GB1596251A - Alpha-oxy (oxo) sulphides ethers and mercaptan compounds and their use in food and perfume compositions - Google Patents

Description

PATENT SPECIFICATION

( 11) 1 596 251 ( 21) Application No 36255/77 ( 22) Fil E ( 31) Convention Application No's 723529 723535 723534 730535 730537 730538 ( 33) United States of America (US) ed 30 Aug 1977 ( 32) Filed 15 Se Sep.

Sep.

7 Oct.

7 Oct.

7 Oct.

( 44) Complete Specification Published 26 Aug 1981 ( 51) INT CL 3 C 07 C 149/14 A 23 L 1/226 A 61 K 7/46 C 07 C 49/17 149/26 149/32 153/017 Cll D 3/50 9/44 // C 07 C 49/16 49/80 49/413 ( 52) Index at Acceptance C 2 C1182 200 209 20 Y 220 225 226 227 22 Y 30 Y 313 31 Y 338 339 351 353 355 360 362 364 366 368 36 Y 371 373 37 Y 386 388 390 440 500 Y 553 612 613 623 624 625 628 635 655 699 771 803 80 Y AA QQ QT QU QZ UF UP UU UV A 2 B411 601 603 604 611 613 614 615 616 620 621 625 660 BCC A 2 C 20 HX A 5 BFD C 5 D 6 B 12 A 6 B 12 B 1 6 B 12 B 2 6 B 12 E 6 B 12 G 6 6 B 12 H6 B 136 B 46 B 86 C 66 C 8 ( 54) IMPROVEMENTS IN OR RELATING TO ALPHA-OXY(OXO) SULFIDES, ETHERS AND MERCAPTAN COMPOUNDS AND THEIR USE IN FOOD AND PERFUME COMPOSITIONS ( 71) We, INTERNATIONAL FLAVORS & FRAGRANCES INC, a Corporation of the State of New York, of 521 West 57th Street, New York, N Y 10019, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-

The invention pertains to a genus of alpha-oxy(oxo) sulfides, ethers and mercaptan compounds represented by the structure:

-R 1 ' - _ z wherein Q is:

0 -Cor OH CH p.

_, ( 19) 1976 1976 1976 1976 1976 1976 in 2 1 9 5 Z is sulfur or oxygen; when R 1, R 2, R,, and R 2 are taken separately, R 1 and R' are each the same or different and are each hydrogen or C 1-C 3 alkyl, and R 2 and R 2 are each the same or different and are each hydrogen or methyl; when R 1 and R 2 and R, and R are taken together with the carbon atoms to which they are attached, R 1 and R 2 and R, and R 2 form phenyl moieties; or when Z is sulphur, R 1 and R, are optionally taken together to complete 5 a cyclododecyl group; and Y is hydrogen, C 1-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethacetonyl; with the proviso that Y is hydrogen when either (i) R 1 and R, are jointed to complete a cyclododecyl ring, and Q is O 10 11 -C15 and R 2 and R 2 are each hydrogen; or (ii) R 2 and R 2 are each hydrogen; R 1 is ethyl and R, is propyl; and Y is not hydrogen when R 1 and R, are each hydrogen and R 2 and R 2 are both hydrogen or both methyl and Q is _ _ 20 0 II 11 C _ 25 Preferably Y is not hydrogen when Z is oxygen Individual members of this genus or combinations thereof are useful, interalia, for augmenting or enhancing the aromas or tastes of foodstuffs, chewing gums, medicinal products, tobaccos, chewing tobaccos, 30 flavoring compositions therefor, perfume compositions, colognes and perfumed articles such as soaps, cosmetic powders and detergents All of the alpha-oxy(oxo) sulfides and ethers as well as a plurality of mercaptans of the afore-stated genus are novel compounds in their own right.

The afore-stated alpha-oxy(oxo)sulfides and ethers are obtained by reacting an alkanone 35 with SO 2 C 12 to form an alpha-chloroketone; or they may be reacted with another halogenating agent to form an alpha-halo ketone; then reacting the alphahaloroketone with either an alkali metal mercaptide or an alkali metal alkoxide (depending on whether Z is sulfur or oxygen) to form either an alpha-oxo sulfide mercaptide or alpha-oxo ether which can be used for its food flavor properties; or, if desired, reacting the resulting alpha-oxo 40 sulfide or alpha-oxo ether with a reducing agent such as an alkali metal borohydride in order to obtain an alpha-oxy sulfide or an alpha-oxo ether Thus, the aforementioned reaction sequence is illustrated as follows:

1 596 251 _ 3 1 596 251 3 5 Z\y 10 wherein X is a halogen, M is an alkali metal, Z is sulfur or oxygen; where R 1, R,, R 2 and R 2 are taken separately, R 1 and R' are each the same or different and are each hydrogen or Cl-C 3 alkyl, and R 2 and R 2 are each the same or different and are each hydrogen or methyl; and when R 1 and R 2 and R, and R 2 are taken together with the carbon atoms to which they 15 are attached they form, phenyl moieties; or when Z is sulfur R 1 and R 2 can be joined to complete a cyclododecyl ring; and Y is hydrogen, C 1-C 4 alkyl or acetyl, with the proviso that Y is hydrogen, when either (i) R 1 and R, are joined to complete a cyclododecyl ring and the final reducing step is not carried out and R 2 and R 2 are each hydrogen, or (ii) R 2 and R 2 are each hydrogen, R 1 is ethyl and R; is propyl, and Y is not hydrogen when R 1 and 20 R; are each hydrogen and R 2 and R 2 are both hydrogen or both methyl and the final reducing step is not carried out.

The reaction between the SO 2 C 12 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 C 12 is preferably added to the ketone At the end of the reaction, the reaction mass is worked up, the chlorinated ketone 25 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 30 chlorinated ketone is preferably contained in an inert solvent, e g, in a 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 35 evaporation and distillation techniques or GLC trapping whereby the alphaoxo sulfide or alpha-oxo ether (as the case may be) is recovered The resulting alpha-oxo sulfide or ether is then used ("as is") 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 40 temperature of between 20 C and 35 C A solution in anhydrous ethanol of the alpha-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 p H of between 2 and 3 and then extracted with an 45 inert extraction solvent such as methylene chloride The methylene chloride extract is then dried, evaporated, and the resulting alpha-oxy sulfide or ether is distilled in vacuo or isolated by GLC trapping.

Alternatively, the alpha-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 50 the corresponding alpha-mercapto-ketone or alpha-hydroxy-ketone The alphamercaptoketone or alpha-hydroxy-ketone may then, if desired, be reacted with base (e g, sodium methoxide) to form the alkali metal salt The alkali metal salt of the alpha-mercapto-ketone or alpha-hydroxy-ketone is then reacted with a halide (e g, methallyl chloride) thereby forming the desired alpha-oxo sulfide or alpha-oxo ether which may then, if desired, be 55 used as such for its organoleptic properties, or it can be reduced with reducing agent (e g, sodium borohydride) to the corresponding alpha-oxy sulfide or alpha-oxy ether This reaction sequence is illustrated as follows:

1 596 251 4 1 596 251 4 à=_ -Rl 0 R 1 v R _ _ X / Ij / I R 2 z Y 1 wherein M is an alkali metal; Z is oxygen or sulphur; X is a halogen; Y 1 is C 1-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl or 1,3-diethylacetonyl; when R, , R', R 2 and R' are taken separately, R, and R' are the same or different and each is hydrogen or methyl, and R 2 and R 2 are each the same or different, and are each methyl; and when the pairs of moieties R, and R 2, and R{ and R 2 are taken together with the carbon atoms to which they are attached, R, and R 2, and R, and R 2 each form phenyl moieties, or when Z is sulfur, and the last two reactions are not carried out R, and R' can be taken together complete a cyclododecyl ring, with the proviso that when R, and R' are hydrogen and R 2 and R' are methyl and Z is sulphur, the alpha mercapto ketone is reacted with base and the resulting salt reacted with the halide Specific examples of a-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):

1 596 251 R 2 1 596 251 TABLE I

Compound 3-methylthio-4heptanone 3-propylthio-4heptanol Structure OH 3-isobutylthio-4heptanone Flavor property Green, piney, Neroli-like fruity, blackcurrant, bucchu-like and concord grape aroma characteristic and a sweet, fruity blackcurrant, concord grape-like, minty and astringent flavor characteristics at 1 0 ppm "Violet leaves," melon, cucumber, green, fruity, vegetable and floral aroma characteristics with violet leaves, melon, cucumber, green, citrus, vegetable, garlic flavor characteristics with a lasting mouthfeel.

Sweet/floral, citrus, fruity, neroli, bergamot, jasmin aroma characteristic with a green/floral, minty, petitgrain, fruity, citrus, sulfury flavor characteristic at 2 ppm.

Sweet, floral, jasmin and berry-like aroma characteristic with sweet/floral, jasmin, grapefruit and blackcurrant flavor characteristic at 2 ppm.

3-propylthio-4heptanone 3-(methallylthio)-2,6dimethyl-4-heptanone S Citrus, grapefruit, floral, celery stalk-like rosey aroma characteristic with citrus, grapefruit, floral, spicey, green/fruity, astringent flavor characteristic at 2 ppm.

1 596 251 TABLE I (cont) Compound 3-crotylthio-2,6dimethyl-4heptanone 3-allylthio-2,6dimethyl-4heptanone Structure S 3 l(methoxycarbonyl)methylthiol-4 heptanone 3-methoxy-4-heptanone CH 3 Flavor property Floral, citronellal-like, citrus, grapefruit, istic and a citrus, grapefruit, corianderlike flavor characteristic at 3 ppm.

A sweet, grapefruit, floral, citrus, green/ spicey, neroli-like aroma characteristic with a sweet, citrus, floral/ green, citronellal-like, "decaying fruit-"like flavor characteristic at 4 ppm.

At 10 ppm, a sweet, sulfury, nutty, meaty, cereal aroma character and a sweet, meaty, nutty, cereal flavor characteristic with an outstanding mouthfeel effect.

At 3 ppm, a sweet, fruity, gooseberry-like, grape, almond aroma character with a sweet, fruity, gooseberry-like, nutty, grape flavor character.

1-propylthio-1,3diphenyl-2propanone 1,3-diethylacetonyl) 1,3-diisopropylacetonyl) sulfide S, 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 along with the fresh onion notes.

At 10 ppm, a grapefruit, floral and woody aroma character with a sweet, sulfury, grapefruit-like, mandarin flavor characteristic and bitter nuances.

1 596 251 Compound 3-acetylthio-4heptanone TABLE I (cont) Structure Flavor property At 1 ppm a fresh fruity, blackcurrant-like, buchu leaf oil-like, aroma with meaty and sulfury nuances and a fresh fruit, blackcurrant-like flavor characteristic with an oniony aftertaste.

Furthermore, specific examples of a-oxy(oxo) sulfides and ethers produced using the afore-mentioned processes and their perfumery properties are as follows: (as set forth in Table II, below) TABLE II

Compound 3-methylthio-4heptanol 3-methylthio-4heptanone 3-propylthio-4heptanol 3-thioacetyl-2,6dimethyl-4heptanone Structure OH +S.

S No CH 3 SCH 3 CH 3 Aroma At 1 % in food grade ethanol, a sweet, green, floral, herbal, vegetative note.

At 1 % in food grade ethanol a green, minty, herbaceous note with vegetative basil notes Fatty, cucumber, onion (scallion, shallot) aroma with some green melon and floral nuances.

At 1 % in food grade ethanol, a sweet, meaty, vegetable aroma with somewhat of a grapefruit topnote.

8 1 596 251 8 Compound 3-isobutylthio-4heptanone 3-isobutylthio-2,6dimethyl-4-heptanol 3-methylthio-2,6dimethyl-4-heptanone Structure OS OH S - Aroma Evaluated at 1 % in food grade ethanol, a meaty, onion aroma with a green, spicey and peppery nuance and an underlying bergamot note.

Evaluated at 1 % in food grade ethanol, a vegetable, green, horseradish, somewhat rubbery, onion-like aroma containing notes of hyacinth and narcisse.

Evaluated at 1 % in food grade ethanol, a sweet, sulfurous, slightly floral and fruity and berry nuance.

3-(methallylthio)-2,6dimethyl-4-heptanone At 1 % in ethanol, a fruity, grapefruit, somewhat floral aroma with underlying yara neroli notes and bready, vegetative nuances.

It will be apparent that some of the above compounds may have methyl groups substituted for hydrogen in the position of the moieties R 2, R', e g the corresponding structure to 2-methylthio-4-heptanol with additional methyl groups is 3methylthio-2,6dimethyl-4-heptanol Likewise those illustrated with methyl groups such as 3-thioacetyl-2,6dimethyl-4-heptanone may have the methyl groups replaced by hydrogen to form, for example 3-thioacetyl-4-heptanone (see Table 1) Also when Z is sulphur and Y is methyl, methallyl, 1 propyl, 2-methyl-1-propyl or acetyl, the moieties R 2, R' may be the same or different, either being hydrogen or methyl.

The foregoing genus also includes the novel compositions, perfumed articles and colognes containing alpha-oxy(oxo)sulfides, ethers or mercaptans having the structure:

R 3 x@'C R 4 H $ SY S 1 596 251 1 596 251 wherein Q is one of:

OH I C 5 H OR 10 O II 15 and R 3 and R 4 are the same or different, and each of R 3 and R 4 is, in the alternative, one of methyl ethyl, 1-propyl, 2-propyl or 1-butyl; and Y is hydrogen, methyl or methallyl having 20 the structure 3 25 _ CH 2 30 1-propyl, 2-methyl-1-propyl or acetyl, with the proviso that when Y is hydrogen and Q is 0 II 35 C R 3 and R 4 are not both methyl or both ethyl and processes for manufacturing such 40 compositions, perfumed articles and colognes, 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.

Briefly, the present invention provides, interalia, the alpha-oxy(oxo) mercaptans having the structure: 45 R 3 i HQ, R 4 H 50 SH wherein R 3 and R 4 are 1-propyl, 2-propyl or 1-butyl in perfume and fragrance modifying 55 materials and perfumed articles including soaps, detergents and powders, as well as colognes.

Such a-oxy(oxo)mercaptans may be obtained by reacting an alkanone with a halogenating agent such as SO 2 C 12 to form an a-chloroalkanone; reacting the achloroalkanone with an alkali metal hydrosulfide to form an a-mercaptoalkanone which can be used for its 60 perfumery properties; and, if desired, reacting the a-mercaptoalkanone with a reducing agent such as an alkali metal borohydride in order to obtain an ahydroxymercaptoalkane.

Thus, the aforementioned reaction sequence is illustrated as follows:

1 596 251 0 O R 3 NH)H X H SO 2 CL 2 R 3 >H R 4 H H H cl 5 Cl 10 0 OH Rs H R R 3,H 1 R N-l H Na BH 4 H 15 SH SH wherein R 3 and R 4 are the same or different and are 1-propyl, 2-propyl or 1-butyl 20 The reaction between the SO 2 C 12 and ketone preferably takes place in the absence of a solvent at a temperature between 15 C and 40 C The SO 2 C 12 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 preferably reacted with sodium hydrosulfide, which is 25 pre-prepared by reaction of hydrogen sulfide with sodium methylate in methanol The chlorinated ketone is preferably contained in an inert solvent, e g, in methanolic solution.

Preferably the solution of chlorinated ketone is slowly added simultaneously with the addition of hydrogen sulfide to the sodium methylate solution at a temperature of between O C and about 10 C; preferably between O C and 4 C At the end of the reaction, the 30 reaction mass is concentrated, quenched with water, and made alkaline After insoluble products are extracted, the reaction mass is acidified to a p H of between 1 and 3 at which time it is extracted with a solvent such as methylene chloride The resulting extract is then worked up using evaporation and distillation techniques whereupon the amercaptoalkanone is recovered The resulting a-mercaptoalkanone is then used for its 35 perfumery properties; or it may be further reacted with a reducing agent such as 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 a-mercaptoalkanone is added to a solution in anhydrous ethanol of sodium borohydride The reaction is carried out over a period of time of between 2 and 10 hours 40 At the end of the reaction, the reaction mass is concentrated and is then admixed with water The resulting mixture is acidified to a p H of between 1 and 3 and is then extracted with an inert extraction solvent such as methylene chloride The methylene chloride extract is then dried, evaporated and the resulting a-mercaptoalkanol is then distilled in vacuo or isolated by GLC trapping 45 Specific examples of a-oxy(oxo)mercaptans produced using the aforementioned process and their perfumery properties are as follows (as set forth in Table III, below).

1 596 251 TABLE III

Compound 3-mercapto-4-heptanone 3-mercapto-4-heptanol Structure SH OH SH Aroma Strong, green, buchu, grapefruit character with a cassis note.

Strong, buchu, grapefruit character.

4-mercapto-5-nonanone 4-mercapto-S-nonanol I SH OH SH Green, fruity, grapefruit aroma with minty and leafy nuances.

Grapefruit aroma with green pepper nuance.

5-mercapto-6-undecanone 5-mercapto-6-undecanol 3-mercapto-2,6-di methyl-4-heptanone 3-mercapto-2,6-dimethyl-4-heptanol SH OH SH SH Grapefruit aroma with vetiver nuances.

Grapefruit, buchu oil-like aroma with minty nuances.

Powerful green, tart grapefruit aroma with concord grade nuance.

Green, fruity aroma having concord grape and grapefruit oillike nuances.

1 '1 1 596 251 The invention also encompasses novel solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefor having green, grapefruit-like, fruity, buchu leaf oil-like, floral, green vegetable and/or minty aroma characteristics and grapefruit-like, green, citrus, bitter, lemon, buchu leaf oil-like blackcurrant-like, green vegetable-like, minty and/or cooling flavor characteristics which 5 may be provided by the utilization of one or more alpha-oxy(oxo) mercaptans (also included in the first-mentioned genus) which have the more specifically defined formula:

10, 10 R R H SH 15 where Q is one of:

O 20 11 OH II -c Cl _ H _ 25 or and R 5 and R 6, taken separately, are the same and are methyl, ethyl, 1propyl or 2-propyl or R 5 and R 6 taken together, is nonylene having the structure: 30 _QC H 2) L 35 with the proviso that when Q is 40 45 R 5 and R 6 are not both ethyl or both methyl in foodstuffs, chewing gums, toothpastes, and medicinal products Various adjuvants may be included in these products.

Specifically, these alpha-oxy(oxo)mercaptans of our invention are as follows:

3-mercapto-4-heptanol; 50 4-mercapto-5-nonanol; 4-mercapto-5-nonanone; 3-mercapto-2,6-dimethyl-4-heptanone; 2-mercaptocyclododecanone-1; and 55 Such alpha-oxy(oxo)mercaptans are obtained by reacting an alkanone or a cycloalkanone with a halogenating agent such as SO 2 C 12 to form an alphachloroalkanone or an alpha-chlorocycloalkanone; reacting the alpha-chloroalkanone or an alphachlorocycloalkanone with an alkali metal hydrosulfide to form an alphaoxo mercaptan, which maybe an alpha-mercaptoalkanone or an alpha-mercaptocycloalkanone, which can 60 be used for its flavor properties; and if desired, reacting the alphamercaptoalkanone or alpha-mercapto-cycloalkanone with a reducing agent such as an alkali metal borohydride in order to obtain an alpha-oxy mercaptan, which may be an alphahydroxymercaptoalkane or an alpha-hydroxymercaptocycloalkane Thus, the aforementioned reaction sequence is illustrated as follows: 65 13 1 596 251 13 I' I R 5 C R 6 so 2 ct 2 R 5; C ICR 554 H O C % R H C -6 5 H H H i 10 , O " OH f 11 '," {t Nai BH 15 SH SH wherein Rs and R 6 taken separately, are the same and are either methyl, ethyl, 1-propyl or 20 2-propyl or R 5 and R 6 taken together is nonylene having the structure:

C H 2 25 L 30 with the proviso that when R 5 and R 6 are both methyl or both ethyl the alpha-oxo mercaptan is reduced to an alpha oxy mercaptan.

The reaction between the SO 2 C 12 and ketone preferably takes place in the absence of a solvent at a temperature of between 15 C and 40 C The SO 2 C 12 is preferably added to the ketone At the end of the reaction, the reaction mass is worked up, the chlorinated ketone 35 being distilled in vacuo.

The resulting chlorinated ketone is preferably reacted with sodium hydrosulfide, which is pre-prepared by reaction of hydrogen sulfide with sodium methylate in methanol The chlorinated ketone is preferably contained in an inert solvent, e g in methanolic solution.

Preferably the solution of chlorinated ketone is slowly added simultaneously with the 40 addition of hydrogen sulfide to the sodium hydrosulfide solution at a temperature of between O C and 10 C; preferably between O C and 4 C At the end of the reaction, the reaction mass is concentrated, quenched with water and made alkaline After insoluble products are extracted, the reaction mass is acidified to a p H of between 1 and 3 at which time it is extracted with a solvent such as methylene chloride The resulting extract is then 45 worked up using evaporation and distillation techniques whereupon the amercaptoalkanone or a-mercaptocycloalkanone is recovered The resulting amercaptoalkanone or a-mercaptocycloalkanone is then used for its flavor properties; or it may be further reacted with a reducing agent such as sodium borohydride The reaction with sodium borohydride takes place in an inert solvent such as anhydrous ethanol at a 50 temperature of between 20 C and 35 C A solution in anhydrous ethanol of the at-mercaptoalkanone or a-mercaptocycloalkanone is added to the solution in anhydrous ethanol of sodium borohydride The reaction is carried out over a period of time of between 2 and 10 hours At the end of the reaction, the reaction mass is concentrated and is then admixed with water The resulting mixture is acidified to a p H of between 1 and 3 and is 55 then extracted with an inert extraction solvent such as methylene chloride The methylene chloride extract is then dried, evaporated and the resulting amercaptoalkanol or a-mercaptocycloalkanol is distilled in vacuo or isolated by GLC trapping.

Specific examples of ac-oxy(oxo)mercaptans produced using the aforementioned process and their flavor properties are as follows (as set forth in Table IV, below) 60 1 596 251 TABLE IV

Compound 3-mercapto-4-heptanol 4-mercapto-5-nonanone 4-mercapto-5-nonanol 3-mercapto-2,6-dimethyl-4-heptanone Structure OH SH Aroma Sulfury, green aroma with grapefruit-like nuance and sulfury, grapefruit-like, green flavor with meaty nuance at 2 ppm.

Sulfury, fruity, rubbery and grapefruitlike aroma with fruity, sulfury, citrus-and grapefruit-like flavor at 0 2 ppm.

OH SH SH Sulfury and fruity aroma with sulfury, rubbery, fruity, grapefruit and bitter flavor characteristics at 0 2 ppm.

Grapefruit-like, citruslike, sulfury, pulegone mercaptan-like aroma with grapefruit-like lemon-like, citrus-like, pulegone mercaptan-like, blackcurrant-like flavor characteristics at 2 ppm.

2-mercaptocyclododecanone-1 (CH, 0 HC) H 2-mercapto-3-pentanone Floral, vegetable greens-like, minty camphoraceous, sulfury aroma with vegetable greens-like, minty, cooling, sulfury flavor characteristics at 10 ppm.

Sweet, sulfury, meaty, allium-like aroma with sulfury, roasted, grapefruitlike, meaty flavor characteristics at 0.05 ppm.

The invention also includes an edible composition comprising an edible carrier and an alpha-oxy(oxo) sulfide or ether having the structure:

1 596 251 R 1 R 1, R 2 O R 2 z "Y 10 wherein Q is:

O OH 15 11 OR l C CI 20 Z is sulfur or oxygen; when R 1 and R 2 and R, and R 2 are taken separately, R 1 and R are each hydrogen or methyl, and R 2 and R 2 are each methyl; and when the pairs of moieties R 1 and R 2 and R, and R 2 are taken together, R 1 and R 2 and R' and R 2 represent phenyl 25 moieties; and Y 1 is, in the alternative, one of C 1-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl.

Another aspect of the invention provides a perfume composition comprising at least one alpha-oxy(oxo) mercaptan having the structure:

30 R O tR SH 35 wherein R is 1-propyl, 2-propyl or 1-butyl, and Q is:

40 OH O 1 _ OR 11 C C 45 and at least one adjuvant comprising natural perfume oils, synthetic perfume oils, alcohols, 50 aldehydes, ketones, esters, nitriles or lactones.

Yet another aspect of the invention provides a perfume comprising a carrier and a compound having the structure:

55 R R Q 60 Sy wherein R is hydrogen or methyl, and Q is:

i 5 16 1 596 251 16 0 OH II 11 OR -C -C 5 and Y is miethyl methallyl having the structure:

1 ( 010 f C 3 15 CH 2 _ I-propyl 2-methyl-propyl or acetvl.

The invention also encompasses an alnpha-oxy(oxo) sulfide or elther having the structure: 20 R 1 R 1 R 1, I 25 t >" I ' I'", o>, 25 xy 30 wherein Q is O OH 35 11 OR 1 C CH 40 Z is sulfur or oxygen: when R, and R 2 are taken separately R, is hydrogen or methyl, and R, is methyl: and when R, and R 2 are taken together, R, and R 2 form phenyl moieties; and Y is Cl-C 4 alkyl C 3 or C 4 alkenyl acetyl methoxycarbonylmethyl, or 1,3diethylacetonyl 45 More specific compounds within the invention have the structure:

R R Q 50 S\ 55 wherein R is hydrogen or methyl Q is:

0 OH _ OR _ C C_ H H 1 596 251 1 596 251 and Y is methyl, methallyl having the structure:

3 5 _ CH 2 _ 10 1-propyl, 2-methyl-1-propyl or acetyl.

This invention also encompasses use as a flavourant in augmenting or enhancing the organoleptic properties of foodstuffs, chewing gums, medicinal products, or tobacco or in perfumery or perfumed articles for augmenting or enhancing the aroma thereof, of one or 15 more members of the alpha-oxy(oxo) sulphides, ethers or mercaptans having like structure:

20 7 Zsy I 25 wherein R 5 and R 6 are each the same or different, and R 5 and R 6 can be taken together or separately and when R 5 and R 6 are taken separately, each represents C 1C 4 alkyl or phenyl, and when R 5 and R 6 are taken together they complete a cyclododecyl ring; Z' is sulfur or oxygen; Y' is hydrogen, Cl-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl or 1,3-diethylacetonyl; and Q is, in the alternative, one of 30 0 OH OR O 35 C CH 40 with the proviso that when Y' is hydrogen and R 5 and R 6 are each alkyl, and Q is 0 Il_ 45 then Rs and R 6 are each C 3 or C 4 alkyl 50 Another aspect of the invention includes an organoleptically effective composition useful for affecting the sense of taste or smell comprising one or more members of a genus of alpha-oxy(oxo) sulfides, ethers or mercaptans, including the compounds claimed in one or more of claims 1-21, inclusive, having the structure:

R 5 \/Q yl Nsyi 1 596 251 wherein R 5 and R 6 are each the same or different, and R 5 and R 6 can be taken together or separately and when R 5 and R 6 are taken separately, each represents C 1C 4 alkyl or phenyl, and when R 5 and R 6 are taken together they complete a cyclododecyl ring; Z' is, in the alternative, one of sulfur or oxygen; Y is, in the alternative, one of hydrogen, C 1-C 4 alkyl,C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl or 1,3-diethylacetonyl; and Q is, in the 5 alternative, one of:

0 OH I OR 10 C CCC H _ I 15 with the proviso that when Y' is hydrogen Q is O 20 II C25 and R 5 and R 6 are alkyl, then R 5 and R 6 are C 3 or C 4 alkyl.

