Classifications

• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
  • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
  • A24B15/18—Treatment of tobacco products or tobacco substitutes
  • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
  • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
  • A24B15/32—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by acyclic compounds

Definitions

• ABSTRACT An article of manufacture comprising tobacco and a small but effective amount of one or a mixture of monoesters of monoand/or di-alkylmalonates as a flavorant composition.
• the indicated malonates de compose during smoking of the tobacco by decarboxylation to give the corresponding alkanoate esters which improve the taste and aroma of tobacco smoke.
• monoethyl sec-butylmalonate in a cigarette at a level of about one ppm on the tobacco will produce a smoke flavor characterized by a fermented apple-peel with an English walnut-like taste.
• the flavor and taste apparently arise from the conversion of the monoethyl sec-butylmalonate to ethyl B-methylvalerate.
• lt is therefore an object of the present invention to provide tobacco compositions having improved flavoring agents.
• Another object of this invention is to provide relatively non-volatile flavoring agents for tobacco which are stable during storage and upon smoking of the tobacco provide a pleasant aroma and taste.
• This invention is directed to tobacco compositions comprising a small but effective amount of at least one monoester of monoand di-alkylmalonates having the formula wherein R.
• R are independently selected from the group consisting of straight or branched-chain alkyl, and aralkyl radicals having from one to eight carbon atoms, and R" is either hydrogen or lower alkyl radical having from one to six carbon atoms and R' is hydrogen or alkali or alkaline earth metal.
• a preferred embodiment of the present invention is a tobacco composition comprising monoethyl secbutylmalonate.
• This compound is synthesized by procedures which have been published in the chemical literature. Specifically, monoethyl sec-butylmalonate is prepared by hydrolysis of diethyl sec-butylmalonate with one equivalent of potassium or sodium hydroxide.
• the diethyl sec-butylmalonate can be obtained by the reaction of diethyl malonate with 2-bromobutane in the presence of a base such as sodium ethoxide.
• alkyl, or aralkyl substituted malonate diesters can be obtained by the reaction of dialkyl malonate with the desired haloalkane, such as bromoalkane, in the presence of a base such as sodium ethoxide.
• R" substitution may be achieved by reaction of the corresponding alkyl substituted malonate diester with sodium and the sodium derivative reacted with the desired alkyl halide.
• the salts of the monoesters of the substituted malonic acids may also be used according to this invention. These can be prepared by reaction of the appropriate malonate half-ester with an equivalent amount of a hydroxide or carbonate of the alkali or alkaline earth metals. Use of basic ion-exchange resins may also accomplish the desired results.
• the compounds of this invention are useful to modify the flavor of smoked tobacco products and are especially useful as cigarette and pipe tobacco flavorants. They may be applied to tobacco or reconstituted tobacco sheet or to cigarette paper by spraying in a suitable solvent such as ethanol, propylene glycol, glycerine, or casing solution, by dipping into a solution containing the product, or by incorporation into a flavor formulation normally applied to tobacco, reconstituted tobacco sheet or cigarette paper.
• a suitable solvent such as ethanol, propylene glycol, glycerine, or casing solution
• the concentration of flavorants may vary from 0.00001 to 0.1 percent by weight of tobacco or tobacco product although higher and lower concentrations may be employed if desired.
• the compounds of the present invention are not flavorants per se, but decompose when heated to give flavorant alkyl alkanoates.
• Low molecular weight alkyl alkanoate esters are relatively volatile and generally highly aromatic substances with very low odor threshold values. These properties limit their usefulness as tobacco flavorants because of the problem of evaporation on prolonged storage of the treated tobacco.
• Monoesters of monoand di-alkylmalonates are relatively non-volatile, non-odorous,
• the monoethyl sec-butylmalonate is non-volatile, non-odorous, and stable on tobacco during manufacture and storage but decomposes during smoking to give high yields ofethylB -methylvalerate.
• the present invention offers economic advantages as well in that no loss due to volatilization of material during application and storage is incurred.
• a 250-m1, 3-necked flask equipped with a condenser was charged with 70 ml anhydrous ethanol and 3.5g (0.152 moles) of sodium. The last amounts of sodium were dissolved by warming the flask on a steam bath.
• the ethanol was distilled directly from the reaction flask. Twenty ml. of water was added to the cooled mixture, the layers were separated, and the organic layer was distilled. The product was collected at 112-119 /2025mm; yield 239 g (72%); )t f 5.70 and 5.76
• the ethanol solution (containing a small amount of white precipitate) was cooled to and neutralized by addition of 5.2 ml concentrated hydrochloric acid. The mixture was filtered by gravity and the ethanol was removed on the rotary evaporator.
• EXAMPLE lll Monomethyl sec-Butylmalonate Freshly cut sodium (1.5 g, 0.065 moles) was dis solved in 50 ml. of anhydrous methanol. The solution was cooled to room temperature and a solution of 4.5 g (0.024 m) of monoethyl-sec-butylmalonate in 5 ml. methanol was added in one portion. The reaction solution was refluxed on a steam bath for 1 day.
• the NMR spectrum shows a methoxysinglet at 6T3?ziiidThEBtEfiEGf absorption due to an ethoxy ester group.
• Mass Spectrum no molecular ion; major peaks at m/e 118, 101, 100, 87, 69 and 41.
• Gas chromatographic analysis give a single peak having the same retention time as that of authentic methyl/3 -methylvalerate.
