US3920027A - Flavored tobacco product - Google Patents

Abstract

The organoleptic properties of a tobacco product are improved by adding thereto 6-methyl-hepta-3,5-dien-2-one.

Description

United States Patent 1191 1111 3,92 Demole [4 Nov. 18, 1975 [5 FLAVORED TOBACCO PRODUCT [51] Int. Cl. A24B 3/12; A24B 15/04 [75 Inventor: Edouard P. Demle, Geneva FIG 0 Search l3 Hi7, 2, i44- Switzerland R f ed e erences 1t [73] Assignce. gdsn, Geneva, UNITED STATES PATENTS 4 R 1 l [3| 1? R [22] Filed: June 24, 1974 3 380 456 H968 oberts e! a 2] A I N I 2 7 FOREIGN PATENTS OR APPLICATIONS l 1 6 [38.612 10/1960 U SS.R 131/144 ux Related US. Application Data [62] 01mm of Scr. No 219.136. Jan. 19. 1972. Pat. No Examiner-Robert Michell 3,84lHl23. Attorney, Agent. or Firm-Pennie & Edmonds 130] Foreign Application Priority Data 57 STR CT Jan. I9. I97] Switzerland .1 773/7! June 23, 197! Switzerland 9l56/7l Jan. I l [972 Switzerland 380/72 US. Cl. 131/17 R; l3l/l44 The organoleptic properties of a tobacco product are improved by adding thereto 6-methyl-hepta-3,S-dien- Z-one.

2 Claims, No Drawings FLAVORED TOBACCO PRODUCT This is a division of application Ser. No. 2l9.l36. filed Jan. l9. l972. now US. Pat. No. 3,840,023.

DESCRIPTION OF THE INVENTION The present invention relates to compositions and a process for improving, enhancing or modifying the flavouring properties of foodstuffs, feedstuffs. beverages, pharmaceutical preparations and, more particularly, tobacco products.

It is well known that tobacco used for the preparation of cigarettes. for example, is composed essentially of a mixture of different types of tobacco which gives the characteristic flavour and aroma that is desired in the tobacco smoke produced. Thus. cigarettes currently manufactured usually contain mixtures of Virginia, Maryland or Kentucky tobacco in combination with oriental or turkish tobacco.

The respective proportions of the various types of tobacco are varied in order to obtain the particular flavour and aroma desired. It is also common practice to employ flavouring substances and humectants as additives to these tobacco mixtures to further enhance the organoleptic properties thereof.

Accordingly, it is an object of the present invention to provide a process for improving, enhancing or modifying the organoleptic properties of a tobacco product by incorporating therein an aromatic composition or certain synthetic flavouring agents.

In accordance with one preferred embodiment of the present invention, the flavour and aroma of tobacco smoke is improved by adding to the tobacco (which may be natural tobacco or a tobacco substitute of natural or synthetic origin) a flavouring composition containing at least one compound selected from the following groups:

I. Amides of formula wherein R and R represent an alkyl radial comprising 1 to 6 carbon atoms, or a hydrogen atom.

Specific examples of the compounds comprised by formula I include:

Ber.. 58. 2017 (1925) Compt. rend. l76. H59 I923) a) N-isoumylacetamide bl N-isoamylfurmamide 2. Cycloaliphatic derivatives:

f) 3.5.5-trimethyl-4-hydroxy-4-[ but- 1 J.Org.Chem.. 33.

en-3-onej-cyelohex-Z-en-l-one 3566 (1968) gt 3.5.5-trimethyl-2-hydroxy-cyclohex- Phytochermstry.

Z-cne-lA-diunc 2755 ll97ll h) 3.5.5-trimcthyl-cyclohex-2-en-2- .Lorgfhem. 24,

ull -onc (I966) 3. Phenol derivatives:

at) 2-hydroxy 5-methyl-acetophenone ca b) Z-methyl-S-isopropenyl-anisole Helv. Chim. Acta. 454

4. Heterocyclic ketones of formula containing a double bond in one of the positions indicated by the dotted lines, and wherein X represents either a hydrogen atom or a hydroxyl group when the double bond is in the ring. or an oxygen atom when the a) 2.5-dimethyl4.5-dihydrofuran Swiss patent No.