Another aspect of the invention resides in tobacco flavoring compositions and tobacco products having sweet, aromatic, hazelnut-like, fruity, grapefruit and/or nut-like flavors 30 and aromas prior to and on smoking which are provided by adding to tobacco flavors and/or to tobaccos themselves a compounds having the structure:

O 1 35 S 40 A specific example of the compound contemplated within the scope of our invention, and 45 their tobacco flavor properties prior to and on smoking are as follows:

TABLE V

Compound name 3-(methallylthio)-2,6dimethyl-4-heptanone Compound structure Organoleptic properties prior to smoking A sweet, fruity, grapefruitlike aroma with green and spicey nuances S I Organoleptic properties of tobacco smoke flavor Sweeter, more body and less harsh, more aromatic in aroma and taste; with excellent sweet, fruity and grapefruit-like nuances 1 596 251 20 It has been found that the tobacco additives of our invention when incorporated into tobacco products imparts a flavor and aroma both before and during smoking which many smokers consider to be desirable in smoking products However, it is pointed out that the methods for defining or characterizing the quality of a flavor or aroma in the tobacco art are almost purely subjective and different smokers may define the same flavor quite differently 5 Also as indicated in the above table, the compounds included within the scope of this invention may impart different flavors or aromas depending upon the substituents therein.

Thus, the compounds comprehended by this invention, by subjective tests, impart characteristic flavors which are desirable in tobacco products and the smoke therefrom even though the exact character thereof cannot be described on the basis of known standards 10 In accordance with this invention, one or more of the sulfides of our invention or mixtures thereof is added to tobacco or applied to a smoking article or its component parts in amounts of about 50-5,000 parts per million (ppm) based on dry weight of the tobacco product Prefcrably the amount of additive is between about 100 and 500 ppm by weight in order to provide a tobacco product having a desired flavor and aroma However, the 15 amount used will depend upon the amount of flavor and aroma desired and the particular compound or mixture thereof that is used.

The additive may be incorporated at any step in the treatment of the tobacco, but is preferably added after aging, curing and shredding and before the tobacco is formed into cigarettes Likewise it will be apparent that only a portion of the tobacco need be treated 20 and the thus-treated tobacco may be blended with other tobaccos before the cigarettes or other smoking articles are formed In such case the treated tobacco may have the additive in excess of the amounts above indicated so that when blended with other tobaccos, the final product will have the percentage within the indicated range.

The additives falling within the scope of this invention may be applied to the tobacco by 25 spraying, dipping or otherwise, utilizing suitable suspensions or solutions of the additive.

Thus, water or volatile organic solvents, such as alcohol, ether, acetone or volatile hydrocarbons, may be used as the carrying medium for the additive while it is being applied to the tobacco Also, other flavor and aroma producing additives, such as:

30 (a) Esters, for example:

Ethyl butyrate; Ethyl acetate; Ethyl valerate; Amyl acetate; 35 Phenyl ethyl isovalerate; and Methyl heptynyl carbonate; (b) Aldehydes, for example:

3-phenyl-2-pentenal; 40 3-phenyl-3-pentenal; phenyl acetaldehyde; Cinnamaldehyde; and Beta-ethyl-cinnamaldehyde; (c) Ketones, for example:

Benzylidene acetone; Acetophenone; Maltol; and Ethyl maltol; 50 (d) Acetals, for example:

3-phenyl-4-pentenal dimethyl acetal; and 3-phenyl-4-pentenal diethyl acetal (described in U S Patent 3,922,237 55 issued on November 25, 1975); 21 1 596 251 21 (e) Natural oils and extracts, for example:

Vanilla; Coffee extract; Origanum Oil; Cocoa extract; 5 Oil of cloves; Nutmeg oil; Celery seed oil; Bergamot oil; and Ylang-ylang oil 10 (f) Lactones, for example:

Delta-decalactone; Delta-undecalactone; Delta-dodecalactone; 15 Gamma-undecalactone; and Coumarin; (g) Ethers, for example:

Dibenzyl ether; 20 Vanillin; and Eugenol; (h) Pyrazines, for example:

2-Acetyl pyrazine; 25 2-Acetyl-6-methyl pyrazine; 2-Ethyl pyrazine; 2,3-Dimethyl pyrazine; 2,5-Dimethyl pyrazine; and 30 2-Ethyl-5-methyl pyrazine; (i) Pyrroles, for example:

N-cyclopropyl pyrrole; and N-cyclooctyl pyrrole; 35 (j) ( 2,6-dimethyl-2-pyrazinyl)( 2-methyl-3-furyl) sulfide as well as those additives disclosed in United States Patents Nos 2,766, 145; 2,905,575; 2,905,576; 2,978,365; 3,041,211; 2,766,149; 2,766,150; 3,589,372; 3,288, 146; 3,402,051 and 3,380,457 as well as Australian Patents 444,545; 444,507 and 444,389 may be incorporated 40 into the tobacco with the additives of this invention The foregoing compound mentioned at (j) is the subject of our copending application 8013898 (Serial No 1594260).

While this invention is principally useful in the manufacture of cigarette tobacco, it is also suitable for use in connection with the manufacture of pipe tobacco, cigars or other tobacco products Furthermore, the compounds may be added to certain tobacco substituents of 45 natural or synthetic origin and by the term "tobacco" as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substituted materials or both (e g, dried lettuce leaves and cabbage leaves).

Also, the invention has been particularly described with reference to the addition of the 50 compounds directly to tobacco However, it will be apparent that the compound may be applied to the paper of the cigarette or to the wrapper of a cigar Also, it may be incorporated into the filter tip, the packaging material or the seam paste employed for gluing the cigarette paper Thus, a tobacco product is provided which includes the specified additives and tobacco although in every instance the compound need not be admixed with 55 the tobacco as above specifically described.

One or more of the aforementioned alpha-oxy(oxo) sulfides or mercaptans is an olfactory agent and can be incorporated into a wide variety of compositions each of which will be enhanced or augmented by its sweet, green, floral, herbal, vegetative, basil-like, minty, melony, grapefruit, fruity and/or alliaceous notes and/or yara yara, neroli and/or verdima 60 nuances, or by its grapefruit oil-like and/or green fruity and/or concord grape-like and/or buchu leaf oil-like and/or minty notes.

The alpha-oxy(oxo) sulfides or mercaptans or mixtures of alpha-oxy(oxo) sulfides or mercaptans can be added to perfume compositions as pure compounds or can be added to mixtures of materials in fragrance-imparting compositions to provide a desired fragrance 65 22 1 596 251 22 character to a finished perfume material The perfume and fragrance compositions obtained according to this invention are suitable in a wide variety of perfumed articles and can also be used to enhance, modify or reinforce natural fragrance materials It will thus be appreciated that the alpha-oxy(oxo) sulfides or mercaptans of our invention is(are) useful as olfactory agent(s) and fragrance(s) 5 The term "perfume composition" is used herein to mean a mixture of compounds including, for example, natural oils, synthetic oils, alcohols, aldehydes, ketones, esters, lactones, nitriles and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance Such perfume compositions usually contain (a) the main note or the "bouquet" or foundation-stone of the 10 compositior; (b) modifiers which round-off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation and (d) top-notes which are usually low-boiling, fresh-smelling materials Such perfume compositions of our invention can be used in conjunction with carriers, vehicles, solvents, dispersants, 15 emulsifiers, surface-active agents, aerosol propellants, and the like.

In perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient Thus, one or more of the alpha-oxy (oxo) sulfides or mercaptans of our invention can be used to alter, augment, modify or enhance the aroma characteristics 20 of a perfume composition or a perfumed article, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient of the composition.

The amount of one or more of the alpha-oxy(oxo)sulfides or mercaptans of our invention which will be effective in perfume compositions depends upon many factors, including the other ingredients, their amounts and the effects which are desired It has been found that 25 perfume compositions containing as much as 2 % or as little as O 005 % by weight of the compounds of this invention or mixtures thereof, or even less, can be used to impart a buchu leaf oil-like aroma or a grapefruit oil-like aroma to soaps, cosmetics and other products The amount employed will depend upon considerations of cost, nature of the end products, the effect desired in the finished product, and the particular fragrance sought 30 One or more of the alpha-oxy(oxo)sulfides or mercaptans of our invention as disclosed herein can be used alone, in a fragrance modifying composition, or in a perfume composition as an olfactory component in detergents (anionic detergents, cationic detergents, and nonionic detergents) and soaps; space deodorants; perfumes; colognes, bath preparations such as bath oil, bath salts; hair preparations such as lacquers, 35 brilliantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun screens; powders such as talcs, dusting powders or face powders When one or more of the alpha-oxy(oxo)sulfides or mercaptans of our invention is used in perfumed articles such as the foregoing, it can be used in amounts of 0 01 % or lower.

Generally, it is preferred not to use more than about 2 % in the finished perfumed article, 40 since the use of too much will tend to unbalance the total aroma and will needlessly raise the cost of the article.

When the alpha-oxy(oxo)sulfide, ether or mercaptan compound or compounds of our invention are used as food flavour adjuvants, or are used to augment or enhance the flavor or aroma characteristics of foodstuffs, the nature of the co-ingredients included with the 45 said alpha-oxy(oxo)sulfide, ether or mercaptan in formulating the product composition will also serve to augment the organoleptic characteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the term "augment" in its various forms means "supplying or imparting flavor character or note to otherwise bland, relatively tasteless 50 substances or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard supplementing the existing flavor impression to modify its quality, character or taste " As used herein in regard to food flavors, the term "enhance" is used herein to mean the intensification of a flavor or aroma characteristic or note without the modification of the 55 quality thereof Thus, "enhancement" of a flavor or aroma means that the enhancement agent does not add any additional flavor note.

As used herein the term "foodstuff" includes both solids and liquids, and ingestible materials or chewable but non-ingestible materials such as chewing gum Such materials usually do but need not, have nutritional value Thus, foodstuffs include soups 60 convenience foods, beverages, gelatin desserts, dairy products, candies, vegetables, cereals, soft drinks and snacks.

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 It is required that any such material be "ingestibly acceptable," and thus non-toxic or otherwise 65 23 1 596 251 23 non-deleterious, particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material does not cause the consumable material to have unacceptable aroma and taste nuances.

It is a further requirement that such material be organoleptically compatible with the foodstuff with which it is used so that the flavor and aroma nuances of such material, taken 5 together with the flavor and aroma nuances of the foodstuff (as a whole) give rise to a harmoniously aesthetically pleasing aroma and taste profile Such materials, in general, may be characterized as flavoring adjuvants or vehicles comprising broadly, stabilizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e g, sodium chloride; antioxidants, e g, 10 calcium sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2 and 3 tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene ( 2,6-ditertiary-butyl-4-methyl phenol), and propyl gallate and sequestrants, e g, citric acid.

Thickener compounds include carriers, binders, protective colloids, suspending agents and emulsifiers, e g, agaragar, carrageenan; cellulose and cellulose derivatives such as 15 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, skimn milk powder, hexoses, pentoses, disaccharides, e g, sucrose and corn syrup.

Surface active agents include emulsifying agents, e g, fatty acids such as capric acid, 20 caprylic acid, palmitic acid and myristic acid, mono-and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate and hydrogenated tallow alcohol.

Conditioners include compounds such as bleaching and maturing agents, e g, benzoyl peroxide, calcium peroxide and hydrogen peroxide; starch modifiers such as peracetic acid, 25 sodium chlorite, sodium hypochlorite, propylene oxide and succinic anhydride, buffers and neutralizing agents, e g, sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid and vinegar; colorants, e g, carminic acid, cochineal, tumeric and curcuma; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e g, aluminum calcium sulfate and tribasic 30 calcium phosphate; enzymes; yeast foods, e g, calcium lactate and calcium sulfate; nutrient supplements, e g, iron salts such as ferric phosphate and ferrous gluconate, riboflavin, vitamins, zinc sources such as zinc chloride and zinc sulfate.

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 35 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, nbutanal, crotonal, diacetyl, beta, beta-dimethyl-acrolein, n-hexenal, 2-hexanal, cis-3hexenal, 2-heptanal, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone, methyl-3butanone, 2 40 pentanone, 2-pentenal and propanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2hexenol-1, cis-3hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol, phydroxyphenvl-2-ethanol, isoamyl alcohol, isofenchyl alcohol, phenyl-2-ethanol, aloha-terpineol, cis-terpineol hydrate; esters, such as butyl acetate, ethyl acetate, eth'yl acetoacetate, ethyl benzoate, ethyl 45 butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyl alpha-methylbutyrate, et'yl propionaie, ethyl salicylate, trans-2hexenyl acetate, hexyl acetate, 2-hexenyl butvrate, he yl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl caproate, me:hyl isobutyrate, alpha-methylbutyrate, propyl acetate, amyl acetate, arryl butvrate, benzyl salicylate, 50 dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutyl cinnamate and terpenyl acetate; essential oils, such as jasmine absolute, rose absolute, orris absolute, lemon essential oil, Bulgarian rose, yara yara, natural raspberry o O l and vanilla; lactones; sulfides, e g, methyl sulfide and other materials such as maltol, pulegone mercaptan, a-phellandrene, ethyl maltol, 2,2,4,4,6,6-hexameth-1-S-trithiane, acetoin and acetals, 55 (e.g, 1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane) The specified flavoring adjuvant selected for use may be,ither 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 alpha-oxy(oxo)sulfides, ethers or mercaptans can be dispersed or admixed to provide a 60 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 compo'itions ingredient selection will vary in accordance with the foodstuff to which the flavor ani aroma are to be imparted In contradistinction, in the preparation of solid products, e g, simulated foodstuffs, 65 24 1 596 251 24 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 alphaoxy(oxo)sulfides, ethers or mercaptans employed in a particular instance can vary over a relatively wide range whereby to its desired organoleptic effects having reference to the nature of the product are 5 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 10 composition, whether foodstuff per se or flavoring composition.

The use of insufficient quantities of alpha-oxy(oxo)sulfides, ethers or mercaptans 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 "effective amount" and 15 "sufficient amount" is to be accorded a significance in the context of the present invention consistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, it is found that quantities of alpha-oxy(oxo)sulfides, ethers or mercaptans 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 20 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 alpha-oxy(oxo)sulfides, ethers or mercaptans are added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that 25 the total quantity of flavoring composition employed by sufficient to yield an effective alpha-oxy(oxo)sulfide, ether or mercaptan concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the present invention preferably contain the alpha-oxy(oxo)sulfides, ethers or mercaptans in concentrations ranging from about 0 1 % up to about 15 % by weight based on the total weight of said 30 flavoring composition, and in some cases more particularly from 0 05 % to 5 % by weight.

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 35 compositions in the form of particulate solids can be conveniently prepared by mixing the alpha-oxy(oxo)sulfides, ethers or mercaptans with, for example, gum arabic, gum tragacanth or carageenan, and thereafter spray-drying the resultant mixture whereby to obtain the particular solid product Pre-prepared flavor mixes in powder form, e g a fruit-flavored powder mix, are obtained by mixing the dried solid components, e g, starch 40 or sugar, and alpha-oxy(oxo)sulfides, ethers or mercaptans in a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the alpha-oxy(oxo)sulfides, ethers or mercaptans the following adjuvants:

45 p-Hydroxybenzyl acetone; Geraniol; Acetaldehyde; Maltol; Ethyl methyl phenyl glycidate; 50 Benzyl acetate; Dimethyl sulfide; Vanillin; Methyl cinnamate; Ethyl pelargonate; 55 Methyl anthranilate; Isoamyl acetate; Isobutyl acetate; Alpha ionone; Ethyl butyrate; 60 Acetic acid; Gamma-undecalactone; Naphthyl ethyl ether; Diacetyl; Ethyl acetate; 65 1 596 251 25 Anethole; Isoamyl butyrate; Cis-3-hexenol-1; 2-Methyl-2-pentenoic acid; Elemecine ( 4-allyl-1,2,6-trimethoxy benzene); 5 Isoelemecine ( 4-propenyl-1,2,6-trimethoxy benzene); 2-( 4-hydroxy-4-methylpentyl) norbornadiene; Natural blackcurrant juice; Buchu leaf oil; ca-phellandrene; 10 Cis-3-hexen-l-ol; Terpinenol-4; Ethyl maltol; Methyl benzoate; Benzaldehyde; 15 Coriander oil; Ethyl heptanoate; Limonene; n-octanal; n-decanal; 20 geraniol; cadinene; dimethyl anthranilate; Ethyl anthranilate; Cinnamic alcohol; 25 Amyl valerinate; Cinnamyl propionate; Rhodinyl acetate; Methyl P-hydroxy butyrate; Ethyl 3-hydroxy butyrate; 30 2-phenyl-3-carboethoxyfuran; Cyclohexyl disulfide; Grapefruit oil; Vanillin; Amyl butyrate; 35 Nootkatone; Bergamot oil; Citral; Amyl alcohol; 5-phenyl-4-pentenal; 40 5-phenyl-2-pentenal; Allyl caproate; 2-(n-pentyl) thiazole; 2-(i-butyl) thiazole; 2-(i-propyl) thiazole; 45 2-(n-propyl) thiazole; 2-phenyl-4-pentenal; 2-phenyl-4-pentenaldimethylacetal; Methional; 4-methylthiobutanal; 50 2-ethyl-3-acetylpyrazine; Tetramethyl pyrazine; 2-methyl pyrazine; trans-2-hexenal; Hydrolyzed vegetable protein; 55 Monosodium glutamate; Dimethyl disulfide Methyl propyl disulfide; Methyl propenyl disulfide; Methyl allyl disulfide; 60 Allyl propyl disulfide; Propyl propenyl disulfide; Dipropyl disulfide; Diallyl disulfide; Propyl propenyl trisulfide: 65 26 1 596 251 26 Thiopropanol-S-oxide; Thiobutanal-S-oxide; Thioethanal-S-oxide; Thiohexanal-S-oxide; and Propyl propene thiosulfonate 5 2-phenyl-4-pentenal diethyl acetal 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 10 The following are trade marks:

Primol, Shop-Rite Carbowax and Cab-O-Sil.

EXAMPLE I

Part (A) Preparation of 3-chloro-4-heptanone 15 Reaction:

0 O -l-502 Ct, + so 2 t 20 c + HCL CL 25 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 1000 g 4heptanone Addition of 30 434 g of SO 2 C 12 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 Na OH solution.

The reaction mass is periodically sampled using GLC analysis until such time as about 35 % mono 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 p H 40 of about 1 The upper organic phase is washed with 700 ml saturated sodium bicarbonate solution to a p H 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 94 % chlorinated ketone and 68 12 % original ketone starting material This material is then vacuum distilled by first adding it to a 2000 ml, three-necked, 45 round-bottom flask equipped with a 2 5 x 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 50 (mm Hg) 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 55 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 60 103 94 144 5 g 9 30:70 54 110 95 85 0 g 10 30:70 54 119 102 28 0 g 11 30:70 140 80 45 0 g 12 30:70 Cut No Percent low Boilers 0.09 6 7 8 9 11 Percent 4Heptanone 96.15 % 9 28 trace Percent 3-Cl 4-Heptanone 2.97 % 87.09 95.78 91.38 69.14 8.32 Percent High Boiler (A) 2.43 3.22 4.89 7.27 2.07 Percent High Boiler (B) 0.57 1.00 3.34 19.88 49.28 Percent High Boiler (C) 0.21 3.71 39.69 Percent High Boiler (D) 0.47 8.1 w E n CM p W O P) a-h n 0 0 j M,.o A 4:

Gn oo OR x :A.z cn m 0 0 < 0 D 4 h 28 1 596 251 28 Cuts 8, 9 and 10 are blended (weight 266 5 gms) and are analyzed by GLC as follows:

0.95 % 4-heptanone 93.89 % 3-chloro-4-heptanone 3 60 % high boiler A 5 1.57 % high boiler B Part (B) Preparation of 3-mercapto-4-heptanone Reaction: 10 0 0 No HS, 15 Cl SH Into a 50 ml, three-necked, round-bottom flask, equipped with magnetic stirrer, pot 20 thermometer, six inch distillation column with gas outlet at top attached to rubber tubing leading above stirring solution of 10 % sodium hydroxide solution, gas inlet tube (for hydrogen sulfide bubbling), gas bubbler, empty trap between hydrogen sulfide cylinder and bubbler, hydrogen sulfide cylinder, and isopropanol/dry-ice bath, is added a solution of 1 62 g sodium methoxide dissolved in 13 5 ml anhydrous methanol The sodium methoxide 25 solution is cooled to -10 C and the hydrogen sulfide bubbling is commenced below the surface of the sodium methoxide solution The reaction is maintained at a temperature of -5 C to -10 C, while continuing the hydrogen sulfide bubbling and stirring the reaction mass for a period of 1-1/2 hours At this point 5 ml of the cold sodium hydrosulfide solution is transferred to a 25 ml Erlenmeyer flask equipped with magentic stirrer, dry nitrogen flow, 30 pot thermometer and isopropanolldry-ice bath At -4 C to O C, 0 75 g ( O 005 moles) of 3-chloro-4-heptanone is added dropwise over one minute using a pipette After all of thechlorinated ketone is added, a heavy solid precipitate forms which is stirred at O C for 15 minutes, then allowed to warm to 23 C over an additional 50 minute time period About 4 ml of 10 % sodium hydroxide solution is then added to the reaction mass while stirring 35 under a nitrogen blanket Unreacted chloro ketone is extracted with 7 ml of methylene chloride and separated The basic aqueous phase is acidified to a p H of 2 with 10 % aqueous hydrochloric acid The oil out is extracted twice with 10 ml methylene chloride The methylene chloride extracts are combined, washed with saturated sodium chloride solution, dried and concentrated to yield 0 55 gms of product GLC, IR and NMR analyses of 40 trapped product yield the information that the product is 3-mercapto-4heptanone.

The NMR spectrum is set forth in Figure 1 The infra-red spectrum is set forth in Figure 2.

1 596 251 The NMR analysis is as follows: O II 1.04 ppm (t) CH 3-C-C-C5 O O 6 H II 1.00 (t) CH 3-C-C-Ci S 10 -CH 22.20-1 40 (m) 5 H -SH 15 0 11 2.62 (m) -CH 2-C 2 H 20 3.26 (m) O=C-CH-S 1 H The infra-red analysis is as follows:

1130 cm-1, 1360, 1370, 1400, 1450, 1705, 2540, 25 2870, 2930, 2960.

Part (C) Preparation of 3-mercapto-4-heptanol Reaction:

30 0 OH Nc BH 4 35 SH SH 40 Into a 25 ml, round-bottom flask, equipped with magnetic stirrer, nitrogen inlet tube, gas outlet tube, dry-ice/acetone bath and reflux condenser is added 2 5 ml of a 95 % ethanolic solution containing 0 06 gms of sodium borohydride ( 0 0015 moles) While maintaining the reaction mass at a temperature of between 25 C and 35 C over a period of about 5 minutes, 45 0.44 gins ( 0 003 moles) of 3-mercapto-4-heptanone in 95 % ethanol ( 2 5 ml) is added to the sodium borohydride solution During this time, the reaction mass is stirred under a blanket of dry nitrogen.

The reaction mass is then continued to be stirred for a period of three hours at which time the reaction mixture is concentrated on a rotary evaporator using water aspirator vacuum to 50 3 ml of a thick slurry To the slurry is added 10 ml water with stirring, and the solid then dissolves The aqueous solution is then acidified to a p H of 6 with 4 % aqueous hydrochloric acid, at which time the reaction mass exists in two phases; an aqueous phase and an organic phase The organic phase is extracted with two 10 ml portions of methylene chloride The extracts are combined, dried over anhydrous sodium sulfate, gravity filtered and 55 concentrated on a rotary evaporator to yield a yellow oil weighing 0 3 gms GLC analysis (conditions: 8 ' x 1/4 " SE-30 column) indicates 96 3 % 3-mercapto-4heptanol NMR and IR analyses of trapped product confirm the structure of this material.

The NMR spectrum is set forth in Figure 3 The IR spectrum is set forth in Figure 4.

1 596 251 30 The NMR analysis is as follows:

1.28-0 92 CH 3 + -SH 7 H 1 48 (m) -CH 2 6 H 5 1.96 (s) OH 1 H 2.74 (m) HC-S 1 H 10 3.58 (m) HC-O 1 H The infra-red analysis is as follows:

1000 cm-1, 1050, 1070, 1110, 1130, 1280, 1370, 1450, 2540, 2860, 2920, 2950, 3400 15 EXAMPLE II

Part (A) Preparation of 4-chloro-5-nonanone Reaction: 20 CL SO 2 C 12 25 30 Into a 250 ml, three-necked, round-bottom flask, equipped with magnetic stirrer, six inch Vigreux column (with gas outlet to vacuum), cold water bath, pot thermometer, water aspirator vacuum and 50 ml addition funnel are placed 99 gms of 5nonanone 31 6 gms ( 18 7 ml; 0 234 moles) of SO 2 C 12 are added dropwise from the addition funnel over a period of one hour while maintaining the reaction mass at a temperature of between 24 C and 35 27 C Water aspirator vacuum is applied to the reaction flask while stirring, in order to remove acidic gases.

The reaction mass is then warmed to 30 C and evaporated on a rotary evaporator.

The weight of crude material is 108 gms and contains 73 % nonanone, and 21 4 % of 4-chloro-5-nonanone 40 A 250 ml, three-necked, round-bottom flask, equipped with magnetic stirrer, 1 3 x 30 cm distillation column, packed with 6 mm Raschig Rings, reflux head, heating mantle, pot thermometer, vacuum pump, and dry-ice/isopropanol trap is used in order to distill the chlorononanone from the reaction mass The 4-chloro-5-nonanone is then distilled at a temperature from 105 C-108 C and a pressure of 22 5-23 mm Hg yielding 16 7 gms of 45 product This material is used in Part (B), supra.

