Process for preparing 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones
BACKGROUND OF THE INVENTION 
     The present invention relates to a process for preparing 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones. Compositions using one or more of such 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones or &#34;cis&#34; or &#34;trans&#34; isomers thereof alter, modify, augment or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials. 
     There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors to (or in) various consumable materials. These substances are used to diminish the use of natural products, some of which may be in short supply and to provide more uniform properties in the finished product. Coffee-like, roasted, cocoa-like, caramel-like, licorice, and roasted almond aroma and flavor characteristics are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors. Sweet, caramel/coffee aromas and flavors prior to smoking and sweet, caramel/coffee, nutty/pyrazine and roasted nutty aroma and taste characteristics on smoking are particularly desirable in tobaccos as well as tobacco flavoring compositions and in tobacco substitutes and flavoring compositions for such tobacco substitutes. 
     When one mole of diactyl is reacted with one mole of furfuryl mercaptan a coffee flavored reaction product is produced which has been found to contain a small percentage (about 10% by weight) of 5-actyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone with one of the &#34;cis&#34; - &#34;trans&#34; isomers in a ratio to the other of the &#34;cis&#34; - &#34;trans&#34; isomers being about 2:1. The process for preparing such a reaction product (without describing the constituents of the products) is set forth in Swiss Pat. No. 128,720 published on Nov. 16, 1928. It is stated in the example at column 2 on page 1 thereof that when one mixes furfuryl-2-mercaptan and diacetyl the product (alpha-oxy-alpha-acetylethyl)furfuryl-2-sulfide is produced. There is no disclosure in Swiss Pat. No. 128,720 that an additional mole of diacetyl added to the resulting reaction product will produce the compound having the structure: ##STR1## or any of its &#34;cis&#34; or &#34;trans&#34; isomers having the structures: ##STR2## In addition there is no disclosure either explicit or implicit in Swiss Pat. No. 128,720 that the compound having the structure: ##STR3## can be produced having a very high intensity and long lasting aroma and taste characteristics of the nature described herein. 
     U.S. Pat. No. 1,696,419 issued on Dec. 25, 1928 (Title: &#34;Method of Producing Artificial Coffee Aroma&#34;) discloses the production of a coffee flavor using: 
     &#34;one part of diacetyl, four parts of acetyl propionyl, four parts of methyl ethyl acetaldehyde, three parts of acetaldehyde, two parts of alpha methyl furfural, one part of furfural, three parts of pyridine, two parts of isovaleric acid, one part of phenol, one part of isoeugenol, 0.5 parts of guiacol, 0.5 parts of alpha methyl cyclopentenolone, 0.6 parts of methyl mercaptan, 0.3 parts of furfuryl mercaptan, 0.3 parts of n-octyl alcohol and 0.4 parts of thioguiacol&#34; 
     at page 3, column 1, lines 29-39. 
     The compound having the structure: ##STR4## is not indicated to be produced as a result of admixing at higher temperatures the foregoing ingredients. 
     Nothing in the prior art discloses the reaction of a dimer of an alpha beta diketone having from 4 up to 6 carbon atoms with furfuryl mercaptan to form the genus of compounds having the structure: ##STR5## 
     Canadian Pat. No. 1,002,383 entitled: &#34;Popcorn-Like Flavor and Process for Preparing Same&#34; issued on Dec. 28, 1976 discloses the use of the reaction product of glyoxal or glycol aldehyde with a sulfur containing compound such as hydrogen sulfide to form a popcorn flavorant. Other sulfur containing compounds listed are L-Cysteine and other dicarbonyl compounds set forth in 1,002,383 are 2,3-pentanedione and 2,4-pentanedione but is indicated on page 8 of Canadian Pat. No. 1,002,383 that these other dicarbonyl compounds do not give the same effect as glyoxal or glycol aldehyde. None of the reaction products disclosed teach either explicitly or implicitly the process of our invention. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1. represents the NMR spectrum for isomer &#34;A&#34;, peak 1, produced according to the process of Example I and is the spectrum for the compound having one of the structures: ##STR6## 
     FIG. 2 represents the NMR Spectrum for isomer &#34;B&#34;, peak 2, produced according to the process of Example I and is the spectrum for the compounds having one of the structures: ##STR7## 
     FIG. 3 is the infrared spectrum for isomer &#34;A&#34;, peak 1, of the reaction product produced according to Example I. 
     FIG. 4 represents the infrared spectrum for isomer &#34;B&#34;, peak 2 of the reaction product to Example I. 
     FIG. 5 represents the GC profile of the reaction product of Example I wherein one mole of diacetyl was reacted with one mole of furfuryl mercaptan. 
     FIG. 6 represents the mass spectrum for isomer &#34;A&#34;, peak 1, for the reaction product produced according to Example I. 
     FIG. 7 represents the mass spectrum for isomer &#34;B&#34;, peak 2, produced according to Example I. 
     FIG. 8 represents the GC profile for the reaction product of the diacetyl dimer with furfuryl mercaptan one hour and 52 minutes after addition of diacetyl dimer to the mixture of hydrochloric acid and furfuryl mercaptan as carried out according to Example II. 
     FIG. 9 represents the GC profile for the reaction product of diacetyl dimer with furfuryl mercaptan at that point in time after carrying out the reaction of diacetyl dimer with furfuryl mercaptan in the presence of hydrochloric acid for 6 hours and 20 minutes at 50° C. according to Example II. 
    