474.500 3 ol-4-one bl 2.5-dimethyl4.5-dihydrothio phen-3-ol4one e) Z-methyl-5-ethyl-4.5-dihydro- D.O.S. No. 1,932,800

Swiss patent No. 49l.904 furan-3-ol-4-one d) 2ethyl-5-methyl-4.5dihydro Swiss patent No.

491.904 furan-3-ol-4-one c) 2.5-dimethyl-2,3-dihydrofuran- Helv. ChimAeta.

3-one 5. Caryophyllene derivatives: a. caryophyllenepoxide of formula Helv.Chim.Acta, t, h9 itls8) b. and c. caryophyllene alcohols of formula and l-lelv. Chim. Acta,

6. Miscellaneous vouring effects can be achieved with amounts ranging from I to l,000 ppm, based on the weight of the product flavoured. However, special effects may be achieved by proportions as high as or even l0 percent. Typically, proportions comprised in between about and 200 ppm are preferably used.

In all cases. the ranges given above may be varied, depending upon the specific odoriferous or flavouring effect it is desired to achieve.

A further object of the present invention is to provide a process for the preparation of a new cyclic ketone, the 4,4,o-trimethyl-cyclohexa-2,S-dien-2-ol-l-one. The

b) b-methyhhepta-3,5 dien-2-one c) 3-isopropyl-cyclopenbZ-eml-one d) octa-3.5-dien-2-one e) nonane-2.S.8-trione l) Z-methyl-S-lamethyla-hydroxyethyl)-cyclohex-2-en-l-one g) 4-methylthiobutan-2-one Ben. 76. I83 (I943) Ben. 38. 1719 (1905) C.A., 52, 9l4le U958) Helv.Chim.Acta.29,l829 (I946) USSR patent No. 138,6l2 ].Org.Chem.. 33. H556 (I968) Belgian patent No. 660.099

In the hereinabove list of compounds of the groups I to 6, immediately following the chemical name of each member there is given the commercial source or a literature reference giving a method for its preparation. Commercially available products are identified by the abbreviation c.a., and may be obtained from FLUKA A.G., Buchs 5.0., Switzerland; ALDRICH CHEM. C0., Milwaukee, Wis.; or K. & K. LABORATORIES lNC., Mainview, N.Y. H803.

In those instances wherein new compounds are described a detailed method of preparation is given in the course of this description or in one of the examples. New compounds are identified by the abbreviation n.c.

The results of the organoleptic evaluation tests are set out in the specific examples.

An additional object of the present invention is to provide compositions for flavouring tobacco or tobacco substitutes comprising at least one compound selected from the groups listed above.

The compounds listed above have been divided into groups based more on similarities of their chemical structure than on their specific organoleptic properties. The wide range of organoleptic properties associated with the compounds described above makes it possible to achieve a variety of effects depending on the nature of the individual components used in a given aromatic mixture.

The compounds and/or flavouring compositions described herein may be used in a variety of forms. It is preferable, however, to utilize these compounds or compositions in the form of solutions thereof. The chemical nature, solubility and stability determine the form in which a given compound or composition is to be employed.

A convenient method for flavouring tobacco consists in spraying the tobacco with an alcoholic solution of the compound or flavouring mixture. Combinations of solvents such as alcohol and propylene glycol may also be used.

The proportions of the new compounds to be used in said compositions or in accordance with the process of the present invention can vary within wide limits. Said proportions depend particularly on the specific organoleptic effects it is desired to achieve and on the origin of the tobacco products to which the mentioned flavouring ingredients are added. For instance. interesting flaprocess in accordance with the invention comprises treating isophorone with a halogenating agent, such as for example N-bromosuccinimide, to afford a 3,5,5- trimethyl-4-halocyclohex-2-en-l -one, and oxidizing the ketone thus obtained by means of a tertiary amine oxide, such as trimethylamine oxide.