Part (B) Preparation of 4-mercapto-5-nonanone Reaction:

50 CL SH Na SH 55 Into a 250 ml, three-necked, round-bottom flask equipped with magnetic stirrer, pot 60 thermometer, six inch distillation column with gas outlet at top with rubber tubing leading above a 10 % sodium hydroxide solution, a gas inlet tube (sub-surface), a gas bubbler, an empty trap between the hydrogen sulfide cylinder and bubbler, a dryice/isopropanol bath, and a 10 ml addition funnel, the following materials are added with stirring at 25 C to 40 C:

1 596 251 31 1 596 251 31 ml anhydrous methanol 4.88 gms sodium methylate ( 0 0903 moles).

While maintaining the temperature of the reaction mass at between -5 C and -15 C addition of hydrogen sulfide is commenced, bubbling the hydrogen sulfide below the 5 surface of the reaction mass The hydrogen sulfide bubbling is continued for a period of two hours at which time it is ceased and addition of the 4-chloro-5-nonanone produced in Example I (A), supra, is commenced The 4-chloro-5-nonanone is added over a period of minutes while maintaining the reaction mass at a temperature of between 9 C and -10 C 10 The reaction mass is then stirred at O C, while hydrogen sulfide addition continues for a period of one hour.

The reaction mass is then concentrated to a yellow solution containing a white solid precipitate on a rotary evaporator to 15 ml 35 ml water is then added with stirring followed by 35 gmins of a 10 % aqueous sodium hydroxide solution Stirring is continued for a period of 15 minutes while maintaining the resulting mixture at a temperature of between 24 C and 27 C The resulting basic aqueous solution is then extracted with two portions ( 35 ml each) of methylene chloride and the extracts are combined, dried, and concentrated yielding an oil weighing 1 1 gmins The aqueous solution is then acidified to a p H of 1-2 using 42 ml, 10 % hydrochloric acid while being cooled to 25 -30 C It is then extracted with four 25 ml 20 portions of methylene chloride and the extracts are combined, and washed with two 30 ml portions of saturated sodium chloride The methylene chloride extracts are dried over anhydrous sodium sulfate, gravity filtered, and concentrated on a rotary evaporator to yield a light yellow oil having a weight of 6 6 gms.

GLC, IR and NMR analyses yield the information that this light yellow oil contains 25 94.36 % 4-mercapto-5-nonanone.

The NMR spectrum is set forth in Figure 5 The infrared spectrum is set forth in Figure 6.

The NMR analysis is as follows:

30 0.94 ppm (t) CH 3-CH 2 6 H 1.72 (d) SH 35 2.04-1 18 (m) -CH 2 9 H 0 II 2 60 (m) -CH 2-C 2 H 40 0 Il 3.32 (m) -C-HC-S 1 H 45 The infra-red analysis is as follows:

1040 cm-l, 1150, 1355, 1375, 1400, 1430, 1460, 1700, 2250, 2870, 2960.

50 Part (C) Preparation of 4-mercapto-5-nonanol Reaction:

SH SH 0,a Na BH 4 0 H 32 1 596 251 32 Into a 25 ml, round-bottom, three-necked flask, equipped with magnetic stirrer, pot thermometer, reflux condenser and nitrogen inlet tube is added 0 066 gmins of sodium borohydride dissolved in 3 ml ethyl alcohol Under nitrogen, 0 554 gms of 4-mercapto-5nonanone produced according to the process of Example II (B) is dissolved in 2 5 ml of anhydrous ethanol and the resulting solution is added by pipette to the sodium borohydride 5 solution over a period of four minutes at 23 C to 34 C The reaction mass then cools to 25 C and is maintained at a temperature of from 23 C-25 C for a period of one hour.

GLC analysis indicates that 74 4 % of 4-mercapto-5-nonanol is formed at this point An additional 0 033 gmins of sodium borohydride in 1 5 ml ethyl alcohol is added and the reaction mass is stirred for three hours 10 The reaction mass is concentrated on a rotary evaporator (using water aspirator vacuum) to a volume of about 3 ml and a thick slurry is obtained 7 ml of water is then added and the solid dissolves yielding a turbid and oily liquid having a p H of about 10 The reaction mass is then neutralized to a p H of between four and five with 35 drops of a 10 % aqueous HCI solution The reaction mass is then extracted with two 10 ml portions of methylene chloride 15 and the extracts are combined, washed with 3 ml water and then dried over anhydrous sodium sulfate The methylene chloride solution is gravity filtered and evaporated on a rotary evaporator to yield 0 44 gms of a pale yellow oil GLC analysis indicates that the resulting material is 98 2 % 4-mercapto-5-nonanol.

IR and NMR analyses confirm the structure The NMR spectrum is set forth in Figure 7 20 The infra-red spectrum is set forth in Figure 8.

The NMR analysis is as follows:

0 94 ppm (diffuse triplet) CH 3-CH 2 6 H 25 1.20 (d) SH 1 H 1.46 (broad) -CH 2 10 H 30 2.06 OH 1 H 2.80 (m) HC-S 1 H 3 54 (m) HC-O 1 H 35 The infra-red analysis is as follows:

1020 cm-', 1115, 1370, 1460, 2550, 2870, 2920, 2950, 3420.

40 EXAMPLE III

Part (A) Preparation of 5-chloro-6-undecanone Reaction:

0 0 45 s O CLC 50 Into a 250 ml, three-necked, round bottom flask, equipped with magnetic stirrer, thermometer, six inch Vigreux column, with gas outlet (vacuo) at top, cold water bath, pot thermometer, water aspirator vacuum and 50 ml addition funnel is added 100 gms of 6-undecanone 27 0 gmins ( 16 ml; 0 200 moles) of SO 2 C 12 is then added, dropwise, over a 55 period of one hour while maintaining the reaction mass at a temperature of between 25 C and 35 C At the end of the one hour period, water aspirator vacuum is applied slowly to the reaction mass in order to remove acidic gases.

106 gmins of the resulting reaction product (containing 22 5 % of 5chloro-6-undecanone) is then placed in a 250 ml, three-necked, round-bottom flask, equipped with a 2 0 x 30 cm 60 distillation column, packed with 1/8 " helices, a reflux head, a magnetic stirrer, a heating mantle, and a vacuum pump The desired product is then distilled at a temperature of between 86 C and 89 C and a pressure of 2 mm Hg Mass spectral analysis, NMR and IR analysis confirm that the resulting product is 5-chloro-6-undecanone This material is used in Example III (B), infra 65 33 1 596 251 33 Part (B) Preparation of 5-mercapto-6-undecanone Reaction:

0 O 5 Na SH 9, CL SH 10 Into a 250 ml, three-necked, round bottom flask, equipped with magnetic stirrer, pot thermometer, six inch distillation column, with gas outlet at top attached to rubber tubing 15 leading above stirring 10 % sodium hydroxide solution, gas inlet tube (for hydrogen sulfide) (sub-surface), gas bubbler, empty trap between hydrogen sulfide cylinder and bubbler, hydrogen sulfide cylinder, isopropyl alcohol dry-ice bath and 10 ml addition funnel is added 4.65 gms of sodium methoxide dissolved in 40 ml anhydrous methanol Hydrogen sulfide is then bubbled below the surface of the sodium methoxide solution while maintaining the 20 temperature between -3 C and -15 C While bubbling in hydrogen sulfide and maintaining the pot temperature at -3 C to -8 C, 5-chloro-6-undecanone ( 9 05 gms) is added dropwise to the solution over a period of 15 minutes.

Hydrogen sulfide is then continued to be bubbled into the solution for a period of one hour The reaction mass is then warmed to room temperature and concentrated on a rotary 25 evaporator (with water aspirator vacuum applied) to a pale yellow solution containing a white solid (volume: 15 ml) 35 ml of water are added to the reaction mass, with stirring, causing the solid to dissolve 35 gms of a 10 % aqueous sodium hydroxide solution is then added to the reaction mass with stirring while maintaining the temperature at 25 C The basic aqueous solution is then extracted with two 35 ml portions of methylene chloride, and 30 the methylene chloride extracts are combined, dried, and concentrated yielding 1 5 gms of an oil containing about 80 % 5-mercapto-6-undecanone.

The basic aqueous solution is then acidified with 50 ml 10 % hydrochloric acid while maintaining the temperature at 25 C 30 C The solution is then extracted with three 35 ml portions of methylene chloride and the methylene chloride extracts are combined The 35 methylene chloride extracts are then washed with two 30 ml portions of saturated sodium chloride, dried over anhydrous sodium sulfate and concentrated on a rotary evaporator to a weight of 6 7 gms.

The 5-mercapto-6-undecanone is trapped out using preparative GLC (conditions: 8 ' x 1/4 " SE-30 column, programmed at 10 C per minute; starting at 130 C) GLC, NMR and IR 40 analyses confirm that the resulting product is 5-mercapto-6-undecanone.

The NMR spectrum is set forth in Figure 9 The IR spectrum is set forth in Figure 10.

The NMR analysis is as follows:

45 0.90 ppm (t) CH 3-CH 2 6 H 1.32 (broad) -CH 213 H 1 70 (d) SH 50 0 II 2.60 (m) -CH 2-C 2 H 55 0 11 3.28 (m) -C-HC-S 1 H 60 The infra-red analysis is as follows:

1135 cm-1, 1370, 1400, 1460, 1700, 2550, 2880, 2920, 34 1 596 251 34 Part (C) Preparation of 5-mercapto-6-undecanol Reaction:

O OH 5 Na BH 4 10 SH SH Into a 25 ml, three-necked round-bottom flask, equipped with magnetic stirrer, pot thermometer, and six inch Vigreux column with cotton plug, is added 0 113 gms ( 0 003 15 moles) of sodium borohydride dissolved in 5 ml ethanol 0 61 gms of 5mercapto-6undecanone produced according to Example III (B), supra, dissolved in 2 5 ml anhydrous ethanol, is then added to the sodium borohydride-ethanol solution over a period of two minutes with stirring, while maintaining the reaction mass at a temperature in the range of between 23 C and 38 C The reaction mass is then stirred for a period of two hours while 20 the temperature of the reaction mass remains at 24 C.

The reaction mass is then concentrated on a rotary evaporator (using a water aspirator vacuum) to a volume of about 3 ml, yielding a thick slurry 9 ml water is then added to the resulting slurry with stirring and the solid dissolves (p H = 10) The resulting mixture is then acidified to a p H of between 2 and 3 using 10 % aqueous HCI The resulting mixture is then 25 extracted with two 10 ml portions of methylene chloride, and the methylene chloride extracts are combined and washed with 4 ml saturated chloride solution The washed methylene chloride extracts are then dried over anhydrous sodium sulfate, gravity filtered, and concentrated using a rotary evaporator to yield a pale yellow oil, weighing 0 38 gms and having a purity of about 99 % based on GLC analysis The resulting material is then trapped 30 out on a SE-30 column ( 8 ' x 1/4 " column), 130 C, programmed at 10 C per minute.

The NMR spectrum is set forth in Figure 11 The IR spectrum is set forth in Figure 12.

The NMR analysis is as follows:

35 0.97 ppm (t) CH 3-CH 26 H 0.91 (t) CH 3-CH 2 1 20 (d) -SH 40 H 1.44 1 32 (broad) -CH 22.04 -OH 1 H 45 2.78 (m) HC-S 1 H 3.53 (m) HC-O 1 H 50 The infra-red spectrum is as follows:

1020 cm-', 1120, 1375, 1460, 2550, 2850 2920, 3400.

EXAMPLE IV

Part (A) Preparation of 2,6-dimethyl-3-chloro-heptanone-4 55 Reaction:

0 O l-l SO 2 CL 2 _ J P 1 596 251 3 Into a one-liter, three-necked, round-bottom flask, equipped with "Ytube", pot thermometer, mechanical stirrer, 125 ml addition funnel, gas outlet tube, cold water bath, and water aspirator vacuum is placed 356 gmins of 2,6-dimethyl-4heptanone 67 5 gmins ( 0 5 moles) of SO 2 C 12 is then added to the ketone, with stirring, while maintaining the reaction mass at a temperature of between 23 C and 35 C, over a period of one hour 5 At the end of the addition of the SO 2 C 12, most of the acidic gases are removed using water aspirator vacuum The reaction mass is then transferred to a onenecked, one-liter, round-bottom flask and evaporated on a rotary evaporator using water aspirator vacuum yielding a crude product weighing 371 gmins This crude material is then transferred to a 500 ml, three-necked, round-bottom flask, equipped with a 2 0 x 30 cm column, packed with 10 1/8 " helices, reflux head, magnetic stirrer, heating mantle, and vacuum pump The 2,6-dimethyl-3-chloro-heptanone-4 is then distilled at a vapor temperature of 106 C-107 C and a pressure of 45-46 mm Hg, yielding 37 gmins of product.

Mass spectral, NMR and IR analyses confirm that the resulting material is 2,6-dimethyl3-chloro-heptanone-4 This material is used in the process of Example IV (B), infra 15 Part (B) Preparation of 2,6-dimethyl-3-mercapto-heptanone-4 Reaction:

O O 20 Na SH SH 25 Cl SH Into a 250 ml, three-necked, round-bottom flask, equipped with a magnetic stirrer, pot thermometer, six inch Vigreux distillation column with gas outlet at top leading over 200 ml 30 of a 10 % aqueous sodium hydroxide solution, a hydrogen sulfide gas inlet tube (sub-surface), a "Y-tube", a 50 ml addition funnel, gas bubbler, a dryice/isopropyl alcohol bath, and a cold water bath, is added 11 6 gmins of sodium methylate dissolved in 90 ml anhydrous methanol While maintaining the temperature at between -5 and 10 C, hydrogen sulfide bubbling is commenced and continued over a period of two hours At the 35 end of the two hour period, while continuing hydrogen sulfide bubbling, 2, 6-dimethyl-3chloro-heptanone-4 ( 18 2 gmins) is added to the solution while maintaining the reaction temperature at between -5 and -9 C The addition of the chloro ketone takes place over a period of 13 minutes Hydrogen sulfide bubbling is continued for a period of four hours while maintaining the reaction mass at temperatures of between O C and 26 C ( 25 C-26 C 40 for the last 1 5 hours).

The resulting reaction mass is then concentrated to a yellow solution containing a white solid ( 25 ml volume) on a rotary evaporator to which is applied a water aspirator vacuum.

ml of distilled water is added to the reaction product with stirring while maintaining the reaction mass at 25 C whereupon the solid dissolves yielding a turbid yellow solution 85 45 gmins of a 10 % aqueous sodium hydroxide solution is then added to the reaction mass while maintaining same at 25 C-28 C (p H = 10-11) The reaction mass is then extracted with two 70 ml portions of methylene chloride and the methylene chloride extracts are combined, dried and concentrated yielding 1 7 gmins of an oil.

The basic aqueous solution is then acidified with 115 ml aqueous 10 % hydrochloric acid 50 to a p H of between one and two The resulting acidified solution is extracted with four 50 ml portions of methylene chloride and the methylene chloride extracts are combined and washed with two 35 ml portions of saturated sodium chloride and dried over anhydrous sodium sulfate The resulting material is gravity filtered and concentrated on a rotary evaporator to yield 15 5 gmins of a pale yellow liquid containing 96 1 % 2,6-dimethyl-3 55 mercapto-heptanone-4 as confirmed by Mass spectral, NMR and IR analyses The reaction product is trapped using 8 ' x 1/4 " SE-30 GLC column, programed at 130 C, at 7 5 C/minute.

The NMR spectrum is set forth in Figure 13 The IR spectrum is set forth in Figure 14.

1 596 251 1 596 251 The NMR analysis is as follows:

0.98 methyl protons 12 H 1 62 -SH 1 H 5 2.12 methine protons 2 H O II 10 2.46 CH 2-C 2 H 3.10 HC-S 1 H 15 The infra-red analysis is as follows:

1040 cm-1, 1365, 1375, 1465, 1705, 2550, 2870, 2920, 2960.

20 13.27 gms of material produced according to this example is placed in a 25 ml, three-necked, round-bottom, equipped with a 1 6 x 15 cm Vigreux column, equipped with a magnetic stirrer, reflux head, heating mantle and vacuum pump The material is distilled at a vapor temperature of 77 5 C-78 C and a vacuum of 6 mm Hg, and the thus-distilled material has the same physical properties as set forth above, for 2,6dimethyl-3-mercapto 25 heptanone-4.

Part (C) Preparation of 2,6-dimethyl-3-mercapto-heptanol-4 Reaction:

30 0 OH j 4 bb BH 4 35 SH Into a 25 ml, round-bottom flask, equipped with thermometer, 15 cm Vigreux column 40 fitted with cotton plug, and magnetic stirrer, is added 0 1 gmins of sodium borohydride dissolved in 4 5 ml ethanol While maintaining the reaction mass at a temperature of between 25 C and 36 C, and over a period of six minutes, the 2,6dimethyl-3-mercaptoheptanone-4 produced in Example IV (B), supra ( 0 53 gmins dissolved in 2 5 ml anhydrous ethyl alcohol) is added to the reaction mass with stirring The reaction mass is then 45 maintained at a temperature of 25 C-65 C (intermittent heating to 65 C for a period of 11 hours, at which time it is determined by GLC analysis to contain 51 0 % 2, 6-dimethyl-3mercapto-heptanol-4 (An additional 0 3 gmins of sodium borohydride in 7 ml of ethanol was added during this time period).

The reaction mass is then concentrated on a rotary evaporator (to which is applied a 50 water aspirator vacuum) to a volume of 2 ml (thick slurry) 10 ml water is added and the solid dissolves yielding a turbid aqueous solution The resulting solution is acidified to a p H of 1-2 with approximately 2 ml, 10 % hydrochloric acid The product is then extracted with two 10 ml portions of methylene chloride and the extracts are combined and washed with 8 ml saturated sodium chloride solution, dried over anhydrous sodium sulfate, gravity filtered 55 and concentrated on a rotary evaporator to yield 0 23 gms of an oil, containing 51 % of 2,6-dimethyl-3-mercapto-heptanol-4.

The resulting product is trapped out on a GLC column (conditions: 8 ' x 1/4 " SE-30 column, programmed at 130 C at 7 5 C per minute).

The NMR Spectrum is set forth in Figure 15 The IR Spectrum is set forth in Figure 16 60 37 1 596 251 37 The NMR analysis is as follows:

1.00 ppm Methyl protons 12 H I 5 1.48-2 10 -CH 2 + HC 5 H 2.20 SH 1 H 2 62 HC-S 1 H 10 3.70 HC-O 1 H The infra-red analysis is as follows: 15 1020 cm-1, 1050, 1100, 1130, 1360, 1380, 1460, 2550, 2860, 2940, 3400.

EXAMPLE V

Both 3-mercapto-4-heptanone and 3-mercapto-4-heptanol produced according to Exam 20 ple I are useful in creating a synthetic grapefruit oil as follows (where 3-mercapto-4heptanone is added at a concentration of 1 ppm and 3-mercapto-4-heptanol is added at a concentration of 20 ppm:

Ingredient I II 25 Orange Oil Florida 98 0 97 0 Nootkatone ( 1 % in 1 0 1 0 30 Limonene) 3-mercapto-4-heptanone 1 0 ( 0.01 % in Limonene) 35 3-mercapto-4-heptanol 2 0 ( 0.1 % in Limonene) At the levels demonstrated, these powerful aroma chemicals twist the odor of Orange Oil to 40 the fresh bitter grapefruit character Even with the Nootkatone as the only additive to the Orange Oil, the grapefruit character does not come alive until the addition of either of the above compounds, the 3-mercapto-4-heptanone and the 3-mercapto-4-heptanol The recommended preferred use level of 3-mercapto-4-heptanone and 3-mercapto4-heptanol is in the range of from about 0 1 ppm (part per million) up to about 50 ppm 45 EXAMPLE VI

A 0 1 % solution of 3-mercapto-2-6-dimethyl-4-heptanone prepared according to Example IV, Part (B) is added to Orange Oil Florida at the rate of 1 % The resulting Orange Oil aroma profile is transformed into a grapefruit-like essence 50 38 1 596 251 3 Rv EXAMPLE VII

The following intense, long lasting prepared:

Ingredient 3-mercapto-4-heptanone ca-pinene myrcene limonene menthone isomenthone pulegone pulegyl acetate a-terpineol geraniol methyleugenol cedryl acetate eucalyptol terpinen-4-ol buchu-type essence having grapefruit nuances is Parts by weight 0.08 0.10 0.15 1.00 1.40 2.60 0.80 0.15 0.10 0.04 0.10 0.05 0.30 0.15 The 3-mercapto-4-heptanone is responsible for adding grapefruit/buchu nuance to this otherwise bland essence.

the pleasant highly valuable EXAMPLE VIII

*Preparation of soap composition One hundred grams of soap chips are mixed with one gram of the perfume composition of Example VII until a substantially homogeneous composition is obtained The perfumed soap composition manifests an excellent buchu leaf oil type character with warm citrusy (grapefruit-like) nuances.

EXAMPLE IX

Preparation of a detergent composition A total of 100 grams of a detergent powder (essentially water soluble nonionic detergent and stable laundry enzyme as described in United States Patent No 3,953, 353, issued on April 27, 1976) is mixed with 0 15 grams of the perfume composition of Example VII until a substantially homogeneous composition is obtained This composition has an excellent buchu leaf oil-like aroma with strong citrusy nuances.

EXAMPLE X

Preparation of a cosmetic powder composition A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder with 0.25 grams of the product obtained from the process of Example I (Part B) It has an excellent grapefruit/buchu leaf oil-like aroma A similar material having strong grapefruitlike aroma is prepared using the material produced according to Example IV, Part (B).

1 596 251 39 1 596 251 39 EXAMPLE XI

Perfumed liquid detergent Concentrated liquid detergents with a strong buchu leaf oil-like aroma with intense grapefruit nuances are prepared containing 0 10 %, 0 15 % and 0 20 % of 3mercapto-4heptanone They are prepared by adding and homogeneously mixing the appropriate 5 quantity of 3-mercapto-4-heptanone in the liquid detergent described according to British Patent No 1,092,149 containing 2 % by weight ethylene/maleic anhydride copolymer (specific viscosity 0 5-1 0) and 0 42 weight percent methyl vinyl ethyl/maleic anhydride copolymer (specific viscosity 0 4) as stabilizer and 8 % by weight of a sultaine detergent.

The detergents all possess a strong buchu leaf oil-grapefruit fragrance, the intensity 10 increasing with greater concentration of 3-mercapto-4-heptanone A similar effect with additional minty nuances is obtained when using 2,6-dimethyl-3-mercapto-4heptanone produced according to Example IV, Part (B).

EXAMPLE XII 15 The compound produced according to the process of Example IV, Part (B), 2,6-dimethyl-3-mercapto-4-heptanone, is incorporated into a cologne at a concentration of 2.5 % in 85 % aqueous ethanol; and into a handkerchief perfume at a concentration of 20 % (in 95 % aqueous ethanol) A distinct and definite strong buchu leaf oillike aroma with intense grapefruit nuances is imparted to the cologne and to the handkerchief perfume A 20 substantially similar result is obtained when using 3-mercapto-4heptanone and 3-mercapto4-heptanol produced, respectively, according to Example I, Part (B) and Example I, Part (C).

EXAMPLE XIII 25 The composition of Example VI is incorporated into a cologne at a concentration of 2 5 in 85 % aqueous ethanol; and into a handkerchief perfume at a concentration of 20 % (in % aqueous ethanol) The use of the 3-mercapto-4-heptanone in the composition of Example VI affords a distinct and definite strong buchu leaf oil-like note with citrusy (grapefruit-like) nuances to the handkerchief perfume and to the cologne 30 EXAMPLE XIV

Uses of ac-oxy(oxo)mercaptans in perfumery The following examples set forth the uses and comparisons of several aoxy(oxo)mercaptans of our invention 35 4-mercapto-5-nonanone has a green, minty, grapefruit note and is approximately five times stronger than its corresponding alcohol It is specified in the table below as "compound I".

4-mercapto-5-nonanol specified as "compound II" in the table set forth below, has a green pepper, grapefruit note 40 2,6-dimethyl-3-mercapto-heptanol-4, specified as "compound III" in the table below, has green, fruity, grape, grapefruit note.

2,6-dimethyl-3-mercapto-heptanone-4 specified as "compound IV" in the table below, has a powerful, green, tart, grapefruit note and is approximately ten times stronger than the alcohol 45 5-mercapto-6-undecanol, specified as "compound V" in the table below, has a grapefruit, buchu note, with some vetiver nuances.

5-mercapto-6-undecanone, specified as "compound VI" in the table set forth below, has a green grapefruit note, with woody, vetiver nuances and is approximatelyfive times stronger than its corresponding alcohol 50 The use of the above-mentioned mercapto compounds (a-oxy(oxo)mercaptans) may be demonstrated by blending them separately into the following synthetic perfume formulation (II) wherein they perform in such a way as to "twist" the odor of the Orange Oil into that of grapefruit Each synthetic grapefruit oil, produced, however, is slightly different and unique in its own right due to the different character imparted by the mercapto ketone or 55 alcohol.

Formulations A-G are first produced and these are separately added to synthetic perfume oils II and III below (in Table VI) 1 596 251 1 596 251 TABLE VI

FORMULATION A B C D E F G Ingredient Orange Oil Nootkatone Compound I Compound II Compound III Compound IV Compound V Compound VI 98.99 1.0 0.01 98.90 1.0 98.90 1.00 0.10 0.10 98.99 1.00 98.90 1.00 98.99 1.00 99.0 1.00 0.01 0 10 00 100 00 100 00 100 00 0.01 00 100 00 100 00 41 1 596 251 41 The synthetic oils (A-F) may be used to replace natural formulations I, II and III.

grapefruit oil in the following I Oakmoss absolute 50 % in Diethyl Phthalate Helional Hedione (Manufactured by Firmenich et Cie of Geneva, Switzerland) Coumarin II III 20 20 10 10 20 20 Musk ketone 80 80 Isocyclocitral ( 10 % in Diethyl Phthalate) Galbanum Oil ( 10 % in Diethyl Phthalate) Rosemary Oil Pine Needle Oil Fir Balsam Absolute ( 10 % in Diethyl Phthalate 10 10 10 10 60 60 10 10 Grapefruit Oil Benzyl Acetate Linalool Indol ( 10 % in Diethyl Phthalate) Undecalactone ( 10 % in Diethyl Phthalate) Ylang Ylang Oil Lemon Oil 470 470 470 80 80 12 12 12 32 32 32 14 14 14 One of Formulations A-F contains an a-oxy(oxo)mercaptan of our invention Formulation G (containing only Orange Oil and Nootkatone, but not containing any a-oxy(oxo)mercaptan The addition of these synthetic oils produces a similar effect to that of natural grapefruit oil Each fragrance has a novel difference in nuance due to the differences exhibited by the a-oxy(oxo)mercaptans of our invention However, when the synthetic oils without the a-oxy(oxo)mercaptans of our invention are incorporated into the fragrance an entirely different effect away from the "grapefruit" effect is obtained.