    
     Copending application for U.S. Letters Patent Ser. No. 819,957 filed on July 28, 1977 (Title: &#34;5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones and Organoleptic Uses Thereof&#34;) discloses that novel solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefor having coffee, roasted, cocoa-like, caramel-like, licorice and roasted almond aroma and flavor characteristics as well as novel tobacco and tobacco flavoring compositions as well as substitute tobacco and substitute tobacco flavoring compositions having sweet, caramel/coffee-like aromas and taste prior to and on smoking and nutty/pyrazine-like aroma and flavor characteristics prior to and on smoking with roasted nut-like nuances may be provided by the utilization of one or more 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones (either &#34;cis&#34; or &#34;trans&#34; isomers or mixtures of &#34;cis&#34; and &#34;trans&#34; isomers) having the generic formula: ##STR8## in foodstuffs, chewing gums, toothpastes, medicinal products, tobaccos and tobacco substitutes (wherein each of R 1  &#39;, R 2  &#39;, R 3  &#39; and R 4  &#39; are the same or different and each can be hydrogen or methyl. 
     The 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones useful as indicated supra are produced by one of two alternate routes of a process using one or more C 4  -C 6  alpha, beta diketones and furfuryl mercaptan as reactants. A first route (not claimed herein) involves reaction of one or more alpha, beta diketones with furfuryl mercaptan to form one or more addition products defined by the structure: ##STR9## wherein R 5  &#39; and R 6  &#39; are the same or different and each represents hydrogen or methyl. In this reaction where one alpha, beta diketone is used as a reactant, two compounds would be formed in the event that R 5  &#39; and R 6  &#39; are different; one wherein R 5  &#39; is methyl and R,6 is hydrogen and the other wherein R 5  &#39; is hydrogen and R 6  &#39; is methyl. The addition product(s) having the structure(s): ##STR10## is (are) then reacted in this first route with one or more alpha, beta diketone having the structure: ##STR11## (Which may be the same or different from the first alpha, beta diketone in the initial reaction.) Wherein a mixture of isomers (and compound if different alpha, beta diketones are used as reactants) is produced having the generic structure: ##STR12## wherein R 1  &#39;, R 2  &#39;, R 3  &#39; and R 4  &#39; are the same or different and each represents hydrogen or methyl. A mixture of isomers is formed in the event that R 5  &#39; and R 6  &#39; are different in the case of one or both C 4  -C 6  alpha, beta diketone reactants or if mixtures of alpha, beta diketones are used in one or both reactions. Thus, in this first route, if R 5  &#39; and R 6  &#39; are different (e.g. hydrogen and methyl respectively) and if in the second reaction R 5  &#34; and R 6  &#34; of the alpha beta diketone reactant having the structure: ##STR13## are the same (e.g. both hydrogen or both methyl, respectively) then the isomer mixture for the product having the structure: ##STR14## will be such that R 3  &#39; and R 4  &#39; are either both hydrogen or both methyl and R 1  &#39; and R 2  &#39; are interchanged; that is, one of the isomers is the compound wherein R 1  &#39; is methyl and R 2  &#39; is hydrogen and the other of the isomers is the case where R 2  &#39; is methyl and R 1  &#39; is hydrogen. Furthermore, each of the aforesaid two isomers exists in 2 &#34;geometric&#34; forms a &#34;cis&#34; form and a &#34;trans&#34; form having the structures, respectively: ##STR15## 
     The second and claimed route for the process of our invention for producing one or more 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones having the structure: ##STR16## reacting one or more dimers of one or more C 4  -C 6  alpha, beta diketones, which dimers are defined by the structure: ##STR17## with furfuryl mercaptan having the structure: ##STR18## in the presence of an acid catalyst, preferably a mineral acid catalyst such as hydrochloric acid, phosphoric acid, para-toluene sulfonic acid or sulfuric acid. The C 4  -C 6  alpha, beta diketone dimer substance can be a mixture of dimers resulting from dimerization of an unsymmetrical diketone or resulting from dimerization of two different diketones or it can be a substantially pure dimer resulting from dimerization of a symmetrical alpha, beta diketone. Thus, and more specifically, in the case of pure dimers having the generic structure: ##STR19## wherein R 1  &#39;, R 2  &#39;, R 3  &#39; and R 4  &#39; are the same or different and each represents hydrogen or methyl. Such a substantially pure dimer is formed from the C 4  -C 6  alpha, beta diketone having the structure: ##STR20## wherein R 5  &#39; and R 6  &#39; are the same; that is both represent hydrogen or both represent methyl. On the other hand, the C 4  -C 6  alpha, beta diketone dimer substance (or composition) can be formed by dimerizing one or more C 4  -C 6  alpha, beta diketone wherein in at least one of the alpha, beta diketones R 5  &#39; and R 6  &#39; are different for example R 5  &#39; is hydrogen and R 6  &#39; is methyl or R 6  &#39; is hydrogen and R 5  &#39; is methyl; in which case a mixture of dimers would be formed as a result of the dimerization reaction and wherein in at least one of the dimers formed, R 1  &#39; and R 2  &#39; are different, one of them being hydrogen and the other being methyl, and R 3  &#39; and R 4  &#39; are different, one of them being hydrogen and the other of them being methyl. Still further in the dimerization reaction where two different C 4  -C 6  alpha, beta diketones are reacted (the reaction taking place in the presence of a basic material such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate) each of the diketones, individually, will dimerize and the different diketones will also dimerize with one another, thereby forming up to 16 isomers, each isomer being in both a &#34;cis&#34; and &#34;trans&#34; form. As a specific example, when the two alpha, beta diketones 2,3-pentanedione having the structure: ##STR21## and 2,3-butanedione having the structure: ##STR22## are reacted in the presence of base. The structures of the dimers formed are as follows: ##STR23## and the most practical and commercially feasible method of operation is to react the entire mixture of thse dimers with furfuryl mercaptan according to the process of our invention. 
     The aforementioned two reaction sequences, the one using as starting materials furfuryl mercaptan and one or more C 4  -C 6  alpha, beta diketones and the other using the dimer of the C 4  -C 6  alpha, beta diketones and furfuryl mercaptan are set forth below: ##STR24## More specifically this is exemplified by the use of diacetyl or the diacetyl dimer and furfuryl mercaptan as set forth below: ##STR25## With reference to the first route as set forth above, the reaction of furfuryl mercaptan with the C 4  -C 6  alpha, beta diketone(s) to form the intermediate having the structure: ##STR26## and subsequent reaction of said intermediate with the same or a different C 4  -C 6  alpha, beta diketone. The mole ratio of C 4  -C 6  alpha, beta diketone:furfuryl mercapan is 2:1 up to about 10:1 with a preferred ratio range of from 2:1 up to 3:1. It is preferred in this first reaction sequence that the reaction is carried out under reflux condition at temperature in the range of from about 100° C up to about 150° C for a period of time of from about 3 hours up to about 20 hours. Although the reaction may be carried out in the absence of a solvent, if a solvent is to be used it is preferred that said solvent can be easily removed at the end of the reaction and that the solvent have a boiling point such that the reaction temperature range is in the range of from about 110° C up to 150° C. The reaction is conveniently carried out at atmospheric pressure, however higher than atmospheric pressures or subatmospheric pressures may be used depending upon the desired temperature of reaction and solvent (if any) used with the reactants. The temperatures and pressures of reaction are preferably the same for both stages (i) the preparation of the intermediate having the structure: ##STR27## and (ii) the reaction of said intermediate with the additional mole of C 4  -C 6  alpha, beta diketone. 
     Insofar as the second and claimed reaction sequence is concerned wherein one or more C 4  -C 6  alpha, beta diketone is reacted to form one or more &#34;dimers&#34; defined by the generic structure: ##STR28## the said dimer(s) is (are) prepared by methods well known in the art (e.g. dimerization of the C 4  -C 6  alpha, beta diketone in the presence of base). The reaction of the dimer with the furfuryl mercaptan preferably takes place in the presence of a solvent at temperatures in the range of from about 40° C up to about 100° C depending upon the solvents used and the time of reaction used. Preferably the solvent used is one wherein the reflux temperature of the reaction mass will be at temperatures of between 40° C and 100° C such as for example tetrahydrofuran. The pressure of reaction is preferably and most conveniently about one atmosphere, however, pressures of reaction of greater than one atmosphere or less than one atmosphere may be used without detrimentally affecting the yield of desired product. In order to avoid problems relating to the recovery of excess reactants it is preferable to use a mole ratio of C 4  -C 6  alpha, beta diketone:furfuryl mercaptan of 1:1 although either of the reactants may be used in excess without detrimentally affecting the yield of reaction. 
     One or more of the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones produced according to the process of our invention is capable of supplying and/or potentiating certain flavor and aroma notes usually lacking in many coffee, caramel, roasted nut and licorice flavors as well as tobacco flavors heretofore provided. 
     When the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones produced according to the process of our invention are used as food flavor adjuvants the nature of the coingredients included with each of the said 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones in formulating the product composition will also serve to alter or augment the organoleptic characteristics of the ultimate foodstuff treated therewith. 
     As used herein in regard to foodstuff flavors and chewing gum flavors and medicinal product flavors, the terms &#34;alter&#34;, &#34;modify&#34; and &#34;augment&#34; in their various forms mean &#34;supplying or imparting flavor character or notes to otherwise bland, relatively tasteless substances or augmenting the existing flavor characteristics where a natural flavor is deficient in some regard or where a specific flavor composition containing several ingredients some of which may be natural is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste&#34;. 
     The term &#34;enhance&#34; is used herein to mean the intensification of a flavor 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 which are ingestible materials which usually do, but need not, have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, dairy products, candies, vegetables, cereals, soft drinks, snacks and the like and in addition intended herein to mean petfoods. 
     As used herein the term &#34;medicinal product&#34; includes both solids and liquids which are ingestible non-toxic materials which have medicinal value such as cough syrups, cough drops, aspirin, vitamin, lozenges and chewable medicinal tablets. 
     The term &#34;chewing gum&#34; is intended to mean the composition which comprises a substantially water-insoluble, chewable plastic gum base such as chicle, or substitutes therefor, including jelutong, guttakay, rubber or certain comestible natural or synthetic resin or waxes. Incorporated with the gum base in admixture herewith by the plasticizers or softening agents, e.g., glycerine; and a flavoring composition which incorporates one or more of the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones produced according to the process of our invention and, in addition, sweetening agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners such as cyclamates or saccharin. Other optional ingredients may also be present. 
     Suitable substances for use herein as coingredients or &#34;flavoring adjuvants&#34; are well known in the art for such use, being extensively described in the relevant literature. It is a requirement that any such material be &#34;ingestibly&#34; acceptable, non-toxic and otherwise non-deleterious particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used is not caused to have unacceptable aroma and taste nuances. 
     Those materials which in general may be characterized as &#34;flavoring adjuvants&#34; comprise broadly vehicles, 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., 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 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 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; 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: 
     (i) Insofar as coffee flavors are concerned 
     Hydrogen sulfide 
     Formaldehyde 
     Formic acid 
     Methanol 
     Methyl mercaptan 
     Carbon disulfide 
     Acetaldehyde 
     Acetic acid 
     Methyl formate 
     Ethanol 
     Dimethyl sulfide 
     Dimethyl disulfide 
     Acrylonitrile 
     Acrolein 
     Propanal 
     Acetone 
     Propionic acid 
     Acetol 
     Methyl acetate 
     Ethyl formate 
     Methyl ethyl sulfide 
     Methyl ethyl disulfide 
     Furan 
     Thiophene 
     Crotonolactone 
     Pyrazine 
     3-Butene nitrile 
     Pyrrole 
     Methyl vinyl ketone 
     Diacetyl 
     Butyrolactone 
     Crotonic acid 
     i-Butanal 
     Butanal 
     Butanone 
     i-Butyric acid 
     Acetoin 
     Ethyl acetate 
     Furfural 
     Pyridine 
     2-Pyrrolaldehyde 
     2-Methylfuran 
     Furfuryl alcohol 
     2-Methylpyrazine 
     N-methylpyrrole 
     Isoprene 
     Pentadiene 
     Cyclopentanone 
     Pentane-2,3-dione 
     2-Methyltetrahydrofuran-3-one 
     Senecioic acid 
     Acetylacetone 
     Acetol acetate 
     2-Methylbutanal 
     3-Methylbutanal 
     Valeraldehye 
     2-Hydroxy-3-pentanone 
     3-Hydroxy-2-pentanone 
     i-Valeric acid 
     2-Methylbutyric acid 
     Phenol 
     5-Methylfurfural 
     2-Acetylfuran 
     Furfuryl formate 
     Dimethylmaleic anhydride 
     2-Methyl-3-hydroxy-2-pyrone 
     2-Acetylthiophene 
     3-Methylpyridine 
     2-Acetylpyrrole 
     N-methylpyrrole-2-aldehyde 
     5-Methylpyrrole-2-aldehyde 
     2,5-Dimethylfuran 
     3-Methylcyclopentane-1,2-dione 
     2,3-Dimethylpyrazine 
     2,5-Dimethylpyrazine 
     2,6-Dimethylpyrazine 
     Furfuryl methyl sulfide 
     2-Methyl-3-ethylacrolein 
     1-(2&#39;-furyl)-propane-1,2,-dione 
     Methyl nicotinate 
     Toluene 
     m-Cresol 
     Guaiacol 
     5-Methyl-2-acetylfuran 
     Furfuryl acetate 
     Methyl ethyl maleic anhydride 
     2-Propionylpyrrole 
     N-methyl-2-acetylpyrrole 
     N-methyl-5-methylpyrrole-2-aldehyde 
     2-Propylfuran 
     3,4-Dimethylcyclopentane-1,2-dione 
     3,5-Dimethylcyclopentane-1,2-dione 
     3,3-Diethylcyclopentane-1,2-dione 
     3-Methylcyclohexane-1,2-dione 
     2,3-Dihydroxyacetophenone 
     1-(2&#39;-Furyl)-butane-1,2-dione 
     1-[(5&#39;-Methyl)-2&#39;furyl]-propane-1,2-dione 
     2-Butylfuran 
     2,2&#39;-Difurylmethane 
     N-furfuryl-2-pyrrole 
     4-Vinylguaiacol 
     4-Ethylguaiacol 
