WO1990011995A1

WO1990011995A1 - Oxo-ionol carbonates useful as tobacco flavorants

Info

Publication number: WO1990011995A1
Application number: PCT/US1989/001423
Authority: WO
Inventors: Philip A. Christenson; Robert G. Eilerman; Brian J. Drake
Original assignee: Basf Corporation
Priority date: 1988-02-23
Filing date: 1989-04-06
Publication date: 1990-10-18
Also published as: AU641358B2; DK170491D0; JPH04506204A; AU3566589A; DK170491A; BR8907886A; JP2763637B2

Abstract

Novel oxo-ionol derivatives are described which have a but-1-en-3-ol carbonate side chain. These derivatives are stable tobacco enhancers which impart a slight hay-like flavor to tobacco smoke.

Description

Oxo-lonol Carbonates Useful As Tobacco Flavor ants

Background of the Invention

Megastigmatrienone (3,5,5-trimethyl-4-(2-butenylidene)- cyclohex-2-en-l-one, as a mixture of isomers) 1 is a component of Burley as well as Turkish and Greek tobaccos (see D.L. Roberts and W.A. Rhode, Tobacco Science. 1972. 16. 107; E. Demole and D. Berthet, Helv. Chi . Acta. 1972. 55. 1866; A.J. Aasen, B. Kimland, S. Almqvist and C.R. Enzell, Acta. Chem. Scand.. 1972. 26, 2573; and J. . Schumacher and L. Vestal, Tobacco

Science. 1974, 43) and is known to make an important contribution to the overall flavor character of tobacco.

Megastigmatrienone can be considered a dehydration product of 3-oxo-o(-ionol Zr also a constituent of tobacco (see A. J. Aasen, B. Kimland and C.R. Enzell, Acta Chem. Scand. , 1971. 2£, 1481). Glycosidyl derivatives of 2. have been described as useful smoke flavoring compositions (see R.C. Anderson, D.M. Gunn and J.A. Andrew, Ger. Offen. 2,634,304). Recently, R. Kaiser (Eur. Pat. Appl. 175,251) has disclosed various esters of oxo-ionols of formula 3_ as useful tobacco flavorants.

R is C, - C₁₈ alkyl;

A problem associated with the use of megastigmatrienone 1, however, is its tendency to polymerize making it difficult to store, transport and formulate.

Summary of the Invention

Accordingly, it is an object of the invention to develop a tobacco flavorant that has little or no tendency to polymerize and will be easy to store, transport and formulate. This and other objects are achieved by the present invention which is directed to tobacco flavorants formulated from oxo-ionol derivatives having formulas 4. and 5. wherein R is lower alkyl of 1 to 6 carbons.

Detailed Description of the Invention

Oxo-ionol derivatives of formulas 4. and 5. are stable at ambient temperature. This stability makes them useful in a variety of tobacco flavor systems. They impart no odor themselves to unsmoked tobacco, however upon smoking undergo a thermal elimination reaction producing in the smoke-stream megastigmatrienones 1 or 6., carbon dioxide and ethanol (in this case R = ethyl).

The oxo-ionol derivatives of the invention blend especially well with other flavors and upon smoking, function primarily as a flavor modifier or enhancer by rounding-out and smoothing the overall flavor. In addition, they impart a slight, desirable, hay-like note to the flavor and also mask papery off-notes and other less desirable notes present in the smoke-stream.

The oxo-ionol derivatives of the invention can be added to tobacco or applied to a smoking article or its component parts in amounts of 1 ppm to 1000 pp . Preferably, the amount to be added is between 10 ppm and 500 ppm. The most preferred amount of additive is between 25 ppm and 150 ppm. Typically, they can be sprayed or dripped onto processed or dried whole tobacco or can be used in the form of a dip or solution into which the processed or raw tobacco is placed. The solutions useful for such dips, sprays and drips comprise the appropriate amount of oxo-ionol derivative and ethanol. Alternatively, the oxo-ionol derivatives can be applied neat to the finished tobacco product.

