AU641358B2 - Oxo-ionol carbonates useful as tobacco flavorants - Google Patents

Description

OPI DATE 05/11/90 AOJP DATE 06/12/90 APPLN. ID 35665 89 PCT NUMBER PCT/US89/01423

PCT

INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 90/11995 C07C 68/00, A24B 15/30 Al (43) International Publication Date: 18 October 1990 (18.10.90) (21) International Application Number: PCT/US89/01423 (81) Designated States: AT (European patent), AU, BB. BE (European patent), BF (OAPI patent), BG, BJ (OAPI (22) International Filing Date: 6 April 1989 (06.04.89) patent), BR, CF (OAPI patent), CG (OAPI patent), CH (European patent), CM (OAPI patent), DE (European patent), DK, FI, FR (European patent), GA (OAPI pa- (71) Applicant: BASF CORP. [US/US]; 1255 Broad Street, P.O. tent), GB (European patent), HU, IT (European patent), Box 6001, Clifton, NJ 07015-6001 JP, KP, KR, LK, LU (European patent), MC, MG, ML (OAPI -atent), MR (OAPI patent), MW, NL (European (72) Inventors: CHRISTENSON, Philip, A. 118 Busteed patent), NO, RO, SD; SE (European patent). SN (OAPI Drive, Midland Park, NJ 07432 EILERMAN, Ro- patent), SU, TD (OAPI patent), TG (OAPI patent).

bert, G. 2020 Van Roo Avenue, Merrick, NY 11566 DRAKE, Brian, J. 18 Montgomery Avenue, Clifton, NJ 07011 Published With international search report.

(74) Agents: MAYER, Richard, L. et al.; Kenyon Kenyon, One Broadway, New York, NY 10004 (US).

64135 (54) Title: OXO-IONOL CARBONATES USEFUL AS TOBACCO FLAVORANTS (57) 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.

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-I-

Ozo-Ionol Carbonates Useful As Tobacco Flaorants Background of thei Invetion MegaStigmatrienone (3,5,5-trimethyl-4-(2-butenylidene)cyclohex-2-en-l-one, as a mixture of isomers) I is a component of Burley as well as Turkish and Greek tobaccos (see D.L. Roberts and Rhode, 12tSgga Scinri.g 1L2JI Ik, 107; E. Demole and D. Berthet, gjeihe ghjMj_ =A J7J, U, 1866; A.J. Aasen, B. Kimland, S.

Almqvist and C.R. Enzell, gm gin JU2, 2i 5 2573; and J.W. Schumacher and L. Vestal, =AGCO j j:gj ~Sij~4r, 43) and is .known to make an important contribution to the overall flavor character of tobacco.

OH

r*r -a *1040 0 2.

WO 90/11995 PCT/US89/01423 -2- Megastigmatrienone I can be considered a dehydration product of 3-oxo-o-ionol 2, also a constituent of tobacco (see A. J. Aasen, B. Kimland and C.R. Enzell, Acta Chem. Scand., 1911, 251, 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 1

C

18 alkyl; Z is oxo and---- 0 R indicates a single or double bond.

Z 0 3 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.

WO 90/11995 PCT/US89/01423 -3- 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 OCO2R OCO2R 0 0 4 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).

0 6 WO 90/11995 PCT/US89/01423 -4- The oxo-ionol derivatives of the invention blend especially well with other flavors andupon 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 ppm.

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 Z 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.

WO 90/11995 SPCT/US89/01423 reaction of alcohols 2 or 7 with alkyl halo-formates in the presence of base provides compounds 4 and 1.

Alternatively, transesterification reactions between alcohols a and 7 and dialkyl carbonates can be effected with various catalysts.

OH

7 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

OCO

2 C2 H5 c2C2H

O

A solution of ethyl chloroformate (5.42g, 0.05 mol) in WO 90/11"5 WO 9011995PCIr/US89/o1423 -6dichioromethane (lOmL) was added dropwise over a minute period to a cold (10 0 C) solution of 3-oxo-rk-ionol (5.20g, 0.025 moll which may be prepared as described by A.J. Aasen, B. Kimland and C.R. Enzell, in &qt ChM j7*, 2107-2114) and pyridine (3.96g, 0.05 mol) in dichioromethane (8OmL). The mixture w as stirred at 25 0 C for 18 hours. Dichioromethane (lO0mL) was then added and the mixture washed with 5% phosphoric acid solution (3 X lO0mL), saturated sodium bicarbonate solution until neutral and dried (sodium sulfate).

Evaporation of solvent and chromatography of the residue followed by kugelrohr distillation (1500C both temp. mm) provided 4-(3-hydroxy-l-butenyl)-3,5,5,-trimethyl- 2-cyclohexen-l-one ethyl carbonate (2.15g, GLC purity; 87%) lH-NMR(CDCl 3 9 0.97 (3Mrs), 1.05 (3H, 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 4.25 (2H,q, J=7Hz), 5.0-5.4 5.5-5.8 5.95 IR (film) Vmax 2960, 1750, 1670, 1630, 1470, 1450, 1370, 1260 cm- 1

MS

m/e 280, 224, 190, 175, 134, 108.

Example 2 OCO 2C 2H 0 A mixture of 3-oxo-O(-ionol (271g, 1.3 mol,, diethyl WO 90/11995 PCT/US89/01423 -7carbonate (1.5L) and dibutyl tin oxide (16g) was heated at 105-115 0 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; Example 3 OCO 2C2 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 (50C) solution of 4-oxo-o-ionol (3.33g, 0.016 mol, which may be prepared as described by R.

Kaiser and D. Lamparsky, elyv Chin. Ata, 197r, JL, 2328-2335), pyridine (1.28g, 0.016 mol) and dichloromethane (30mL). After stirring the mixture at 5-10 0 C for 2 hours it was added to ice water 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°C, 0.5 mm) gave 2.0g (GLC purity; of 3-(3-hydroxy-l-butenyl)- Wo "/11995 9011995PCr/US89/01423 -8- 2,4,4-trimethyl-2-cyclohexten-l-one ethyl carbonate.

IH-NMR (CDCl 3 S 1.12 1.35 (3H,d,J=7Hz), 1.40 (3H,t,J=7HzI, 1.77 1.7-2.7 4.20 (2H,q,J=7Hz), 4.8-5.4 5.53 (lH,dd,J=16 and 6Hz), 6.31 (1H,d,J=l6Hz)t IR (film)v mx2960, 1745, 1665,.

1460, 1440, 13651 1250 cm- 1 MS m/e 280, 265, 236, 207, 191, 134.

Example 4 Use in a F.ull 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 Burley Oriental Flue Cured Stems To a portion of the above cigarettes was added by injection 4-(3-hydroxy-l-butenyl)-3,5,5-trimethyl-2cyclohexen-l-one ethyl carbonate (.A,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 WO 90/11995 PCT/US89/01423 -9was 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 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 Parts by Weight Flue Cured Burley 26 Oriental 14 Homogenized Leaf To a portion of the above cigarettes was added by injection 4-(3-hydroxy-l-butenyl)-3,5,5-trimethyl-2cyclohexen-l-one ethyl carbonate (A,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.

WO 90/11995 PCT/US89/01423 Example 6 Use in a Low Tar American Blend Ciarette Cigarettes, typical of a low tar American blend cigarette, were produced using the following tobacco formulations: Ingredients Parts by Weicht Expanded Flue Cured Expanded Burley Oriental Expanded Flue Stems To a portion of the above cigarettes was added by injection 4-(3-hydroxy-l-butenyl)-3,5,5-trimethyl-2cyclohexen-l-one ethyl carbonate 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.

WO 9/1199 PC'/US89/01423 -11- Example 7 Use in a Full Tar American Blend Cigarette Cigarettes, typical of a full tar American blend, were produced using the following tobacco formulation: Ingrediints Parts by Weight Flue Cured Burley Oriental Flue Cured Stems To a portion of the above cigarettes was added by injection 3-(3-hydroxy-l-butenyl)-2,4,4-trimethyl-2cyclohexen-l-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 (1)

12- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 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 1 to 1000 ppm of an oxo-ionol derivative of claim 1. 4. A tobacco composition according to claim 3 wherein R is ethyl. 5. An oxo-ionol derivative of formula I or formula II according to the invention or a tobacco composition comprising said derivative as herein described according to any one of the examples. Dated this 23rd day of March, 1993 BASF CORPORATION by its Patent Attorneys DAVIES COLLISON CAVE 93Q323,q:\opcr\jmw,35665.SUB 1,12 IN4TERNATIONAL SEARCH REPORT itatlonal Application No, PCTA1S89/0 1423 1. CLASSIFICATION OF SUBJECT MATTER III several ChaSsification eymhftt. apl indicate all) According to Intsrnational Patent CtesificAtiOn (IPCl of to both National classification and IPC IPC(4): C07C 68/00; A24B 13/30 U.S. Cl.: 558/260, 275; 131/276 11. FIELDS SEARCHED Minimum Documnntation Searched Classification Syatem Classification Symbols U.S. 558/260, 275; 1331/276 Documentation Searched other than Minimum Documnenttion to the Extent that such Documeants are Included in the Fields Searched Chemical Abstract a-Manual-vol. 1 (3907)- Vol. 109 (to date) CA on-line (computer) 1967-1989 11l. DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, It with indication, where appropriate, ot the relevant passage% 12 Relevant to Claim No. 13 A A, 4,327,601 (GRUBBES, ET. AL.) published 28 1-4 November 1978. (28.13.78) See Entire Document. Special categories ot cited documents: later document Published slier the international fiting date document defining teral state of the ari,4hich is not 0 or prority, dais a not in conflict with the application but conidee o e gonrtcla eleac citedito Understand the principie or theory underlying the consd rd tobe paricuar rlevnceinvention earlier document but Published on or alter the international document of particular reloence: the claimed invention filing date cannot be considered novel or cannot be consiaied to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date at another document ot Particular relevance: the claimed Invention citation or other special reason (as sPecified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use. exthibition or document is combined with one or more other such docu- other means ments. such combination being obvious to a person skilled document Published Prior to the international filing date but in Ins art. later than the Priority date claimed document member a1 the Same patent tamitly IV. CERTIFICATtON Oate ot the Actual Completion of the international Search Date at Maiting of this International Search Report July 1989JU '19 international Searching Authority Signa I h~r Jffct,\ ISA/S r C.Whttebag ForilPCTASA41tp iia aslilfte.11 417