     Insofar as cocoa flavors are concerned, aliphatic compounds such as: 
     Acetaldehyde 
     Acetic acid 
     Acetone 
     Acetoxyacetone 
     Acrolein 
     2-Aminobutane 
     n-Amyl acetate 
     n-Amyl alcohol 
     Amyl butyrate 
     Amyl propionate 
     2,3-Butandiol 
     2,3-Butanedione 
     2-Butanon-3-ol 
     n-Butyl acetate 
     n-Butyraldehyde 
     n-Butyric acid 
     Caproic acid 
     Caprylic acid 
     Citronellal 
     Crotonaldehyde 
     Dimethylamine 
     Ethanol 
     Ethyl acetate 
     Ethylamine 
     Ethyl caproate 
     Ethyl propionate 
     Formic acid 
     Geraniol 
     3-Heptadecanone 
     1-Hexanol 
     Hexyl butyrate 
     Hexyl propionate 
     Isoamyl acetate 
     Isoamylamine 
     Isobutanol 
     Isobutyl acetate 
     Isobutylamine 
     Isobutyraldehyde 
     Isovaleraldehyde 
     Linalool 
     Linalyl acetate 
     Methanol 
     Methyl acetate 
     Methylamine 
     α-Methylbutyric acid 
     Methyl disulfide 
     2-Methyl-2-hepten-6-one 
     Methyl sulfide 
     Methyl trisulfide 
     2,4-Octadien-1-ol 
     1-Octen-3-ol 
     Pelargonic acid 
     2,3-Pentandione 
     2-Pentyl acetate 
     1-Propanol 
     2-Propanol 
     Propionaldehyde 
     Propionic acid 
     1-Propyl acetate 
     2-Propyl acetate 
     Propyl trisulfide 
     Triethylamine 
     Trimethylamine 
     n-Valeric acid; 
     Alicyclic compounds such as: 3-Methyl-1,2-cyclopentanedione 
     Aromatic compounds such as: 
     Acetophenone 
     Benzaldehyde 
     Benzene 
     Benzonitrile 
     Benzyl alcohol 
     Cresol 
     3,4-Dihydroxybenzoic acid 
     6,7-Dihydroxycoumarin 
     Ethyl benzoate 
     p-Ethylphenol 
     Ethyl phenylacetate 
     Eugenol 
     Guaiacol 
     o-Hydroxyacetophenone 
     p-Hydroxybenzoic acid 
     p-Hydroxycinnamic acid 
     4-Hydroxy-3,5-dimethoxy-benzoic acid 
     4-Hydroxy-3-methoxy-benzoic acid 
     4-Hydroxy-3-methoxy-cinnamic acid 
     o-Hydroxyphenylacetic acid 
     p-Hydroxyphenylacetic acid 
     p-Methoxybenzoic acid 
     4-Methylguaiacol 
     Methyl phenylacetate 
     Phenol 
     Phenyl acetate 
     Phenylacetic acid 
     Phenylacetic aldehyde 
     2-Phenylethyl acetate 
     1-Phenylethyl alcohol 
     2-Phenylethyl alcohol 
     2-Phenylethylamine 
     2-Phenyl-2-propanol 
     Toluene 
     Heterocyclic compounds such as: 
     γ-Butyrolactone 
     γ-Caprolactone 
     Furan 
     Furfural 
     Furfuryl acetate 
     Furfuryl alcohol 
     2-Furyl methylacetone 
     Maltol 
     α-Methyl-γ-butyrolactone 
     2-Methylfuran 
     Methyl-5-methylfurfuryl sulfide 
     2-Methyl-3-tetrahydrofuranone 
     γ-Valerolactone 
     cis-2-Vinyl-2-methyl-5-(1-hydroxy-1-methylethyl)-tetrahydrofuran 
     Pyrrole compounds such as: 
     2-Acetylpyrrole 
     2-Formylpyrrole 
     1-Methyl-2-formylpyrrole 
     5-Methyl-2-formylpyrrole 
     Pyrrole 
     Pyrazine compounds such as: 
     2,5-Dimethyl-6-ethylpyrazine 
     2,6-Dimethyl-3-ethylpyrazine 
     2,3-Dimethylpyrazine 
     2,5-Dimethylpyrazine 
     2,6-Dimethylpyrazine 
     2-Ethyl-5-methylpyrazine 
     2-Ethyl-6-methylpyrazine 
     Methylpyrazine 
     Tetramethylpyrazine 
     Trimethylpyrazine 
     2-Ethyl-3,5,6-trimethylpyrazine 
     3-Isoamyl-2,5-dimethylpyrazine 
     5-Isoamyl-2,3-dimethylpyrazine 
     2-Isoamyl-3,5,6-trimethyl-pyrazine 
     Isopropyl dimethylpyrazine 
     Hydrocarbons such as: 
     Dimethyl naphthalene 
     Dodecane 
     Methyl diphenyl 
     Methyl naphthalene 
     Myrcene 
     Naphthalene 
     Octadecane 
     Tetradecane 
     Tetramethyl naphthalene 
     Tridecane 
     Trimethyl naphthalene 
     Undecane 
     Alcohols and Ketoalcohols such as: 
     Acetoin 
     2-Heptanol 
     Linalool 
     1-Pentanol 
     Aldehydes such as: 
     Isopentanal 
     2-Methylbutanal 
     Ketones such as: 
     2-Heptanone 
     2-Methyl-2-hepten-6-one 
     2-Octanone 
     2-Undecanone 
     Esters and lactones such as: 
     Benzyl acetate 
     Ethyl caprate 
     Ethyl caproate 
     Ethyl caprylate 
     Ethyl cinnamate 
     Ethyl laurate 
     Ethyl myristate 
     Isoamyl acetate 
     γ-Nonalactone 
     Acids such as: 
     Isovaleric acid 
     2-Methylbutyric acid 
     Phenols such as: 2-Methoxy-4-methylphenol. 
     Insofar as licorice flavor is concerned: 
     Lavender essential oil 
     Clary sage essential oil 
     Rosemary essential oil 
     Thyme essential oil 
     Fennel essential oil 
     Mint essential oil 
     Angelica essential oil 
     Anise essential oil 
     Lemon essential oil 
     Wormwood essential oil 
     Cinnamon essential oil 
     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, (i) be organoleptically compatible with the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones produced according to the process of our invention by not covering or spoiling the organoleptic properties (aroma and/or taste) thereof; (ii) be non-reactive with the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones produced according to the process of our invention and (iii) be capable of providing an environment in which the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones produced according to the process of our invention 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, chewing gum, medicinal product or toothpaste to which the flavor and/or aroma are to be imparted, modified, altered or enhanced. In contradistinction, in the preparation of solid products, e.g., simulated footstuffs, 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 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones employed in a particular instance can vary over a relatively wide range, depending upon the desired organoleptic effects to be 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, modify or enhance the organoleptic characteristics of the parent composition whether foodstuff per se, chewing gum per se, medicinal product per se, toothpaste per se, or the flavoring composition itself. 
     The use of insufficient quantities of 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantites of 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones prove needlessly costly and in extreme cases, may disrupt the flavor-aroma balance, thus proving selfdefeating. 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, chewing gum compositions, medicinal product compositions and toothpaste compositions, it is found that quantities of 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones (in combination) ranging from a small but effected amount, e.g., 0.01 parts per million up to about 100 parts per million based on total composition are suitable. Concentrations in excess of the maximum quantity stated are not normally recommended, since they fail to provide commensurate enhancement or augmentation of organoleptic properties. In those instances, wherein the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones 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 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone concentration in the foodstuff product. 
     Food flavoring compositions prepared in accordance with the present invention preferably contain the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones (in combination) in concentrations ranging from about 0.05% up to about 20% 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, ice creams, liquers and soft drinks and 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 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones 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 mixes in powder form, e.g., cocoa-flavored powder mixes and coffee flavored powder mixes are obtained by mixing the dried solid components, e.g., starch, sugar and the like and an 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones in a dry blender until the requisite degree of uniformity is achieved. 
     It is presently preferred to combine with the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones of our invention the following adjuvants: 
     Diacetyl 
     Benzaldehyde 
     Furfural 
     Furfuryl propionate 
     Trimethyl pyrazine 
     2,6-Dimethoxyphenol 
     Pyruvic acid 
     Furfuryl mercaptan 
     Furfuryl acetate 
     An additional aspect of our invention provides an organoleptically improved smoking tobacco product and additives therefor, as well as methods of making the same which overcome specific problems heretofore encountered in which specific desired &#34;sweet, caramel/coffee-like, nutty, and roasted nutty&#34; flavor characteristics of natural tobacco are created or enhanced and may be readily controlled and maintained at the desired uniform level regardless of variations in the tobacco components of the blend. 
     This invention further provides improved tobacco additives and methods whereby various desirable natural aromatic tobacco flavoring characteristics with sweet, caramel/coffee, nutty and roasted nutty notes may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavor characteristics. 
     In carrying out this aspect of our invention, we add to smoking tobacco materials or a suitable substitute therefor (e.g., dried lettuce leaves) an aroma and flavor additive containing as an active ingredient at least one 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or a combination of 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanones. 
     In addition to the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones of our invention other flavoring and aroma additives may be added to the smoking tobacco material or substitutes therefor either separately or in admixture with the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone of furanones as follows: 
     (i) Synthetic materials: 
     Beta-ethyl-cinnamaldehyde; 
     Beta-cyclohomocitral; 
     Eugenol; 
     Dipentene; 
     Damascenone; 
     Damascone; 
     Maltol; 
     Ethyl Maltol; 
     Delta undecalactone; 
     Delta decalactone; 
     Benzaldehyde; 
     Amyl acetate; 
     Ethyl butyrate; 
     Ethyl valerate; 
     Ethyl acetate; 
     2-Hexenol-1 
     2-Methyl-5-isopropyl-1,3-nonadiene-8-one; 
     2,6-Dimethyl-2,6-undecadiene-10-one; 
     2-Methyl-5-isopropyl acetophenone; 
     2-Hydroxy-2,5,5-8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene; 
     Dodecahydro-3a,6,6,9a-tetramethyl naphtho-[2,1,b]-furan; 
     4-hydroxy hexanoic acid, gamma lactone; 
     Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372 issued on June 29, 1971. 
     (ii) Natural Oils: 
     Celery seed oil; 
     Coffee extract; 
     Bergamot oil; 
     Cocoa extract; 
     Nutmeg oil; 
     Origanum oil 
     An aroma and flavoring concentrate containing a 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones and, if desired, one or more of the above indicated additional flavoring additives may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper. The smoking tobacco material may be shredded, cured, cased and blended tobacco material or reconstituted tobacco material or tobacco substitutes (e.g., lettuce leaves) or mixtures thereof. The proportions of flavoring additives may be varied in accordance with taste but insofar as enhancement or the inparting of natural and/or sweet, coffee/caramel, nutty or roasted nutty notes, we have found that satisfactory notes are obtained if the proportion by weight of the sum total of 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones to smoking tobacco material is between 10 and 1,500 ppm (0.001-0.15%) of the active ingredients to the smoking tobacco material. We have further found that satisfactory results are obtained if the proportion by weight of the sum total of 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones used to flavoring material is between 2,500 and 15,000 ppm (0.25%-1.5%). 
     Any convenient method for incorporating the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones into the tobacco product may be employed. Thus, the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, diethyl ether, tetrahydrofuran and/or volatile organic solvents and the resulting solution may either be sprayed on the cured, cased and blended tobacco material or the tabacco material may be dipped into such solution. Under certain circumstances, a solution of the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones taken alone or taken further together with other flavoring additives as set forth above, may be applied by means of a suitable applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be applied to the filter by either spraying, or dipping, or coating. 
     Furthermore, it will be apparent that only a portion of the tobacco or substitute therefor need be treated and the thus treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed. In such cases, the tobacco treated may have the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones in excess of the amounts of concentrations 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 example of our invention, an aged, cured and shredded domestic burley tobacco is sprayed with a 20% ethyl alcohol solution of 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3[2H]furanone (mixture of &#34;cis&#34; and &#34;trans&#34; isomers produced according to Example II, infra) in an amount to provide a tobacco composition containing 50 ppm by weight of 5-acyl-2-(furfurylthio)dihydro-2,5-dimethyl-3[2H]furanone on a dry basis. Thereafter, the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. The cigarette when treated as indicated has a desired and pleasing aroma which is detectable in the main and side streams when the cigarette is smoked. This aroma is described as being sweeter, more aromatic and having sweet, caramel/coffee-like, nutty/pyrazine-like and roasted nutty-like aromas and tastes. 
     While our invention is particularly useful in the manufacture of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fines may also be used. Likewise the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones of our invention can be incorporated with materials such as filter tip materials, seam paste, packaging materials and the like which are used along with tobacco to form a product adapted for smoking. Furthermore, the 5-acyl-2-(furfurylthio)dihydro-2,5-dialkyl-3-[2H]furanone or furanones can be added to certain tobacco substitutes of natural or synthetic origin (e.g., dried lettuce leaves) and, accordingly, by the term &#34;tobacco&#34; as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substitute materials or both. 
     The following examples serve to illustrate techniques for practicing our invention. It will be understood that these examples are illustrative and that the invention is to be considered restricted thereto only as indicated in the appended claims. 
     All parts and percentages given herein are by weight unless otherwise specified. 
     EXAMPLE I 
     PREPARATION OF 5-ACETYL-2-(FURFURYLTHIO)DIHYDRO-2,5-DIMETHYL-3[2H]FURANONE BY REACTION OF DIACETYL WITH FURFURYL MERCAPTAN FOLLOWED BY ADDITIONAL REACTION OF THE RESULTING PRODUCT WITH DIACETYL ##STR29## 
     Into a 250 ml three-necked flask equipped with dual pass condenser, caustic safety trap and cold water circulating cooler is placed the following materials: 
     Furfuryl mercaptan; 122 grams (1.070 moles) 
     Diacetyl; 92.035 grams (1.065 moles) 
     the reaction mass is then refluxed for a period of 6 hours at 118° C, following reflux the reaction mass is allowed to &#34;age&#34; for approximately three weeks. 
     The resulting reaction product is then analyzed by direct injection on a 400 ft. × 0.032 inch (I.D.) SE-30 glass capillary mounted on a Varian MAT III GC-MS instrument. The following results are obtained: 
     