• Thermogravimetric analysis indicated decomposition to occur from about 1 10 to C. The decomposition product possessed a sweet, apple, fruity aroma.
• EXAMPLE 1V Diethyl methyl-n-propylmalonate Freshly cut sodium (1.14 g, 0.0496 m) was dissolved in 50 ml. of anhydrous ethanol. The solution was warmed and 10g (0.0495 in) of diethyl npropylamalonate was added with stirring over a period of 5-10 minutes. The reaction mixture was warmed and stirredari additional 15 minutes and allowed to cool to room temperature. Methyl iodide (9.6g, 0.0676 m) was then added with stirring over a period of 3-4 minutes. The solution was then stirred and refluxed gently for 4.5 hours.
• EXAMPLE V1 Monooctyl sec-Butylmalonate To 25 g of n-octyl alcohol was added 1.1 g of sodium hydride (50% dispersion). After the sodium hydride had dissolved (about 1 hour stirring), 3 g monoethyl sec-butylmalonate was added in one portion. The mixture was stirred at 4550 for 6 hours, then at 2530 for hours.
• the mixture was cooled to 0 and 1.5 ml. of concentrated hydrochloric acid was added dropwise. Ether and water were added and the mixture was shaken in a separatory funnel. The ether layer was extracted twice with dilute sodium hydroxide solution and the combined aqueous layers were cooled and reacidifled with concentrated hydrochloric acid. The aqueous layer was then extracted with ether and the ether layer was washed with a solution of 20 ml. water and 0.5 ml.
• EXAMPLE Vll Calcium monoethyl see-Butylmalonate To a cooled solution of 2.5 g (0.0133 m) monoethyl sec-butylmalonate in 10 ml. ethanol was added with stirring over about 2 minutes 0.492 g (0.00665 m) calcium hydroxide. The solution was maintained cool at 10 and stirred for an additional 10 minutes, at which time it became viscous. The reaction mixture was then allowed to warm to room temperature and stirred for an additional 2.5 hours. Subsequently, the solvent was evaporated on the rotary evaporator. The infrared spectrum of the white powder product, when measured in KBr pellet, showed absorption maxima at 5.77, 5.84, 6.3, 7.17, 7.52, and 9.67 characteristic for a mixed ester salt of the type expected.
• EXAMPLE Vlll Samples of a commercial blend of tobaccos were treated with several of the compounds of this invention at various levels of application.
• the treated tobaeeos were manufactured into cigarettes and these were evaluated organoleptically by experienced flavor panels.
• the intensity of the aroma, flavor and taste effects increased with increasing levels of the additive in the eigarettes and at levels above 10 ppm. the effects were described as being overpowering.
• Cigarettes containing monoethyl methyl-npropylmalonate ate at a level of 25 ppm in the tobacco were judged to deliver a heavy walnut flavor and aroma to the smoke.
• Cigarettes containing tobacco treated with monomethyl sec-butylmalonate at ppm produced a smoke described as having a sweet, apple-cider and walnut-like taste.
• the side-stream smoke aroma of the cigarettes was described as a sweet, winey-walnut" complex.
• the sweet, apple, walnut-like complex aromas described herein are not due to the mono-esters of the malonates of this invention, but rather to the alkyl alkanoate esters emanating from their thermal decarboxylation. These aromas are found in the smoke of the treated cigarettes not only immediately after treatment of the tobacco, but also after several months of age, without any noticeable diminution in the levels of taste. This cannot be achieved by the simple addition of alkyl alkanoate esters of the type that are useful as flavorants on tobacco.
• the flavorant alkyl alkanoate esters themselves are much too volatile to remain on the tobacco during the prolonged shelf storage experienced by packaged tobacco products.
• EXAMPLE 1X A 10 g sample of a commercial blend of cased and cut tobaccos, containing 9.1 mg of added ethyl B -methylvalerate, was placed in an empty desiccator (A). In the center of the desiccator was placed a small Petri dish containing ml squalene. in a similar manner, a 12 g sample of the same tobacco blend, which in this instance contained 52.2 mg of added monoethyl sec-butylmalonate, was placed in desiccator (B). A Petri dish with 5 ml. of squalene was placed in this desiccator as well. The desiccators were covered tightly and stored side by side on a lab bench.
• the squalene samples were monitored periodically for ethyl B -methylvalerate content by suitable gas chromatogrphic techniques. One would expect ethyl ,5 -methylvalerate to transfer from the tobacco into the squalene by volatilization and solubilization.
• ethyl B -methylvalerate is so volatile that the tobacco in desic cator (A) had lost 98 percent of the added material after days of storage. as calculated from the presence of 8.9 mg of ethyl B -methylvalerate in the squalene of that desiccator.
• the squalene in desiccator (B) was essentially void of any ethyl B -methylvalerate.
• Tobacco smoking compositions comprising tobacco and a small but effective amount of at least one monoester of monoand di-alkylmalonates having the formula: I
• R, R' are independently selected from the group consisting of straight or branched-chain alkyl and aralkyl radicals having from one to eight carbon atoms, R" is either hydrogen or lower alkyl radical having from one to six carbon atoms, and R is hydrogen or an alkali or alkaline earth metal.
• composition of claim 1 wherein said malonatc is monoethyl sec-butylmalonate.
• composition of claim 1 wherein said malonatc is monomethyl sec-butylmalonate.
• composition of claim 1 wherein said malonate is monoethyl methyl-n-propylmalonate.
• composition of claim l wherein said malonate is monooctyl sec-butylmalonate.
• composition of claim 1 wherein said malonate is calcium monoethyl sec-butylmalonate.
• composition of claim 1 wherein said malonate comprises from about 0.00001 to about 0.1 percent by weight based on the weight of said tobacco.
• a process for the preparation of a tobacco smoking composition which comprises applying to tobacco at small but effective amount of a relatively nonvolatile, non-odorous and stable flavoring agent of mono-esters of monoand di-alkylmalonates having the formula:
• R, R and R" are as defined above.