1 596 251 42 1 596 251 42 EXAMPLE XV

Part (A) Preparation of 2-Chloro-Cyclododecanone Reaction:

+ + SO 2 t + k-lc t CL Into a 1000 ml three-necked, round-bottom flask, equipped with "Y-tube", mechanical stirrer, thermometer, 125 ml addition funnel, vacuum adapter to water aspirator and water bath is placed a solution of 100 g of cyclododecanone in 100 ml anhydrous benzene The cyclododecanone is dissolved in the benzene with stirring at 25 C and the solution cools by itself as the solution occurs, to 10 C The solution then is allowed to warm up to 26 C, at which point dropwise addition of SO 2 C 12 is commenced with stirring Addition of SO 2 C 12 continues for a period of one hour at 26 C-33 C, during which time acidic gases are removed using a water aspirator vacuum At the end of the addition, stirring is continued for another one hour period The reaction mass is then transferred to a 1000 ml, one-neck, round-bottom flask and concentrated on a rotary evaporator during which time the benzene solvent is trapped in a dry-ice/acetone trap GLC analysis on an 8 ' x " SE-30 column yields the information that the reaction product contains approximately 24 % chlorinated ketone The reaction product ( 117 g) is introduced into a 250 ml, threenecked round-bottom flask, equipped with a 2 0 x 30 cm distillation column, packed with 1/8 " helices, reflux head, magnetic stirrer, heating mantle, high vacuum pump and dry-ice trap.

Unreacted cyclododecanone ( 72 5 g) is recovered, distilling at 95 C-113 C vapor temperature and 0 6-1 2 mm Hg pressure The residue ( 30 3 g) is transferred to a 100 ml, three-necked, round bottom flask, equipped with a 1 3 x 17 cm unpacked distillation column Fractionation proceeds as follows:

Pot Pressure Temperature 0.4 mm Hg 123 5 C 0.5 mm Hg 128 C 0.5 mm Hg 140 C 0.5 mm Hg 195 C Vapor Temperature C C 112 C C Weight of Analysis of Fraction Fraction 35 2.23 g 7.27 g 39.2 % starting ketone and 60.8 % chlorinated ketone 21.8 % starting ketone and 78.0 % chlorinated ketone 13.53 g 4 5 % starting ketone and 94 % chlorinated ketone 1.36 g 1.5 % starting ketone and 62.8 % chlorinated ketone Mass spectral, NMR and IR analyses of GLC trapped product ( 8 ' x F' SE30 column) confirm the resulting material is 2-chloro-cyclododecanone The distilled product ( 94 % chlorinated ketone) is used in the process of Example IV (B), infra.

1 596 251 1 596 251 Part (B) Preparation of 2-Mercapto-Cyclododecanone Reaction:

I C= O /'"'C C=O (C 10 H 20) I + Na SH -(C 10 H 20) 1 + Na CI \ H-C-Cl \H-C-SH t 10 Into a 250 ml, three-necked, round-bottom flask, equipped with magnetic stirrer, pot thermometer, six inch distillation column with gas outlet at top attached to rubber tubing leading above a stirring 10 % Na OH solution, gas inlet tube (for hydrogen sulfide bubbling), 15 gas bubbler (Primol), empty trap between hydrogen sulfide cylinder and bubbler, hydrogen sulfide cylinder, isopropanol/dry-ice bath and 50 ml addition funnel is added a solution of 4.65 g of sodium methoxide dissolved in 45 ml anhydrous methanol The sodium methoxide solution is cooled to -10 C, at which point hydrogen sulfide bubbling is commenced below the surface of the sodium methoxide solution The reaction is maintained at a temperature 20 of -5 C to -10 C, during which time the hydrogen sulfide bubbling proceeds while stirring the reaction mass for a period of 1- hours At this point in time, 90 ml anhydrous methanol is used to dissolve completely the chlorinated ketone starting material at room temperature.

While maintaining the reaction mass at O C-4 C, the methanolic solution of chlorinated ketone is added dropwise during simultaneous slow flow of hydrogen sulfide After all the 25 chlorinated ketone solution is added (after another hour) a heavy solid precipitate forms which is stirred under hydrogen sulfide flow At the end of an additional three minutes, a sample of the reaction mass is acidified to a p H of between 1 and 2 and extracted with methylene chloride The methylene chloride extract sample is washed with water, dried and concentrated on a rotary evaporator The resulting sample contains 2 2 % product by GLC 30 The reaction mass is continued to be treated with hydrogen sulfide for an additional three hours while warmed to 17 C-35 C ( 25 C-35 C for the last hour) The reaction mass is concentrated on a rotary evaporator to 15 ml (a thick yellow slurry) Distilled water ( 35 ml) and 53 g of 10 % Na OH solution is added to the reaction mass and stirred for 20 minutes under a nitrogen blanket at 25 C-30 C The reaction mass is then extracted with two 35 ml 35 portions of methylene chloride and the extracts are combined, dried and concentrated yielding 2 6 g oil.

The basic aqueous solution is acidified with 65 ml aqueous 10 % hydrochloric acid to p H = 2 The acidifed solution is extracted with three 40 ml portions of methylene chloride The extracts are combined and washed with 30 ml saturated sodium chloride and dried over 40 anhydrous sodium sulfate The resulting material is gravity filtered and concentrated on a rotary evaporator to yield 6 2 gmins of a heavy yellow oil containing 99 3 % 2-mercaptocyclododecanone having the structure:

45 C= O (C 10 20) 50 H -HC CSH 55 This structure is confirmed by NMR, IR and Mass Spectral analyses of GLC trapped material ( 8 ' x 1 " SE-30 column).

The NMR spectrum is set forth in Figure 17 The IR spectrum is set forth in Figure 18.

3.5 gmins of material produced according to this example is distilled yielding 2 0 gmis of a white solid (M P 41 C-42 C)) at a vapor temperature of 107 C-109 C and a vacuum of 0 2 60 mm Hg GLC analysis ( 8 ' x "SE-30 column) indicates 99 5 % pure 2mercaptocyclododecanone.

1 596 251 The NMR analysis is as follows:

1.30 ppm (broad singlet) -CH 2 14 H 1 82 (d) -SH 5 7 H 3.06-1 65 (m) -CH 23.62 (triplet of doublets) O=C-HC-S 1 H 10 The IR analysis is as follows:

1245 cm-1, 1355, 1440, 1470, 1700, 2550, 2860, 2920.

The Mass spectral analysis is as follows: 15 15 m/e Relative Intensity 41 842 1001 60 704 20 67 44 69 45 81 48 87 833 95 36 25 98 545 M 214 506 EXAMPLE XVI

Part (A) Preparation of 2-Chloro-3-Pentanone 30 Reaction:

0 O 35,+ SO 2 Ct 2 + 502 +IH Ct 3 Cl40 Into a 1000 ml, three-necked, round-bottom flask, equipped with "Y-tube", pot thermometer, 125 ml addition funnel, cold water bath and mechancal stirrer is placed 215 gmins ( 2 5 moles) of diethyl ketone ( 3-pentanone) Over a period of one hour, 67 5 gms-( 40 ml; 0 5 moles) of SO 2 C 12 is added, dropwise, from the addition funnel, with stirring, while 45 maintaining the pot temperature at 30 C-35 C At the end of the addition of the SO 2 C 12, water aspirator vacuum is applied with stirring to remove the acidic gases; sulfur dioxide and hydrogen chloride.

Water aspirator vacuum is applied for a period of two hours.

GLC analysis (conditions: 8 ' x " SE-30 column, 75 C-225 C, programmed at 50 4 C/minute) yields the information that the reaction product is 19 1 % 2chloro-3pentanone.

The crude material is charged to a 500 ml, three-necked, round-bottom flask, equipped with reflux head, magnetic stirrer, 2 0 x 30 cm distillation column, packed with 1/8 " helices, heating mantle and pot thermometer The distillation is carried out at atmospheric 55 pressure and yielding the following fractions.

1 596 251 45 Percent Chlorinated Pot Vapor Weight Product, 2-chloroTemperature Temperature of Fraction 3-pentanone by GLC 112 C 100 C 17 7 gms 0 % (only starting 5 material) C 100 C 98 0 gms 134 C 105 C 24 2 gms 0 % 10 5 C 114 C 6 8 gms 0 % 138 C 117 5 C 5 0 gms 49 1 % 139 C 116 5 C 4 9 gms 76 0 % 15 C 122 5 C 3 3 gms 85 6 % 141 5 C 122 C 7 4 gms 92 % 20 143 C 123 C 24 4 gms 88 5 % The 92 % pure material is used in Part (B), supra.

Part (B) Preparation of 2-Mercapto-3-Pentanone 25 Reaction:

0 O CH 30 H 30 q+ NQSH _ 50 _ 50 l CL SH 35 Into a 250 ml, three-necked, round-bottom flask, equipped with magnetic stirrer, pot thermometer, six inch distillation column with gas outlet at top attached to rubber tubing leading above stirring 10 % Na OH solution, gas inlet tube for hydrogen sulfide (sub-surface), gas bubbler, isopropyl alcohol/dry-ice bath and 10 ml addition funnel is placed a solution of 7 gms of sodium methoxide in 70 ml anhydrous methanol While 40 maintaining the reaction mass temperature at between -13 C and -9 C, hydrogen sulfide is added thereto over a period of 1 5 hours While maintaining the reaction mass at a temperature of between -9 C and -3 C, the 2-chloro-3-pentanone prepared in Part (A) of this example, is added to the reaction mass over a period of 15 minutes and hydrogen sulfide is continued to be bubbled into the reaction mass for another hour while maintaining 45 the temperature of the reaction mass at between -3 C and + 5 C.

GLC analysis (conditions: 8 ' x -" SE-30 column) of an extracted sample indicates that no chlorinated ketone remains at this point The reaction mass is then flushed with nitrogen and allowed to warm up to room temperature The reaction mass is then concentrated on a rotary evaporating using water aspirator vacuum to a volume of 20 ml (yielding a thick 50 white slurry), 55 ml distilled water is then added thereto causing the reaction mass to become a "turbid-yellow" solution 53 gms of 10 % aqueous sodium hydroxide is then added to the reaction mass with stirring while maintaining the temperature at 22 C-25 C (p H= 10-11) The reaction mass is then extracted with two 50 ml portions of methylene chloride The remaining basic aqueous solution is then acidified with 65 ml 10 % HCI to 55 p H= 2 and the resulting acidic solution is extracted with three 50 ml portions of methylene chloride The methylene chloride extracts are combined and washed with two 30 ml portions of saturated sodium chloride solution The extracts are then dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 6 0 gms The desired product, 2-mercapto-3-pentanone is trapped out using preparative GLC 60 (conditions: 8 ' x " SE-30 column, operated at 75 C-225 C, programmed at 4 per minute).

Mass Spectral, IR and NMR analyses confirm that the resulting product is 2-mercapto-3pentanone.

The NMR spectrum is set forth in Figure 19 The IR spectrum is set forth in Figure 20 65 1 596 251 The NMR analysis is as follows:

1.12 ppm (t) 1.48 (d) 1.86 (d) 2.64 (m) 3.48 (m) 0 II CH 3-C-CCH 3-C-C=O I S-SH -CH 2-CO=C-HC-S3 H 3 H 1 H 2 H 1 H The Mass Spectral analysis is as follows:

m/e 27 29 41 57 59 61 M 118 Relative Intensity 274 437 7 7 7 1001 loo' 9.56 9 612 225 The infra-red spectrum is set forth in Figure 20.

The infra-red analysis is as follows:

950 cm', 1060, 1130, 1345, 1370, 1405, 1450, 1710, 2250, 2940, 2980.

The resulting product, 2-mercapto-3-pentanone, is disclosed in U S Patent 3,773,524 issued on November 20, 1973, to be useful in augmenting meat flavors.

EXAMPLE XVII

Grapefruit formulation The following formulation is prepared:

Ingredients Grapefruit oil Bergamot oil Citral Amyl alcohol Ethyl acetate 5-Phenyl-4-pentenal Parts by Weight SC 3-Mercapto-4-heptanol 0.5 6 C When the above grapefruit formulation is added to water at the rate of 1 %, an excellent grapefruit drink is prepared The 3-mercapto-4-heptanol prepared according to Example I 1 596 251 gives an intense citrusy note to the instant formulation thereby rendering it more desirable.

The effect rendered by the 3-mercapto-4-heptanol can be also rendered by the following materials (individually or in admixture) in the following relative parts by weight:

Ingredients Parts by Weight 5 4-Mercapto-5-nonanone 1 0 4-Mercapto-5-nonanol 1 3 10 3-Mercapto-2,6-dimethyl-4-heptanone 0 4 (also gives strong pleasant desirable buchu leaf oil character) 2-Mercapto-3-pentanone 1 6 15 EXAMPLE XVIII

Vegetable flavor formulation 2-Mercaptocyclododecanone-1 is added directly to a food product prior to processing and canning The following illustrates the beneficial flavor effect when 2 20 mercaptocyclododecanone-1 prepared according to Example IV is added directly to several food products just prior to their consumption:

(i) In blended vegetable sauce at approximately 30 ppm:

Brings out the green vegetable notes with minty nuances 25 (ii) In vegetable soup at 40 ppm:

Imparts a fresh vegetable flavor The green notes give the entire vegetable flavor a fuller body.

30 (iii) In bean tomato sauce at approximately 20 ppm:

Modifies the flavor by reducing the harsh character of the tomato spice mixture while at the same time adding green fresh notes and developing the "cooked" tomato note to a "fresh" tomato note.

35 The levels of concentration of the 2-mercaptocyclo-dodecanone-1 may be reduced by % when 2-isobutyl thiazole is added at the rate of 5 ppm in addition to the 2-mercapto-cyclododecanone-1 to the various products set forth above It should be understood that noticeable differences in the flavor are discernable at other concentrations.

40 EXAMPLE XIX

Use of 2-Mercaptocyclododecanone-1 to enhance the vegetable flavor of vegetarian vegetable soup 2-Mercaptocyclododecanone-1 is added at the rate of 2 ppm to condensed Vegetarian Vegetable Soup (Shop-Rite brand) One liter of water is added to one liter of soup and 45 thoroughly admixed The resulting mixture is then simmered ( 200 F) for a period of 10 minutes The resulting soup is compared by a bench panel with a soup which has no 2-mercaptocyclododecanone-1 added thereto The soup having the 2mercaptocyclododecanone-1 added thereto is unanimously preferred as having a more vegetable-like taste with fuller mouthfeel and better aroma, and in addition, pleasant slight minty nuances 50 EXAMPLE XX (A) Preparation of 3-Chloro-4-Heptanone Reaction:

0 0 -i-SO 2 Ct + 5021 cl + HCL l 48 1 596 251 4 R 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 1000 g 4heptanone Addition of 434 g of SO 2 C 12 drop-wise into the 4-heptanone is commenced while maintaining the pot S 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 % 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 mixtuire 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 p H of about 1 The upper organic phase is washed with 700 ml saturated sodium bicarbonate solution to a p H 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 x 60 cm vacuum jacketed column packed with 6 mm Raschig Rings, and then 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 (mm Hg) Temp.

Vapor Weight of Temp Fraction 62 80 71 51 0 g Cut No Reflux Ratio 1 60:40 62 81 5 58 82 5 59 89 5 71 149 0 g 157 5 g 175 0 g 59 96 75 110 g 59 100 58 101 58 102 103 54 110 54 119 140 24 5 g 16 0 g 94 37 5 g 94 144 5 g 85 0 g 102 28.0 g 45 0 g 2 40:60 3 30:70 4 30:70 30:70 6 50:50 7 50:50 8 30:70 9 30:70 30:70 11 30:70 12 30:70 GLC analysis on each of cuts 5-12 (conditions 8 ' information:

X 1 "SE-30 column) yields the following 50 1 596 251 4 R Cut No Percent low Boilers 0 09 Percent 4Heptanone 96.15 Percent 3-Cl 4-Heptanone 2.97 Percent High Boiler (A) Percent High Boiler (B) Percent High Boiler (C) Percent High Boiler (D) % 50 % 8 9 28 87 09 trace 95 78 91 38 69 14 8 32 Cuts 8, 9 and 10 are blended (weight 266 5 gi 0.95 % 4-heptanone 93.89 % 3-chloro-4-heptanone 3.60 % high boiler A 1.57 % high boiler B 2.43 0 57 -.

3.22 1 00 -.

4.89 3 34 O 7.27 19 88 3 2.07 49 28 3 ms) and are analyzed as follows:

1 C 121 ).21 9.69 t, Li 0.47 1 596 251 EXAMPLE XX (B) Preparation of 3-Thioacetyl-4-Heptanone Reaction:

5 0 O Ui CH 3 H 1 CH 3-C-SH +Na OCH 3 P CH 30 H 3-C-SN + CH 3 30 H CL 10 i SNo CL SOOCH 3 15 Into a 25 ml, three-necked, round-bottom flask equipped with magnetic stirrer, nitrogen inlet tube, 6 " Vigreux column with cotton plug and pot thermometer is added a solution of 20 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 ( O 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 25 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 (condition:

8 ' x -" SE-30 column) yields the following data:

15 6 % 3-chloro-4-heptanone 30 3.0 % chloro heptanone, high boiler 77.67 % major peak 35 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 p H of the aqueous phase is 5-6 The organic phase is extracted with two 10 ml portions of methylene chloride The methylene 40 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 ' x " SE-30 column operated at 120 C, programmed at 5 C/minute) yields a compound having a molecular weight of 188 and 45 having a mass spectral analysis, NMR analysis and IR analysis which causes confirmation of the structure:

50 SC O CH 3 55 The NMR spectrum is set forth in Figure 21 The IR spectrum is set forth in Figure 22.

51 1 596 251 51 The NMR analysis is as follows:

0 5 3-thioacetyl-4-heptanone H 3 101 U,10 0.92 ppm (t) CH 3 CH 2 6 H 0 96 (t) CH 3 C C S 15 2.01-1 44 (m) CH 2 4 H 0 II 20 2.39 (s) CH 3 C S O 5 H 2 53 (m) CH 2 C 25 4.20 (t) O = C-HC S C =O 1 H The IR analysis is as follows:

620 cm-1, 950, 1125, 1350, 1450, 1690, 2320, 30 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.

35 EXAMPLE XX (C) Preparation of 3-Thiomethyl-4-Heptanone Reaction:

0 O 40 + Na SCH CH 30 H Cl t SCH 3 45 5HSCH 3 + No OCH 3 3 Into a 50-ml, three-necked, round-bottom flask equipped with magnetic stirrer, dry ice 50 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 55 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-4heptanone 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 60 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 p H of the aqueous phase is in the range of 5-6 The oil phase is then extracted with two 12-ml portions 65 52 1 596 251 52 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:

5 10 SCH 3 as confirmed by NMR, IR and mass spectral analyses of trapped compound.

The NMR spectrum is set forth in Figure 23 The IR spectrum is set forth in Figure 24 15 The NMR analysis is as follows:

3-thiomethyl-4-heptanone O 20 20 SCH 3 25 0.94 ppm (t) CH 3 CH 2 6 H 30 0.97 (t) CH 3 C C S 1.68 (m) CH 2 4 H 1 92 (s) CH 3 S 3 H 35 0 11 II 2.60 (m) CH 2 C 2 H 40 3.08 (t) C HC -S 1 H II 0 The IR analysis is as follows: 45 1360 cm-l, 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 50 EXAMPLE XX (D) Preparation of 3-thiomethyl-4-heptanol Reaction:

0 OH onhydrous Et OH + No BH 4 i SCH 3 SCH 3 53 1 596 251 53 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 (Na BH 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 5 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 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 10 mass is the Q 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 p H of 2-3 using 10 % H Cl solution The organic phase is extracted with two 12ml portions of 15 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 an 8 ' x -" SE-30 GLC column, and MS, NMR and IR analyses confirm that the resulting compound has the structure: 20 OH 25 SCH 3 30 The NMR spectrum is set forth in Figure 25 The infrared spectrum is set forth in Figure The NMR analysis is as follows:

35 0.94 ppm (t) CH 3 CH 26 H 1 06 (t) CH 3 C C S 40 1.51 (m) CH 2 6 H 2.06 (s) CH 3 S 3 H 45 2.36 (m) HC S 2.62 (broad) OH 2 H 3 52 (m) HC O 1 H 50 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 55 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.

54 1 596 251 54 EXAMPLE XXI

Preparation of 3-methallylthio-2,6-dimethyl-4-heptanone (A) Preparation of 3-chloro-2,6-dimethyl-4-heptanone Reaction:

5 502 CL 2 10 CL Into a one-liter, three-necked, round-bottom flask equipped with "Y" tube, pot thermometer, mechanical stirrer, 125 ml addition funnel, gas outlet tube, cold water bath 15 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 502 C 12 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 20 removing most of the acidic gases resulting from the foregoing reaction.

The reaction mass is then transferred to a one-necked, one-liter, roundbottom 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 x 30 cm distillation column packed with 1/s" helices, reflux head, magnetic stirrer, heating 25 mantle and vacuum pump and the rsulting 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 30 Reaction:

0 O Na SH 35 CH 30 H CL SH 40 Into a 250 ml, round bottom, three-necked flask equipped with magnetic stirrer, pot thermometer, 6 " Vigreux distillation column with gas outlet at top leading over 200 ml 10 %sodium hydroxide solution, H 2 S gas inlet tube (sub-surface), "Y" tube, 50 ml addition funnel, gas bubbler, and dry ice-isopropyl alcohol bath, and cold water bath is added a À 45 solution of 11 6 grams of sodium methoxide dissolved in 90 ml anhydrous methanol The 45 sodium methoxide solution is cooled to a temperature of -15 C using the dry ice-isopropanol bath While maintaining the temperature of the sodium methoxide solution at -10 to -5 C, hydrogen sulfide is bubbled 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-imethyl-4heptanone prepared in 50 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 in the range of -5 to -9 C, the 3-chloro-2,6-dimethyl-4heptanone prepared in 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 55 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 (p H = 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 60 aqueous solution is then acidified with 115 ml 10 % hydrochloride acid to a p H 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 p H 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 % 65 1 596 251 1 596 251 55 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 77 578 C and a pressure of 6 mm Hg.

EXAMPLE XXI 5

C Preparation of 3-methallylthio-2,6-dimethyl-4-heptanone Reaction:

O O 10 No OCH 3 + CH 30 H SH S Na 15 20 2 CLJ CH 30 H 25 Into a 25 ml, three-necked, round bottom flask equipped with magnetic stirrer, "Y" tube, nitrogen inlet, reflux condenser with cotton plug, cold water bath and warm water 30 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-2,6dimethyl-4-heptanone dissolved in 3 ml anhydrous methanol, with stirring After stirring 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 35 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 p H of 1-2 with 3 drops of 10 % 40 hydrochloric acid The reaction mass is then extracted with three 8 ml portions of methylene chloride and the extracts are combined, 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-methallylthio2,6-dimethyl-4-heptanone as confirmed by MS, IR and NMR analyses of trapped product 45 The NMR spectrum is set forth in Figure 27 The infrared spectrum is set forth in Figure 28.

561 596 251 51; The mass spectral analysis is as follows:

Relative Intensity 443 376 435 932 444 o 100 o The NMR analysis is as follows:

1.92 ppm, 2 06 1.78 2.12 2.47 2.82 3.01 4.86 ( 2 doublets) (s) (m) (t) (d) (s) (s) H CH 3 C= C CH 3 methine protons CH 2 O = C-C-SH = C CH 2 S -f H C = C H 12 H 3 H 2 H 2 H 1 H 2 H 2 H The IR analysis is as follows:

890 cm-', 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-4heptanone.

mie .69 109 142 143 M 228 1 596 251 ;A 57 1 596 251 57 EXAMPLE XXI

D Preparation of 3-crotylthio-2,6-dimethyl-4-heptanone Reaction:

5 No OCH 3 + CL.

CH 30 H SH S Na 10 1 XX 15 Into a 25 ml, three-necked, round bottom flask equipped with magnetic stirrer, reflux 20 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 230 C at which point a solution of 0 52 grams ( 0 003 moles) of 3-mercapto-2,6-dimethyl-4heptanone in 2 ml anhydrous methanol is added to the sodium methoxide solution While maintaining the 25 temperature of the reaction mass at 24-290 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) is 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 30 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 ' x 1/4 " Carbowax column) NMR, mass spectral and IR 35 analyses yield the information that the resulting material is 3crotylthio-2,6-dimethyl-4heptanone having the structure:

0 40 S > 45 The NMR spectrum is set forth in Figure 29 The infrared spectrum is set forth in Figure 30.

58 1 596 251 58 The mass spectral analysis is as follows:

mle Relative Intensity 41 20 5 902 57 375 10 366 87 1001 89 33 15 141 22 142 454 20 143 633 M 228 13 25 The NMR analysis is as follows 0.84 ppm, 1 08 (doublets) CH 3 12 H 1 70 (d) = C CH 3 3 H 30 2.14 (m) methine protons 2 H 2.48 (m) CH 2 C = O 2 H 35 2.82 (d) O = C-HC S 1 H 2.99 (m) = C CH 2 S 2 H 5 50 (m) olefinic protons 2 H 40 The infrared analysis is as follows:

960 cm-1, 1035, 1135, 1160, 1285, 1360, 1380, 1400, 1465, 1695, 2870, 2930, 2960, 3020 45 EXAMPLE XXI

E Preparation of 3-allylthio-2,6-dimethyl-4-heptanone Reaction: 50 0 O No OCH 3 + Br J CH 30 H SH S Na 59 1 596 251 59 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 230 C At 230 C a solution of 0 522 grams ( 0 003 moles) of 3-mercapto-2,6-dimethyl-4-heptanone dissolved in 3 ml 5 anhydrous methanol is added to the sodium methoxide solution Subsequent to the addition of the mercapto ketone, after stirring for 15 minutes at 230 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 warms to 330 C and is continued to be stirred at 25-330 C for a period of 2 hours It is concentrated on a rotary evaporator using water 10 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 % H Cl is added to the resulting material thereby reducing the p H from 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 15 sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 0 55 grams (pale yellow oil) GLC analysis ( 8 ' x 1/ ' 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:

20 25 S 30 The NMR spectrum is illustrated in Figure 31 The infrared spectrum is illustrated in Figure 32.