The above mentioned process is better illustrated by the following reaction scheme:

halogen halogenation R NO R alkyl The use of tertiary amine oxides for promoting the oxidation of haloderivatives is known and described in the chemical literature [see for example Berichte der Chemie. 94. l360 1961 )1. In agreement with the prior art teachings, said oxidation was expected to proceed through a quaternary salt intermediate having the formula 0 its to yield as final product a cyclohexane-l,4-dione. We have unexpectedly found that by the oxidation of 3.5.5- trimethyl-4-halocyclohex-2-en-l-one. in accordance with the process of the present invention. a l.2-dione derivative was formed instead. Said diketone was in equilibrium with its keto-enol form according to the above given scheme.

The present invention relates further to the new compounds which have been listed above.

Said compounds may be prepared in accordance with the methods described hereinbelow:

2. h) 3.5,5 Trimethyl-2,3-epoxy-cyclohexanc-1.4-dione 2ml of a 6N aqueous solution of NaOH have been added during a period of 15 minutes at 15C to a mixture of 3,5.5-trimethyl-cyclohex-2-en-1,4-dione (3.7 g) and hydrogen hydroperoxide (8.3 ml of a 30 percent solution) in 27 ml of methanol. The mixture was kept under stirring during 3 hours at 2025C, treated with water and extracted with ether. The combined organic extracts were washed with water until neutrality, dried over MgSO and evaporated. 3.33g (81.5%) of the desired product, b.p. 40C/0.001 Torr. were thus obtaincd.

IR: 1715 cm; MS M 168; m/e: 56. NMR (CCI 1.05 (3H,s); 1.25 (3H,s); 1.50 (3H,s); 2.08 (lH,d, J=l3 cps); 3.09 {1H,d. J=13 cps); 3.47 (1H,s) 6 ppm.

3,5,S-Trimethyl-cyclohex-2-en-1,4-dione, used as starting material for the above described preparation. may be obtained in accordance with the procedure described in Tetrahedron. Suppl. 8, Part 1, p. l (1966).

2. c) 2,6,6-Trimethyl-cyclohex-2-en-4-ol-l -one Prepared in accordance with the procedure described in Tetrahedron, Suppl. 8, Part 1, p. 1 (1966), starting from isophorone.

In addition to the ketal intermediate of formula as described, we have obtained a ketal of formula which has been separated by column chromatography on silicagel (elution: benzene ethyl acetate).

Ketal (b) has been reduced by LiAlH in either solution and the product thus obtained directly hydrolysed in a mixture of dioxane and 5% H 50 at 20C.

NMR(CC1,): 1.10 (6H,s)', 1.72 (3H,s); 1.85-2.40 (2H.m); 4.50 (2H. s broad); 6.64 (1H. s broad) 8 ppm.

2. d) 4,4.6-Trimethyl-cyclohcxa-2.5-dien-2-ol 1 one Prepared according to Example 2.

2. e) 3,5.S-Trimethyl-cyclohex-3-en-l-yl acetate Prepared by reduction by means of sodium borohydridc in methanol of Bisophorone [obtained according to .1. Am. Chem. Soc. 63, 2308 (1941 )1 and subse- 6 quent acetylation of the obtained 3,5.5-trimethylcyclohex-3-en-l-ol by means of acetic anhydride in the presence of sodium acetate at 50C during 20 hours.

NMR(CC1 1.0 (6H,s); 1.62 (3H,s); 1.92 (3H,s); 5.10 (1H,s); 4.6-5.2 (1H,m) 8 ppm The invention also relates to a method for modifying, improving or enhancing the organoleptic properties of foodstuffs, feedstuffs, beverages and pharmaceutical preparations, which comprises adding to said materials a small but effective quantity of at least one compound selected from the class consisting of group 2 and the following group; 3,5,S-trimethyl-cyclohex-Z-ene-l,4- dione, 2,2,6-trimethylcyclohexan-4-ol-l-one, 3,5,5- trimethyl-eyclohexan-4-ol-l-one. 3,5,5-trimethyl-4- methylene-cyclohexQ-en-l-onc and 3,5,5-trimethylcyclohexaneJA-dione. The preparation of the hereinabove mentioned compounds has been described in US. Pat. No. 3,380,456.

We have surprisingly found that whenever said compounds were incorporated to said materials or to flavouring compositions containing among their ingredients phenol or phenol derivatives, the harshness and the chemical character of their phenolic taste was reduced or even suppressed.

Such a finding is ofgreat interest to the flavour industry, particularly for modifying the roasted character of the taste of certain beverages such as infusions or decoctions prepared from tea, coffee. limeblossom tea. Moreover, their use is particularly interesting for the flavouring of meat, more specifically of smoked meat, of roasted cereals and roasted nuts. When taken separatcly, said compounds can also impart to the products to which they are added a caramelor straw-like character and find a useful application in the flavouring of infusions or decoctions and certain fermented foodstuffs in general.

The proportions previously indicated for tobacco flavouring equally apply for the use of the above compounds in accordance with the hereinabove described method. For the purpose of the present specification. the term foodstuff" is used broadly; and it is deemed to indicate also products such as coffee, tea and cocoa.

The invention is better illustrated by the following examples.

EXAMPLE 1 7 g of a 1% alcoholic solution of 3,5,5-trimethyl-2,3- epoxy-cyclohexane-l.4-dione (in ethyl alcohol) were sprayed onto a mixture of tobacco of american blend g). The tobacco thus flavoured was used to manufacture test cigarettes, the smoke of which was then subjected to organoleptic evaluation by comparison with non flavoured cigarettes (control). The tobacco used to prepare the control cigarettes was preliminarily treated with 95% ethyl alcohol.

The panel of experts unanimously defined the taste of the test cigarettes as being sweeter than that of the control cigarettes; moreover, the smoke possessed a note with an improved herb-like character and was reminiscent of the taste of cigar smoke.

By following the same procedure as that given in above Example 1. other samples were evaluated. The hereinbelow table gives the list of the tested compounds as well as the quantities employed and the flavour effect observed.

TABLE Compound Amount lgl" Organoleptic Evaluation" l. a) 1.0 10.0 Nutty. chocolate taste 1. b) 1.0 10.0 Rich nutty taste: sweet flue-cured character; chocolate; adds body 2. a) 1.0 10.0 Sweet. flue-cured character 2. b) Sweet. phenolic flue-cured character; some nutty chocolate taste 2. c) Flue-cured character; slight nutty. phenolic taste; some ionone character 2. d) 7.0 Sweet. woody character; anise-like note; more pleasant 2. e) 1.0 10.0 Sweet. woody.

flue-cured character 2. f) 1.0 10.0 Sweet. flue-cured character 2. g) 1.0 10.0 Sweet. woody. herb-like 2. h) 1.0 10.0 Sweet. herb-like 3. a) 1.0 10.0 Rich sweet. nutty taste; adds flue-cured character 3. b) Phenolic taste; slight Burley effect 4. a) Sweet. slightly woody. caramel and honey-like 4. b) 1.0 Fruity. woody, slightly sulphur-like 1.0 5.0 Sweet. caramel 4. c) 4. d) Sweet. caramel 4. d) 0.1 0.5 Caramel 5. a) 1.5 2.5 Woody. cigar smoke-like; orient tobacco note 5.1)) and c) 2.5 5.0 as above 6. a) 1.0 Sweet. nutty. chocolate taste; adds body; some flue-cured character 6. b) 10.0 Sweet. nutty. chocolate taste; adds body 6. c) 10.0 Sweet. green note 6. d) 10.0 Adds body; flue-cured flavour note 6. e) 100 Sweet. nutty. chocolate taste; some flue-cured character 6. f) 10.0 Flue-cured character. phenolic; nutty. chocolate taste; adds body 6. g) 10.0 Some Burley character "The amounts indicated refer to the quantities of a l "k alcoholic solution (95 k ethyl alcohol) "'The characters given refer to specific flavour properties of the tested compounds on tobacco as compare with a non flavoured tobacco. "The amount indicated refers to the quantities of a 2 ll alcoholic solution (95 )1 ethyl alcohol).

EXAMPLE 2 a. A mixture of isophorone (13.82 g; 0.1 Mole) and N-bromo-succinimide (17.80 g; 0.1 Mole) in the presence of traces of 01,0:'-azodiisobutyronitrile was refluxed in 500 ml of CCl. during minutes. 500 ml of petrol-ether (-50C) were then added to the cool reaction mixture and the succinimide thus precipitated was filtered off. By evaporating the volatile components of the clear filtrate, crude 3.5.5-trimethy1-4- bromo-cyclohex-2-en- 1 -one was obtained.

NMR (CCI 1.16 (3H.s); 1.25 (Ill-Ls); 2.11 (3H.s); 2.07 (ll-[,d, .l=16 cps); 2.53 (1H,d. .l=16 cps); 4.45 (ll-Ls); 5.78 (1H,s) 8 ppm.

b. During a period of 30 minutes 3.5,5-trimethy1-4- bromo-cyclohex-Z-en- 1 -one (43.4g) was added to a solution kept at 40C of anhydrous trimethylamine N- oxide (32 g) in 100 ml of anhydrous chloroform. The reaction was slightly exothermic and the temperature of the mixture was kept at 45-50C by external cooling during the whole addition. After cooling to room temperature. said mixture was poured onto 1 10 ml of 10% H 80. and the organic layers which separated were washed with water (3 X), a 10% solution of sodium carbonate (3 X) and finally with water again (3 X) until neutralisation.

By evaporation of the volatile components. and subsequent distillation of the resulting residue a product was obtained at b.p. 47-60C/0.001 Torr. This product was treated with petrol-ether (30-50C) and then successively washed with a 5% aqueous solution of sodium carbonate (2 X) and a 2% aqueous solution of NaOH (5 X). The mother liquors were acidified and immediately extracted with diethyl ether.

The combined extracts were washed. dried over MgSO, and evaporated at reduced pressure. 8 g of the desired product were thus obtained (95 percent purity). The subsequent purification was carried out by sublimation at 7080C/10 Torr. and yielded 6 g of pure 4.4,6-trimethyl-cyclohexa-2,5-dien-2-ol-1-one.

30 The product had a positive test when treated with a solution of ferric chloride (blue-violet colour); m.p. 46C.

1R (CCL): 1630. 1650. 3440 cm. UV: 2.... 205. 249. 310 mp. (F5650, 7880, 2420 respectively). MS: M 152; m/e: 109. NMR (CC1 l.27(6H,s); 1.92 (3H,s); 5.97 (11-1. pseudo d, J= ca. 2.5 cps); 6.34 (1 1-1. m); 6.65 (1H.m) 8 ppm.

Under the conditions used for carrying out the above given analysis, the compound showed a keto-enol structure represented by the following formula However, under other conditions it is reasonable to assume that the keto-enol equilibrium may be in favour of a diketonic structure according to the following aliphatic or cycloaliphatic amine oxides analogous results were achieved. Further. halogenating reagents other than N-bromo-succinimide. able to afford positive halogens. may be used for promoting the halogenation step.

EXAMPLE 3 The following flavouring compositions were prepared by admixing (parts by weight):

(test) A (control) B p-ethylguaiacol l 1 l I0 20 guaiacol l '/1 l l5 30 3.5.54rimethyl-cyclohexanel.4-dione I096 30 30 95 C4 ethyl alcohol 975 945 920 I000 I000 I000 in J5 It ethyl alcohol Flavours A, B and C were then compared in a concentration of 0.06 g of flavour for 60 ml of sugar syrup (prepared by dissolving 650 g of sucrose in 1350 ml of water).

The finished syrups were tested by a panel of qualified tasters who expressed their views on the value of the flavours used for their preparation. These persons declared unanimously that the taste of the syrup which had been flavoured with composition B had a more diffuse note than the syrup flavoured with composition A; moreover, the typical phenolic character shown by this latter syrup was well masked. By using composition C, analogous results were obtained although less pronounced.

Flavours A, B and C were then compared in a concentration of 0.06 g of flavour for 60 ml of salt solution (prepared by dissolving 0.5 g of NaCl in I00 ml of water).

in this case also the flavour experts declared that the taste of the beverages which had been flavoured with compositions B and C lacked the phenolic character of the beverage flavoured with composition A.

EXAMPLE 4 The following flavouring compositions were (test) A (control) B p-ethyl phenol l 1' l0 I0 20 phenol I it l5 I5 30 4.4.6-trimethyl cyclohexa 2.5-dien-2-ol-l-one l0 1' 30 30 '14 ethyl alcohol 975 945 920 I000 I000 I000 in 95 Z ethyl alcohol The above given flavours were then compared in a sugar syrup and in salt aqueous solution exactly as indicated in Example 3. The flavour experts declared that the taste of the beverages which had been flavoured with compositions B and C lacked the phenolic taste note of the beverages flavoured with composition A; the overall note was more rounded-off and possessed a better flavour harmony.

By replacing 4,4,64rimethyl-cyclohexa-2,5-dien-2- ol-l-one by 3,5,S-trimethyl-Z,3-epoxy-cyclohexanel,4-dione, 2,6,6-trimethyl-cyclohex-2-en-4-ol- I -one, 3.5,5-trimethyl-cyclohex-3-en-l-yl acetate, 3,5,5- trimethyl-4-hydroxy-4-lbut-I-en-3-one]-cyclohex-2- en- I -one, 3,5 .S-trimethyl-cyclohex-Z-ene-l .4-dione, 3,5,5-trimethyl-cyclohex-2-en-4-ol-l -one, 2,2,6- trimethyl-cyclohexan-4-ol-l-one, 3,5,5-trimethyl-4- methylene-cyclohex-Z-en-l-one, 3,5,5-trimethyl-2- hydroxy-cyclohex-Z-ene-1,4-dione, 3,5,5-trimethylcyc1ohexan-4-ol-l-one. 3,5 ,5-trimethyl-cyclohexane-l ,4- dione or 3,5,5-trimethyl-cyclohex-2-en-2-ol- I -one.

I claim:

1. A process for improving, enhancing or modifying the organoleptic properties of a tobacco product, which comprises adding thereto about 1 to about I000 parts per million based on the weight of tobacco of 6- methyl-hepta-3,5-dien-2-one.

2. A tobacco or tobacco product having added thereto about 1 to about L000 parts per million based on the weight of tobacco of 6-methyl-hepta-3,5-dien- 2-one.

* i i t I UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,920,027

OATH) November 18, 1975 INVENTOM I Edouard P. Demole it 15 unmixed U12! mar nppems 1n lhe above-memlfied men and that said i etters Paiem are hereby correcnd 2;.) shown below:

Column 1, line 56, "Suppl. B" should read -Suppl. 8.

Column 2, line 5, "Acta. 45" should read Acta. 48.

Signed and Scalzd this Arrest:

RUTH C. MASON AIM-sung ()jjirer C. MARSHALL DANN (mnmissinm'r uj' I'ulcnts and Trademarks

Claims (2)

1. A PROCESS FOR IMPROVING, ENHANCING OR MODIFYING THE ORGANOLEPTIC PROPERTIES OF A TOBACCO PRODUCT WHICH COMPRISES ADDING THERETO ABOUT 1 TO ABOUT 1000 PARTS PER MILLION BASED ON THE WEIGHT OF TOBACCO OF 6-METHYL-HEPTA-3,5-DIEN2-ONE.

2. A tobacco or tobacco product having added thereto about 1 to about 1,000 parts per million based on the weight of tobacco of 6-methyl-hepta-3,5-dien-2-one.