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• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Toxicology (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Manufacture Of Tobacco Products (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (3)

• 1973
  • 1973-09-24 US US00399981A patent/US3854485A/en not_active Expired - Lifetime
• 1974
  • 1974-01-01 AR AR255547A patent/AR208292A1/es active
  • 1974-08-28 AU AU72765/74A patent/AU462520B2/en not_active Expired
  • 1974-08-29 BE BE148043A patent/BE819354A/xx unknown
  • 1974-08-29 GB GB3782274A patent/GB1455630A/en not_active Expired
  • 1974-08-29 ZA ZA00745528A patent/ZA745528B/xx unknown
  • 1974-09-03 PH PH16237A patent/PH11327A/en unknown
  • 1974-09-06 FR FR7430321A patent/FR2244414B1/fr not_active Expired
  • 1974-09-09 CA CA208,692A patent/CA1017136A/en not_active Expired
  • 1974-09-18 DE DE19742444670 patent/DE2444670A1/de active Pending
  • 1974-09-23 IE IE1966/74A patent/IE40400B1/xx unknown
  • 1974-09-23 BR BR7882/74A patent/BR7407882D0/pt unknown
  • 1974-09-24 JP JP49108935A patent/JPS5242879B2/ja not_active Expired
  • 1974-09-24 CH CH1289274A patent/CH593634A5/xx not_active IP Right Cessation
  • 1974-09-24 NL NL7412571A patent/NL7412571A/xx not_active Application Discontinuation

Patent Citations (3)

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