         ______________________________________                                    
Substance           Percent Composition                                   
______________________________________                                    
Diacetyl            37                                                    
Furfuryl mercaptan  49                                                    
Phenylacetaldehyde  0.7                                                   
Furfurylether       0.2                                                   
Difurfurylsulfide   0.6                                                   
Difurfuryldisulfide 0.9                                                   
5-Acetyl-2-(furfurylthio)                                                 
 dihydro-2,5-dimethyl-3-                                                  
 [2H]-furanone (cis or                                                    
 trans isomer)      6.9                                                   
5-Acetyl-2-(furfurylthio)                                                 
 dihydro-2,5-dimethyl-3-                                                  
 [2H]-furanone (trans or                                                  
 cis isomer)        3.2                                                   
______________________________________                                    
 
    
     The two isomers of 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]-furanone were fully characterized following their enrichment on 5% deactivated silica gel column eluted with 20% diethyl ether in isopentane. Based upon high resolution mass spectra, NMR and IR the compounds are determined to have the structure: ##STR30## and each represents one of the isomers: ##STR31## 
     These conclusions are further supported by the chemistry involved in the synthesis set forth in Example II, infra. 
     FIG. 1 represents the NMR spectrum for one of the isomers having the structures: ##STR32## represented as isomer &#34;A&#34; which is peak &#34;1&#34; of the GC Profile of FIG. 5. The NMR spectrum gives rise to the following NMR Analysis: 
     
