JP2763637B2 - Oxo-ionol carbonate useful as a tobacco flavor - Google Patents

Description

Description: BACKGROUND OF THE INVENTION Megastigmatrienone (3,5,5-trimethyl-4-)
(2-butenylidene) -cyclohexene-2-ene-1
-One, as a mixture of isomers) 1 is a component of burley and Turkish and Greek tobacco (DLRo
berts and WARhode, Tabacco Science, 1972 , 16 , 107;
E. Demole and D. Berthet, Helv . Chem. Acta , 1972 , 55 , 18
66; AJAasen, B. Kimland, S. Almqvist and CREnzell, A
cta. Chem. Scand. , 1972 , 26 , 2573; and JW Schumacher
and L. Vestal, Tabacco Science, 1974 , 43), and are known to make important contributions to the overall flavor profile of tobacco.

Mega stigmasterol Triester non 1 is believed to dehydration product of 3-oxo -α- Io <br/> Nord 2, also a component of tobacco (AJAasen, B.Kimland and CREnzell, Acta .
Chem. Scand. , 1971 , 25 , 1481). Two glycosidyl derivatives have been described as useful smoke flavor compositions (RCAnderson, DM Gunn and JA Andrew, Ger.O.
ffen. 2,634,304). Recently, R. Kaiser (European Patent Application No. 175,251) disclosed various esters of oxo-ionols of formula 3 as useful tobacco flavors.

Wherein R is C ₁ -C ₁₈ alkyl; Z is oxo, and Represents a single or double bond. However, a problem with the use of megastigmatrienone 1 is its tendency to polymerize, which makes it difficult to store, transport and formulate.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to develop tobacco flavors that have little or no tendency to polymerize and are easy to store, transport and formulate.

For this and other purposes, the following formulas 4 and 5 (where R is 1
The present invention is directed to tobacco flavors formulated from oxo-ionol derivatives of the formula:

Detailed description of the invention The oxo-ionol derivatives of formulas 4 and 5 are stable at ambient temperature. This stability makes them useful in various tobacco flavor systems. They do not impart odor itself to cigarettes, however, on the basis of smoking, the thermal desorption that produces, in the smoke stream, megastigmatrienone 1 or 6 , carbon dioxide and ethanol (in this case R = ethyl) Receive a reaction.

The oxo-ionol derivatives of the present invention are particularly well-blended with other flavoring agents, and function primarily as flavor improvers or enhancers by smoking and rounding the overall flavor after smoking. In addition, they impart flavoring with a few desirable hay-like features and also mask the paper-like and other unwanted features present in the smoke stream.

The oxo-ionol derivative of the present invention has a concentration of 1 ppm to 1000 pp.
m, may be added to tobacco or applied to smoking products or component parts thereof. Preferably, the amount added is
It is between 10 ppm and 500 ppm. The most preferred amount of the additive is between 25 ppm and 150 ppm. Typically, they can be sprayed or dripped onto processed or dried whole tobacco, or used in the form of dips or solutions, in which processed or raw tobacco is incorporated. Is placed.
Useful solutions for such immersion liquids, sprays and drops are:
Contains the appropriate amount of oxo-ionol derivative and ethanol. On the other hand, oxo-ionol derivatives can also be suitably applied to finished tobacco products.

The oxo-ionol derivatives of formulas 4 and 5 can be prepared from their corresponding oxo-ionols 2 and 7 by standard methods known to those skilled in the art. (CABuehler an
d DEPearson, “Survey of Organic Synthesis”, Vol.
1,802-822 (1970) and Vol. 2,715-724 (1977), Wiley Interscience). For example, reaction of an alcohol 2 or 7 with an alkylhalo-formate in the presence of a base provides compounds 4 and 5 . On the other hand, the transesterification between alcohols 2 and 7 and the dialkyl carbonate can be effected by various catalysts.

The following examples illustrate the synthesis of the oxo-ionol derivatives of the present invention and their use as tobacco flavors. These examples are merely illustrative of embodiments of the present invention and do not limit the scope of the claims.

A solution of ethyl chloroformate (5.42 g, 0.05 mol) in dichloromethane (10 mL) was added to dichloromethane (80 mL)
Medium, 3-oxo-α-ionol (5.20 g, 0.025 mol,
AJAasen, B. Kimland and CREnzell, Acta. Chem. Scan
d. , 1973 , 27 , can be prepared as described by 2107-2114) and pyridine (3.96 g, 0.05 mol) in a cold solution (10 ° C.) dropwise over 30 minutes. The mixture was stirred at 25 ° C. for 18 hours. Then dichloromethane (100 mL) was added and the mixture was washed with 5% phosphoric acid solution (3 × 100 mL), washed with saturated sodium bicarbonate solution until neutral and dried (sulphuric acid). sodium). Chromatography of the residue after evaporation of the solvent and Kugelrohr distillation (both at a temperature of 150 ° C., 0.5 mm) comprises 4- (3-hydroxy-1-butenyl) -3,5,5-trimethyl-2-cyclohexene. -1
-Onethyl carbonate (2.15 g, GLC purity; 87%) was applied. ¹ H-NMR (CDCl ₃ ) δ 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), 24−2.7 (1H, m), 4.25 (2H, q, J = 7H
z), 5.0-5.4 (1H, m), 5.5-5.8 (2H, m), 5.95 (1H,
s); IR (film) V _max 2960,1750,1670,1630,1470,1450,13
70,1260 cm ^-1 ; MS m / e 280,224,190,175,134,108. 3-oxo- α -ionol (271 g, 1.3 mol), diethyl carbonate (1.5 L) and dibutyltin oxide (16
The mixture of g) was heated at 105-115 ° C for 40 hours. During this reaction, the ethanol was removed by distillation. Distillation of the crude product gave a GLC analysis of 51.5% of 4- (3-hydroxy-1
-Butenyl) -3,5,5-trimethyl-2-cyclohexen-1-one
173.2 g was given. Additional purification by chromatography provided 72.56 g of carbonate 4 (GLC purity; 85%).