The mass spectral analysis is as follows:

35 mle Relative Intensity 41 335 55 24 40 57 326 69 18 45 73 403 30 87 432 50 30 129 100 l 55 142 384 M 214 1 596 251 60 The NMR analysis is as follows:0.84 ppm, 1 08 (doublets) CH 3 12 H 2 14 (m) methine protons 2 H 5 2.48 (m) CH 2 C = O 2 H 2.84 (d) = C-HC S 1 H 10 3.04 (m) = C CH 2 S 2 H H 5.22-5 04 (m) C = H 2 H H 15 5.96-5 56 (m) HC = C 1 H The IR analysis is as follows: 20 914 cm-1, 980, 1035, 1160, 1360, 1380, 1465, 1695, 2870, 2930, 2960.

EXAMPLE XXI 25 F Preparation of ( 1,3-diethyl acetonyl) ( 1,3-diisopropylacetonyl) sulfide Reaction:

30 ,$ 30 Ci SH S Na C Il Nc OCH 3 + CH 30 H 35 0 O 40 Into a 50 ml, round bottom, three-necked flask equipped with magnetic stirrer, pot thermometer, "Y" 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 45 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 50 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 55 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 ' x 1/4 " 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:

61 1 596 251 61 5 S 10 The NMR spectrum is set forth in Figure 33 The IR spectrum is set forth in Figure 34.

15 The mass spectral analysis is as follows:

mle Relative Intensity 41 506 20 43 823 33 25 57 892 71 565 85 1001 30 114 674 39 35 201 36 M 286 29 40 The NMR analysis is as follows:

1.07 ppm, 0 86 CH 3 18 H 1 62 CH 2 + methine protons 6 H 45 2.46 CH 2 C = O 4 H 3.15 and 2 96 O II 50 C HC S 2 H 11 The IR analysis is as follows:

1155 cm-1, 1360, 1380, 1460, 1700, 2870, 2930, 2960 55 w 62 1 596 251 62 EXAMPLE XXI

G Preparation of 3-l(methoxycarbonyl)methylthiol-2,6-dimethyl-4-heptanone Reaction:

5 0 0 10,Is NOOCH 3 + l CH 30 H 10 SH S Na 15 O 20 Into a 50 ml, round-bottom, three-necked flask equipped with magnetic stirrer, pot 25 thermometer, "Y" tube, nitrogen inlet tube, reflux condenser with cotton plug, H 2504 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 25-280 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 30 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 WC The reaction mass is allowed to cool to 240 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 35 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 ' X 1/4 " SE-30 column), with mass spectral, IR and NMR analyses confirm that the resulting product has the structure: 40 45 o O 50 The NMR spectrum is set forth in Figure 35 The IR spectrum is set forth in Figure 36.

1 596 251 The mass spectral analysis is as follows:

mle Relative Intensity 29 11 41 246 43 12 24 57 533 464 101 1001 129 325 161 752 M 246 21 The NMR analysis is as follows:

0.94, 1 10 ppm 2.12 H CH 3 C Me H C Me 12 H 2 H 2.50 O II CH 2 C 2 H 11 3.03 O H II S C C 1 H 3.19 O II S CH 2 C O 2 H 3.70 O II CH 3 O C 3 H The IR analysis is as follows:

1145 cm-', 1185, 1285, 1360, 1375, 1430, 1460, 1695, 1735, 2860, 2920, 2960.

64 1 596 V 251 EXAMPLE XXI (H) Preparation of 3-l(Methoxycarbonyl)methylthiol-4-heptanone Reaction:

0 O 5 HSJ No OCH 3 No + J O CH 30 H O + O O 10 0 Into a 50 ml, three-necked, round-bottom flask equipped with magnetic stirrer, pot thermometer, "Y" 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 20 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 25 is stirred in the temperature range of 25-35 C for a period of 21/2 hours.

ml water is then added to the reaction mass with stirring, and the solid present therein dissolves (p H = 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 30 sodium sulfate, gravity filtered and concentrted on a rotary evaporator using water aspirator vacuum to a weight of 3 77 grams (light yellow oil) GLC analysis (Conditions: 8 ' x 1/4 " SE-30 column) indicates 92 0 % product NMR, mass spectral and IR analyses of GLC isolated material confirm that the resulting product is:

35 40 S The mass spectral analysis is as follows:

mle Relative Intensity 45 27 11 41 21 50 43 544 12 55 11 55 71 593 87 1001 60 415 147 902 356 1 596 251 M 218 1 596 251 65 The NMR analysis is as follows:

0.98 ppm methyl protons 6 H 2 06 1 46 CH 2 4 H 5 2.60 CH 2-C = O 2 H 3.22 S CH 2 C = O 3 H 10 3.30 O = C HC S 3.72 O II CH 3 O C 3 H 15 The IR analysis is as follows:

1000 cm-', 1150, 1185, 1275, 1430, 1450, 1695, 1730, 2860, 2920, 2960 20 The NMR spectrum is set forth in Figure 37 The infrared spectrum is set forth in Figure 38.

EXAMPLE XXI 25 (I) Preparation of 3-thioacetyl-2,6-dimethyl-4-heptanone Reaction:

0 O U CH 30 H lI 30 CH 3-C-SH + NOOCH 3 CH 3-C-S Na + O 35 CL SCOCH 3 40 Into a 25 ml, three-necked, round-bottom flask equipped with magnetic stirrer, nitrogen inlet tube at top of 6 " Vigreux column, reflux condenser with cotton plug, pot thermometer, water bath and heating mantle is placed a solution containing 0 27 grams of sodium 45 methoxide ( 0 005 moles) in 3 ml anhydrous methanol To the sodium methoxide solution is added a solution of 0 38 grams ( 0 005 moles) of thioacetic acid in 3 ml anhydrous methanol, with stirring, while maintaining the reaction mass temperature in the range of 23-25 C The addition takes place over a period of 10 minutes While maintaining the reaction mass temperature at 23 C, a solution of 0 883 grams ( 0 005 moles) of 3chloro-2,6-dimethyl-4 50 heptanone (prepared according to Part A) in 2 ml anhydrous methanol is added to the reaction mass While maintaining the reacion mass temperature between 35 and 45 C and over a period of 3 hours, the reaction mass is stirred At the end of the 3-hour period only 6 % of product is formed The reaction mass is then refluxed at 66-76 C for a period of 12 hours, at which point it is indicated by GLC, NMR, IR and mass spectral analyses that 55 3-thioacetyl-2,6-dimethyl-4-heptanone is formed in an amount of 65 %.

The reaction mass is then concentrated on a rotary evaporator using water aspirator vacuum to 4 ml of an oily product Ten ml water is then added, and the solid dissolves The oil layer is extracted with three 8 ml portions of methylene chloride, and the extracts are combined and washed with one 8 ml water portion The extracts are then dried over 60 anhydrous sodium sulfate, gravity filtered and concentrated yielding 0 54 grams of a yellow oil The desired product is trapped on a GLC SE-30 column (Conditions: 8 ' x 1/4 ").

66 1 596 251 66 The NMR analysis is as follows:

1.01-0 88 ppm Methyl protons 12 H 2 42-2 03 Methine protons 5 2.44 CH 2 CII O 7 H 10 0 I 2.40 CH 3 C S 15 O O 11 I 11 4.14 C C S CH 20 The infrared analysis is as follows:

6.20 cm-1, 950, 1100, 1130, 1360, 1380, 1465, 1695, 2870, 2930, 2960.

25 The mass spectral analysis is as follows:

mie Relative Intensity 30 411 145 43 403 55 12 35 57 602 100 l 40 89 274 131 126 141 9 45 173 11 M 216 7 50 The NMR spectrum is set forth in Figure 39 The infrared spectrum is set forth in Figure 40.

67 1 596 251 67 EXAMPLE XXII

A Preparation of 3-propylthio-4-heptanone Reaction:

0 5 No SCH 2 CH 2 CH 3 Me OH CL 10 Na OCH 3 CH 3 OH HSCH 2 CH 2 CH 3 15 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 20 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 used the water bath to a temperature in the range of 25-30 C The 25 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 30 water and dried over anhydrous sodium sulfate and filtered and then concentrated GLC, MS, NMR and IR analyses of trapped product yield the information that the subject material is 3-propylthio-4-heptanone.

The NMR spectrum is set forth in Figure 41 The IR spectrum is set forth in Figure 42.

35 The NMR analysis is as follows:

0.87-1 04 ppm superimposed CH 3 9 H signals 40 1.63 (m) CH 2 6 H 2.38 (t) CH 2 S 2 H 45 0 II 2.60 (t) CH 2 C 2 H 3 11 (t) O = C HC S 1 H 50 The IR analysis is as follows:

1130 cm-', 1165, 1290, 1360, 1380, 1405, 1460, 1700, 2880, 2940, 2960.

68 1 596 251 68 The mass spectral analyses is as follows:

m/e Relative Intensity 41 204 5 43 263 5 10 71 10 352 114 10 15 117 1001 118 106 20 119 9 M 188 165 25 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 30 Reaction:

0 OH 35 + Na BH 4 anhyd Et OH S S " o /" 40 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 45 moles sodium borohydride) With stirring, a solution of 1 0 grams of 3propylthio-4heptanone 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 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 50 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 p H 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, 55 mass spectral and NMR analyses after GLC trapping (Conditions: 8 ' x 1/" SE-30 column) yield the information that the crude material is 96 % product having the structure 3-propylthio-4-heptanol.

The NMR spectrum is set forth in Figure 43 The IR spectrum is set forth in Figure 44.

69 1 596 251 69 The NMR analysis is as follows:

1.13-0 96 ppm superimposed methyl protons 9 H signals 5 1.44 (m) CH 2 8 H 2.47 (s) OH 4 H 2 49 (m) HC S CH 2 10 3.50 (m) HC O -1 H The IR analysis is as follows: 15 1290 cm-1, 1380, 1460, 2880, 2940, 2970, 3460 Material prepared similarly to above example was vacuum distilled yielding 99 8 % pure 20 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 XXIII

Preparation of 3-isobutylthio-4-heptanone 25 Reaction:

0 H 3 CH 30 + c C-CH 2-S Na CH 30 H CH 3 25-350 C S No OCH 3 H 3 C 35 N CH 30 H 3 C 2 CH 3 OH 'HCH-CH 2-SH 40 Into a 50 ml, three-necked, round bottom flask equipped with magnetic stirrer, reflux condenser, pot thermometer, water bath, 15 cm Vigreux column with nitrogen inlet at top is added a solution of 0 54 grams of sodium methoxide ( 0 01 moles) in 6 ml anhydrous methanol The reaction mass is cooled to 25 C and a solution of 0 90 grams of isobutyl 45 mercaptan ( 2-methyl-1-propanethiol) dissolved in 6 ml anhydrous methanol is added over a period of one minute After keeping the reaction mass at 24 C with stirring for a period of minutes, 1 50 grams of 3-chloro-4-heptanone dissolved in 2 ml anhydrous methyl alcohol ( 0.01 moles of 3-chloro-4-heptanone) is added to the reaction mass which then warms to 37 C The reaction mass is allowed to cool to a temperature of 24 C and stirred at that 50 temperature for a period of 6 hours.

The reaction mass is then concentrated on a rotary evaporator using water aspirator vacuum to a volume of 4 ml yielding an oily solid Ten ml water is then added, and the solid dissolves yielding two phases: an oil phase and an aqueous phase The oil phase is extracted with three 9 ml portions of methylene chloride, and the extracts are combined and washed 55 with 9 ml water The extracts are then dried over anhydrous sodium sulfate, filtered and concentrated to a weight of 1 78 grams.

Mass spectral, infrared, NMR and IR analyses yield the information that the reaction mass contains 90 9 % product which is 3-isobutylthio-4-heptanone.

The NMR spectrum is set forth in Figure 45 The IR spectrum is set forth in Figure 46 60 7 U 1 596 251 70 The NMR analysis is as follows:

0.96 ppm (d) CH 3 H CH 3 5 0.98 (t) CH 3 CH 2 12 H 10 0.91 (t) CH 3 C C S C= O 15 1.70 (m) -CH 2 + HC 5 H 20 2.26 (d) S CH 2 2 H 25 2.60 (t) -CH 2 C 2 H II 0 30 3.10 (t) O = C-HC S 1 H The IR analysis is as follows:

1365 cm-', 1380, 1460, 1700, 2880, 2940, 2960 35 EXAMPLE XXIV

A Preparation of 1-chloro-1,3-diphenyl-2-propanone Reaction:

L 40 02 A 2 O 45 Into a 250 ml, three-necked flask equipped with 15 cm Vigreux column with vacuum 50 outlet at top, pot thermometer, magnetic stirrer, 125 ml addition funnel and cold water bath is placed 99 grams ( 0 470 moles) of 1,3-diphenylacetone Over a period of 1 1/2 hours, 21 2 grams ( 0 157 moles) of SO 2 C 12 is added while maintaining the reaction temperature in the range of 23-30 C, and with stirring At the end of the addition of the SO 2 C 12, water aspirator vacuum is applied to remove the acidic gases, HCI and SO 2 An additional 21 2 55 grams of SO 2 C 12 is then added over a 45 minute period, but allowing the reaction temperature to rise to a maximum of 38 C (without cooling) The reaction mass is then stirred for an additional hour while maintaining the temperature thereof at 24-38 C and acidic gases are again removed using water aspirator vacuum, over a period of 2 hours The reaction mass is then transferred to a 250 ml, three-necked, round bottom flask equipped 60 with pot thermometer, nitrogen inlet capillary tube, 1 8 x 30 cm distillation column packed with 1/4 " helices, reflux distillation head, vacuum pump and heating mantle After 15 minutes of distillation, the packed column was replaced with a 2 8 x 30 cm Vigreux column.

Four cuts were removed at a vacuum of 0 2-0 5 mmm Hg, and a vapor temperature of 153-163 C 65 1 596 251 Thin layer chromatography was carried out on the fractions since the GLC analysis cannot distinguish between the chlorinated derivative and the starting material TLC and mass spectral analyses yield the information that the distillate is a mixture of starting material and the desired product, having the structure:

10 B Preparation of 1-propylthio-1,3-diphenyl-2-propanone Reaction: 15 cl K H i + l S Na 20 Into a 50 ml, three-necked, round-bottom flask equipped with magnetic stirrer, "Y" 25 tube, reflux condenser, pot thermometer and nitrogen inlet tube is placed a solution of 0 54 grams sodium methoxide dissolved in 6 ml anhydrous methanol The reaction mass is cooled and remains at 250 C while a solution of 0 76 grams of npropylmercaptan ( 0 01 moles) dissolved in 6 ml anhydrous methanol is added to the sodium methalate solution A solution of 2 5 grams of the mixture of 1-chloro-1,3-diphenyl-2-propanone and 1,3 30 diphenyl-2-propanone dissolved in 3 ml anhydrous methanol (prepared according to the procedure of Part A) is added to the reaction mass while allowing the reaction mass to warm to a temperature of 290 C.

The reaction mass is maintained at a temperature of between 25 and 39 MC over a period of 4 hours At the end of the four-hour period the reaction mixture is concentrated on a 35 rotary evaporator using water aspirator vacuum to a slurry which is an amber liquid and a white solid Ten ml water are added to the mixture in order to dissolve the solid The organic phase is then extracted with three 8 ml portions of methylene chloride, and the extracts are combined and washed with two 8 ml portions of water The combined extracts are dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary 40 evaporator using water aspirator vacuum to yield an orange amber oil weighing 2 2 grams.

GLC analysis ( 8 ' x 1/4 " SE-30 column) as well as mass spectral, IR, NMR and thin layer chromatography ( 30 % diethyl ether in hexane) analyses confirm that the desired product (isolated by GLC trapping) is 1-propylthio-1,3-diphenyl-2-propanone, having the structure:

45 0050The NMR spectrum is set forth in Figure 47 The IR spectrum is set forth in Figure 48.

72 1 596 251 72 The mass spectral analysis is as follows:

mle 118 123 166 167 210 M 284 Relative Intensity 472 203 oo 1001 144 The NMR analysis is as follows:

0.88 ppm 1.49 2.34 3.76 4.68 7.32-7 01 (t) CH 3 (m) -CH 2(t) CH 2 S (AB) O CH 2 3 H 2 H 2 H 0 O C(s) O = C HC 0 (m) aromatic protons (mn) aromatic protons 2 H 1 H H The IR analysis is as follows:

690 cm-', 1450, 1490, 1710, 2920, 2960, 3020.

Material prepared similarly to above example was vacuum distilled yielding 98 5 % pure product (boiling boint 160-163 C at 0 4 mm Hg) The thus-distilled material has the same physical properties as set forth above for 1-propylthio-1,3-diphenyl-2propanone.

EXAMPLE XXV (A) Preparation of 3-methylthio-2,6-dimethyl-4-heptanone Reaction:

0 I No OCH 3 + CH 35 HI Na SCH 3 CH 30 H Cl ( onhyd) 1 596 251 73 1 596 251 73 Into a 50 ml, three-necked, round bottom flask equipped with pot thermometer, magnetic stirrer, gas inlet tube (subsurface), gas bubbler, methyl mercaptan gas cylinder, 15 cm Vigreux column, gas outlet tube leading to 10 % sodium hydroxide solution, and cold water bath is added a solution of 0 54 grams of sodium methoxide in 12 ml anhydrous methanol ( 0 01 moles sodium methoxide) The reaction mass warms to 30 WC, and it is 5 cooled to 230 C using the cold water bath Over a period of 20 minutes the methyl mercaptan is bubbled in below the surface of the liquid while maintaining the temperature of the reaction mass at 22-230 C The reaction flask is then flushed with dry nitrogen, and a solution of 1 77 grams of 3-chloro-2,6-dimethyl-4-heptanone dissolved in 2 ml anhydrous methanol is then added to the reaction mass The reaction mass remains at 23-250 C and is 10 stirred at that temperature for a period of 2 5 hours GLC analysis indicates 79 % product.

The reaction mass is then warmed to 35 'C and maintained at 28-350 C for another 1 5 hours.

The reaction mass is then concentrated to a volume of 5 ml using a rotary evaporator to which water aspirator vacuum is applied 15 ml distilled water is then added to dissolve the solid yielding a two phase mixture (an aqueous phase and an organic phase) The reaction 15 mass is then extracted with three 10 ml portions of methylene chloride, and the extracts are combined and washed with 10 ml of water The combined extracts are then dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 1 56 grams GLC, MS, NMR and IR analysis yield the information that the resulting material is 89 6 % product, 3-methylthio-2,6-dimethyl-4heptanone The pure 20 material is trapped out using preparative GLC (conditions: 8 ' x 1/4 " SE30 column).

The NMR spectrum is set forth in Figure 49 The IR spectrum is set forth in Figure 50.

The mass spectral analysis is as follows:

mle Relative Intensity 25 41 85 322 30 57 123 61 5 69 5 35 76 102 6 40 103 100 ' 104 6 M 188 104 45 The NMR analysis is as follows:

0 94, 1 08 ppm Methyl protons 12 H 50 1.90 CH 3 S 3 H 2.37 1 96 Methine protons 2 H 55 2.49 CH 2 C 2 H 60 2.78 HC S 1 H The IR analysis is as follows:

1035 cm-', 1160, 1360, 1380, 1400, 1465, 1695, 2870, 2920, 2960 65 74 1 596 251 74 B Preparation of 3-methylthio-2,6-dimethyl-4-heptanol Reaction:

5 + Na BH 4 Et OH SCH 3 SCH 3 10 Into a 25 ml, three-necked, round bottom flask equipped with magnetic stirrer, reflux condenser, pot thermometer, warm water bath, nitrogen inlet (to flush with dry nitrogen) is placed a solution of 0 10 grams ( 0 00265 moles) of sodium borohydride dissolved in 4 ml 15 anhydrous ethanol Over a period of 1 minute with stirring, at 23 C, a solution of 0 9 grams of 3-thiomethyl-2,6-dimethyl-4-heptanone in 4 ml anhydrous ethanol (prepared according to Part A) is added to the reaction mass The reaction mass remains at 23 C for a period of one hour, and then is warmed to a temperature of 31 C and maintained at 24-31 C for a period of 25 hours, after which time 0 2 grams additional sodium borohydride dissolved in 6 20 ml anhydrous ethanol is added The reaction mass is continued to be stirred for a period of 3 hours at which time it is determined by GLC analysis ( 8 ' x 1/4 " SE-30 column) that the reaction mass contains 56 9 % desired product After adding another 0 15 grams of sodium borohydride dissolved in 5 ml anhydrous ethanol with stirring, and stirring the reaction mass for a period of 4 hours at room temperature, it is determined that 73 4 % desired 25 product exists.

The reaction mass is then concentrated on a rotary evaporator (using water aspirator vacuum) to a 4 ml volume slurry Six ml water is added to the resulting slurry and the solid dissolves The reaction mass now exists in two phases; an aqueous phase and an organic phase The reaction mass is neutralized with 10 % HCI solution to a p H of 5-6 The oil is 30 extracted with two 20 ml portions of methylene chloride The extracts are washed with water, dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 0 58 grams (pale yellow liquid) GLC, MS, NMR and IR analyses yield the information that the resultant product contains 79 1 % 3methylthio-2,6-dimethyl4-heptanol The pure material is trapped out using preparative GLC (Conditions: 8 ' x 1/4 " 35 SE-30 column) and has the structure:

OH 40 S 45 The NMR spectrum is set forth in Figure 51 The infrared spectrum is set forth in Figure 52.

1 596 251 The mass spectral analysis is as follows:

Relative Intensity 554 256 355 683 o 100 o 772 The NMR analysis is as follows:

1.12 ppm 0 90 1.34 1.92 2.16 2.36 3.84 methyl protons methine protons CH 2 CH 3 S S HC C O HC O 12 H 2 H 2 H 3 H 1 H 1 H The IR analysis is as follows:

1050 cm-1, 1360, 1385, 1460, 2860, 2920, 2950, 3460.

EXAMPLE XXVI

Preparation of 3-methoxy-4-heptanone Reaction:

fonhyd + Na OCH 3 CH 30 H W C 13 oc Cl OCH 3 A solution of 1 5 grams of 3-chloro-4-heptanone in 3 ml anhydrous methanol ( 0 01 moles 3-chloro-4-heptanone) is placed into a 25 ml, three-necked, round bottom flask equipped with magnetic stirrer, pot thermometer, reflux condenser (with drying tube), 10 ml addition funnel with nitrogen inlet at top an ice water-salt bath, and nitrogen bubbler The 3-chloro-4-heptanone solution is cooled to a temperature of between 0 and 1 C Into the 10 ml addition funnel is placed a solution of 0 54 grams of sodium methoxide dissolved in 7 ml anhydrous methanol ( 0 01 moles sodium methoxide) Over a period of one hour, while maintaining the reaction mass at a temperature of between 0 and 1 C, the sodium methoxide solution is added to the 3-chloro-4-heptanone The reaction mass is then permitted to warm up to room temperature It is then vacuum filtered thereby separating m/e 103 104 M 190 1 596 251 the white precipitate from the filtrate The white solid precipitate is washed with 25 ml methylene chloride, and the washings are combined with the filrate prior to concentration.

After concentration of the filtrate, the concentrate is dried over anhydrous sodium sulfate and further concentrated to a weight of 1 0 grams (white oil) The major peak is isolated by GLC trapping ( 8 ' x 1/4 " SE-30 column) NMR, IR and mass spectral analyses confirm that 5 the resulting material has the structure:

10 CH 3 15 The NMR spectrum is set forth in Figure 53 The IR spectrum is set forth in Figure 54.

The NMR analysis is as follows:

20 0.95 ppm (t) CH 3 6 H 1.64 (m) CH 2 4 H O 25 II 2.49 (t) CH 2 C 2 H 3.36 (s) CH 3 O 3 H 30 3.54 (t) HC O 1 H The infrared analysis is as follows:

1090 cm-1, 1120, 1195, 1355, 1375, 1450, 1710, 2820, 2880, 2940, 2960 35 EXAMPLE XXVII

Raspberry flavor formulation The following basic raspberry flavor formulation is produced:

40 Ingredient Parts by weight Vanillin 2 0 Maltol 5 0 45 Parahydroxybenzylacetone 5 0 Alpha-ionone ( 10 % in propylene glycol) 2 0 so 50 Ethyl Butyrate 6 0 Ethyl Acetate 16 0 Dimethyl Sulfide 1 0 55 Isobutyl Acetate 13 0 Acetic Acid 10 0 60 Acetaldehyde 10 0 Propylene Glycol 930 0 1 596 251 3-methoxy-4-heptanone produced according to Example VII is added to half of the above formulation at the rate of 0 2 % The formulation with the 3-methoxy-4heptanone produced according to Example XXVI is compared with the formulation without the 3-methoxy-4-heptanone produced according to Example XXVI at the rate of 0 01 percent ( 100 ppm) in water and evaluated by a bench panel 5 The flavor containing the 3-methoxy-4-heptanone produced according to Example XXVI is found to have a substantially more pleasant and better raspberry aroma It is the unanimous opinion of the bench panel that the chemical, 3-methoxy-4heptanone produced according to Example XXVI, rounds the flavor out and contributes to a very natural fresh aroma and taste as found in full ripe raspberries Accordingly, the flavor with the addition 10 of the 3-methoxy-4-heptanone produced according to Example XXVI is considered as substantiafly better than the flavor without the 3-methoxy-4-heptanone produced according to Example XXVI.

EXAMPLE XXVIII 15 The following formulations are produced:

Formulation A 1 9 gm Natural black currant juice, concentrate 20 0.1 gm Natural black currant esters 10.0 ml Sugar Syrup 32 Be 25 q.s 100 ml Spring water Formulation B 30 1.9 gm Natural black currant juice, concentrate 0.1 gm Buchu leaf oil 0 1 % (ethanol 95 %) 10 0 ml Sugar Syrup 32 Be 35 q.s 100 ml Spring water Formulation C 40 1.9 gm Natural black currant juice, concentrate 0.1 gm Niribine 10 % (ethanol 95 %) 45 10.0 ml Sugar Syrup 32 Be q.s 100 ml Spring water 50 Niribine is produced by distilling an alcoholic macerate of black currant buds.