         ______________________________________                                    
 δ      Interpretation                                              
______________________________________                                    
1.50 ppm (s)                                                              
               ##STR33##       3H                                         
1.70 (s)                                                                  
               ##STR34##       3H                                         
2.40 (s)                                                                  
               ##STR35##       3H                                         
3.80 (s)      CCCH.sub.2S      2H                                         
3.70 &amp; 2.30 (AB)                                                          
               ##STR36##       2H                                         
6.26 (m)      furan protons    2H                                         
7.38 (m)      furan protons    1H                                         
______________________________________                                    
 
    
     FIG. 2 represents the NMR Spectrum for the second isomer having one of the structures: ##STR37## identified as isomer &#34;B&#34; which is peak &#34;2&#34; of the GC profile set forth in FIG. 5. The NMR spectrum gives rise to the following NMR Analysis: 
     
         ______________________________________                                    
 δ      Interpretation                                              
______________________________________                                    
1.63 ppm (s)                                                              
               ##STR38##       3H                                         
1.70 (s)                                                                  
               ##STR39##       3H                                         
2.84 (AB)                                                                 
               ##STR40##       2H                                         
2.98 (s)      CCCH.sub.2S      2H                                         
6.28 (m)      furan protons    2H                                         
7.36 (m)      furan protons    1H                                         
______________________________________                                    
 
    
     FIG. 3 represents the infrared spectrum for one of the isomers: ##STR41## designated as isomer &#34;A&#34; which is peak &#34;1&#34; from the GC profile of FIG. 5. The infrared spectrum gives rise to the following peaks: 
     
         ______________________________________                                    
            Isomer &#34;A&#34;                                                    
______________________________________                                    
            13.40 microns                                                 
            10.60                                                         
            10.40                                                         
             9.80                                                         
             9.10                                                         
             8.90                                                         
             8.60                                                         
             5.80                                                         
             5.70                                                         
______________________________________                                    
 
    
     FIG. 4 represents the infrared spectrum for one of the isomers having one of the structures: ##STR42## designated as isomer &#34;B&#34; which is peak &#34;2&#34; from the GC profile of FIG. 5. The infrared spectrum gives rise to the following infrared analysis: 
     
         ______________________________________                                    
            Isomer &#34;B&#34;                                                    
______________________________________                                    
            13.35 microns                                                 
            10.60                                                         
             9.80                                                         
             9.10                                                         
             8.65                                                         
             7.30                                                         
             7.20                                                         
             5.80                                                         
             5.70                                                         
______________________________________                                    
 
    
     FIG. 5 represents the GC profile for the reaction product of this example. 
     FIG. 6 represents the mass spectrum for isomer &#34;A&#34;, peak &#34;1&#34;. 
     FIG. 7 represents the mass spectrum for isomer &#34;B&#34;, peak &#34;2&#34;. 
     EXAMPLE II 
     PREPARATION OF 5-ACETYL-2-FURFURYLTHIODIHYDRO-2,5-DIMETHYL-3,2H-FURANONE ACCORDING TO THE REACTION OF FURFURYL MERCAPTAN AND THE DIACETYL DIMER ##STR43## 
     Into a 5 liter reactor equipped with reflux condenser, stirrer and cooling bath is added the following ingredients: 
     Diacetyl; 320 grams 
     Water; 3,200 ml 
     the reaction mass is cooled to 3° C at which point a solution of 54.4 grams of potassium hydroxide and 1,600 ml of water is added over a period of 20 minutes. 85 grams of 50% sulfuric acid is then added to the reaction mixture bringing the pH to 5. 10 ml concentrated HCl is then added bringing the pH to 1.5. 
     The reaction mass is then heated to 95° C and refluxed for a period of 6 hours whereupon 50 grams of a 30% aqueous sodium hydroxide solution is added. The pH of the reaction mass is now 6. The reaction mass is then saturated with 1600 grams of sodium chloride and then extracted with four 200 ml portions of methylene dichloride. The reaction mass is then dried over anhydrous sodium sulphate and stripped of solvent. The resulting product is then distilled through a 6 inch Vigreaux column followed by redistillation yielding the diacetyl dimer. 
     Into a 250 ml reaction flask equipped with reflux condenser, stirrer, thermometer and heating mantle is placed 20 grams (17.7 ml) of furfuryl mercaptan. 10 ml tetrahydrofuran and 1/2 ml concentrated HCl is then added. The reaction mass is heated to 50° C and, over a 10 minute period, 30 grams of diacetyl dimer prepared as above in 20 grams of tetrahydrofuran is added. 20 ml tetrahydrofuran additional used to rinse the addition flask is then added. 
     The reaction mass is then stirred for 5 hours at 50° C with GC samples taken each hour. 
     The resulting material is labeled &#34;Batch No. 1&#34;. 
     Into another 250 ml flask equipped with stirrer, thermometer, reflux condenser and heating mantle is placed 1.7 grams of the diacetyl dimer prepared as above, 4 ml tetrahydrofuran and 1.3 grams (1 ml) of furfuryl mercaptan. Reaction mass is stirred for a period of 2 hours at which time 2 drops of concentrated hydrochloric acid is added. The reaction mass is then heated to 50° C and stirred at 50°-52° C for a period of one hour. 
     This last prepared material is labeled &#34;Batch No. 2&#34;. 
     Batch 1 and Batch 2 are combined and to the combined batch is added 20 ml saturated sodium bicarbonate. The resulting mixture is transferred to a separatory funnel containing 200 ml of water and in the separatory funnel the oil phase is separated from the aqueous phase. The aqueous phase is extracted with one portion (30 ml) of methylene dichloride and the extract is combined with the oil layer. The resulting material is dried over anhydrous sodium sulphate, filtered and then stripped at atmospheric pressure and 80° C. The resulting product is then distilled through a micro Vigreaux column yielding the following fractions: 
     
         ______________________________________                                    
         Vapor       Liquid      Vacuum                                   
Fraction Temp.       Temp.       mm                                       
______________________________________                                    
 3       131         160         2.0                                      
4        147         170         2.0                                      
5        150         175         1.9                                      
6        154         205         1.9                                      
______________________________________                                    
 
    
     This material is then redistilled through a micro Vigreaux column yielding the following fractions: 
     
         ______________________________________                                    
       Vapor      Liquid     Vacuum   Weight                              
Fraction                                                                  
       Temp.      Temp.      Temp.    (g)                                 
______________________________________                                    
1      132/147    145/149    1.6/1.6  2.4                                 
2      148        150        1.6      7.0                                 
3      148        151        1.6      12.3                                
4      147        190        1.6      2.2                                 
______________________________________                                    
 
    
     Fractions 1-4, inclusive are then bulked for use in Examples 3 and 4. 
     FIG. 8 represents the GC profile for the reaction mass one hour and 52 minutes after the addition of diacetyl dimer for Batch No. 1 (conditions: 25% SE-30 column programmed at 150°-220° C at 8° C per minute). 
     FIG. 9 represents the GC profile for Batch No. 1 where the reaction mass was heated for 6 hours and 20 minutes at 50° C after which time it was allowed to remain at 25° C for a period of 16 hours after addition of the diacetyl dimer (Conditions: 25% SE-30 column operated at 150°-220° C at 8° C per minute). 
     EXAMPLE III 
     USE IN COFFEE FLAVORS OF 2,5-DIMETHYL-5-ACETYL-2-(FURFURYLTHIO)DIHYDRO-3-[2H]FURANONE 
     &#34;Cafeol&#34; a natural concentrated coffee extract produced by Mero Aromatics, of New York, New York, it is made up into a 0.1% solution. This solution is divided into 2 portions. To a first portion at the rate of 0.02 ppm is added 2,5-dimethyl-5-acetyl-2-(furfurylthio)dihydro-3-[2H]furanone. To the second portion nothing is added. Both the portion with and the portion without the 2,5-dimethyl-5-acetyl-2-(furfurylthio)dihydro-3-[2H]furanone are compared by a bench panel of 5 individual expert tasters. The coffee extract solution with the addition of the 2,5-dimethyl-5-acetyl-2-(furfurylthio)dihydro-3-[2H] furanone is indicated by the bench panel to have a substantially stronger coffee aroma and taste and is therefor unanimously preferred by all the tasters of the bench panel. 
     EXAMPLE IV 
     USE IN COFFEE FLAVORS OF 2,5-DIMETHYL-5-ACETYL-2-(FURFURYLTHIO)DIHYDRO-3-[2H]FURANONE 
     The following basic coffee flavor formulation is prepared: 
     
         ______________________________________                                    
Ingredients          Parts by Weight                                      
______________________________________                                    
Diacetyl (10% in 95% 1                                                    
food grade aqueous                                                        
ethanol)                                                                  
Benzaldehyde         1                                                    
Furfural             0.5                                                  
Furfural Propionate  10                                                   
Trimethyl Pyrazine (10%                                                   
                     1                                                    
in 95% aqueous food                                                       
grade ethanol)                                                            
2,6-Dimethoxy phenol 2                                                    
Pyruvic acid         15                                                   
Furfural Mercaptan (1%                                                    
                     1.0                                                  
solution in 95% food                                                      
grade ethanol)                                                            
Furfural acetate     0.5                                                  
Propylene glycol     68                                                   
______________________________________                                    
 