Oxo-ionol derivatives of formulas 4. and 5. can be prepared from the corresponding oxo-ionols 2. and 2 by standard methods known to those skilled in the art.

(See C.A. Buehler and D.E. Pearson, "Survey of Organic Synthesis", Vol. 1, p. 802-822 (1970) and Vol. 2, p. 715-724 (1977), Wiley Interscience) . For example, reaction of alcohols 2 or 7 with alkyl halo-formates in the presence of base provides compounds A and 5_. Alternatively, transesterification reactions between alcohols 2 and 1 and dialkyl carbonates can be effected with various catalysts.

The following examples are set forth herein to illustrate methods of synthesis of the oxo-ionol derivatives of this invention and their use as tobacco flavorants. These examples are intended only to illustrate the embodiments of this invention and are in no way meant to limit the scope thereof.

Example 1

A solution of ethyl chloroformate (5.42g, 0.05 mol) in dichloromethane (lOmL) was added dropwise over a 30 minute period to a cold (10°C) solution of 3-oxo-cλ-ionol (5.20g, 0.025 mol, which may be prepared as described by A.J. Aasen, B. Kimland and C.R. Enzell in Acta Chem. Scand., 1973. 21, 2107-2114) and pyridine (3.96g, 0.05 mol) in dichloromethane (80mL). The mixture was stirred at 25°C for 18 hours. Dichloromethane (lOOmL) was then added and the mixture washed with 5% phosphoric acid solution (3 X lOOmL), saturated sodium bicarbonate solution until neutral and dried (sodium sulfate).

Evaporation of solvent and chromatography of the residue followed by kugelrohr distillation (150°C both temp. 0.5 mm) provided 4-(3-hydroxy-l-butenyl)-3,5,5,-trimethyl- 2-cyclohexen-l-one ethyl carbonate (2.15g, GLC purity; 87%) ^1H-NMR(CDC1₃) & 0.97 (3H,s), 1.05 (3H, s), 1.31 (3H, t, J=7Hz), 1.41 (3H, d, J=7Hz), 1.92 (3H,s) 2.1-2.3 (2H,dd), 2.4-2.7 (lH,m), 4.25 (2H,q, J=7Hz), 5.0-5.4 (lH,m), 5.5-5.8 (2H,m), 5.95 (1H,S); IR (film) _Vmaχ 2960, 1750, 1670, 1630, 1470, 1450, 1370, 1260 cm^"1; MS m/e 280, 224, 190, 175, 134, 108.

Example 2

carbonate (1.5 ) and dibutyl tin oxide (16g) was heated at 105-115°C for 40 hours. During the reaction, ethanol was removed by distillation. Distillation of the crude product provided 173.2g of material which GLC analysis indicated contained 51.5% of 4-(3-hydroxy-l-butenyl)- 3,5,5-trimethyl-2-cyclohexen-l-one ethyl carbonate. Further purification by chromatography provided 72.56g of carbonate 4. (GLC purity; 85%).

Example 3

0

A solution of ethyl chloroformate (1.74g, 0.016 mol) in dichloromethane (lOmL) was added dropwise over a 1 hour period to a cold (5^βC) solution of 4-oxo-(5-ionol (3.33g,

0.016 mol, which may be prepared as described by R.

Kaiser and D. Lamparsky, Helv. Chim. Acta. 1978. 61.

2328-2335), pyridine (1.28g, 0.016 mol) and dichloromethane (30mL). After stirring the mixture at 5-10°C for 2 hours it was added to ice water (20mL).

The organic layer was washed with 5% phosphoric acid solution until neutral and dried over sodium sulfate.

The solvent was removed and the residue chromatographed.