Formulation D 1 9 gm Natural black currant juice, concentrate 55 0.1 gm 3-methylthio-4-heptanone 10 0 ml Sugar Syrup 32 Be 60 60 Spring Water q.s 100 ml 78 1 596 251 78 Formulation E 1.9 gm Natural black currant juice, concentrate 10 0 ml Sugar Syrup 320 Be 5 q.s 100 ml Spring Water Each of the above-mentioned formulations is compared with one another by a panel 10 composed of 10 tasters Formulation E is generally considered by the panel to be flat and not very characteristic for fresh black currant Formulations B, C and D are considered as having substantially fresh and more pleasant notes than formulation E In summary, formulation D is preferred as the best black currant flavor, the material 3-methylthio-4heptanone can be used at rates of one-tenth of that of Buchu leaf oil in black currant juice 15 It is further to be concluded that 3-methylthio-4-heptanone can successfully replace Bucchu leaf oil, Niribine and/or natural black currant esters wherever the ingredient is used in reinforced black currant juices, substituted black currant juices and imitation black currant flavors.

79 1 596 251 79 EXAMPLE XXIX

Basic black currant formulation 3-(methallylthio)-2,6-dimethyl-4-heptanone produced according to Example XXI(C) has been added to a basic black currant flavor formulation at the rate of 1 5 % Both flavors have been compared in water at the rate of 200 ppm and evaluated by a bench panel The 5 flavor containing 3-(methallylthio)-2,6-dimethyl-4-heptanone has had the characteristic aroma and taste of ripe black currants or fresh black currant juice This typical note was not present in the basic black currant formulation Therefore all members of the panel preferred the flavor containing 3-(methallylthio)-2,6-dimethyl-4heptanone Detailed below is the Basic Black Currant Formulation to which is added 3(methallylthio)-2,6 10 dimethyl-4-heptanone at the rate of 1 5 %.

Ingredient Parts by Weight Cis-3-hexen-1-ol 5 15 Alpha-phellandrene 1 5 Terpineol-4 10 % (in ethyl alcohol) 3 20 Para-hydroxy benzyl acetone 5 Vanillin 2 Ethyl maltol 6 25 Methyl benzoate 2 Benzaldehyde 2 30 Benzylpropionate 4 Isobutylacetate 5 Coriander oil 0 5 35 Ethylbutyrate 8 Dimethylsulfide 3 40 Fusel oil 8 Acetic acid 10 Alpha-ionone 10 % (in ethyl alcohol) 0 5 45 Ethyl heptanoate 0 5 Propylene glycol 934 50 1000 1 596 251 80 EXAMPLE XXX (A) 120 grams of the flavor composition of Example XXIX is emulsified in a solution containing 300 gm gum acacia and 700 gm water The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 250 c f m of air with an inlet temperature of 500 TF, an outlet temperature of 200 TF, and a wheel speed of 50,000 r p m 5 (B) The following mixture is prepared:

Ingredient Parts by Weight Liquid flavor composition of 10 Example XXIX 25 Propylene glycol 1 Cab-O-Sil M-5 (Brand of Silica 3 15 produced by the Cabot Corporation of 125 High Street, Boston, Mass 02110; Physical properties:

*Surface area: 200 m 2/gm 20 Nominal Particle size: 0 012 microns Density: 2 3 lbs /cu ft) Ethyl cellulose 8 25 The Cab-O-Sil and ethyl cellulose is dispersed in the liquid flavor composition of Example XXIX with vigorous stirring, thereby resulting in a viscous liquid 65 Parts by weight of the powder flavor composition of Part A is then blended into said viscous liquid, with stirring, at 250 C for a period of 30 minutes resulting in a dry, free flowing, sustained release flavor powder 30 EXAMPLE XXXI

Chewing gum parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XXX 300 Parts of sucrose and 100 parts of corn syrup are added 35 Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0 1 inches in thickness The strips are cut into lengths of 3 inches each On chewing, the chewing gum has a pleasant, long-lasting black currant flavor 40 1 596 251 EXAMPLE XXXII

Chewable vitamin tablets The flavor material produced according to Example XXX is added to a Chewable Vitamin Tablet Formulation at a rate of 5 gm/Kg which Chewable Vitamin Tablet Formulation is prepared as follows: 5 In a Hobart Mixer, the following materials are blended to homogeneity:

Vitamin C (ascorbic acid) as ascorbic acidsodium ascorbate mixture 1:1 70 0 10 Vitamin Bl (thiamine mononitrate) as Rocoat thiamine mononitrate 33 1/3 % (Hoffman La Roche) 4 0 Vitamin B 2 (riboflavin) as Rocoat riboflavin 15 33 1/3 % 5 0 Vitamin B 6 (pyridoxine hydrochloride) as Rocoat pyridoxine hydrochloride 33 1/3 % 4 0 20 Niacinamide as Rocoat niacinamide 33 1/3 % 33 0 Calcium pantothenate 11 5 Vitamin B 12 (cyanocobalamin) as Merck 25 0.1 % in gelatin 3 5 Vitamin E (dl-alpha tocopheryl acetate) as dry Vitamin E acetate 33 1/3 % Roche 6 630 30 d-Biotin 0 044 Certified lake color 5 O Flavor of Example XXX 2 5 35 Sweetener sodium saccharin 1 0 Magnesium stearate lubricant 10 0 40 40 Mannitol q s to make 500 0 Preliminary tablets are prepared by slugging with flatfaced 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 45 Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong black currant flavor for a period of 12 minutes.

EXAMPLE XXXIII 0 5 % 3-propylthio-4-heptanone is added to a commercial quality of grapefruit oil The 50 oils with and without this chemical are compared in water at the rate of 10 ppm The aroma and taste characteristics of the modified oil is considered as much more characteristic of grapefruit peel than of the oil without this chemical Therefore, a bench panel unanimously prefers the oil containing 3-propylthio-4-heptanone.

82 1 596 251 82 EXAMPLE XXXIV

The following mixture is prepared:

Ingredients Parts by Weight Methyl anthranilate 11 0 Ethyl acetate 9 O Ethyl anthranilate 2 5 10 Ethyl butyrate 2 0 Ethyl methyl phenyl glycidate 1 5 15 Cinnamic alcohol 0 3 Cognac oil 0 1 Ethyl alcohol 73 6 20 The above mixture is judged to be an acceptable grape flavor when evaluated in a sweetened and acidified aqueous tasting solution 1 5 Parts of 3methylthio-4-heptanone is added to the above flavor and a significant improvement in aroma and taste is noted When this is evaluated in the afore-mentioned tasting solution, it is judged to have an improved 25 grape character and grape fidelity It contains more fresh concord grape character, true fruitiness with a nuance of wine In addition, it is judged to be a more rounded and natural flavor, superior to the product made without the addition of 3-methylthio4-heptanone in both aroma and taste.

Similar results obtained when using 2 5 parts of 3-methoxy-4-heptanone prepared 30 according to Example XXVI.

33 1 596 251 83 EXAMPLE XXXV

Basic black currant formulation 3-Acetylthio-4-heptanone has been added to a basic black currant flavor formulation at the rate of 1 5 % Both flavors have been compared in water at the rate of 200 ppm and evaluated by a bench panel The flavor containing 3-acetylthio-4-heptanone has had the 5 characteristic aroma and taste of ripe black currants or fresh black currant juice This typical note was not present in the basic black currant formulation Therefore all members of the panel preferred the flavor containing 3-acetylthio-4-heptanone Detailed below is the Basic Black Currant Formulation to which is added 3-acetylthio-4heptanone at the rate of 1 5 %: 10 Ingredient Parts by Weight Cis-3-hexen-1-ol 5 15 Alpha-phellandrene 1 5 Terpineol-4 10 % (in ethyl alcohol) 3 Para-hydroxy benzyl acetone 5 20 Vanillin 2 Ethyl maltol 6 25 Methyl benzoate 2 Benzaldehyde 2 Benzylpropionate 4 30 Isobutylacetate 5 Coriander oil 0 5 35 Ethylbutyrate 8 Dimethylsulfide 3 Fusel oil 8 40 Acetic acid 10 Alpha-ionone 10 % (in ethyl alcohol) 0 5 45 Ethyl heptanoate 0 5 Propylene glycol 934 1000 84 1 596 251 84 EXAMPLE XXXVI

Grapefruit flavor The following formulation is prepared:

Ingredients Parts by Weight Grapefruit oil 92 10 Bergamot oil 2 Citral 3 Amyl alcohol 1 15 Ethyl acetate 1 ( 1,3-diethylacetonyl) ( 1,3-diisopropylacetonyl) sulfide 1 20 When the above grapefruit formulation is added to water at the rate of 1 %, an excellent grapefruit drink is prepared The ( 1,3-diethylacetonyl) ( 1,3diisopropylacetonyl) sulfide gives a fruitier peeliness to the instant formulation thereby rendering it more desirable The 25 effect rendered by the ( 1,3-diethylacetonyl) ( 1,3-diisopropylacetonyl) sulfide can also be rendered by using 0 5 parts of 3-methylthio-4-heptanone or 3-propylthio-4heptanone or 3-(methallylthio)-2,6-dimethyl-4-heptanone or 3-crotylthio-2,6-dimethyl-4heptanone or 3-allylthio-2,6-dimethyl-4-heptanone.

30 EXAMPLE XXXVII 3-Propylthio-4-heptanol is added to a commercial instant tomato soup mix ("Tomatancreme Suppe, 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 "control" is prepared 35 which is identical to the initial sample except for the absence of the 3propylthio-4heptanol 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 40 which is not present in the soup prepared without using the 3-propylthio4-heptanol.

EXAMPLE XXXVIII 1-Propylthio-1,3-diphenyl-2-propanone is dissolved in 95 % ethanol to provide a 2 % solution, and is held at room temperature for 24 hours It is then diluted with water to 0 1 % 45 and this solution has an aroma of fresh green onions.

Various water solutions are prepared, as shown in the following Table VII and evaluated for taste.

50 TABLE VII

Concentration (ppm) Evaluation 55 0.002 Green onion character; near threshold level 0.010 Fresh green onion taste 60 The material is added to a chicken broth to obtain a concentration of 0 010 ppm, and it is found that the chicken taste is deepened and that a light brown aftertaste is added.

Increasing the concentration to 0 030 ppm adds an onion aroma, and the fresh onion taste is dominating 65 ss 1 596 251 85 Repetition of the foregoing with beef broth shows no significant difference at 0 010 ppm; a slightly lachrymatory aroma and an improved general taste at 0 030 ppm; and a dominating onion note with the beef broth changed to onion soup at 0 2 ppm.

It is judged that this flavor additive can replace all flavor areas where fresh onion is used, and it is interesting enough to be used alone to develop onion soup flavor characteristic 5 EXAMPLE XXXIX

Three meat-loaf type products are prepared according to the following formulation:

10 Ingredient Amount TVP, minced 1 cup 15 Ground beef 1 cup Water 1 cup Beef suet 1/3 cup 20 Bread crumbs, dry, unflavored 1 cup Whole milk 1 cup 25 Egg albumen 3 tbsp.

Salt 1 1/4 tbsp.

Black pepper 1/4 tsp 30 Catsup 1/4 cup Water 32 ml.

35 The "TVP" is a texturized vegetable protein mixture made by ArcherDaniels-Midland Company.

Three separate portions prepared according to the foregoing formulation are made into three meat loaves Loaf A contains no additional additive, Load B contains 32 ml of fresh 40 pressed onion juice to replace the 32 ml of water, and Loaf C contains 0 6 ppm of 1-propylthio-1,3-diphenyl-2-propanone.

Three three loaves are baked at 3500 F for one hour and evaluated for flavor by a panel of twelve judges The consensus of the judges is that Loaves B and C are superior to Loaf A because the onion character of B and C enhances the overall taste and covers the dry, 45 cardboard-like cereal character of Loaf A It is accordingly apparent that the product of this invention is a valuable ingredient for a wide variety of flavors and types of foodstuffs.

86159 5 EXAMPLE XL

A white bread dough mix is prepared by mixing 1350 g wheat flour and 800 ml water To the mix is added:

5 Ingredient Amount (grams) Yeast 27 0 10 Sodium chloride 27 0 Sucrose 67 5 Shortening 54 15 Non-fat dry milk powder 40 5 Yeast food (Arkady; Manufactured by Fleischmann, Div of 20 Standard Brands) 0 50 Softening agent (succinylated monoglycerides; Manufactured by Kraft Div of National 25 Dairy Products Corporation) 3 4 The dough is then mixed for 8 minutes, 3-l(methoxy-carbonyl)methylthiol-4heptanone ( 8 grams) is then mixed with the resulting product for a period of 8 minutes The dough is 30 then allowed to rise for 45 minutes at 40 C The dough is then baked for 45 minutes at 210 C.

The breadstuff product obtained has a flavor note reminiscent of the crust of home made Italian bread and has acceptable and persistent flavor properties for a period of one week and has good flavor characteristics when spread with margarine 35 By way of comparison, breadstuffs similarly prepared by omitting the sulfur-free amino acid-cyclic ketone reaction product and the 3-l(methoxycarbonyl) methylthiol-4-heptanone have a flat taste, show typical flavor deterioration on storage during a period of one week and require an expensive butter spread to provide an acceptable flavor.

40 EXAMPLE XLI

A Preparation of 3-isobutylthio-2,6-dimethyl-4-heptanone Reaction:

0 045 H/ CH 3 CH 3 OH + Na S-CH 2 -C \ CH 3 I CH 3 S 1 50 Me OH Na OCH 3 H 3 C _ Into a 50 ml, three-necked, round bottom flask equipped with pot thermometer, magnetic stirrer, gas inlet tube (for nitrogen) at top of 15 cm Vigreux column, nitrogen bubbler and cold water bath is added a solution of 0 54 grams ( 0 01 moles) of sodium methoxide dissolved in 6 ml anhydrous methanol The solution is cooled to 24 C and a solution of 0 90 grams ( 0 01 moles) of isobutyl mercaptan dissolved in 6 ml anhydrous methanol is then added to the reaction mass After stirring at 24 C for a period of 10 minutes, a solution of 1 77 grams of 3-chloro-2,6-dimethyl-4-heptanone dissolved in 2 ml 1 596 251 37 1 596 251 87 anhydrous methanol is added to the reaction mass with stirring at 24 C25 C The reaction mass is then stirred for a period of 8 hours.

The reaction mass is then concentrated on a rotary evaporator using water aspirator vacuum to 5 ml of a thick oil/solid slurry 15 ml water is added and the solid dissolves The resulting liquid mixture being in 2 phases; an aqueous phase and an organic phase The 5 reaction mass is then extracted with three 10 ml portions of methylene dichloride and the extracts are combined and washed with 8 ml water The extracts are then dried over anhydrous sodium sulfate, gravity filtered and concentrated on a rotary evaporator to a weight of 1 89 grams (pale yellow oil) GLC, NMR, IR and mass spectral analyses yield the information that the resulting product is 79 2 % 3-isobutylthio-2,6dimethyl-4-heptanone 10 The NMR analysis is as follows:

0 94 ppm, 1 10 methyl protons 18 H 15 2.26-1 60 methine protons 3 H 2.26 -CH 2 S 2 H 20 0 II 2.50 -CH 2 C 2 H 2 80 HC S 1 H 25 I -C= O The IR analysis is as follows: 30 1035 cm-', 1160, 1285, 1360, 1380, 1460, 1700, 2870, 2930, 2960.

The mass spectral analysis is as follows:

35 m/e Relative Intensity 29 7 40 41 115 174 57 422 45 69 6 8 50 89 333 1001 146 96 55 M 230 8 The NMR spectrum is set forth in Figure 55 The IR spectrum is set forth in Figure 56.

1 596 251 B Preparation of 3-isobutylthio-2,6-dimethyl-4-heptanol Reaction:

O OH 5 ony + Na BH 4 anhd Et OH 10 Into a 25 ml, three-necked, round bottom flask equipped with magnetic stirrer, reflux condenser, pot thermometer and nitrogen inlet tube to flush with dry nitrogen, is added a solution of O 1 grams ( 0 00265 moles) of sodium borohydride dissolved in 4 ml anhydrous 15 ethanol While the temperature of the sodium borohydride solution is at 24 C, a solution of 1.1 grams of 3-isobutylthio-2,6-dimethyl-4-heptanone (prepared according to Part A) dissolved in 4 ml anhydrous ethanol is added to the reaction mass slowly The reaction mass is then stirred for a period of 6 5 hours.

The reaction then shows 30 % product ( 3-isobutylthio-2,6-dimethyl-4heptanol) by GLC 20 analysis An additional 0 2 grams of sodium borohydride dissolved in 6 ml anhydrous ethanol is added, and the reaction mass is continued to be stirred for a period of 4 hours.

GLC analysis shows 59 % product Another 0 15 grams of sodium borohydride in 5 ml anhydrous ethanol is added and stirred for an additional 4 hours GLC analysis then shows 78 % product 25 The reaction mixture is then concentrated on a rotary evaporator using water aspirator vacuum to 5 ml of an oily solid 6 ml water is then added and the solid dissolves yielding two liquid phases; an organic phase and an aqueous phase The reaction mass is neutralized with % HCI to a p H of 5 The oil is then extracted with 20 ml methylene dichloride, and the extracts are washed with water The extracts are then dried over anhydrous sodium sulfate, 30 filtered and concentrated on a rotary evaporator to a weight of 0 82 grams (pale yellow oil).

GLC analysis indicates that the material is 86 4 % product NMR and IR analyses of GLC trapped compound yield the information that the product is 3-isobutylthio2,6-dimethyl-4heptanol.

The NMR spectrum is set forth in Figure 57 The IR spectrum is set forth in Figure 58 35 The NMR analysis is as follows:

1 10-0 89 ppm superimposed CH 3 18 H 40 signals 1.34 (m) methine 3 H protons 45 1.84 (m) -CH 2-C-O 2 H 2.44 (m) -CH 2-S-, HC-S 3 H 2 79 (broad) -OH 1 H 50 3.72 (m) HC OH 1 H 55 The IR analysis is as follows:

1055 cm-1, 1365, 1385, 1465, 2880, 2930, 2960, 3460.

39 1 596 251 89 EXAMPLE XLII

Otto of rose perfume formulation The following mixture is prepared:

5 Ingredients Parts by Weight Phenyl acetic acid 5 10 Hydroxycitronellal 10 Geraniol 125 Citronellol 150 15 Phenyl ethyl alcohol 50 Phenyl ethyl acetate 4 20 Ethyl phenyl acetate 5 Citronellyl formate 20 Geranyl acetate 25 25 Linalool 15 Terpineol 10 30 Eugenol 3 Phenyl acetaldehyde dimethyl acetal 5 Benzyl acetate 3 35 Guaiacwood Oil 5 3-methylthio-4-heptanone produced according to the process of Part "C" of Example XX 10 40 The 3-methylthio-4-heptanone, produced according to the process of Part "C" of Example XX imparts a green, fruity, spicy topnote so characteristic of rose otto to this formulation.

1 596 251 90EXAMPLE XLIII

Oriental vetivert The following mixture is prepared:

5 Ingredients Parts by Weight Orange oil Florida 150 10 Lemon Oil 75 Oil of bitter orange 100 Grapefruit oil 200 15 Neroli oil 20 Isocyclemone E (a product produced according to the process of Example VI 20 of U S Patent 3,907,321, issued on Sept 23, 1975, which comprises reacting myrcene with 3-methyl-3-pentene-2-one in the presence of aluminum chloride and then cyclizing the resulting Diels-Alder 25 adduct) 40 Gamma methyl ionone 15 Ylang estra 5 30 Auralva (The Shiff base of methyl anthranilate and hydroxy citronellal, specifically described in Section 1735 of Arctancer, "Perfume and Flavor Chemicals (Aroma 35 Chemicals)" 1969) 15 Lyral 4-( 4-methyl,4-hydroxyamyl) A 3cyclohexene carboxaldehyde 30 40 Grisalva (produced by the 50 % sulfuric acid treatment of 3-ethyl-1 l 2,2,6-trimethylcyclohexene-5-yl-1 lhexen-3-ol-6) 10 3-(methallylthio)-2,6-dimethyl-4-heptanone, 45 produced according to the process of Example XXI (C) 50 The 3-(methallylthio)-2,6-dimethyl-4-heptanone, produced according to the process of 50 Example XXI(C) imparts a sweet, orange-flower, green beta vetivone, woody character to this composition.

91 1 596 251 91 EXAMPLE XLIV

Narcisse formulation The following mixture is prepared:

5 Ingredient Parts by Weight Benzyl alcohol 50 10 Benzyl benzoate 25 Terpineol 30 Nerol 15 15 Phenyl ethyl alcohol 50 Geraniol 40 20 Linalool 50 Para cresyl phenyl acetate 10 Benzyl acetate 6 25 Acetyl isoeugenol 20 Heliotropin 30 30 Ylang extra 5 Para cresol 1 3-methylthio-4-heptanol, produced according 35 to the process of Example XX Part "D" 20 The 3-methylthio-4-heptanol, produced according to the process of Example XX Part "D" imparts a green, floral, tobacco-like oriental middle and undertone necessary for 40 narcisse.

1 596 251 EXAMPLE XLV

Comparison of substituted thioheptanones and their corresponding alcohols 3-methylthio-4-heptanone (hereinafter referred to as "chemical I") has a powerful green, minty, herbaceous odor.

3-methylthio-4-heptanol (hereinafter referred to as "chemical II") has a green, floral, herbal odor, about one-fifth the strength of chemical I.

3 (methallylthio)2,6-dimethyl-4-heptanone (hereinafter referred to as "chemical III") has a floral, herbaceous aroma with a fruity, grapefruit (nootkatone) character.

The foregoing materials, chemicals I, II and III may be used in perfumery to give unusual and novel effects to various fragrance types They are useful in creating modern blends which are in some cases far removed from the classical concepts of perfumery The use of chemicals I, II and III may be demonstrated in the following modemrn herbal formulation:

Ingredients A B C Oakmoss Absolute 50 % in diethylphthalate cc-methyl-3,4-methylene-dioxyhydrocinnamic aldehyde methyl dihydrojasmonate (produced by Firmenich et Cie of Geneva, Switzerland) Coumarin 20 20 10 10 20 20 Musk Ketone Isocyclocitral ( 10 % in diethylphthalate) Galbanum Oil ( 10 % in diethylphthalate) Rosemary Oil 80 80 10 10 10 10 Pine Needle Oil Fir Balsam Absolute ( 10 % in diethylphthalate) Bergamot Oil Lemon Oil 60 60 10 10 60 60 14 14 14 468 Benzyl Acetate Linalool 460 460 80 80 Indol ( 10 % in diethylphthalate) Undecalactone ( 10 % in diethylphthalate) Ylang Ylang Oil Alkylthio chemical I Alkylthio chemical II 12 12 12 32 32 32 Alkylthio chemical III 1 596 251 The addition of 0 2 % by weight of chemical I gives increased strength to the fragrance as well as modifying the herbal character and rendering it unusual and novel The material can be used in perfumery at from approximately 1 ppm ( 0 0001 %) up to approximately 1 %.

The weaker alcohol, chemical II, is added to the fragrance at 1 % by weight The addition of this material gives a softer effect but alters the herbal effect to an unusual and novel character Chemical II may be used in perfumery from approximately 0 01 % to 5 % by weight For special effects up to 50 % may be used.

The addition of 1 % of chemical III gives quite a different effect In this case the herbal character is not altered as in the other examples, but the citrus notes are enhanced and strengthened This chemical may be used in perfumery from approximately 0 01 % to 10 % by weight For special effects up to 50 % may be used.

In all cases of the above examples, the fragrance is improved by the addition of the alkylthio materials chemicals I, II and III and rendered more desirable and novel.

EXAMPLE XLVI

Preparation of soap compositions Grams of soap chips are mixed with 1 gram of the chemical set forth in Table VIII below until a substantially homogeneous composition is obtained The perfumed soap composition manifests an aroma according to the aroma set forth in Table VIII below:

TABLE VIII

Compound Aroma 3-methylthio-4-heptanol 3-methylthio-4-heptanone 3-propylthio-4-heptanol 3-thioacetyl-2,6-dimethyl4-heptanone 3-isobutylthio-4-heptanone 3-isobutylthio-2,6-dimethyl4-heptanol 3-methylthio-2,6-dimethyl4-heptanone 3-(methallylthio)-2,6dimethyl-4-heptanone A sweet, green, floral, herbal, vegetative aroma with an underlying verdima nuance.

A green, minty, herbaceous aroma with basil nuances.

A green aroma with floral nuances A grapefruit oil-like aroma.

A green, spicey and peppery aroma with an underlying bergamot note.

A green aroma containing notes of hyacinth and narcisse.

A sweet, slightly floral and berry nuances.

A fruity, grapefruit, somewhat floral aroma with underlying yara and neroli notes and bready, vegetative nuances.

EXAMPLE XLVII

Preparation of a detergent composition A total of 100 grams of a detergent powder (a non-ionic detergent powder containing a proteolytic enzyme prepared according to Example I of Canadian Patent 985, 190 issued on March 9, 1976) is mixed with 0 15 grams of the alpha-oxy(oxo)sulfides set forth in Table IX below until a substantially homogeneous composition is obtained This composition has an excellent aroma as defined in Table IX below:

94 1 596 251 94 TABLE IX

Compound Aroma 3-methylthio-4-heptanol 3-methylthio-4-heptanone 3-propylthio-4-heptanol 3-thioacetyl-2,6-dimethyl4-heptanone 3-isobutylthio-4-heptanone 3-isobutylthio-2,6-dimethyl4-heptanol 3-methylthio-2,6-dimethyl4-heptanone 3-(methallylthio)-2,6dimethyl-4-heptanone A sweet, green, floral, herbal, vegetative aroma with an underlying verdima nuance.

A green, minty, herbaceous aroma with basil nuances.

A green aroma with floral nuances A grapefruit oil-like aroma.

A green, spicey and peppery aroma with an underlying bergamot note.

A green aroma containing notes of hyacinth and narcisse.

A sweet, slightly floral and berry nuances.

A fruity, grapefruit, somewhat floral aroma with underlying yara and neroli notes and bready, vegetative nuances.

EXAMPLE XLVIII Preparation of cosmetic powder compositions 1 Cosmetic powders are prepared by mixing in a ball mill 100 grams of talcum powder with 0.25 grams of each of the compounds set forth in Table X below Each of these powders has an excellent aroma as set forth in Table X below:

1 596 251 1 596 251 TABLE X

Compound 3-methylthio-4-heptanol 3-methylthio-4-heptanone 3-propylthio-4-heptanol 3-thioacetyl-2,6-dimethyl4-heptanone 3-isobutylthio-4-heptanone 3-isobutylthio-2,6-dimethyl4-heptanol 3-methylthio-2,6-dimethyl4-heptanone 3-(methallylthio)-2,6dimethyl-4-heptanone Aroma A sweet, green, floral, herbal, vegetative aroma with an underlying verdima nuance.

A green, minty, herbaceous aroma with basil nuances.

A green aroma with floral nuances A grapefruit oil-like aroma.

A green, spicey and peppery aroma with an underlying bergamot note.