    
     The foregoing formulation is divided into 2 parts. The first part 0.2% by weight of 2,5-dimethyl-5-acetyl-2-(furfurylthio)dihydro-3-[2H]furanone prepared according to Example II is added. To the other portion nothing is added. Both formulations are compared in water at the rate of 20 ppm. The coffee flavor with the 2,5-dimethyl-5-acetyl-2-(furfurylthio)dihydro-3-[2H]furanone has a fresh roasted aroma and better coffee taste. Therefor a panel of expect tasters prefers the flavor with the 2,5-dimethyl-5-acetyl-2-(furfurylthio)dihydro-3-[2H]furanone as more characteristic and more natural coffee-like. 
     EXAMPLE V 
     A. POWDER FLAVOR COMPOSITION 
     20 Grams of the flavor composition of Example IV is emulsified in a solution containing 300 grams gum acacia and 700 grams water. The emulsion is spraydried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500° F., an outlet temperature of 200° F., and a wheel speed of 50,000 r.p.m. 
     B. SUBSTAINED RELEASE FLAVOR 
     The following mixture is prepared: 
     
         ______________________________________                                    
Ingredient          Parts by Weight                                       
______________________________________                                    
Liquid Coffee Flavor                                                      
Composition of Example IV                                                 
                    20                                                    
Propylene glycol    9                                                     
Cab-O-Sil.sup.R M-5                                                       
(Brand of Silica produced                                                 
by the Cabot Corporation                                                  
of 125 High Street, Boston,                                               
Mass. 02110;                                                              
Physical Properties:                                                      
 Surface Area: 200 m.sup.2 /gm                                            
 Nominal particle size:                                                   
 0.012 microns                                                            
 Density: 2.3 lbs/cu.ft.)                                                 
                    5.00                                                  
______________________________________                                    
 
    
     The Cab-O-Sil is dispersed in the liquid coffee flavor composition of Example IV with vigorous stirring, thereby resulting in a viscous liquid. 71 Parts by weight of the powder flavor composition of Part A, supra, is then blended into the said viscous liquid, with stirring at 25° C for a period of 30 minutes resulting in a dry, free flowing sustained release flavor powder. 
     EXAMPLE VI 
     10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150° F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120° F. 20 Parts by weight of the liquid coffee flavor composition of Example IV is added to the solution which is then homogenized to form an emulsion having a particle size typically in the range of 5-40 microns. This material is kept at 120° F. under which conditions the gelatin will not jell. 
     Coascervation is induced by added, slowly and uniformly, 40 parts by weight of a 20% aqueous solution of sodium sulphate. During coascervation, the gelatin molecules are deposited uniformly about each oil droplet as a nucleus. 
     Gelation is effected by pouring the heated coascervate mixture into 1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65° F. The resulting jelled coascervate may be filtered and washed with water at temperatures below the melting point of jelatin, to remove the salt. 
     Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove residual formaldehyde. 
     EXAMPLE VII 
     CHEWING GUM 
     100 parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example V. 300 Parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co. 
     The resulting chewing gum blend is then manufactued into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant long lasting coffee flavor. 
     EXAMPLE VIII 
     CHEWING GUM 
     100 Parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example VI. 300 Parts of sucrose and 100 parts of corn syrup are then added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co. 
     The resulting chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant long lasting coffee flavor. 
     EXAMPLE IX 
     TOOTHPASTE FORMULATION 
     The following separate groups of ingredients are prepared: 
     
         ______________________________________                                    
Parts by Weight Ingredient                                                
______________________________________                                    
Group &#34;A&#34;                                                                 
30.200          Glycerin                                                  
15.325          Distilled Water                                           
 .100           Sodium Benzoate                                           
 .125           Saccharin Sodium                                          
 .400           Stannous Fluoride                                         
Group &#34;B&#34;                                                                 
12.500          Calcium Carbonate                                         
37.200          Dicalcium Phosphate                                       
                 (Dihydrate)                                              
Group &#34;C&#34;                                                                 
 2.000          Sodium N-Lauroyl Sarcosinate                              
                 (foaming agent)                                          
Group &#34;D&#34;                                                                 
 1.200          Flavor Material of                                        
Example VI                                                                
100.00 (Total)                                                            
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Procedure:                                                                
1.        The ingredients in Group &#34;A&#34; are stirred                        
          and heated in a steam jacketed kettle to                        
          160° F.                                                  
2.        Stirring is continued for an additional                         
          three to five minutes to form a homogenous                      
          gel.                                                            
3.        The powders of Group &#34;B&#34; are added to the                       
          gel, while mixing until a homogenous paste                      
          is formed.                                                      
4.        With stirring, the flavor of &#34;D&#34; is added                       
          and lastly the sodium n-lauroyl sarcosinate.                    
5.        The resultant slurry is then blended for                        
          one hour. The completed paste is then                           
          transferred to a three roller sill and                          
          then homogenized, and finally tubed.                            
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     The resulting toothpaste when used in a normal toothbrushing procedure yields a pleasant coffee flavor of constant strong intensity throughout said procedure (1-1.5 minutes). 
     EXAMPLE X 
     CHEWABLE VITAMIN TABLETS 
     The flavor material produced according to the process of Example V is added to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/gm which Chewable Vitamin Tablet Formulation is prepared as follows: 
     In a Hobart Mixer, the following materials are blended to homogeneity: 
     
         ______________________________________                                    
                      Gms/1000 Tablets                                    
Vitamin C (ascorbic acid)                                                 
as ascorbic acid-sodium ascorbate                                         
mixture 1:1             70.0                                              
Vitamin B.sub.1 (thiamine mononitrate)                                    
as Rocoat.sup.R thiamine monomitrate                                      
33 1/3%                 4.0                                               
Vitamin B.sub.2 (roboflavin)                                              
as Rocoat.sup.R riboflavin 33 1/3%                                        
                        5.0                                               
Vitamin B.sub.6 (pyridoxine hydrochloride)                                
as Rocoat.sup.R pyridoxine hydro-                                         
chloride 33 1/3%        4.0                                               
Niacinamide                                                               
as Rocoat.sup.R niacinamide 33 1/3%                                       
                        33.0                                              
Calcium pantothenate    11.5                                              
Vitamin B.sub.12 (cyanocobalamin)                                         
as Merck 0.1% in gelatin                                                  
                        3.5                                               
d-Biotin                0.044                                             
Certified lake color    5.0                                               
Flavor of Example V     10.0                                              
Sweetener - sodium saccharin                                              
                        1.0                                               
Magnesium stearate lubricant                                              
                        10.0                                              
Mannitol q.s. to make   500.0                                             
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 Preliminary tablets are prepared by slugging with flat-faced punches and 
 grinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 g    
 Vitamin D are then added as beadlets. The entire blend is then compressed
 using concave punches at 0.5 g each.                                     
 
    
     Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong coffee flavor for a period of 12 minutes. 
     EXAMPLE XI 
     CHEWING TOBACCO 
     Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15% Pennsylvania leaf) the following casing is sprayed at a rate of 30%: 
     