Kugelrohr distillation (bath temp. 150^βC, 0.5 mm) gave 2.0g (GLC purity; 85%) of 3-(3-hydroxy-l-butenyl)- 2,4,4-trimethyl-2-cyclohexen-l-one ethyl carbonate. ^^■H-NMR (CDC1₃) .¹-¹² (6H,S), 1.35 (3H,d,J=7Hz) , 1.40 (3H,t,J=7Hz), 1.77 (3H,s), 1.7-2.7 (4H,m), 4.20 (2H,q,J=7Hz), 4.8-5.4 (lH,m), 5.53 (lH,dd,J=16 and 6Hz), 6.31 (lH,d,J=16Hz); IR (filra _^ 2960, 1745, 1665, . 1460, 1440, 1365, 1250 cm^"1; MS m/e 280, 265, 236, 207, 191, 134.

Example 4

Use in a Full Tar American Blend Cigarette

Cigarettes, typical of a full tar American blend, were produced using the following tobacco formulation:

Ingredient Parts by Weight

Flue Cured 45

Burley 30 Oriental 20

Flue Cured Stems 5

To a portion of the above cigarettes was added by injection 4-(3-hydroxy-l-butenyl)-3,5,5-trimethyl-2-. cyclohexen-1-one ethyl carbonate ( _,R=ethyl) at a rate of 90 ppm. The experimental cigarettes were smoked and compared to the smoke from unflavored (control) cigarettes. The smoke from the experimental cigarettes was smoother, rounder and less irritating than that from the control cigarettes. No distinctive taste was noted from compound 4_ (R=ethyl) on its own but its presence in the experimental cigarettes promoted balance in the taste of the smoke.

Example 5

Use in a Charcoal Filter American Blend Cigarette

Cigarettes, typical of a charcoal filter American blend cigarette, were produced using the following tobacco formulation.

Ingredient Pai :ts by Weight

Flue Cured 50

Burley 26

Oriental 14

Homogenized Leaf 10

To a portion of the above cigarettes was added by injection 4-(3-hydroxy-l-butenyl)-3,5,5-trimethyl-2- cyclohexen-1-one ethyl carbonate (4.,R=ethyl) at a rate of 75 ppm. Upon smoking, the injected cigarettes have a substantially reduced charcoal off-taste which is found in the control cigarettes. Smoke from the injected cigarettes is cleaner with a reduced after taste. Example 6

Use in a Low Tar American Blend Cigarette

Cigarettes, typical of a low tar American blend cigarette, were produced using the following tobacco formulations:

Ingredients Parts by Weight

Expanded Flue Cured 40

Expanded Burley 40

Oriental 15

Expanded Flue Stems 5

To a portion of the above cigarettes was added by injection 4-(3-hydroxy-l-butenyl)-3,5,5-trimethyl-2- cyclohexen-1-one ethyl carbonate (4., R=ethyl) at a rate of 125 ppm. When smoked, the injected cigarettes have an enhanced tobacco taste with a reduction of the papery taste characteristic noted in the smoke from the control cigarettes. In addition the injected cigarettes have a pleasant, hay-like taste which is compatible with the taste of the blend. Example 7

Use in a Full Tar American Blend Cigarette

Cigarettes, typical of a full tar American blehd, were produced using the following tobacco formulation:

Ingredients Parts bv Weight

Flue Cured 45

Burley 30

Oriental 20

Flue Cured Stems 5

To a portion of the above cigarettes was added by injection 3-(3-hydroxy-l-butenyl)-2,4,4-trimethyl-2- cyclohexen-1-one ethyl carbonate (5. R=ethyl) at the rate of 100 ppm. The injected cigarettes upon smoking displayed improved overall character of the smoke in comparison to the unflavored cigarettes.

Claims

csiaa:

1. An oxo-ionol derivative of the formula I or II

wherein R is lower alkyl of 1 to 6 carbons.

2. A derivative of claim 1 wherein R is ethyl.

3. A tobacco composition comprising tobacco and from about 1 to about 1000 ppm of an oxo-ionol derivative of claim 1.

4. A tobacco composition according to claim 3 wherein R is ethyl.