A green aroma containing notes of hyacinth and narcisse.

A sweet, slightly floral and berry nuances.

A fruity, grapefruit, somewhat floral aroma with underlying yara and neroli notes and bready, vegetative nuances.

EXAMPLE XLIX

Perfumed liquid detergent Concentrated liquid detergents with rich, pleasant aromas as set forth in Table XI below are prepared containing 0 10 %, 0 15 % and 0 20 % of an alpha-oxy(oxo) sulfide as set forth in Table XI below They are prepared by adding and homogeneously admixing the appropriate quantity of alpha-oxy(oxo)sulfide in the liquid detergent The liquid detergents are all produced using anionic detergents containing a 50:50 mixture of sodium lauroyl sarcosinate and potassium N-methyl lauroyl tauride The detergents all possess a pleasant fragrance as defined in the table below, the intensity increasing with greater concentration of alpha-oxy(oxo)sulfide of this invention.

1 596 251 TABLE XI

Compound Aroma 3-methylthio-4-heptanol 3-methylthio-4-heptanone 3-propylthio-4-heptanol 3-thioacetyl-2,6-dimethyl4-heptanone 3-isobutylthio-4-heptanone 3-isobutylthio-2,6-dimethyl4-heptanol 3-methylthio-2,6-dimethyl4-heptanone 3-(methallylthio)-2,6dimethyl-4-heptanone A sweet, green, floral herbal, vegetative aroma with an underlying verdima nuance.

A green, minty, herbaceous aroma with basil nuances.

A green aroma with floral nuances.

A grapefruit oil-like aroma.

A green, spicey and peppery aroma with an underlying bergamot note.

A green aroma containing notes of hyacinth and narcisse.

A sweet, slightly floral and berry nuances.

A fruity, grapefruit, somewhat floral aroma with underlying yara and neroli notes and bready, vegetative nuances.

EXAMPLE L

An alpha-oxy(oxo)sulfide as set forth in Table XII below is incorporated in a cologne at a concentration of 2 5 % in 85 % aqueous ethanol; and into a handkerchief perfume at a concentration of 20 % (in 95 % aqueous ethanol) A distinct and definite strong fragrance as set forth in Table XII below is imparted to the cologne and to the handkerchief perfume:

1 596 251 TABLE XII

Compound Aroma 3-methylthio-4-heptanol 3-methylthio-4-heptanone 3-propylthio-4-heptanol 3-thioacetyl-2,6-dimethyl4-heptanone 3-isobutylthio-4-heptanone 3-isobutylthio-2,6-dimethyl4-heptanol 3-methylthio-2,6-dimethyl4-heptanone 3-(methallylthio)-2,6dimethyl-4-heptanone A sweet, green, floral, herbal, vegetative aroma with an underlying verdima nuance.

A green, minty, herbaceous aroma with basil nuances.

A green aroma with floral nuances.

A grapefruit oil-like aroma.

A green, spicey and peppery aroma with an underlying bergamot note.

A green aroma containing notes of hyacinth and narcisse.

A sweet, slightly floral and berry nuances.

A fruity, grapefruit, somewhat floral aroma with underlying yara and neroli notes and bready, vegetative nuances.

EXAMPLE LI

Tobacco use of 3-(methallylthio)-2,6-dimethyl-4-heptanone The following tobacco flavor formulation (A) is prepared:

Ingredients Parts Ethyl Butyrate Ethyl Valerate Maltol Cocoa Extract Coffee Extract Ethanol ( 95 % aqueous) Water 0.05 0.05 2.00 26.00 10.00 20.00 41.90 98 1 596 251 QRJ The following tobacco blend Formulation (B) is prepared:

Ingredients Parts 5 Bright Tobacco 40 1 Burley Tobacco 24 9 10 Maryland Tobacco 1 1 Turkish Tobacco 11 6 Stem (Flue-cured) Tobacco 14 2 15 Glycerine 2 8 Water 5 3 20 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 nonflavored tobacco formulations are then formulated into cigarettes by the usual manufacturing procedure:

25 At the rate of 100 parts per million, to one-half of the cigarettes in each group, is added 3-(methallylthio)-2,6-dimethyl-4-heptanone The use of the 3(methallylthio)-2,6dimethyl-4-heptanone in the cigarettes causes the cigarettes prior to smoking to have a sweet, fruity, grapefruit aroma with green and spicey nuances In smoke flavor, the tobacco has a sweeter, less harsh and more aromatic aroma with more body, and 30 sweet, fruity, grapefruit-like nuances which are highly desirable These notes are present whether or not the other flavor ingredients of formulation (A) are present.

35 It will be understood by those skilled in the art from the foregoing description, that the sulfide compounds of our invention can be used in the preparation of a wide variety of tobacco flavors and products.

EXAMPLE LII 40 Tobacco flavor formulation containing 3-(methallylthio)-2,6-dimethyl-4heptanone A tobacco flavor formulation is prepared by admixing the following ingredients:

Ingredients Parts 45 3-(methallylthio)-2,6sa dimethyl-4-heptanone 2 0 50 Ethyl butyrate 05 Ethyl Valebutyrate 0 5 Ethyl Valerate 0 5 Maltol 20 0 55 Cocoa Extract 260 0 Coffee Extract 100 0 60 % Aqueous Ethanol 200 0 1 596 251 OR Water 419 0 156219 This formulation is added to smoking tobacco at the rates of 0 01 %, 0 02 %, 0 03 % and 0.035 % based on the dry weight of the tobacco The tobacco is then manufactured into cigarettes according to standard manufacturing practice On smoking the cigarettes, the aroma and taste is described as "sweet, fruity, grapefruit-like", the tobacco itself on smoking being sweeter, less harsh, more aromatic and having more body 5 Brief description of the drawings:

Figure 1 represents the NMR spectrum for 3-mercapto-4-heptanone produced according to Example I(B).

Figure 2 represents the infra-red spectrum for 3-mercapto-4-heptanone produced 10 according to the process of Example I(B).

Figure 3 represents the NMR spectrum for 3-mercapto-4-heptanol produced according to Example I(C).

Figure 4 represents the infra-red spectrum for 3-mercapto-4-heptanol produced according to Example I(C) 15 Figure 5 represents the NMR spectrum for 4-mercapto-5-nonanone produced according to Example II(B).

Figure 6 represents the infra-red spectrum for 4-mercapto-5-nonanone produced according to Example II(B).

Figure 7 represents the NMR spectrum for 4-mercapto-5-nonanol produced according to 20 Example II(C).

Figure 8 represents the infra-red spectrum for 4-mercapto-5-nonanol produced according to Example II(C).

Figure 9 represents the NMR spectrum for 5-mercapto-6-undecanone produced according to Example III(B) 25 Figure 10 represents the infra-red spectrum for 5-mercapto-6-undecanone produced according to Example III(B).

Figure 11 represents the NMR spectrum for 5-mercapto-6-undecanol produced according to Example III(C).

Figure 12 represents the infra-red spectrum for 5-mercapto-6-undecanol produced 30 according to Example III(C).

Figure 13 represents the NMR spectrum for 2,6-dimethyl-3-mercaptoheptanone-4 produced according to Example IV(B).

Figure 14 represents the infra-red spectrum for 2,6-dimethyl-3-mercaptoheptanone-4 produced according to Example IV(B) 35 Figure 15 represents the NMR spectrum for 2,6-dimethyl-3-mercaptoheptanol-4 produced according to Example IV(C).

Figure 16 represents the infra-red spectrum for 2,6-dimethyl-3-mercaptoheptanol-4 produced according to Example IV(C).

Figure 17 represents the NMR spectrum for 2-mercaptocyclododecanone-1 produced 40 according to Example XV(B).

Figure 18 represents the infra-red spectrum for 2-mercaptocyclododecanone1 produced according to Example XV(B).

Figure 19 represents the NMR spectrum for 2-mercapto-3-pentanone produced according to Example XVI(B) 45 Figure 20 represents the infra-red spectrum for 2-mercapto-3-pentanone produced according to Example XVI(B).

Figure 21 is the NMR spectrum for the product of Example XX(B) wherein 3-thioacetyl-4-heptanone is produced.

Figure 22 is the IR spectrum for the product of Example XX(B) wherein 3thioacetyl-4 50 heptanone is produced.

Figure 23 is the NMR spectrum for the product of Example XX(C) wherein 3-thiomethyl-4-heptanone is produced.

Figure 24 is the IR spectrum for the product of Example XX(C) wherein 3thiomethyl-4heptanone is produced 55 Figure 25 is the NMR spectrum for the product of Example XX(D) wherein 3-thiomethyl-4-heptanol is produced.

Figure 26 is the IR spectrum for the product of Example XX(D) wherein 3thiomethyl-4heptanol is produced.

Figure 27 is the NMR spectrum for the product of Example XXI(C) wherein 60 3-methallylthio-2,6-dimethyl-4-heptanone is produced.

Figure 28 is the IR spectrum for the product of Example XXI(C) wherein 3methallylthio-2,6-dimethyl-4-heptanone is produced.

Figure 29 is the NMR spectrum for the product of Example XXI(D) wherein 3-crotvlthio-2,6-dimethyl-4-heptanone is produced 65 1 596 251 1 596 251 Figure 30 is the IR spectrum for the product of Example XXI(D) wherein 3crotylthio2,6-dimethyl-4-heptanone is produced.

Figure 31 is the NMR spectrum for the product of Example XXI(E) wherein 3-allylthio-2,6-dimethyl-4-heptanone is produced.

Figure 32 is the IR spectrum for the product of Example XXI(E) wherein 3allylthio-2,6 5 dimethyl-4-heptanone is produced.

Figure 33 is the NMR spectrum for the product of Example XXI(F) wherein ( 1,3-diethylacetonyl) ( 1,3-diisopropylacetonyl)sulfide is produced.

Figure 34 is the IR spectrum for the product of Example XXI(F) wherein ( 1,3diethylacetonyl) ( 1,3-diisopropylacetonyl) sulfide is produced 10 Figure 35 is the NMR spectrum for the product of Example XXI(G) wherein 3-l(methoiycarbonyl)methylthiol-2,6-dimethyl-4-heptanone is produced.

Figure 36 is the IR spectrum for the product of Example XXI(G) wherein 3l(methoxycarbonyl)methylthiol-2,6-dimethyl-4-heptanone is produced.

Figure 37 is the NMR spectrum for the product of Example XXI(H) wherein 15 3-lmethoxycarbonyl)methylthiol-4-heptanone is produced.

Figure 38 is the IR spectrum for the product of Example XXI(H) wherein 3lmethoxycarbonyl)methylthiol 4-heptanone is produced.

Figure 39 is the NMR spectrum for the product of Example XXI(I) wherein 3-thioacetyl-2,6-dimethyl-4-heptanone is produced 20 Figure 40 is the IR spectrum for the product of Example XXI(I) wherein 3thioacetyl-2,6dimethyl-4-heptanone is produced.

Figure 41 is the NMR spectrum for the product of Example XXII(A) wherein 3-propylthio-4-heptanone is produced.

Figure 42 is the IR spectrum for the product of Example XXII(A) wherein 25 3-propylthio-4-heptanone is produced.

Figure 43 is the NMR spectrum for the product of Example XXII(B) wherein 3-propylthio-4-heptanol is produced.

Figure 44 is the IR spectrum for the product of Example XXII(B) wherein 3propylthio4-heptanol is produced 30 Figure 45 is the NMR spectrum for the product of Example XXIII wherein 3-isobutylthio-4-heptanone is produced.

Figure 46 is the IR spectrum for the product of Example XXIII wherein 3isobutylthio-4heptanone is produced.

Figure 47 is the NMR spectrum for the product of Example XXIV(B) wherein 35 1-propylthio-1,3-diphenyl-2-propanone is produced.

Figure 48 is the IR spectrum for the product of Example XXIV(B) wherein 1-propylthio-1,3-diphenyl-2-propanone is produced.

Figure 49 is the NMR spectrum for the product of Example XXV(A) wherein 3-methylthio-2,6-dimethyl-4-heptanone is produced 40 Figure 50 is the IR spectrum for the product of Example XXV(A) wherein 3-methylthio-2,6-dimethyl-4-heptanone is produced.

Figure 51 is the NMR spectrum for the product of Example XXV(B) wherein 3-methylthio-2,6-dimethyl-4-heptanol is produced.

Figure 52 is the IR spectrum for the product of Example XXV(B) wherein 3methylthio 45 2,6-dimethyl-4-heptanol is produced.

Figure 53 is the NMR spectrum for the product of Example XXVI wherein 3-methoxy-4-heptanone is produced.

Figure 54 is the IR spectrum for the product of Example XXVI wherein 3methoxy-4heptanone is produced 50 Figure 55 is the NMR spectrum for the product of Example XLI(A) wherein 3-isobutylthio-2,6-dimethyl-4-heptanone is produced.

Figure 56 is the IR spectrum for the product of Example XLI(A) wherein 3isobutylthio2,6-dimethyl-4-heptanone is produced.

Figure 57 is the NMR spectrum for the product of Example XLI(B) wherein 55 3-isobutylthio-2,6-dimethyl-4-heptanol is produced.

Figure 58 is the IR spectrum for the product of Example XLI(B) wherein 3isobutylthio2,6-dimethyl-4-heptanol is produced.

llY

Claims (35)

WHAT WE CLAIM IS:

1 An a-oxy(oxo)sulfide, ether, or mercaptan having the structure:

,,-R'1 ' _ 5 Q 5210 z 15 wherein Q is 0 OH - C or C 20 I Z is sulfur or oxygen; when R 1, R 2, R, and R

2 are taken separately, then R 1 and R, are each 25 the same or different and are each hydrogen or C 1-C

3 alkyl and R 2 R 2 are each the same or different and are each hydrogen or methyl; when R, and R 2 and R' and R 2 are taken together with the carbon atoms to which they are attached, R 1 and R 2 form a phenyl moiety, and R, and R 2 form a phenyl moiety; and when Z is sulfur, R, and R, are optionally joined to complete a cyclododecyl ring; and Y is hydrogen, Cl C

4 alkyl, C 3 or C 4 30 alkenyl, acetyl, methoxycarbonyl-methyl or 1,3-diethylacetonyl, with the proviso that Y is hydrogen when either (i) R 1 and R 1 are joined to complete a cyclododecyl ring, and Q is 0 1 II C 35 C and R 2 and R 2 are each hydrogen, or (ii) R 2 and R are each hydrogen; R 1 is ethyl and R, is propyl; and Y is not hydrogen when R, and R, are each 40 hydrogen and R 2 and R 2 are both hydrogen or both methyl and Q is 0 II -C 45 2 A compound according to claim 1 wherein Q is 50 0 II -55 R, and R' are each hydrogen, R 2 and R 2 are each methyl, Y is methoxycarbonylmethyl, and Z is sulfur a uu 101 1 596 251 1 N 1 102 1 596 251 102 3 A compound according to claim 1 wherein Q is 0 c II

5 R 1 and R' are each hydrogen, R 2 and R 2 are each methyl, Y is methyl and Z is oxygen 10 4 A compound according to claim 1 wherein Q is 0 Ió 15 -C20 R 1 and R 2 taken together form a phenyl moiety, R, and R 2 taken together form a phenyl moiety, Y is n-propyl, and Z is sulfur.

A compound according to claim 1 wherein Q is 25 II C30 R 1 and R' are each methyl, R 2 R 2 are each methyl, Y is 4-oxo-3-heptyl, and Z is sulfur.

6 A compound according to claim 1 wherein Q is 35 0 II C 40 R 1 and R, are each hydrogen, R 2 and R 2 are each methyl, Y is methyl and Z is sulfur.

7 A compound according to claim 1, wherein Q is 45 OH C 50 H R 1 and R, are each hydrogen, R 2 and R 2 are each methyl, Y is n-propyl, and Z is sulfur.

8 A compound according to claim 1 wherein Q is 55 -C 60 R, and R, are each hydrogen, R 2 and R 2 are each methyl, Y is 2-methyl-1propyl, and Z is sulfur 65 102 1 596 251 102 1 596 251

9 A compound according to claim 1 wherein Q is 0 _ 5 l l R 1 and R, are each hydrogen, R 2 and R 2 are each methyl, Y is n-propyl and Z is sulfur

10 A compound according to claim 1 wherein Q is OH I 15 -CCH R, and R' are each methyl, R 2 and R 2 are each methyl, Y is methyl, and Z is sulfur 20

11 A compound according to claim 1 wherein Q is 0 II 25 -CRI and R, are each methyl, R 2 and R' are each methyl, Y is methallyl, and Z is sulfur 30

12 A compound according to claim 1 wherein Q is 0 _ 35 R, and R, are each methyl, R 2 and R are each methyl, Y is crotyl, and Z is sulfur 40

13 A compound according to claim 1 wherein Q is 0 II 45 R 1 and R, are each methyl, R 2 and R' are each methyl, Y is allyl, and Z is sulfur 50

14 A compound according to claim 1 wherein Q is 0 -C 55 RI and RI are each hydrogen, R 2 and R 2 are each methyl, Y is acetyl, and Z is sulfur.

103 103 1 596 251 A compound having the structure:

R 3 R 4 l l 5 S \ y 10 wherein R 3 and R 4 are the same or different and each is, in the alternative, one of hydrogen or methyl, Q is, in the alternative, one of:

15 0 OH C_ 20 CC CX -4 I H and Y is, in the alternative, one of methyl, methallyl having the structure: 25 3 30 _ CH 2 _ 1-propyl, 2-methyl-1-propyl, or acetyl 35

16 A compound according to claim 15, wherein R 3 and R 4 are each hydrogen, Y is methyl, and Q is:

OH 40 I _ H _

17 A compound according to claim 1, wherein Q is 45 0 II -C 50 R 1 and R, are each methyl, R 2 and R 2 are each methyl, Y is acetyl, and Z is sulfur.

18 A compound according to claim 1 which is 2-mercaptocyclododecanone-1 having 55 the structure:

104 104 1 59 25 _ 1 __ 1 V

19 A compound according to claim 1 which has the structure:

SH Q 5 wherein Q' is, in the alternative, one of 10 0 OH V 1 OR O C 15

20 A compound according to claim 19, wherein Q' is 20 OH -CH _ 25

21 A compound according to claim 19 wherein Q' has the structure:

O 30 11 -C35

22 Use as a flavorant in augmenting or enhancing the organoleptic properties of foodstuffs, chewing gums, medicinal products, or tobacco or in perfumery or perfumed articles in augmenting or enhancing the aroma thereof, of one of more members of the alpha-oxy(oxo)sulfides, ethers, or mercaptans, according to one or more of claims 1-21 40

23 Use as a flavorant in augmenting or enhancing the organoleptic properties of foodstuffs, chewing gums, medicinal products, or tobacco or in perfumery or perfumed articles for augmenting or enhancing the aroma thereof, of one or more members of the alpha-oxy(oxo) sulphides, ethers or mercaptans having the structure:

45 Z 5 y 10 so 50 wherein Rs and R 6 are each the same or different, and Rs and R 6 can be taken together or separately and when R 5 and R 6 are taken separately, each represents C 1C 4 alkyl or phenyl, and when R 5 and R 6 are taken together they complete a cyclododecyl ring; Z' is sulfur or 55 oxygen; Y' is hydrogen, C 1-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl or 1,3-diethylacetonyl; and Q is, in the alternative, one of 0 OH II I 11 OR l C C _ H 1 596 251 l 05 1 596 251 with the proviso that when Y' is hydrogen and R 5 and R 6 are each alkyl, and Q is O -C 5 then R 5 and R 6 are each Ca or C 4 alkyl.

24 Use according to Claim 23 of alpha-oxy(oxo) sulfides and mercaptans in a perfume 10 composition or perfumed article comprising at least one alpha-oxy(oxo) sulfide or mercaptan compound having the structure:

R 5 N-%Q 6 15 H wherein each of R' and R' are the same or different, and each is methyl, ethyl, 1-propyl, 20 2-propyl or 1-butyl; Q is 0 OH 11 OR

25 H and wherein Y' is hydrogen, methyl, methallyl having the structure: 30 3 35 _ CH 2 _ 1-propyl, 2-methyl-1-propyl or acetyl, and at least one adjuvant comprising natural perfume 40 oils, synthetic perfume oils, alcohols other than those recited above, aldehydes, ketones other than those recited above, esters other than those recited above, nitriles or lactones, with the proviso that when Y is hydrogen and Q is O 45 11 -C50 R and R 6 are not both methyl or both ethyl.

Use according to claim 23 of alpha-oxy(oxo) sulfides and mercaptans in a perfumed article comprising at least one alpha-oxy(oxo) sulfide or mercaptan as defined in claim 24 in a detergent, soap, bath preparation, hair preparation, cosmetic preparation or cosmetic 55 powder.

26 Use according to Claim 23 or alpha-oxy (oxo)mercaptans and sulfides in a process for producing a perfume composition comprising the step of admixing a composition of matter suitable for perfumery with a fragrance imparting quantity of an alphaoxy(oxo)mercaptan or sulfide as defined in claim 24 60

27 Use according to Claim 23 of alpha-oxy(oxo)mercaptans or sulfides in a cologne composition comprising an alpha-oxy(oxo)mercaptan or sulfide or combination thereof as defined in claim 24 and ethanol and water.

28 Use according to claim 24 wherein, in the alpha-oxy(oxo)mercaptan or sulfide, each of R, and R% is ethyl, and Y' is hydrogen 65 106 106 1 596 251

29 Use according to claim 24 wherein,in the alpha-oxy(oxo)mercaptan or sulfide, each of R and R 6 is 1-propyl, and Y' is hydrogen.

Use according to claim 24 wherein, in the alpha-oxy(oxo)mercaptan or sulfide, each of Rs and R 6 is 2-propyl, and Y' is hydrogen.

31 Use according to claim 24 wherein, in the alpha-oxy(oxo)mercaptan or sulfide, each 5 of Rs and R 6 is 1-butyl, and Y' is hydrogen.

32 Use according to claim 24 wherein, in the alpha-oxy(oxo)mercaptan or sulfide, each of Rs and R 6 is ethyl, Q is O 10 -C15 and Y' is hydrogen.

33 Use according to claim 25 wherein, in the alpha-oxy(oxo)mercaptan or sulfide, R' and R 6 are each ethyl, and Q is:

20 0 II C 25

34 Use according to claim 25 wherein, in the alpha-oxy(oxo)mercaptan or sulfide, R' and RP are both 2-propyl, and Q is:

O 30 II -C 35 Use as claimed in claim 26 wherein, the alpha-oxy(oxo)mercaptan or sulfide is as defined in claim 33.

36 Use as claimed in claim 26 wherein, the alpha-oxy(oxo)mercaptan or sulfide is as 40 defined in claim 34.

0 11 II -C 45 37 Use as claimed in claim 27 wherein, the alpha-oxy(oxo)mercaptan or sulfide used in the cologne is as defined in claim 33 50 38 Use as claimed in claim 27 wherein, the alpha-oxy(oxo)mercaptan or sulfide used in the cologne is as defined in claim 34.

39 Use according to claim 24 wherein, in the alpha-oxy(oxo)mercaptan or sulfide used in the perfume composition, each of R% and R 6 is methyl, Y' is methallyl, and Q is:

_ _ 55 0 II C60 A perfume composition comprising a perfuming quantity of the compound defined according to claim 39, and at least one adjuvant which is, in the alternative, a natural perfume oil, a synthetic perfume oil, an alcohol, an aldehyde, a ketone, other than the ketone recited in Claim 39, a nitrile, an ester or a lactone 65 107 107 1 596 251 41 A perfumed article comprising the compound defined according to claim 39 and, in the alternative, a detergent, a soap, a bath preparation, a hair preparation, a cosmetic preparation or a powder.

42 A process for producing a perfume composition comprising the step of intimately admixing the compound defined according to claim 39 and at least one material which is, in 5 the alternative, a natural perfume, a synthetic perfume oil, an alcohol, an aldehyde, a ketone other than the ketone recited in Claim 39, a nitrile, an ester, or a lactone.

43 A cologne composition comprising the compound defined according to claim 39, and ethanol and water.

44 A process for augmenting or enhancing the fruity or vegetable aroma or taste of a 10 foodstuff which comprises adding thereto from about 0 02 ppm up to about 50 ppm by weight of said foodstuff of 3-mercapto-4-heptanol; 4-mercapto-5-nonanone; 4-mercapto-5-nonanol; 15 3-mercapto-2,6-dimethyl-4-heptanone; or 2-mercaptocyclododecanone-1.

A process according to claim 44 wherein the alpha-oxy(oxo)mercaptan is 3-mercapto-4-heptanol.

46 A process according to claim 44 wherein the alpha-oxy(oxo)mercaptan is 20 4-mercapto-5-nonanone.

47 A process according to claim 44 wherein the alpha-oxy(oxo)mercaptan is 4-mercapto-5-nonanol.

48 A processs according to claim 44 wherein the alpha-oxy(oxo)mercaptan is 3-mercapto-2,6-dimethyl-4-heptanone 25 49 A process according to claim 44 wherein the alpha-oxy(oxo)mercaptan is 2-mercaptocyclododecanone-1.

A process according to claim 44 wherein the alpha-oxy(oxo)mercaptan is a mixture of 3-mercapto-4-heptanol and 3-mercapto-2,6-dimethyl-4-heptanone.

51 A composition for augmenting or enhancing the fruity or vegetable flavor of a 30 foodstuff comprising (i) from 0 05 % up to 5 % by weight of said flavor of at least one sulfur-containing compound which is an alpha-oxy(oxo)mercaptan having the structure:

t 1 35 $B H SH wherein Q is 40 OH C H 4545 OR O 50 C 55 and R 7 and R 8 taken separately are the same or different and are each methyl, ethyl.

1-propyl or 2-propyl; or R 7 and Rs taken together represents nonylene having the structure:

108 108 109 1 596 251 109 5 L with the proviso that when Q is o O 10 11 C15 R 7 and R 8 are not both ethyl or both methylthe remainder of said composition being (i) at least one adjuvant which is, in the alternative, one of:

grapefruit oil; 20 bergamot oil; citral; 25 amyl alcohol; ethyl acetate; 5-phenyl-4-pentenal 30 5-phenyl-2-pentenal; limonene; 35 n-octanal; n-decanal; geraniol; 40 cadinene; dimethylanthranilate; 45 45 methylanthranilate; vanillin; amyl butyrate; 50 2-(n-pentyl)thiazole) 2-(i-butyl)thiazole; 55 2-(i-propyl)thiazole 2-(n-propyl)thiazole; methional; 60 4-methylthiobutanal; 2-ethyl-3-acetyl pyrazine; 109 1 596 251 109 1 596 251 110 tetramethyl pyrazine; 2-methyl pyrazine; 2-trans hexenal; 5 maltol; 2-phenyl-4-pentenal; 10 2-phenyl-4-pentenal dimethyl acetal; or 2-phenyl-4-pentenal diethyl acetal.