         ______________________________________                                    
Ingredients         Parts by Weight                                       
______________________________________                                    
Corn Syrup          60                                                    
Licorice            10                                                    
Glycerine           20                                                    
Fig Juice           4.6                                                   
Prune Juice         5                                                     
Flavor Material of                                                        
Example VI          0.4                                                   
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     The resultant product is redried to a moisture content of 20%. On chewing, this tobacco has an excellent substantially consistent, long-lasting caramel/tobacco/nutty (20 minutes) nuance in conjunction with the main natural tobacco note. 
     EXAMPLE XII 
     TOBACCO CONTAINING 5-ACETYL-2-(FURFURYLTHIO)DIHYDRO-2,5-DIMETHYL-3-[2H]FURANONE 
     The following tobacco flavor formulation (A) is prepared: 
     
         ______________________________________                                    
Ingredients          Parts by Weight                                      
______________________________________                                    
Ethyl Butyrate       0.05                                                 
Ethyl Valerate       0.05                                                 
Maltol               2.00                                                 
Cocoa Extract        26.00                                                
Coffee Extract       10.00                                                
Ethanol (95% aqueous,                                                     
 food grade)         20.00                                                
Water                41.90                                                
______________________________________                                    
 
    
     The following tobacco formualtion (B) is prepared: 
     
         ______________________________________                                    
Ingredients          Parts by Weight                                      
______________________________________                                    
Bright Tobacco       40.1                                                 
Burley Tobacco       24.0                                                 
Maryland Tobacco     1.1                                                  
Turkish Tobacco      11.6                                                 
Stem (Flue-cured)Tobacco                                                  
                     14.2                                                 
Glycerin             2.8                                                  
Water                5.3                                                  
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     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 procedures. 
     At the rate of 20 ppm to half of the cigarettes in each group is added 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone produced according to the process of Example II. The use of the 5-acetyl-2-(furfurylthio) dihydro-2,5-dimethyl-3-[2H]furanone in the cigarettes causes the cigarettes prior to smoking to have a &#34;cigarette pack&#34; aroma and a coffee like aroma and taste prior to smoking. In smoke flavor the cigarettes containing the 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone have sweet, caramel/coffee-like tastes with nutty/pyrazine nuances and roasted nut-like nuances. Each of the tobacco articles containing the 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone whether or not containing other flavor ingredients of Formulation &#34;A&#34; have enhanced tobacco aroma and taste. 
     Similar experiment is carried out as above except that instead of a mixture of isomers of 5-acetyl-2-(furfurylthio) dihydro-2,5-dimethyl-3-[2H]furanone of Example II being used, the mixture of isomers of 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone of Example I is used in this latter case at 100 ppm the 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone imparts body to its Burley and black tobacco notes rather than Virginia tobacco notes. In addition, coffee, cocoa and licorice nuances are present in the cigarettes to which the 5-acetyl-2-(furfurylthio) dihydro-2,5-dimethyl-3-[2H]furanone is added. 
     EXAMPLE XIII 
     TOBACCO FLAVOR FORMULATION 
     A tobacco flavor formulation is prepared by admixing the following ingredients: 
     
         ______________________________________                                    
Ingredients           Parts by Weight                                     
______________________________________                                    
5-acetyl-2-(furfurylthio)                                                 
dihydro-2,5-dimethyl-3-                                                   
[2H] furanone mixture of                                                  
isomers produced according                                                
Example II            0.14                                                
Bergamot Oil Italy    5.00                                                
Ylang Ylang Oil       1.20                                                
2-(2&#39;-methyl-n-propyl)-4,5-                                               
dimethyl-Δ.sup.3 -thiazoline                                        
                      1.40                                                
Acetophenone          1.20                                                
Phenylacetaldehyde    0.50                                                
Phenylethylisovalerate                                                    
                      1.00                                                
Methylheptylcarbonate 0.50                                                
3-Phenyl-4-pentenaldiethyl                                                
acetal                20.00                                               
Aqueous food grade ethanol 95%                                            
                      69.40                                               
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     The foregoing flavor is added to smoking tobacco at the rates of 0.10%, 0.20% and 0.30% based on the weight of dried tobacco. The tobacco is then manufactured into cigarettes according to standard manufacturing practice. The purpose of the 3-phenyl-4-pentenaldiethylacetal is to cause the tobacco on smoking to have a hay, clover-like flavor with fruity notes. The purpose of the 2-(2&#39;-methyl-n-propyl)-4,5-dimethyl-Δ 3  -thiazoline (at concentrations based on the dry weight of tobacco of 200 ppm) is to act to supply strong, intense long-lasting &#34;Bright&#34; notes to the previously blended tobacco flavor formulation. The purpose of the use of the 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone isomer mixture is to add more body and more aroma to the tobacco adding burley and black tobacco notes rather than Virginia notes. In addition, coffee/caramel, cocoa and licorice nuances are added to the taste of the tobacco as well as its aroma on smoking. The level of the 5-acetyl-2-(furfurylthio)dihydro-2,5-dimethyl-3-[2H]furanone in the cigarettes is, respectively, 10 ppm, 20 ppm and 30 ppm. 
     EXAMPLE XIV 
     PREPARATION OF 2,5-DIETHYL-4-METHYL-5-PROPIONYL-2-(FURFURYLTHIO)DIHYDRO-3 [2H]FURANONE ##STR44## 
     Into a 5 liter reactor equipped with a stirrer, thermometer, reflux condenser and cooling coils are placed the following ingredients: 
     3,4-hexandione: 320 grams 
     water: 3200 ml 
     The resulting mixture is cooled to 3° C and over a period of 20 minutes is added a mixture of 544 grams of KOH dissolved in 1600 ml water. Subsequent to the addition of the KOH solution, 85 grams of 50% sulfuric acid is added to the mixture to bring the pH to 5. 10 ml concentrated hydrochloric acid is then added to bring the pH to 1.5. The reaction mass is then heated to 95° C and refluxed for a period of 6 hours. At the end of the 6 hour period 50 grams of 30% sodium hydroxide solution is added bringing the pH to 6. 1600 grams of sodium chloride is added thereby rendering the resulting mixtures saturated with sodium chloride. The mixture is then extracted with four 200 ml portions of methylenedichloride and then the extracts are dried over anhydrous sodium sulfate. The methylenedichloride is stripped at atmospheric pressure to 80° C and the resulting oil is distilled through a  6 inch Vigreux Column followed by redistillation through the same column to yield the dimer of 3,4-hexanedione. 
     Into a 250 ml reactor equipped with stirrer, thermometer, heating mantle and reflux condenser is placed 20 grams (17.7 ml) furfuryl mercaptan, 10 ml tetrahydrofuran and 0.5 ml concentrated hydrochloric acid. The resulting mixture is heated to 50° C and, over a 10 minute period is added 35 grams of the dimer of 3,4-hexanedione dissolved in 20 grams tetrahydrofuran. The separatory funnel from which this material is added is then rinsed out with an additional 20 ml tetrahydrofuran which is then added to the reaction mass. The reaction mass is then stirred for a period of 5 hours at 50° C with GC samples taken each hour. 20 ml Saturated sodium bicarbon solution is then added and the reaction mass is transferred to a separatory funnel containing 100 ml water. The oil phase is separated from the aqueous phase. The aqueous phase is then extracted with one 30 ml portion of methylenedichloride and combined with the oil phase. The combined oil phase is then dried over anhydrous sodium sulphate and filtered. The methylenedichloride is stripped at atmospheric pressure to 80° C and the resulting product is distilled through a micro Vigreux column. NMR, IR and Mass Spectral Analyses confirm that the resulting product has the structure: ##STR45##