A solution of ethyl chloroformate (1.74 g, 0.016 mol) in dichloromethane (10 mL) was prepared using R. Kaiser and D. Lampar.
Sky, Hely . Chim . Acta , 1978 , 61 , 2328-2335, 4-oxo- β -ionol (3.33 g, 0.016 mol), pyridine (1.28 g, 0.016 mol) and 1 in a cold solution (5 ° C) of dichloromethane (30 mL)
Dropped over time. After stirring the mixture at 5-10 ° C for 2 hours, it was added to ice water (20 mL). The organic phase is washed with a 5% phosphoric acid solution until neutral and dried over sodium sulfate. The solvent was removed and the residue was chromatographed. Kugelrohr
2.0g (GLC purity; 85%) for distillation (bath temperature 150 ° C, 0.5mm)
Of 3- (3-hydroxy-1-butenyl) -2,4,4, -trimethyl-2-cyclohexen-1-one ethyl carbonate. ¹ H-NMR (CDCl ₃ ) δ 1.12 (6H, s), 1.35 (3H, d, J = 7H
z), 1.40 (3H, t, J = 7 Hz), 1.77 (3H, s), 1.7-2.7 (4H,
m), 4.20 (2H, q, J = 7Hz), 4.8-5.4 (1H, m), 5.53 (1H,
dd, J = 16 and 6 Hz), 6.31 (1H, d, J = 16 Hz); IR (film)
v _max 2960,1745,1665,1460,1440,1365,1250cm ^-1 ; MS m / e
. 280,265,236,207,191,134 the example 4 cigarettes typical of use and high tar American blend to high tar American blend cigarette, were produced using the following tobacco formulation: Ingredient Parts by Weight flue card (Flue Cured 45 Barii (Burley) 30 Oriental (Oriental) 20 Flue Cured Stems 5 Injection into the cigarette portion at a rate of 90 ppm by 4- (3-hydroxy-1-butenyl) -3,5,5-
Trimethyl-2-cyclohexen-1-one ethyl carbonate ( 4 , R = ethyl) was added. Experimental cigarettes were smoked and smoke from a cigarette without the flavor (control) was compared. The smoke from the experimental cigarette is
It was more mellow, round and less irritating than the smoke from the control cigarette. No clear taste is shown from Compound 4 (R = ethyl) itself, but its presence in the experimental cigarette promoted the smoke taste balance.

Example 5 Use in an American Blend Cigarette with a Charcoal Filter A cigarette typical of an American blended cigarette with a charcoal filter was prepared using the following tobacco formulation: Ingredients by weight Fluid 50 Barley 26 Oriental 14 Homogenized 10 Injection into the cigarette portion at a rate of 75 ppm by injection into 4- (3-hydroxy-1-butenyl) -3,5,5-
Trimethyl-2-cyclohexen-1-one ethyl carbonate ( 4 , R = ethyl) was added. After inhaling the tobacco, the infused cigarette has a substantially reduced charcoal non-taste found in the control cigarette. Smoke from the injected cigarette is a cleaner with a reduced aftertaste.

Example 6 cigarettes is typical of used paper tar American blend cigarette into paper tar American blend cigarette, were produced using the following tobacco formulation: Ingredient Parts by weight expanded flue card 40 extended Barii 40 Oriental 15 Expanded Flustem 5 In the above cigarette part, 4- (3-hydroxy-1-butenyl) -3,5,5-
Trimethyl-2-cyclohexen-1-one ethyl carbonate ( 4 , R = ethyl) was added. When the tobacco is inhaled, the infused cigarette has an enhanced tobacco taste as compared to the loss of appropriate taste characteristics exhibited by smoke from the control cigarette. In addition, the injected cigarette has a pleasant paper quality taste that matches the taste of the blend.

Example 7 Use of a High Tar American Blend Cigarette A cigarette typical of a high tar American blend was made using the following tobacco formulation: Ingredients by weight Flukad 45 Barry 30 Oriental 20 Flukad Stem 5 Cigarette above In the portion of the above, 3- (3-hydroxy-1-butenyl) -2,4,4-
Trimethyl-2-cyclohexen-1-one ethyl carbonate ( 5 , R = ethyl) was added. The infused cigarette, after inhalation, exhibited improved overall characteristics of smoke as compared to the flavorless cigarette.

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Drake, Brian Jay. United States, New Jersey 07011, Clifton, Montgomery Avenue 18 (56) References JP-A-61-226051 (JP, A) (58) Fields investigated (Int.Cl. ⁶ , DB name) C07C 69/96 A24B 15/30 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] (1) The following formula I or II: An oxo-ionol derivative represented by the formula: wherein R is lower alkyl of 1 to 6 carbon atoms. 2. The derivative according to claim 1, wherein said R is ethyl. 3. A tobacco composition comprising from about 1 to about 1000 ppm of tobacco and the oxo-ionol derivative of claim 1. 4. The tobacco composition according to claim 3, wherein said R is ethyl.