US3559656A

US3559656A - Tobacco product

Info

Publication number: US3559656A
Application number: US819951A
Authority: US
Inventors: Robert A Heckman
Original assignee: RJ Reynolds Tobacco Co
Current assignee: RJ Reynolds Tobacco Co
Priority date: 1969-04-28
Filing date: 1969-04-28
Publication date: 1971-02-02
Anticipated expiration: 1988-02-02

Abstract

Flavoring of tobacco products by incorporating therewith a small amount of a chemical compound selected from 1-oxa-8-oxo2,6,10,10-tetramethyl-spiro(4,5)-6-decene and 4-(1-hydroxy-4keto-2,6,6-trimethyl-2-cyclohexen-1-y1)-butan-2-o1.

Description

United States Patent Appl. No.

Robert A. lleckman Winston-Salem, N.C. 819,951 Apr. 28, 1969 Feb. 2, 1971 R. J. Reynolds Tobacco Company Winston-Salem, N.C. a corporation of New Jersey lnventor Filed Patented Assignee TOBACCO PRODUCT 10 Claims, No Drawings Primary Examiner-Samuel Koren Assistant ExaminerDennis J. Donohue Attorney-Pendleton, Neuman, Anderson & Williams ABSTRACT: Flavoring of tobacco products by incorporating therewith a small amount of a chemical compound selected from 1-oxa-8-ox0-2,6,10,10-tetramethyl-spiro[4,5 1-6-decene and 4-( 1-hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexenl -y1 butan-2-o1.

TOBACCO PRODUCT This invention relates to a tobacco product and has for an object the provision of a composition and process for improving the flavor and/or aroma of tobacco and tobacco smoke.

' flavor and aroma characteristics. lt has been the common practice in the tobacco industry to prepare blends of domestic and oriental tobaccos in order to provide smoking tobacco which has a pleasing flavor and aroma before and during smoking. However, such a procedure is costly and may at times become prohibitive in the event that certain types of tobacco may be in short supply. Accordingly, it is a further object of this invention toprovide an additive which when applied to the tobacco products improves and enhances the flavor and aroma of these products and the smoke emitted therefrom thereby increasing or enhancing the pleasure and other values that may be derived by the consumer from the use of these products.

A further object of this invention is the provision of a process for enhancing or otherwise improving the flavor, aroma and other qualities of certain domestic, oriental, reconstituted or synthetic tobaccos which may be deficient in said flavor or aroma or other qualities.

An additional object of this invention is to provide a process of preparing a smoking tobacco or product which when smoked has an enhanced flavor or aroma.

A still further object of this invention is the provision of smoking products, such as cigarettes, cigars or pipe tobacco, and a process for forming same whereby the flavor and aroma before and during smoking are improved or enhanced.

In accordance with the present invention the flavor and/or aroma of a tobacco product is enhanced by incorporating therewith a small amount of a compound selected from l-oxa- 8-oxo-2,6, l0, l-tetramethyl-spiro[ 4,5 -6-decene, known as theaspirone, and 4-(1-hydroxy-4-keto-2,6,6-trimethyl-2- cyclohex en-1-y1)-butan-2-ol. These compounds have the following structures:

CH3 CH3 CH. CH3 CH3 o 2 0H 0 OH 0 CH3 O- OH;

Compound 1 Compound 11 The above compounds 1 and 11 can be synthesized from 4- 1-hydroxy-4-oxo2,6,6-trimethyl-2-cyclohexen-1-yl)-3- buten-2-0ne, for simplicity designated l-hydroxy-4-keto-gionone, which compound is disclosed and claimed in US. Pat. No. 3,410,908.

SYNTHESIS OF COMPOUNDS 1 AND 11 a. Preparation of 4-(1-hydroxy-4-keto-2,6,6-trirnethyl-2- cyclohexen- 1 -yl )-3-buten-2-ol To 5.56 grams of l-hydroxy-4-keto-g-ionone (25 mmole) in 30 milliliters of methanol was slowly added 0.265 gram (7 mmole) of sodium borohydride using magnetic stirring. The mixture was heated under reflux for 1.5 hours, cooled, then it was diluted with 2 milliliters of water, followed by sufficient 0.5 N hydrochloric acid to render the solution only slightly basic. Most of the methanol was evaporated in vacuo and the oil that resulted was poured into salt solution and further acidified with 2N hydrochloric acid. After extraction with chloroform the extract was dried over anhydrous sodium sulfate and evaporated. This yielded 5.70 grams of colorless oil. Trituration of the crude oil with ether-pentane afforded several crops of white, crystalline solid, l 2. 1 grams, melting point l04106; (2) 0.90 gram melting point 99-l02; (3) 0.26 gram, melting point 1 l 1l 13; and (4)0.28 gram, melting point 79--85. These crops were isomers or isomeric mixtures of 4-( l hydroxy-4-keto-2.6,6-trimethyl-2-cyclohexenl yl)-3-buten-2-ol. The first crop showedk 3.04, 6.02, 6.20, 8.88, 9.30, 9.67, 9.76, 10.18 and 10.26 p. (nujol). The third crop exhibited A 2.91, 3.00, 6.06, 6.17. 8.82, 9.09, 9.50 and 10.25 ;t (nujol). The remaining crops appeared by infrared analysis to be largely mixtures of crops 1 )v and (3). The nuclear magnetic resonance spectra (C DC 1 of crops 1 and (3) were virtually identical; absorptions were noted at r 9.05

(5.6), 8.70 (d,3,J= 7H2.), 8.10 (s,3), 7.90 (5,2), 7.68 (m,2), 5.60 (m, 1), and 4.15 (s,3). The mass spectra of crops( 1) and (3) were nearly identical and showed m/e 224, 222, 206, 204, 191, 168, 150, 134 and 124.

b. Preparation of 4-(1-hydroxy-4-keto-2,6,66-trimethy1-2- cyclohexen- 1 -yl)-butan-2-ol (Compound 11) A small amount of platinum oxide was prereduced in l0milliliters of absolute ethanol in a hydrogenator. A solution of 1.12 grams (5 mmole) of the combined crystalline mixtures from above in 10 milliliters of ethanol was injected into the flask by means of a syringe. The sample consumed 1.15 milliliters of 1 M sodium borohydride solution (used for external hydrogen generation, theory =1.25 milliliters) after 2 hours. Filtration of the catalyst on a Celite bed, followed by evaporation of the filtrate, yielded 1.29 grams of an oil.

The oil was then chromatographed on 15 grams of silicic acid using low percentages of methanol in chloroform. A group of fractions eluted with 2 percent methanol in chloroform were combined (4-( l-hydroxy-4-keto-2,6,6- trimethyl-2-cyclohexen-lyl)-butan-2-ol, 0.51 gram); this material showed k,,,,,,2.93, 6.02, 6.15, 8.13, 8.45, 9.00 (broad), 9.55 and 9.78 p. (liquid film). Mass spectral analysis showed peaks at m/e 226 (M+), 208 (M+-H 0), 184, 170, 153, 152, 110, and 83. Nuclear magnetic resonance absorptions (CDCI were noted at r 8.97 (s,3), 8.90 (s,3), 8.81 (d,3,J6.5l-1z.), 7.95 (s,3), 7.65 (m,2), 6.20 (m,1), 6.10 (s,2) and 4.17 (s,1).

c. Preparation of 1-oxa-8-oxo-2,6,10,10-tetramethyl-spiro [4,5 ]-6-decene (Compound 1) The hydrogenated diol (4-(1-hydroxy-4-keto-2,6,6- trimethyl-2-cyclohexen-l-yl)-butan-2-ol, 0.41 gram) was dissolved in 1.6 milliliters of dimethyl sulfoxide and heated in an oil bath at 166 for 2.25 hours (gas-liquid chromatographic analysis indicated conversion was essentially complete in about 2 hours). To the cooled mixture was added 15 milliliters of water and 15 milliliters of pentane; after separation of the layers the aqueous portion was extracted twice more with pentane and the combined pentane extracts were dried over sodium sulfate and evaporated. This gave 167 milligrams of yellow oil (theaspirone) that showed the following spectral data: infrared (liquid film) 6.03, 6.19, 9.13, 9.27, 11.04 and 11.42 p; nuclear magnetic resonance (CDCl 1' 9.03--8.94 (6,3 peaks at 9.03, 8.99 and 8.94 of relative intensities 112:1), 8.73 (d,3,,l =5.8l-lz.), 8.03 (d,3,.l=1.5l-lz.), 7.7 (s,2), 5.78 m,1) and 4.27 (q,1,J1.5l-lz.); mass spectrum m/e 208, 193, 166, 165, 152, 123, and 96. Gas-liquid chromatographic analysis of the oil showed equal amounts of theaspirone (Compound I) and its geometrical isomer.

It has been found that the tobacco additives of the invention when incorporated into tobacco products impart a sweet,

woody, terpenoid aroma during smoking and enhance the burley character and body of thesmoke. 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.

ln accordance with this invention, compound I is added to tobacco or applied to a smoking article or its component parts in amounts of about 0.00005 to 0.2 percent by weight of the product. Preferably the amount of additive is between about 0.0005 and 0.01 percent by weight in order to provide a tobacco product having a desired flavor and aroma. Compound ll is preferably employed in a manner similar to compound I in amounts between about 0.0005 to 2.0, most preferably between 0.005 and 0.! percent by weight. However. the amounts used will depend upon the amount of flavor and aroma desired. The additives can be incorporated at any step in the treatment of the tobacco but are preferably added after aging, curing and shredding and before the tobacco is formed into cigarettes. Likewise, it will be apparent that only a portion of the tobacco need be treated and the thus treated tobacco may be blended with other tobaccos before the cigarettes or other smoking articles are formed. In such case the tobacco treated may have the additives in excess of the amounts above indicated so that when blended with other tobaccos the final product will have the percentage within the indicated ranges.

In accordance with one specific embodiment of this invention, an aged, flue-cured and shredded tobacco is sprayed with a 1 percent ethyl alcohol solution of l-oxa-8-oxo-2,6,l0,l0- tetramethyl-spiro[4,5]-6-decene in an amount to provide a tobacco containing 0.010 percent by weight of the additive on a dry basis. Thereafter the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. It has been found that the cigarette when prepared as indicated has a desired and pleasing flavor.

The additives falling within the scope of this invention can be applied to the tobacco by spraying, dipping or otherwise, utilizing suitable suspensions or solutions of the additives. Thus, water or volatile organic solvents, such as alcohol, ether, acetone, volatile hydrocarbons and the like, can be used as the carrying medium for the additives while being applied to the tobacco. Also, other flavorand aroma-producing additives, such as those disclosed in U.S. Pats. Nos. 2,766,145, 2,905,575, 2,905,576, 2,978,365 and 3,041,2l 1 may be incorporated into the tobacco with the additives of this invention.

While this invention is principally useful in the manufacture of cigarette tobacco, it is also suitable for use in connection with the manufacture of pipe tobacco, cigars or other tobacco products. Furthermore, the additives can be added to certain tobacco substitutes of natural or synthetic origin and by the term tobaccd as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substitute materials or both.

Also, the invention has been particularly described with reference to the addition of the additives directly to tobacco. However, it will be apparent that they can be applied to the paper of the cigarette or to the wrapper of a cigar. Also, they can 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 compounds need not be admixed with the tobacco as above specificallydescribed.

Those modifications and equivalents which fall within the spirit of the invention are to be considered a part thereof.

I claim:

1. A tobacco product having added thereto a small amount of a compound selected from the group consisting of l-oxa-S- oxo-2,6,l0,l0-tetramethyl-sprio[4,5]-6-decene and 4-( lhydroxy-4-keto-2,6,6-trimethyl-2-cyclohexenl -yl )-butan-2- 01 such amount being sufficient to alter the flavor or aroma of the tobacco product.

2. The product recited in claim 1 wherein the amount of said compounds added to the product is between about 0.00005 and 2.0 percent by weight of the product.

3. A tobacco product having added thereto a small amount of l-oxa-8-oxo-2,6, l0, 1 0-tetramethyl-spiro[4,5 ]-6-decene such amount being sufficient to alter the flavor or aroma of the tobacco product.

4. The product recited in claim 3 wherein the amount of the compound added to the product is between about 0.00005 and 0.2 percent by weight of the product.

5. A tobacco product having added thereto a small amount of 4-( l-hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexenl -yl)- butan-2-ol such amount being sufficient to alter the flavor or aroma of the tobacco product.

6. The product recited in claim 5 wherein the amount of the compound added to the product is between about 0.0005 and 2.0 percent by weight of the product.

7. A process for improving the flavor of tobacco which comprises adding thereto a small amount of a compound selected from the group consisting of l-oxa-8-oxo-2,6,l0,l0- tetramethyl-spiro[4,5l-6-decene and 4-( l-hydroxy-4-keto- 2,6,6-trimethyl-2-cyclohexen-lyl)-butan-2-ol, such amount being sufficient to alter the flavor or aroma of the tobacco product.

8. The process of claim 7 wherein the said additives are added in an amount between about 0.00005 and 2.0 percent by weight of the tobacco.

9. A process for improving the flavor of a tobacco product which comprises adding thereto a small amount of l-oxa-8- oxo-2,6,l0, l O-tetramethyl-spiro[4,5 l-o-decene. such amount being sufficient to alter the flavor or aroma of the tobacco product.

10. A process for improving the flavor of a tobacco product which comprises adding thereto a small amount of 4-(1- hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexen- 1 -yl )-butan-2- ol, such amount being sufficient to alter the flavor or aroma of the tobacco product.

Claims

2. The product recited in claim 1 wherein the amount of said compounds added to the product is between about 0.00005 and 2.0 percent by weight of the product.
3. A tobacco product having added thereto a small amount of 1-oxa-8-oxo-2,6,10,10-tetramethyl-spiro(4,5) -6-decene such amount being sufficient to alter the flavor or aroma of the tobacco product.
4. The product recited in claim 3 wherein the amount of the compound added to the product is between about 0.00005 and 0.2 percent by weight of the product.
5. A tobacco product having added thereto a small amount of 4-(1-hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl)-butan-2-ol such amount being sufficient to alter the flavor or aroma of the tobacco product.
6. The product recited in claim 5 wherein the amount of the compound added to the product is between about 0.0005 and 2.0 percent by weight of the product.
7. A process for improving the flavor of tobacco which comprises adding thereto a small amount of a compound selected from the group consisting of 1-oxa-8-oxo-2,6,10,10-tetramethyl-spiro(4,5) -6-decene and 4-(1-hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexen-1yl)-butan-2-ol, such amount being sufficient to alter the flavor or aroma of the tobacco product.
8. The process of claim 7 wherein the said additives are added in an amount between about 0.00005 and 2.0 percent by weight of the tobacco.
9. A process for improving the flavor of a tobacco product which comprises adding thereto a small amount of 1-oxa-8-oxo-2,6,l0,10-tetramethyl-spiro(4,5) -6-decene, such amount being sufficient to alter the flavor or aroma of the tobacco product.
10. A process for improving the flavor of a tobacco product which comprises adding thereto a small amount of 4-(1-hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl)-butan-2-ol, such amount being sufficient to alter the flavor or aroma of the tobacco product.