52 A composition according to claim 51 wherein the sulfur-containing compound is 15 3-mercapto-4-heptanol.

53 A composition according to claim 51 wherein the sulfur-containing compound is 4-mercapto-5-nonanone.

54 A composition according to claim 51 wherein the sulfur-containing compound is 4-mercapto-5-nonanol 20 A composition according to claim 51 wherein the sulfur-containing compound is 3-mercapto-2,6-dimethyl-4-heptanone.

56 A composition according to claim 51 wherein the sulfur-containing compound is 2-mercaptocyclododecanone-1.

57 A composition according to claim 51 wherein the sulfur-containing compound is a 25 mixture of 3-mercapto-4-heptanol and 3-mercapto-2,6-dimethyl-4-heptanone.

58 An edible composition comprising an edible carrier and an alphaoxy(oxo)sulfide or ether having the structure:

1 30 F Rl' R 2 35 z wherein Q is 40 0 OH 11 OR | 45 C -C_ I Z is sulfur or oxygen; when R 1 and R 2 and R, and R 2 are taken separately, R 1 and R' are each hydrogen or methyl, and R 2 and R 2 are each methyl; and when the pairs of moieties R, 50 and R 2 and R, and Rz are taken together, R 1 and R 2 and R' and R% represent phenyl moieties; and Y 1 is, in the alternative, one of C 1-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl.

59 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, Q is: 55 0 II 11 -C60 and R 1 and R, are each hydrogen, R 2 and R 2 are each methyl, Y 1 is methoxycarbonylmethyl, and Z is sulfur.

111 1 596 251 111 A composition according to claim 58 wherein, in the alpha-oxy(oxo)sulfide or ether, Q is0 1 -C 5 and R 1 and RI are each hydrogen, R 2 and R 2 are each methyl, Y 1 is methyl, and Z is 10 oxygen.

61 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, Q is:

0 II 15 C20 the pairs of moieties R 1 and R 2 and R, and R 2, each taken together, form a phenyl moiety, Y 1 is n-propyl, and Z is sulfur.

62 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, Q is:

O 25 11 -C30 R 1 and RI are each methyl, R 2 and R 2 are each methyl, Y 1 is 3-oxo-4heptyl, and Z is sulfur.

63 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, Q is: 35 0 1 I C40 R 1 and R' are each hydrogen, R 2 and R 2 are each methyl, Y 1 is methyl, and Z is sulfur.

64 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, 45 Q is:

OH IH C 50 __ H __ R 1 and RI are each hydrogen, R 2 and R' are each methyl, Y 1 is n-propyl, and Z is sulfur.

65 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, 55 Q is:

0 11 1 ll 1 596 251 111 1 596 251 R 1 and R' are each hydrogen, R 2 and R 2 are each methyl, Y 1 is 2methyl-1-propyl, and Z is sulfur.

66 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, Q is:

5 0 II -C10 R 1 and R, are each hydrogen, R 2 and R 2 are each methyl, Y 1 is npropyl, and Z is sulfur.

67 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, Q is: 15 OH I -l C1 20 _ H R 1 and R are each methyl, R 2 and R 2 are each methyl, Y 1 is methyl, and Z is sulfur.

68 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, 25 Q is:

0 1 l I C 30 R 1 and R, are each methyl, R 2 and R' are each methyl, Y 1 is methallyl, and Z is sulfur.

69 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, 35 Q is:

0 II -C 40 R 1 and R, are each methyl, R 2 and R 2 are each methyl, Y 1 is crotyl, and Z is sulfur.

70 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, 45 Q is:

0 II 1 l C -C 50 R 1 and R' are each methyl, R 2 and R 2 are each methyl, Y 1 is allyl, and Z is sulfur.

71 A composition according to claim 58 wherein, in the alpha-oxy(oxo) sulfide or ether, 55 Q is:

0 -CII -C 112 112 1 596 251 R 1 and R, are each hydrogen, R 2 and R 2 are each methyl, Y 1 is acetyl, and Z is sulfur.

72 A process for augmenting or enhancing the aroma or taste of a foodstuff comprising the step of adding to said foodstuff from about 0 1 ppm up to about 50 ppm by weight of said foodstuff of the alpha-oxy(oxo)sulfide or ether compound defined according to any one S of claims 58 to 71 5 73 A flavor augmenting or enhancing composition comprising from about 0 1 % up to about 15 % by weight based on the total weight of said flavoring composition of at least one alpha-oxy(oxo)sulfide or ether compound defined according to any of claims 58 to 71 and the remainder of said composition being at least one adjuvant therefor selected from:

10 p-Hydroxybenzyl acetone; Geraniol; Acetaldehyde; 15 Maltol; Ethyl methyl phenyl glycidate; 20 Benzyl acetate; Dimethyl sulfide; Vanillin; 25 Methyl cinnamate; Ethyl pelargonate; 30 Methyl anthranilate; Isoamyl acetate; Isobutyl acetate; 35 Alpha ionone; Ethyl butyrate; 40 Acetic acid; Gamma-undecalactone; Naphthyl ethyl ether; 45 Diacetyl; Ethyl acetate; 50Anethole; Isoamyl butyrate; Cis-3-hexenol-1; 55 2-Methyl-2-pentenoic acid; ( 4-allyl-1,2,6-trimethoxy benzene); 60 60 ( 4-propenyl-1,2,6-trimethoxy benzene); 2-( 4-hydroxy-4-methylpentyl) norbornadiene; Natural blackcurrant juice; 65 113 113 114 1 -596 25114 Buchu leaf oil; alpha-phellandrene; Cis-3-hexen-l-ol; Terpineol-4; Ethyl maltol; Methyl beuzoate; 1 Benzaldehyde; Coriander oil; is Ethyl heptanoate; Ethyl anthranilate; 2 Cinnamic alcohol; Amnyl valerinate; Cinnamyl propionate; 25 Rhodinyl acetate; Methyl beta-hydroxy butyrate; 3 Ethyl beta-hydroxy butyrate; 2-Phenyl-3-carboethoxyfurafl; Cyclohexyl disulfide; 35 Grapefruit oil; Nootkatone; 40 Bergamot oil; Citral; Amyl alcohol; 45 5-Phenyl-4-pentenal; 5-Phenyl-2-pentenal; 5 Allyl caproate; 2-(n-pentyl) thiazole; 2-(i-butyl) thiazole; 5 2-(i-propyl) thiazole; 2-(n-propyl) thiazole; 6 2-Phenyl-4-pentenal; 2-Phenyl-4-pentenaldimethylacetal; Methional; 65 114 114 1 596 251 115 4-Methylthiobutanal; 2-Ethyl-3-acetylpyrazine; Tetramethyl pyrazine; 5 2-Methyl pyrazine; Trans-2-hexenal; 10 Hydrolyzed vegetable protein; Monosodium glutamate; Dimethyl disulfide; 15 Methyl propyl disulfide; Methyl propenyl disulfide; 20 Methyl allyl disulfide; Allyl propyl disulfide; Propyl propenyl disulfide; 25 Dipropyl disulfide; Diallyl disulfide; 30 30 Propyl propenyl trisulfide; Thiopropanal-S-oxide; Thiobutanal-S-oxide; 35 Thioethanal-S-oxide; Thiohexanal-S-oxide; and 40 Propyl propene thiosulfonate.

74 A tobacco product having added thereto an amount sufficient to augment or enhance the flavor or aroma of the tobacco product of 3-(methylallylthio)2,6-dimethyl-4heptanone having the structure: 45 50 S 55 A tobacco product according to claim 74 wherein the concentration of sulfide in the tobacco product if from 50 up to 5,000 parts per million based on the total weight of tobacco on a dry basis.

76 A tobacco product according to claim 74 wherein the concentration of sulfide in the tobacco product is from 100 up to 500 parts per million based on the total weight of tobacco 60 on a dry basis.

77 A tobacco flavoring composition comprising 3-(methallylthio)-2,6dimethyl-4heptanone and at least one tobacco flavoring additive selected from 1 596 251 116 1 596 251 116 Esters; Aldehydes; Ketones; 5 Acetals; Natural oils and extracts; 10 Lactones; Ethers; Pyrazines; 15 Pyrroles; and ( 2,6-dimethyl-2-pyrazinyl) ( 2-methyl-3-furyl)sulfide.

20 78 A process for preparing an alpha-oxy(oxo)sulfide, mercaptan; or ether comprising the steps of first reacting a ketone having the structure:

_ _ O 25 R 22 30 with a halogenating agent to form an alpha-halo ketone having the structure:

35 / R, O 1 -'x 40 then reacting said alpha-halo ketone with an alkali metal alkoxide or mercaptide having the 45 formula:

M-Z-Y 50 thereby forming an alpha-oxo sulfide, mercaptan or ether having the formula:

R 2 _ R 2 1 596 251 and then, if desired, reacting said alpha-oxo sulfide, mercaptan or ether with a reducing agent thereby forming an alpha-oxy ether, sulfide or -mercaptan having the formula:

S wherein X is a halogen, M is an alkali metal, Y is hydrogen, Cl-C 4 alkyl or acetyl, Z is oxygen or sulfur, wherein when R 1 and R 2 are taken separately and R' and R 2 are taken separately, R 1 and R, are each the same or different and are each hydrogen or C 1-C 3 alkyl, and R 2 and R 2 are each the same or different and are each hydrogen or methyl; and when the pairs of moieties R 1 and R 2 and R, and R 2 are taken together with the carbon atoms to which there are attached, the pairs of moieties R 1 and R 2 and R' and R 2 each form phenyl moieties; or when Z is sulfur R 1 and R' can be joined to complete a cyclododecyl ring, with the proviso that Y is hydrogen when either (i) R 1 and R' are joined to complete a cyclododecyl ring and R 2 and R 2 are each hydrogen and the final reducing step is not carried out, or (ii) R 2 and R 2 are each hydrogen; R 1 is ethyl and R, is propyl; and Y is not hydrogen when R 1 and Rl are each hydrogen and R 2 and R 2 are both hydrogen or both methyl and the last reducing step is not carried out.

79 A process for preparing an alpha-oxy(oxo)mercaptan, sulfide or ether defined according to claim 1 or defined according to claim 23, comprising the steps of first reacting a ketone having the structure:

with a halogenating agent thereby forming an alpha-halo ketone having the structure:

then reacting said alpha-halo ketone which a compound having the structure:

M-Z-H thereby forming an alpha mercapto ketone or an alpha hydroxy ketone having the structure:

117 117 118 1 596 251 118 _ _ R 1 0 RI 5 R 2 'R H 10 then, if desired, reacting said alpha hydroxy ketone or said alpha mercapto ketone with a base to form the alkali metal salt, reacting this salt with a halide having the formula:

15 Y 1-X thereby forming an alpha-oxo sulfide or ether having the formula:

20 -R 1 O 1 25 R 2 2 30 then, if desired, reacting said alpha-oxo sulfide or ether with a reducing agent thereby forming an alpha-oxy sulfide or ether having the structure:

35 ACH 2) 9 L 40 with the proviso that when R 7 and R 8 are both methyl or both ethyl the alpha oxo mercaptan is reduced to an alpha oxy mercaptan.

FORRESTER, KETLEY & CO, Chartered Patent Agents, Forrester House, 52 Bounds Green Road, London, Nil 2 EY 50 and also at Rutland House, 148 Edmund Street, Birmingham, B 3 2 LD.

and 55 Scottish Provident Building, 29 St Vincent Place, Glasgow, G 1 2 DT.

Agents for the Applicants.

Printed for Her Majesty's Stationery Office, by Croydon Printing Company Limited Croydon Surrey 1981.

Published by The Patent Office 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.

1 124 124

35 1 OH RH40 R 2 R z \y 45 Y 1 wherein M is an alkali metal; Z is oxygen or sulfur; X is halogen; Y 1 is Cl-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl; when R 1 and R 2 and R 50 and R are taken separately, R, and R' are the same or different, and each is hydrogen or methyl; and R 2 and R 2 are each methyl; and when the pairs of moieties, R 1 and R 2 and R.

and R 2 are taken together with the carbon atoms to which they are attached, the pairs of moieties R, and R 2 and R' and R' each form phenyl moieties; or when Z is sulfur and the last two reactions are not carried out R, and R, taken together complete a cyclododecyl 55 ring, with the proviso that when R, and R, are hydrogen and R 2 and R' are methyl and Z is sulphur the alpha mercapto ketone is reacted with the base and the resulting salt reacted with the halide.

A process according to claim 78 wherein M is sodium, Y is hydrogen, Z is sulfur, R.

and R, are each hydrogen, R 2 and R 2 are each methyl, and the reducing agent is sodium 60 borohydride.

81 A process according to claim 78 wherein M is sodium, Y is hydrogen, Z is sulfur, R 2 and R 2 are each ethyl, R, and R' are each hydrogen, and the reducing agent is sodium borohydride.

1 596 251 82 A process according to claim 78 wherein M is sodium, Y is hydrogen, Z is sulfur, R 2 and R 2 are each n-propyl, R 1 and R, are each hydrogen, and the reducing agent is sodium borohydride.

83 A process according to claim 78 wherein M is sodium, Y is hydrogen, Z is sulfur, R 2, R 2, R 1 and R, are each methyl, and the reducing agent is sodium borohydride 5 84 A process according to claim 78 wherein M is sodium, Y is hydrogen, Z is sulfur, R 2 and R 2 are each hydrogen, and R 1 and R, taken together form a cyclododecyl ring.

A process according to claim 78 wherein M is sodium, Z is sulfur, Y is acetyl, R 2 and R 2 are each methyl, and R, and R, are each hydrogen.

86 A process according to claim 78 wherein M is sodium, Z is sulfur, Y is methyl, R 2 10 and R 2 are each methyl, R 1 and R, are each hydrogen, and the reducing agent is sodium borohydride.

87 A process according to claim 78 wherein M is sodium, Z is sulfur, Y is hydrogen, R, R,, R 2 and R 2 are each methyl.

88 A process according to claim 79 wherein M is sodium, Z is sulfur, Y 1 is methallyl, X 15 is chloro, R 2 and R 2 are each methyl, and R 1 and R, are each methyl.

89 A process according to claim 79 wherein M is sodium, Z is sulfur, Y 1 is crotyl, R, R,, R 2 and R 2 are each methyl, and X is chloro.

A process according to claim 79 wherein M is sodium, Z is sulfur, Y 1 is allyl, R 1 and R; are each methyl, R 2 and R 2 ' are each methyl, and X is bromo 20 91 A process according to claim 79 wherein X is chloro, Y 1 is 1,3diethylacetonyl, M is sodium, Z is sulfur, R,, R 2, R, and R 2 are each methyl.

92 A process according to claim 79 wherein X is chloro, Y 1 is methoxycarbonylmethyl, R 1, R 2, R, and R 2 are each methyl, M is sodium, and Z is sulfur.

93 A process according to claim 79 wherein X is chloro, Y 1 is methoxycarbonylmethyl, 25 R, and R, are each hydrogen, R 2 and R' are each methyl, M is sodium, and Z is sulfur.

94 A process according to claim 78 wherein X is chloro, M is sodium, Z is sulfur, Y is acetyl, Rl and R, are each methyl, and R 2 and R 2 are each methyl.

A process according to claim 78 wherein X is chloro, M is sodium, Z is sulfur, Y is n-propyl, R, and R, are each hydrogen, and R 2 and R' are each methyl, and the reduction is 30 carried out using sodium borohydride.

96 A process according to claim 78 wherein X is chloro, M is sodium, Z is sulfur, Y is 2-methyl-1-propyl, R 1 and R, are each hydrogen, and R 2 and R 2 are each methyl.

97 A process according to claim 78 wherein X is chloro, M is sodium, Z is sulfur, Y is n-propyl, R, and R 2 taken together represent phenyl, and R, and R 2 taken together 35 represent phenyl.

98 A process according to claim 78 wherein X is chloro, M is sodium, Z is sulfur, Y is methyl, R, and R' are each methyl, and R 2 and R' are each methyl, and R 2 and R' are each methyl and the reduction is carried out using sodium borohydride.

99 A process according to claim 78 wherein X is chloro, M is sodium, Z is oxygen, Y is 40 methyl, R 1 and R' are each hydrogen, and R 2 and R 2 are each methyl.

A process according to claim 78 wherein X is chloro, M is sodium, Z is sulfur, Y is 2-methyl-1-propyl, R 1, R 2, R, and R' are each methyl, and the reducing agent is sodium borohydride.

101 A process according to claim 78 substantially as herein described with reference to 45 any one of Examples I, II, III, IV, XV, XX(B), XX(C), XX(D), XXI(B), XXI(I), XXII(A), XXII(B), XXIII, XXIV, XXV(A), XXV(B), XXVI, XLI(A), and XLI(B).

102 A process according to claim 79 substantially as herein described with reference to any one of Examples XXI(C), XXI(D), XXI(E), XXI(F), XXI(G) and XXI(H).

103 A process according to claim 80 substantially as herein described with reference to 50 Example I.

104 A process according to claim 81 substantially as herein described with reference to Example II.

A process according to claim 82 substantially as herein described with reference to Example III 55 106 A process according to claim 83 substantially as herein described with reference to Example IV.

107 A process according to claim 84 substantially as herein described with reference to Example XV.

108 A process according to claim 85 substantially as herein described with reference to 60 Example XX(B).

109 A process according to claim 86 substantially as herein described with reference to Examples XX(C) and XX(D).

A process according to claim 87 substantially as herein described with reference to Example XXI(B) 65 119 119 1 596 251 111 A process according to claim 88 substantially as herein described with reference to Example XXI(C). 112 A process according to claim 89 substantially as herein described

with reference to Example XXI(D).

113 A process according to claim 90 substantially as herein described with reference to 5 Example XXI(E).

114 A process according to claim 91 substantially as herein described with reference to Example XXI(F).

A process according to claim 92 substantially as herein described with reference to Example XXI(G) 10 116 A process according to claim 93 substantially as herein described with reference to Example XXI(H).

117 A process according to claim 94 substantially as herein described with reference to Example XXI(I).

118 A process according to claim 95 substantially as herein described with reference to 15 Examples XXII(A) and XXII(B).

119 A process according to claim 96 substantially as herein described with reference to Example XXIII.

A process according to claim 97 substantially as herein described with reference to Example XXIV 20 121 A process according to claim 98 substantially as herein described with reference to Examples XXV(A) and XXV(B).

122 A process according to claim 99 substantially as herein described with reference to Example XXVI.

123 A process according to claim 100 substantially as herein described with reference 25 to Examples XLI(A) and XLI(B).

124 A product produced according to the process of claim 78.

A product produced according to the process of claim 79.

126 A product produced according to the process of claim 88.

127 A product produced according to the process of claim 83 30 128 Use of alpha-oxy(oxo)sulfides, mercaptans or ethers for their organoleptic properties as defined according to claim 23, substantially as herein described with reference to any one of Examples V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XVII, XVIII, XIX, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII, XXXVIII, XXXIX, XL, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, 35 XLIX, L, LI and LII.

129 Use of alpha-oxy(oxo)sulfides or mercaptans for their organoleptic properties in perfume compositions as defined according to claim 24, substantially as herein described with reference to any one of Examples VII, XIV, XII, XIII, XLII, XLV, XLIII, XLIV, and L 40 Use of alpha-oxy(oxo)sulfides or mercaptans for their organoleptic properties in perfume compositions as defined according to claim 26, substantially as herein described with reference to any one of Examples VII, XIV, XII, XII, XIII, XLII, XLV, XLIII, XLIV and L.

131 Use of alpha-oxy(oxo)sulfides or mercaptans for their organoleptic properties in 45 perfumed articles as defined according to any one of claims 25, 39, 41, and 33, substantially as herein described with reference to any of Examples VIII, IX, X, XI, XLVI, XLVII, XLVIII and XLIX.

132 Use of alpha-oxy(oxo)sulfides, mercaptans or ethers for their organoleptic properties as flavorants for foodstuffs, chewing gums or medicinal products as defined 50 according to any one of claims 44, 58, 72 and 73 substantially as herein described with reference to any of Examples V, VI, XVII, XVIII, XIX, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII, XXXVIII, and XL.

133 Use of alpha-oxy(oxo)sulfides or mercaptans for their organoleptic properties in augmenting or enhancing the aroma of colognes as defined according to any one of claims 55 27, 37, and 43, substantially as herein described with reference to any one of Examples XII, XIII, and L.

134 Use of alpha-oxy(oxo)mercaptans for their organoleptic properties as flavorants for foodstuffs, chewing gums, and medicinal products as defined according to any one of claims 44 to 49 and 51 to 56 substantially as herein described with reference to any one of 60 Examples V, VI, XVII, XVIII and XIX.

Use of alpha-oxy(oxo)mercaptans for their organoleptic properties in augmenting or enhancing the aroma of perfumes as defined according to any one of claims 24, 26, 29 to 32, 35, and 36, substantially as herein described with reference to any one of Examples VII and XIV 65 1 596 251 136 Use of alpha-oxy(oxo)sulfides or ethers for their organoleptic properties as flavorants for foodstuffs, chewing gums or medicinal products as defined according to any one of claims 60 to 64 and 66 to 73, substantially as herein described with reference to any one of Examples XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII, XXXVIII, and XL 5 137 Use of alpha-oxy(oxo)sulfides for their organoleptic properties in augmenting or enhancing the aromas of perfumes as defined according to any one of claims 24, 26, 39,

40 and 42 substantially as herein described with reference to any one of Examples XLII, XLIII, XLIV, XLV and L.

138 Use of 3-(methallylthio)-2,6-dimethyl-4-heptanone organoleptic properties as 10 defined according to any one of claims 74 to 77 substantially as herein described with reference to Example I or Example LII.

139 Use of 3-(methallylthio)-2,6-dimethyl-4-heptanone for its organoleptic properties in augmenting or enhancing the flavor of tobaccos or tobacco flavors as defined according to any one of claims 74, 75, 76 and 77 substantially as herein described with reference to 15 Examples LI or Example II.

An organoleptically effective composition useful for affecting the sense of taste or smell comprising one or more members of a genus of alpha-oxy(oxo)sulfides, ethers or mercaptans, including the compounds claimed in one or more of claims 1-21, inclusive, having the structure: 20 s' ZI Xyi 25 wherein R 5 and R 6 are each the same or different, and R 5 and R 6 can be taken together or separately and when R 5 and R 6 are taken separately, each represents C 1C 4 alkyl or phenyl, and when R 5 and R 6 are taken together they complete a cyclododecyl ring; Z' is, in the 30 alternative, one of sulfur or oxygen; Y' is, in the alternative, one of hydrogen, C 1-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl or 1,3-diethylacetonyl; and Q is, in the alternative, one of:

O OH 35 1 l OR l C _ _ _ I _ 40 with the proviso that when Y' is hydrogen, Q is 0 II 45 C and R 5 and R 6 are alkyl, then R 5 and R 6 are C 3 or C 4 alkyl.

141 A composition according to Claim 140 which is a perfume composition, and which 50 includes a perfume adjuvant in addition to said member of said genus of alphaoxy(oxo)sulfides, ethers or mercaptans.

142 A composition according to Claim 140 which is a food flavor composition, and which includes, in addition to the member of the said genus of said alphaoxy(oxo)sulfides, ethers or mercaptans, a food flavor adjuvant 55 143 A composition according to Claim 140 which is a tobacco flavor composition, and which includes in addition to the member of the genus of said alphaoxy(oxo)sulfides, ethers or mercaptans a tobacco flavor adjuvant.

144 A perfume composition comprising at least one alpha-oxy(oxo)mercaptan having the structure: 60 121 121 1 596 251 R QE,,R SH 5 wherein R is 1-propyl,2-propyl or 1-butyl, and Q is:

OH O 10 OR o I -C C I.

" 15 and at least one adjuvant comprising natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, esters, nitriles or lactones.

145 A perfumed article comprising an alpha-oxy(oxo) mercaptan defined according to 20 claim 144 and a detergent, soap, bath preparation, hair preparation or powder.

146 A process for producing a perfume composition comprising the step of admixing a composition of matter with an alpha-oxy(oxo)mercaptan defined according to claim 144.

147 A cologne comprising ethanol, water and an alpha-oxy(oxo)mercaptan defined according to claim 144 25 148 A perfume comprising a carrier and a compound having the structure:

R R 30 S s y 35 wherein R is hydrogen or methyl, and Q is O OH 40 C, C 4545 and Y is methyl, methallyl having the structure:

50 Qq 3 _ CH 2 _ 55 1-propyl,2-methyl-propyl or acetyl.

149 A process for producing a perfumed composition comprising the step of intimately admixing at least one compound defined according to claim 148 and at least one material selected from natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, nitriles, esters and lactones 60 A cologne composition comprising ethanol, water and at least one compound defined according to claim 148.

151 A perfumed article comprising a compound defined according to claim 148 and a detergent soap, bath preparation, hair preparation, cosmetic preparation or powder.

152 An alpha-oxy(oxo) sulfide or ether having the structure: 65 122 122 1 596 251 R 1 I // TR 1 Rj, R1 %, I I R 2v T R 2 z-,,1 wherein Q is:

0 OH 11 OR l -C -C_ IH Z is 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 C 1-C 4 alkyl, C 3 or C 4 alkenyl, acetyl, methoxycarbonylmethyl, or 1,3-diethylacetonyl.

153 A process for preparing an alpha-oxy(oxo) mercaptan comprising the step of first reacting a ketone with a halogenating agent to form an alpha-halo ketone having the structure:

R then reacting the alpha-halo ketone with an alkali metal hydrosulfide to form an alpha-oxo mercaptan having the structure and then, if desired, reacting the alpha-oxo mercaptan with a reducing agent to obtain an alpha-oxy mercaptan having the structure:

in which R is 1-propyl,2-propyl or 1-butyl.

154 A process for preparing an alpha oxy-(oxo) mercaptan comprising the step of first reacting a ketone with a halogenating agent to form an alpha-halo ketone having the structure:

123 123 1 596 251 R 7 5 then reacting the alpha-halo ketone with an alkali metal hydrosulfide to form an alpha-oxo mercaptan having the structure: 10 R R '1 i 8 15 SH and then, if desired, reacting the alpha-oxo mercaptan with a reducing agent to obtain an 20 alpha-oxy mercaptan having the structure:

/ _ 25 R 8 SH 30 in which R 7 and R 8 taken separately are each the same or different and are methyl,ethyl, 1-propyl or 2-propyl; or R 7 and R 8 taken together represent nonylene having the structure: