylthio-4-heptanone is produced. 
     FIG. 19 is the NMR spectrum for the product of Example III(A) wherein 3-n-propylthio-4-heptanol is produced. 
     FIG. 20 is the IR spectrum for the product of Example III(A) wherein 3-n-propylthio-4-heptanol is produced. 
    
    
     EXAMPLE I 
     (A) PREPARATION OF 3-CHLORO-4-HEPTANONE ##STR29## 
     Into a 3000 ml, three-necked, round-bottom flask, equipped with mechanical stirrer, 500 ml addition funnel, Y-tube, pot thermometer and gas outlet tube with rubber tubing leading over a stirring solution of 10% sodium hydroxide is added 1000g 4-heptanone. Addition of 434 g of SO 2  Cl 2  drop-wise into the 4-heptanone is commenced while maintaining the pot temperature in the range of 22°-34° C and is continued over a period of two hours. A water aspirator vacuum is applied to the reaction mass in order to pull the acidic gases; sulfur dioxide and hydrogen chloride, over the sodium hydroxide solution. 
     The reaction mass is periodically sampled using GLC analysis until such time as about 25% chlorinated ketone product is found to be present. 
     While maintaining the reaction mass at 15° C, 1000 ml saturated sodium chloride is added to the mixture, and the mixture is then stirred for a period of 10 minutes. The reaction mass is then transferred to a 5-liter separatory funnel and shaken well, whereupon the organic and aqueous phases separate. The lower aqueous phase (approximately 1000 ml) has a pH of about 1. The upper organic phase is washed with 700 ml saturated sodium bicarbonate solution to a pH of 6-7. The organic phase is then dried over 50 grams anhydrous sodium sulfate and filtered yielding a yellow oil weighing 1063 grams. The organic layer is determined to contain 24.9% chlorinated ketone and 68.1% original ketone starting material. This material is then vacuum distilled by first adding it to a 2000 ml, three-necked, round-bottom flask equipped with a 2.5 × 60 cm vacuum jacketed column packed with 6 mm Raschig Rings, and equipped with an automatic reflux head, a pot thermometer, a heating mantle, a vacuum pump and a dry-ice trap. Fractionation data is as follows: 
     
         ______________________________________                                    
Vacuum Pot     Vapor   Weight of                                          
(mmHg) Temp.   Temp.   Fraction                                           
                               Cut. No.                                   
                                      Reflux Ratio                        
______________________________________                                    
62     80      71       51.0 g 1      60:40                               
62     81.5    71      149.0 g 2      40:60                               
58     82.5    70      157.5 g 3      30:70                               
59     89.5    70      175.0 g 4      30:70                               
59     96      75      110 g   5      30:70                               
59     100     80       24.5 g 6      50:50                               
58     101     90       16.0 g 7      50:50                               
58     102     94       37.5 g 8      30:70                               
55     103     94      144.5 g 9      30:70                               
54     110     95       85.0 g 10     30:70                               
54     119     102      28.0 g 11     30:70                               
15     140     80       45.0 g 12     30:70                               
______________________________________                                    
 
    
     GLC analysis on each of cuts 5-12 (conditions 8 feet × 1/4 inch SE-30 column) yields the following information: 
     
         __________________________________________________________________________
     Percent                                                              
          Percent                                                         
                Percent                                                   
     lon  4-    3-Cl   Percent High                                       
                              Percent High                                
                                     Percent High                         
                                            Percent High                  
Cut No.                                                                   
     Boilers                                                              
          Heptanone                                                       
                h-Heptanone                                               
                       Boiler (A)                                         
                              Boiler (B)                                  
                                     Boiler (C)                           
                                            Boiler (D)                    
__________________________________________________________________________
5    0.09 96.15  2.97  --     --     --     --                            
7         50%   50%                                                       
8    --    9.28 87.09  2.43   0.57   --     --                            
9    --   trace 95.78  3.22   1.00   --     --                            
10   --   --    91.38  4.89   3.34   0.21   --                            
11   --   --    69.14  7.27   19.88  3.71   --                            
12   --   --     8.32  2.07   49.28  39.69  0.47                          
__________________________________________________________________________
 
    
     Cuts 8, 9 and 10 are blended (weight 266.5 gms) and are analyzed as follows: 
     
         ______________________________________                                    
0.95%           4-heptanone                                               
93.89%          3-chloro-4-heptanone                                      
3.60%           high boiler A                                             
1.57%           high boiler B                                             
______________________________________                                    
 
    
     EXAMPLE I(B) 
     PREPARATION OF 3-THIOACETYL-4-HEPTANONE ##STR30## 
     Into a 25 ml, three-necked, round-bottom flask equipped with magnetic stirrer, nitrogen inlet tube, 6 inches Vigreux column with cotton plug and pot thermometer is added a solution of 0.27 grams sodium methoxide in 3 ml anhydrous methanol (0.005 moles sodium methoxide). Under dry nitrogen, 0.38 grams of thioacetic acid dissolved in 3 ml anhydrous methanol (0.005 moles thioacetic acid) is then added to the sodium methoxide solution over a 2-minute period. A solution of 3-chloro-4-heptanone in methanol (0.75 grams 3-chloro-4-heptanone dissolved in one ml anhydrous methanol) prepared according to Part A, supra, (cuts 8, 9 and 10 blended) is then added to the reaction mass which becomes turbid. Stirring is continued for a period of one hour, whereupon GLC analysis (conditions: 8 feet × 1/4 inch SE-30 column) yields the following data: 
     
         ______________________________________                                    
15.6%          3-chloro-4-heptanone                                       
3.0%           chloro heptanone high boiler                               
77.67%         major peak                                                 
2.37%          late peak                                                  
______________________________________                                    
 
    
     With stirring, 15 ml water is added to the reaction mass which then splits up into two phases, an aqueous phase and an organic phase. The pH of the aqueous phase is 5-6. The organic phase is extracted with two 10-ml portions of methylene chloride. The methylene chloride extracts are combined and washed with 5 ml saturated sodium chloride solution. The organic phase is then dried over anhydrous sodium sulfate and concentrated in a rotary evaporator using water aspirator vacuum yielding 0.65 grams of a dark amber oil. GLC trapping of the major peak (Conditions: 8 feet × 1/4 inch SE-30 column operated at 120° C, programmed at 5° C/minute) yields a compound having a molecular weight of 188 and having a mass spectral analysis, NMR analysis and IR analysis which cause confirmation of the structure: ##STR31## 
     The NMR spectrum is set forth in FIG. 1. The IR spectrum is set forth in FIG. 2. 
     The NMR analysis is as follows: 
     
         ______________________________________                                    
 ##STR32##                                                                
 
    
     
         ______________________________________                                    
0.92 ppm                                                                  
        (t)     CH.sub.3CH.sub.2                                          
                                       6H                                 
0.96    (t)     CH.sub.3CCS                                               
2.01 - 1.44                                                               
        (m)     CH.sub.2               4H                                 
2.39    (s)                                                               
                 ##STR33##                                                
                                       5H                                 
2.53    (m)                                                               
                 ##STR34##                                                
4.20    (t)     OCHCSCO                1H                                 
______________________________________                                    
 
    
     The IR analysis is as follows: 
     620 cm -1 , 950, 1125, 1350, 1450, 1690, 2320, 2870, 2930, 2960. 
     Material prepared similarly to above example was vacuum distilled yielding 99.3% pure product (boiling point 93.5°-94.5° C at 2.8 mm Hg). The thus-distilled material has the same physical properties as set forth above for 3-thioacetyl-4-heptanone. 
     (C) PREPARATION OF 3-THIOMETHYL-4-HEPTANONE ##STR35## 
     Into a 50-ml, three-necked, round-bottom flask equipped with magnetic stirrer, dry ice condenser, pot thermometer, cold water bath, reflux condenser with nitrogen inlet tube and nitrogen bubbler, is placed a solution of 0.54 grams of sodium methoxide in 6 ml anhydrous methanol (0.01 moles sodium methoxide). The sodium methoxide solution is then cooled using the cold-water bath to a temperature of 25° C. The nitrogen flow is ceased and methyl mercaptan in methanol (0.48 grams methyl mercaptan in 6 ml anhydrous methanol, 0.01 moles methyl mercaptan) is added to the reaction mass while maintaining same at 24° C. At 24° C, a solution of 1.49 grams of 3-chloro-4-heptanone in 2 ml anhydrous methanol (0.01 moles 3-chloro-4-heptanone) is added to the reaction mass. The 3-chloro-4-heptanone is produced according to the process set forth in part (A), supra. The reaction mass is maintained, with stirring, at 25° C for a period of one hour and  15 minutes. At the end of this period, the reaction mass is flushed with nitrogen. The reaction mass is then concentrated on a rotary evaporator using a water aspirator vacuum to approximately 5 ml. 
     Distilled water (15 ml) is then added to the concentrated reaction mixture whereupon the reaction mixture forms into two phases; an oil phase and an aqueous phase. The pH of the aqueous phase is in the range of 5-6. The oil phase is then extracted with two 12-ml portions of n-hexane and the phases are separated. The hexane extracts are combined, washed with water (5 ml), dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 1.29 grams. The resulting product contains 90.1; % 3-thiomethyl-4-heptanone by GLC analysis having the structure: ##STR36## as confirmed by NMR, IR and mass spectral analyses of trapped compound. 
     The NMR spectrum is set forth in FIG. 3. The IR spectrum is set forth in FIG. 4. 
     The NMR analysis is as follows: 
     
         ______________________________________                                    
 ##STR37##                                                                
 
    
     
         ______________________________________                                    
0.94 ppm                                                                  
        (t)     CH.sub.3CH.sub.2                                          
                                       6H                                 
0.97    (t)     CH.sub.3CCS                                               
1.68    (m)     CH.sub.2               4H                                 
1.92    (s)     CH.sub.3S              3H                                 
2.60    (m)                                                               
                 ##STR38##             2H                                 
3.08    (t)                                                               
                 ##STR39##             1H                                 
______________________________________                                    
 
    
     The IR analysis is as follows: 
     1360 cm -1 , 1375, 1455, 1690, 2330, 2880, 2930, 2960. 
     Material prepared similarly to above example was vacuum distilled yielding 99.2% pure product (boiling point 78°-78.5° C at 8.5 mm Hg). The thus-distilled material has the same physical properties as set forth above for 3-thiomethyl-4-heptanone. 
     (D) PREPARATION OF 3-THIOMETHYL-4-HEPTANOL ##STR40## 
     Into a 25 ml, three-necked, round-bottom flask equipped with magnetic stirrer, nitrogen inlet tube, reflux condenser, pot thermometer, and cold water bath, is added a solution of 0.10 grams sodium borohydride (NaBH 4 ) dissolved in 4 ml anhydrous ethyl alcohol (0.00265 moles sodium borohydride). While maintaining the pot temperature at 25° C, a solution of 0.8 grams of 3-thiomethyl-4-heptanone in 3.5 ml anhydrous ethyl alcohol is added to the sodium borohydride-ethanol solution over a one-minute period. The reaction mass then warms up to about 30° C and is maintained at a temperature of between 25° and 30° C for a period of about 1.5 hours. At the end of this period another 0.05 grams (0.00133 moles) of sodium borohydride and 2 ml ethanol is added. 
     After 10 minutes of stirring while maintaining the reaction mass at 25° C, the reaction mass is then worked up as follows. The reaction mixture is concentrated to about 4 ml of a thick slurry using water aspirator vacuum. The resulting thick slurry is then combined with 12 ml water thereby causing the solid to dissolve, and the reaction mass to exist in two phases; an aqueous phase and an organic phase. The aqueous phase is acidified to a pH of 2-3 using 10% HCl solution. The organic phase is extracted with two 12-ml portions of methylene chloride. The extracts are then combined, washed with 8 ml water, dried over anhydrous sodium sulfate, gravity filtered, and then concentrated on a rotary evaporator (using water aspirator vacuum) to a weight of 0.58 grams. The desired product is trapped out on a 8 inch × 1/4 inch SE-30 GLC column, and MS, NMR and IR analyses confirm that the resulting compound has the structure: ##STR41## 
     The NMR spectrum is set forth in FIG. 5. The infrared spectrum is set forth in FIG. 6. 
     The NMR analysis is as follows: 
     
         ______________________________________                                    
0.94 ppm (t)       CH.sub.3CH.sub.2                                       
                                 6H                                       
1.06     (t)       CH.sub.3 C C S                                         
1.51     (m)       CH.sub.2      6H                                       
2.06     (s)       CH.sub.3 S    3H                                       
2.36     (m)       HC S                                                   
                                 2H                                       
2.62     (broad)   OH                                                     
3.52     (m)       HC O          1H                                       
______________________________________                                    
 
    
     The IR analysis is as follows: 
     980 cm -1 , 1010, 1065, 1370, 1430, 1450, 2320, 2860, 2920, 2960, 3440. 
     Material prepared similarly to above example was vacuum distilled yielding 99.5% pure product (boiling point 64°-64.5° C at 1.5 mm Hg). The thus-distilled material has the physical properties as set forth above for 3-thiomethyl-4-heptanol. 
     EXAMPLE II 
     PREPARATION OF 3-METHALLYLTHIO-2,6-DIMETHYL-4-HEPTANONE 
     (A) Preparation of 3-chloro-2,6-dimethyl-4-heptanone ##STR42## 
     Into a one-liter, three-necked, round bottom flask equipped with &#34;Y&#34; tube, pot thermometer, mechanical stirrer, 125 ml addition funnel, gas outlet tube, cold water bath and water aspirator vacuum is added 356 grams of 2,6-dimethyl-4-heptanone (2.4 moles). Over a period of one hour, 67.5 grams (40 ml; 0.5 moles) of SO 2  Cl 2  is slowly added to the ketone with stirring while maintaining the reaction mass temperature in the range of 23°-35° C. 
     The reaction mass is then evacuated slowly using water aspirator vacuum thereby removing most of the acidic gases resulting from the foregoing reaction. 
     The reaction mass is then transferred to a one-necked, one-liter, round-bottom flask and the last traces of acidic gases are removed thus yielding 371 grams of product. The reaction mass is then transferred to a 500 ml. three-necked, round-bottom flask equipped with a 2.0 × 30 cm column packed with 1/8 inch helices, reflux head, magnetic stirrer, heating mantle and vacuum pump, and the resulting 3-chloro-2,6-dimethyl-4-heptanone is fractionally distilled at a vapor temperature of 106°-107° C and a pressure of 45-46 mm Hg yielding a product of 97% purity as confirmed by GLC, mass spectral, NMR and IR analyses. 
     B. Preparation of 3-mercapto-2,6-dimethyl-4-heptanone ##STR43## 
     Into a 250 ml, round bottom, three-necked flask equipped with magnetic stirrer, pot thermometer, 6 inches Vigreux distillation column with gas outlet at top leading over 200 ml 10% sodium hydroxide solution H 2  S gas inlet tube (sub-surface), &#34;Y&#34; tube, 50 ml addition funnel, gas bubbler, and dry ice-isopropyl alcohol bath, and cold water bath is added a solution of 11.6 grams of sodium methoxide dissolved in 90 ml anhydrous methanol. The sodium methoxide solution is cooled to a temperture of -15° C using the dry ice-isopropanol bath. While maintaining the temperature of the sodium solution at -10° to -5° C, hydrogen sulfide is bubbleed into the reaction mass over a period of 2 hours While continuing to bubble in hydrogen sulfide and maintaining the reaction mass at a temperature in the range of -5° to -9° C, the 3-chloro-2,6-dimethyl-4-heptanone prepared in Part A of this example (18.2 grams; 0.100 moles) is added slowly to the reaction mass from the addition funnel over a period of 13 minutes. The reaction mass is then maintained at a temperature of 0°-26° C for a period of 4 hours (25° C-26° C for the last 1.5 hours). 
     The reaction mass is then concentrated to approximately 25 ml (thick slurry) using a rotary evaporator and water aspirator vacuum. 85 ml distilled water is then added to the reaction mass, with stirring, while maintaining the temperature at 25° C, thereby yielding a turbid yellow solution. 85 grams of 10% aqueous sodium hydroxide is then added to the resulting mixture whereupon the temperature rises from 25° C to 28° C (pH = 10-11). The basic aqueous solution is then extracted with two 70 ml portions of methylene chloride and the extracts are combined, dried and concentrated yielding 1.7 grams of an oil. The basic aqueous solution is then acidified with 115 ml 10% hydrochloride acid to a pH of 1-2. This is then extracted with four 50 ml portions of methylene chloride. The methylene chloride extracts are combined and washed with two 35 ml portions of saturated sodium chloride (to a pH of 5) and dried over anhydrous sodium sulfate. The resulting mixture is gravity filtered and concentrated on a rotary evaporator to yield 15.5 grams of product containing 96.1% 3-mercapto-2,6-dimethyl-4-heptanone as confirmed by mass spectral, NMR and IR analyses. This material is vacuum distilled at a vapor temperature of 77.5°-78° C and a pressure of 6 mm Hg. 
     C. Preparation of 3-methallylthio-2,6-dimethyl-4-heptanone ##STR44## 
     Into a 25 ml, three-necked, round-bottom flask equipped with magnetic stirrer, &#34;Y&#34; tube, nitrogen inlet, reflux condenser with cottom plug, cold water bath and warm water bath is added a solution of 0.162 grams of sodium methoxide dissolved in 2 ml anhydrous methanol. Over a period of 1 minute is added a solution of 0.522 grams of 3-mercapto-2,6-dimethyl-4-heptanone dissolved in 3 ml anhydrous methanol, with stirring. After stirring for 12 minutes at 24°-25° C, a solution of 0.3 grams of 3-chloro-2-methylpropene in 1 ml anhydrous methanol is added. With a water bath the resulting reaction mass is warmed to 31° C and the reaction mass is then stirred while maintaining the temperature in the range of 23°-30° C for a period of 2 hours. 
     The reaction mass is then concentrated on a rotary evaporator using water aspirator vacuum to approximately 4 ml yielding a slurry. To the slurry is added 8 ml water and the solid dissolves. The reaction mass is then acidified to a pH of 1-2 with 3 drops of 10% hydrochloric acid. The reaction mass is then extracted with three 8 ml portions of methylene chloride and the extracts are combined and washed with 10 ml water, dried over anhydrous sodium sulfate and gravity filtered. The extracts are concentrated on a rotary evaporator to yield 0.54 grams of a white oil containing 93.6% by GLC of 3-methallylthio-2,6-dimethyl-4-heptanone as confirmed using MS, IR and NMR analyses of trapped product. 
     The NMR spectrum is set forth in FIG. 7. The infrared spectrum is set forth in FIG. 8. 
     The mass spectral analysis is as follows: 
     
         ______________________________________                                    
m/e               Relative Intensity                                      
______________________________________                                    
41                29                                                      
55                 44.sup.3                                               
57                 37.sup.6                                               
69                10                                                      
85                 43.sup.5                                               
87                 93.sup.2                                               
109               33                                                      
142                44.sup.4                                               
143               100.sup.1                                               
M 228             28                                                      
______________________________________                                    
 
    
     the NMR analysis is as follows: 
     
         ______________________________________                                    
1.92 ppm, 2.06                                                            
           (2 doublets)                                                   
                       ##STR45##     12H                                  
1.78       (s)        CCH.sub.3      3H                                   
2.12       (m)        methine protons                                     
                                     2H                                   
2.47       (t)        CH.sub.2       2H                                   
2.82       (d)                                                            
                       ##STR46##     1H                                   
3.01       (s)        CCH.sub.2S     2H                                   
4.86       (s)                                                            
                       ##STR47##     2H                                   
______________________________________                                    
 
    
     The IR analysis is as follows: 
     890 cm -1 , 1035, 1160, 1200, 1225, 1285, 1360, 1380, 1400, 1460, 1640, 1695, 2870, 2960, 3080. 
     Material prepared similarly to above example was vacuum distilled yielding 99.8% pure product (boiling point 100°-100.5° C at 1.3 mm Hg). The thus-distilled material has the same physical properties as set forth above for 3-methallylthio-2,6-dimethyl-4-heptanone. 
     D. PREPARATION OF 3-CROTYLTHIO-2,6-DIMETHYL-4-HEPTANONE ##STR48## 
     Into a 25 ml, three-necked, round bottom flask equipped with magnetic stirrer, reflux condenser, nitrogen inlet tube and cold water bath is placed a solution of 0.162 grams (0.003 moles) of sodium methoxide dissolved in 2 ml anhydrous methanol. Using the cooling bath the temperature of the sodium methoxide solution is cooled to 23° C at which point a solution of 0.52 grams (0.003 moles) of 3-mercapto-2,6-dimethyl-4-heptanone in 2 ml anhydrous methanol is added to the sodium methoxide solution. While maintaining the temperature of the reaction mass at 24°-29° c and over a period of 2 minutes, a solution of 0.300 grams of 80% crotyl chloride dissolved in 2 ml anhydrous methanol (0.0026 moles crotyl chloride) iss added to the reaction mass with stirring. The reaction mass is continued to be stirred for a period of 2.5 hours and is then concentrated on a rotary evaporator using water aspirator vacuum to 2 ml product (solid/oil slurry). Nine ml water is added to the reaction mass thereby dissolving the solid. The oil is extracted with three 8 ml portions of methylene chloride and the extracts are combined and washed with 6 ml water. The methylene chloride extracts are then dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to 0.59 grams pale-yellow oil. The major product is isolated using GLC apparatus (8 feet × 1/4 inch Carbowax column). NMR, mass spectral and IR analyses yield the information that the resulting material is 3-crotylthio-2,6-dimethyl-4-heptanone having the structure: ##STR49## 
     The NMR spectrum is set forth in FIG. 9. The infrared spectrum is set forth in FIG. 10. 
     The mass spectral analysis is as follows: 
     
         ______________________________________                                    
m/e               Relative Intensity                                      
______________________________________                                    
41                20                                                      
55                 90.sup.2                                               
57                 37.sup.5                                               
85                 36.sup.6                                               
87                100.sup.1                                               
89                33                                                      
141               22                                                      
142                45.sup.4                                               
143                63.sup.3                                               
M 228             13                                                      
______________________________________                                    
 
    
     The NMR analysis is as follows: 
     
         ______________________________________                                    
0.84 ppm, 1.08                                                            
          (doublets) CH.sub.3 --    12H                                   
1.70      (d)        ═ C -- CH.sub.3                                  
                                    3H                                    
2.14      (m)        methine protons                                      
                                    2H                                    
2.48      (m)          CH.sub.2 -- C ═ O                              
                                    2H                                    
2.82      (d)        O ═ C -- HC -- S --                              
                                    1H                                    
2.99      (m)        ═ C -- CH.sub.2 -- S --                          
                                    2H                                    
5.50      (m)        olefinic protons                                     
                                    2H                                    
______________________________________                                    
 
    
     The infrared analysis is as follows: 
     960 cm -1 , 1035, 1135, 1160, 1285, 1360, 1380, 1400, 1465, 1695, 2870, 2930, 2960, 3020. 
     E. PREPARATION OF 3-ALLYLTHIO-2,6-DIMETHYL-4-HEPTANONE ##STR50## 
     Into a 25 ml, round bottom, three-necked flask equipped with magnetic stirrer, reflux condenser, nitrogen inlet tube and cold water bath is placed a solution of 0.162 grams (0.003 moles) of sodium methoxide dissolved in 2 ml anhydrous methanol. Using the water bath the temperature of the sodium methoxide solution is reduced to 23° C. At 23° C, a solution of 0.522 grams (0.003 moles) of 3-mercapto-2,6-dimethyl-4-heptanone dissolved in 3 ml anhydrous methanol is added to the sodium methoxide solution. Subsequent to the addition of the mercapto ketone, after stirring for 15 minutes at 23° C, a solution of 0.40 grams (0.0033 moles) of allyl bromide dissolved in 2 ml anhydrous methanol is added to the reaction mass with stirring. The reaction mass warns to 33° C and is continued to be stirred at 25°-33° C for a period of 2 hours. It is concentrated on a rotary evaporator using water aspirator vacuum to a volume of 3 ml, thus yielding a white slurry. Eight ml water is then added to the slurry thereby dissolving the solid therein. One drop of 10% HCl is added to the resulting material thereby reducing the pH from about 9 to about 5. The reaction mass now existing in two phases is extracted with three 8 ml volumes of methylene chloride. The extracts are combined and washed with 6 ml water and then dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 0.55 grams (pale yellow oil). GLC analysis (8 feet × 1/4 inch SE-30 column), NMR, IR and mass spectral analyses of GLC isolated material confirm that the resulting product is 97% product, 3-allylthio-2,6-dimethyl-4-heptanone, having the structure: ##STR51## 
     The NMR spectrum is illustrated in FIG. 11. The infrared spectrum is illustrated in FIG. 12. 
     The mass spectral analysis is as follows: 
     
         ______________________________________                                    
m/e               Relative Intensity                                      
______________________________________                                    
41                 33.sup.5                                               
55                24                                                      
57                 32.sup.6                                               
69                18                                                      
73                 40.sup.3                                               
85                30                                                      
87                 43.sup.2                                               
95                30                                                      
129               100.sup.1                                               
142                38.sup.4                                               
M 314             17                                                      
______________________________________                                    
 
    
     The NMR analysis is as follows: 
     
         ______________________________________                                    
0.84 ppm, 1.08                                                            
           (doublets) CH.sub.3       12H                                  
2.14       (m)        methine protons                                     
                                     2H                                   
2.48       (m)        CH.sub.2CO     2H                                   
2.84       (d)        CHCS           1H                                   
3.04       (m)        CCH.sub.2S     2H                                   
5.22-5.04  (m)                                                            
                       ##STR52##     2H                                   
5.96-5.56  (m)                                                            
                       ##STR53##     1H                                   
______________________________________                                    
 
    
     The IR analysis is as follows: 
     914 cm -1 , 980, 1035, 1160, 1360, 1380, 1465, 1695, 2870, 2930, 2960. 
     F. PREPARATION OF (1,3-DIETHYL ACETONYL) (1,3-DIISOPROPYLACETONYL) SULFIDE ##STR54## 
     Into a 50 ml, round bottom, three-necked flask equipped with magnetic stirrer, pot thermometer, &#34;Y&#34; tube, nitrogen inlet tube, reflux condenser with cotton plug, and water bath is placed a solution of 0.65 grams (0.012 moles) of sodium methoxide dissolved in 10 ml anhydrous methanol. While maintaining the temperature of the reaction mass at 24°-27° , C, a solution of 2.1 grams of 3-mercapto-2,6-dimethyl-4-heptanone dissolved in 12 ml anhydrous methanol is added to the sodium methoxide solution. 1.78 grams of 3-chloro-4-heptanone is then added to the reaction mass with stirring over a period of 2 minutes, the reaction mass temperature rising to 38° C. Two ml anhydrous methanol used as rinse is then added to the reaction mass, and with stirring the reaction mass temperature cools to 25° C. The reaction mass is continued to be stirred at 25° C for a period of 5 hours. At this point 25 ml distilled water is added, and the resulting solid dissolves. The oil phase is extracted with three 15 ml portions of methylene chloride, and the extracts are combined and washed with one 10 ml portion of water. The extracts are then dried over anhydrous sodium sulfate and gravity filtered and concentrated on a rotary evaporator using water aspirator vacuum to a weight of 3.20 grams (yellow oil). GLC analysis (8 feet × 1/4 inch SE-30 column), NMR, IR and mass spectral analyses of GLC isolated material yield the information that the resulting product is 85% pure and has the structure: ##STR55## 
     The NMR spectrum is set forth in FIG. 13. The IR spectrum is set forth in FIG. 14. 
     The mass spectral analysis is as follows: 
     
         ______________________________________                                    
m/e               Relative Intensity                                      
______________________________________                                    
41                 50.sup.6                                               
43                 82.sup.3                                               
55                33                                                      
57                 89.sup.2                                               
71                 56.sup.5                                               
85                100.sup.1                                               
114                67.sup.4                                               
145               39                                                      
201               36                                                      
M 286             29                                                      
______________________________________                                    
 
    
     The NMR analysis is as follows 
     
         ______________________________________                                    
1.07 ppm, 0.86                                                            
            CH.sub.3            18H                                       
1.62        CH.sub.2+ methine protons                                     
                                6H                                        
2.46        CH.sub.2CO          4H                                        
3.15 and 2.96                                                             
             ##STR56##          2H                                        
______________________________________                                    
 
    
     The IR analysis is as follows: 
     1155 cm -1 , 1360, 1380, 1460, 1700, 2870, 2930, 2960. 
     G. PREPARATION OF 3- (METHOXYCARBONYL)METHYLTHIO!-2,6-DIMETHYL-4-HEPTANONE ##STR57## 
     Into a 50 ml, round-bottom, three-necked flask equipped with magnetic stirrer, pot thermometer, &#34;Y&#34; tube, nitrogen inlet tube, reflux condenser with cotton plug, H 2  SO 4  bubbler for nitrogen, and cold water bath is added a solution of 0.65 grams of sodium methoxide dissolved in 10 ml anhydrous methanol. At a reaction mass temperature of 25°-28° C and over a period of one minute, with stirring, is added a solution of 2.1 grams of 3-mercapto-2,6-dimethyl-4-heptanone dissolved in 2 ml anhydrous methanol. After stirring 8 minutes, 1.30 grams of methylchloroacetate (0.012 moles) is added over a period of 2 minutes, to the reaction mass; the temperature of the reaction mass rising to 38° C. The reaction mass is allowed to cool to 24° C and is stirred for a period of 2 hours. 
     Distilled water (25 ml) is then added to the reaction mass whereupon the solid present dissolves. The organic phase is then extracted with three 15 ml methylene chloride portions. The combined extracts are washed with one 10 ml portion of water and dried over anhydrous sodium sulfate and gravity filtered. The filtered extracts are then concentrated on a rotary evaporator using water aspirator vacuum to a weight of 2.67 grams (pale yellow oil). GLC trapping of the major component (conditions: 8 feet × 1/4 inch SE-30 column), with mass spectral, IR and NMR analyses confirm that the resulting product has the structure: 
     
         ______________________________________                                    
0.94, 1.10 ppm                                                            
               ##STR58##       12 H                                       
2.12                                                                      
               ##STR59##       2 H                                        
2.50                                                                      
               ##STR60##       2 H                                        
3.03                                                                      
               ##STR61##       1 H                                        
3.19                                                                      
               ##STR62##       2 H                                        
3.70                                                                      
               ##STR63##       3 H                                        
______________________________________                                    
 
    
     The NMR analysis is as follows ##STR64## 
     The IR analysis is as follows: 
     1145 cm -1 , 1185, 1285, 1360, 1375, 1430, 1460, 1695, 1735, 2860, 2920, 2960. 
     The mass spectral analysis is as follows: 
     
         ______________________________________                                    
m/e             Relative Intensity                                        
______________________________________                                    
29              11                                                        
31              24.sup.6                                                  
43              12                                                        
55              24                                                        
57              53.sup.3                                                  
85              46.sup.4                                                  
101             100.sup.1                                                 
129             32.sup.5                                                  
161             75.sup.2                                                  
M 246           21                                                        
______________________________________                                    
 
    
     The NMR spectrum is set forth in FIG. 14(A). The infrared spectrum is set forth in FIG. 14(B). 
     (H) PREPARATION OF 3- (METHOXYCARBONYL)METHYLTHIO!-4-HEPTANONE ##STR65## 
     Into a 50 ml, three-necked, round bottom flask equipped with magnetic stirrer, pot thermometer, &#34;Y&#34; tube, nitrogen inlet tube, reflux condenser with cotton plug and cold water bath is placed a solution of 1.08 grams of sodium methoxide dissolved in 11 ml anhydrous methanol (0.02 moles sodium methoxide). Over a period of 2 minutes and at a temperature of 25°-30° C, 2.12 grams (0.02 moles) of methyl thioglycolate dissolved in 2 ml anhydrous methanol is added to the reaction mass with stirring. After 5 minutes, 2.97 grams of 3-chloro-4-heptanone is then added to the reaction mass with stirring while the temperature of the reaction mass warms to 40° C. The reaction mass then cools to 35° C and is stirred in the temperature range of 25°-35° C for a period of 2 1/2 hours. 
     25 ml water is then added to the reaction mass with stirring, and the solid present therein dissolves (pH = 6-7). The reaction mass is extracted with three 20 ml volumes of methylene chloride, and the methylene chloride extracts are combined and washed with one 10 ml portion of water. The methylene chloride extracts are then dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator using water aspirator vacuum to a weight of 3.77 grams (light yellow oil). GLC analysis (conditions: 8 feet × 1/4 inches SE-30 column) indicates 92.0% product. NMR, mass spectral and IR analyses of GLC isolated material confirm that the resulting product is: ##STR66## 
     The mass spectral analysis is as follows: 
     
         ______________________________________                                    
m/e             Relative Intensity                                        
______________________________________                                    
27              11                                                        
41              21                                                        
43              54.sup.4                                                  
45              12                                                        
55              11                                                        
71              59.sup.3                                                  
87              100.sup.1                                                 
115             41.sup.5                                                  
147             90.sup.2                                                  
M218            35.sup.6                                                  
______________________________________                                    
 
    
     The NMR analysis is as follows: 
     
         ______________________________________                                    
0.98 ppm  methyl protons      6H                                          
2.06-1.46 CH.sub.2            4H                                          
2.60      CH.sub.2CO          2H                                          
3.22      SCH.sub.2CO                                                     
                              3H                                          
3.30      OCHCS                                                           
3.72                                                                      
           ##STR67##          3H                                          
______________________________________                                    
 
    
     The IR analysis is as follows: 
     1000 cm -1 , 1150, 1185, 1275, 1430, 1450, 1695, 1730, 2860, 2920, 2960. 
     The NMR spectrum is set forth in FIG. 15. The infrared spectrum is set forth in FIG. 16. 
     EXAMPLE III 
     A. Preparation of 3-propylthio-4-heptanone ##STR68## 
     Into a 50 ml, three-necked, round bottom flask equipped with magnetic stirrer, reflux condenser, nitrogen inlet tube, pot thermometer and cold water bath, is placed a solution of 0.54 grams of sodium methoxide dissolved in 6 ml anhydrous methanol (0.01 moles of sodium methoxide). The sodium methoxide solution is cooled using the water bath to 25° C. A solution of 0.76 grams of n-propyl mercaptan dissolved in 6 ml anhydrous methanol (0.01 moles n-propyl mercaptan) is then added to the sodium methoxide/methanol solution, and the temperature rises to 28° C. 1.5 g (0.01 moles) 3-chloro-4-heptanone dissolved in 2 ml anhydrous methanol is then added, and the temperature of the reaction mass rises to 38° C, whereupon it is cooled using the water bath to a temperature in the range of 25°-30° C. The reaction mass is then stirred under nitrogen for a period of 6 hours. 
     The reaction mass is then concentrated to a volume of 4 ml using a rotary evaporator to which water aspirator vacuum is applied. 9 ml distilled water is then added to the reaction mass concentrate whereupon the solid dissolves. The oil phase is extracted with three 8 ml portions of methylene chloride, and the extracts are combined and washed with 8 ml of water and dried over anhydrous sodium sulfate and filtered and then concentrated. GLC, MS, NMR and IR analyses yield the information that the subject material is 3-propylthio-4-heptanone. 
     The NMR spectrum is set forth in FIG. 17. The IR spectrum is set forth in FIG. 18. 
     The NMR analysis is as follows: 
     
         ______________________________________                                    
0.87- 1.04 ppm                                                            
           superimposed                                                   
                       CH.sub.3      9H                                   
           signals                                                        
1.63       (m)         CH.sub.2      6H                                   
2.38       (t)         CH.sub.2S     2H                                   
2.60       (t)                                                            
                        ##STR69##    2H                                   
3.11       (t)         OCHCS         1H                                   
______________________________________                                    
 
    
     The IR analysis is as follows: 
     1130 cm -1 , 1165, 1290, 1360, 1380, 1405, 1460, 1700, 2880, 2940, 2960 
     The mass spectral analyses is as follows: 
     
         ______________________________________                                    
m/e             Relative Intensity                                        
______________________________________                                    
41              20.sup.4                                                  
43              26.sup.3                                                  
55              5                                                         
71              10                                                        
75              35.sup.2                                                  
114             10                                                        
117             100.sup.1                                                 
118             10.sup.6                                                  
119             9                                                         
M 188           16.sup.5                                                  
______________________________________                                    
 
    
     Material prepared similarly to above example was vacuum distilled yielding 98.4% pure product (boiling point 72°-73° C at 1.5 mm Hg). The thus-distilled material has the same physical properties as set forth above for 3-propylthio-4-heptanone. 
     B. Preparation of 3-propylthio-4-heptanol ##STR70## 
     Into a 25 ml, three-necked, round bottom flask equipped with magnetic stirrer, reflux condenser, pot thermometer, and nitrogen inlet (for flushing with dry nitrogen) is added a solution of 0.15 grams of sodium borohydride dissolved in 6 ml anhydrous methanol (0.004 moles sodium borohydride). With stirring, a solution of 1.0 grams of 3-propylthio-4-heptanone dissolved in 4 ml anhydrous ethyl alcohol is added to the sodium borohydride solution which then warms to 28° C. The reaction mass is stirred for a period of 2 hours at 25° C and then concentrated on a rotary evaporator (using water aspirator vacuum) to a volume of 4 ml yielding an oily solid. 8 ml water is then added to the solid, with stirring, and the solid dissolves yielding two phases: an oil phase and a water phase. The resulting reaction mass is acidified with 10% hydrochloric acid to a pH of between 2 and 3. The oil phase is extracted with three 8 ml volumes of methylene chloride, and the extracts are combined and washed with 8 ml water. The extracts are then dried over anhydrous sodium sulfate, filtered and concentrated to a weight of 0.79 grams (water-white oil). GLC, IR, mass spectral and NMR analyses after GLC trapping (conditions: 8 feet × 1/4 inches SE-30 column) yield the information that the crude is 96% product having the structure 3-propylthio-4-heptanol. 
     The NMR spectrum is set forth in FIG. 19. The IR spectrum is set forth in FIG. 20. 
     The NMR analysis is as follows:  t1 -1.13- 0.96 ppm superimposed methyl protons  9H - signals -1.44 (m) -- CH 2  --? 8H -2.47 (s) --OH -2.49 (m) HC -- S-- CH 2  --? -3.50 (m) HC-- O--  1H? - 
     The IR analysis is as follows: 
     1290 cm -1 , 1380, 1460, 2880, 2940, 2970, 3460. 
     Material prepared similarly to above example was vacuum distilled yielding 99.8% pure product (boiling point 65° C at 0.4 mm Hg). The thus-distilled material has the same physical properties as set forth above for 3-propylthio-4-heptanol. 
     EXAMPLE IV 
     3-Propylthio-4-heptanol is added to a commercial instant tomato soup mix (&#34;Tomatancreme Suppe&#34;, C. H Knorr, Heilbrown, West Germany) at the rate of 2 ppm (based on the weight of the soup as ready to eat, produced by adding 80 g. of the dry soup mix to 1,000 ml water and then bringing the resulting mixture to a boil). A second &#34;control&#34; is prepared which is identical to the initial sample except for the absence of the 3-propylthio-4-heptanol. A four member panel of flavorists compared the control to the soup containing 3-propylthio-4-heptanol. All four members of the panel indicated a strong preference for the tomato soup containing the 3-propylthio-4-heptanol. All four members of the panel indicated that the soup containing the 3-propylthio-4-heptanol includes a fresh tomato note which is not present in the soup prepared without using the 3-propylthio-4-heptanol.