Classifications

• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
  • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
  • A24D3/06—Use of materials for tobacco smoke filters
  • A24D3/061—Use of materials for tobacco smoke filters containing additives entrapped within capsules, sponge-like material or the like, for further release upon smoking
• • 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
  • A24B15/281—Treatment of tobacco products or tobacco substitutes by chemical substances the action of the chemical substances being delayed
• • 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
• • 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
  • A24B15/301—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by aromatic compounds
• • 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
  • A24B15/305—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances of undetermined constitution characterised by their preparation

Definitions

• Unite tates This invention relates to tobacco compositions and to methods for their preparation. More particularly, the present invention relates to tobacco compositions containing additives which improve the aroma and flavor characteristics of the tobacco. The invention also relates to methods for the preparation of said additives and for their incorporation in tobacco compositions.
• Tobacco compositions usually contain a blend of various tobaccos. In addition, they also generally contain additives, such as flavorants, plasticizers and the like, which gimpart additional desirable properties to the tobacco compositions.
• a commonly employed method consists of introducing the flavoring additive directly onto the tobacco. Menthol and most natural flavoring extracts are now added to tobacco in this manner. This method has several disadvantages. In the first place, many of the more desirable organic flavor additives are volatile at normal room temperatures or at temperatures higher than normal room temperatures which may be encountered during the processing of the tobacco. In such event, these flavors are lost during storage of the tobacco products in which they have been incorporated or are lost during processing steps which occur after they have been incorporated in the tobacco composition. In the second place, the flavor additives are generally desired to provide their eflect in the tobacco smoke and they often contribute undesirable odors to the aroma of the tobacco product before it is smoked.
• a flavorant may impart an undesirable odor to a pack of cigarettes, when its purpose is to provide an odor that is desired in the cigarette smoke.
• some additives may also volatilize ahead of the burning area of tobacco, during the smoking of the tobacco product in which they are incorporated. In such a case, their transfer to the aerosol phase of smoke is inefficient and not subject to suflicient control, with regard to the amount of flavor which is imparted to the smoke.
• the high moisture content of tobacco is often suflicient to dissolve the capsules and to release the flavors prematurely.
• the pyrolysis product of the encapsulating agent may impart an undesirable odor to the smoke. Such pyrolysis products may even produce noxious flavors and unhealthy effects which are transmitted in the smoke.
• the present invention overcomes all of the abovementioned disadvantages of the prior art.
• the invention provides novel compositions and a novel method for incorporating an extremely wide variety of flavor additives in tobacco compositions, by a manner in which:
• flavorants are incorporated into tobacco products in the form of Diels-Alder adducts or their salts, the flavorants being the diene and/or dienophile, as will be more fully ex plained in the remainder of this specification.
• Diels-Alder adducts or their salts are nonvolatile and stable under the conditions which exist during processing and storage of the tobacco product so that the flavors are maintained and preserved.
• the flavors and aromas are released only upon smoking of the tobacco composition, whereby the Diels-Alder adduct or its salt is broken down by the heat into the flavorant, which is almost always the starting diene and dienophile but may also be other break-down products of the adduct which are flavorants, which then volatilizes into the smoke stream.
• the non-volatile, flavor-containing Diels-Alder adducts which can be employed in accordance with the present invention include in their structures six-membered hydroaromatic rings and can be prepared in accordance with procedures which are well known in the art.
• the reactions may be conducted in accordance with the teaching of Kloetzel on pages 1-60 of Organic Reactions, volume 4, John Wiley and Son, Inc. (1948) or the teachings of Holmes on pages 60-174 of the same volume. In these procedures two reactants are employed:
• At least one of the two reactants is a flavorant and the other reactant is either an innocuous non-flavorant or a second flavorant.
• Acyclic conpugates such as butadiene, alkylbutadienes, e.g. isoprene, arylbutadienes, and conjugated polyenes.
• alkylbutadienes e.g. isoprene
• arylbutadienes e.g. isoprene
• conjugated polyenes e.g. butadiene, alkylbutadienes, e.g. isoprene, arylbutadienes, and conjugated polyenes.
• Specific examples of such acyclic compounds include:
• Acyclic compounds which are particularly useful as fiavonants for use in this invention include:
• Trans-1,3-pentadiene (trans-pipe-rylene), 2-methyl-1,3-butadiene (isoprene), 1,3-hexadiene,
• Alicyclic conjugates including- (a) Wholly alicyclic systems, such as cyclopentadiene, 1,3-cyclohexadiene, fulvenes, alpha-phellandrene and alpha-terpinene;
• alicyclic compounds include:
• Alicyclic compounds which are particularly useful as flavorants for use in this invention include:
• Aromatic conjugates including (a) Wholly aromatic systems, such as antr-acene, 9,10- dialkyl-anthnacenes and pentacenes;
• Aromatic-acyclic systems such as isosafrole, 1- vinylnaphthalene, and 9-vinyl phenanthrene;
• aromatic compounds include:
• Aromatic compounds which are particularly useful as flavorants for use in this invention include:
• Heterocyclic compounds such as furan, isobenzofurans and alpha-pyrone.
• heterocyclic compounds include:
• Furfural diacetate Furfuryl methyl ether, 2,5-dimethy1furan, Z-methyl-S-isopropylfuran,
• Heterocyclic compounds which are particularly useful as flavorants for use in this invention include:
• dienophiles include: acrolein, crotonaldehyde, cinnamaldehyde, acetylethylene (methyl vinyl hetone) ethylidene acetone, vinyl phenyl hetone, benzal acetone, benzalacetophenone, debenzal acetone, 1- cyclopenten-2-one and its derivatives, 1-cyclohexen-3 -one, diacetylethylene, diaroylethylenes, acrylic acids, crotonic acid, crotonyl chloride, cinnamic acids and esters, 3,4- dehydro-l-naphthoic acids and esters, coumarin, betaaroyl acrylic 'acids, -alkylidene-malonic, and acetoacetic esters, ethylene tetra-carboxylic acid and ester, azodicar
• Prefenred compounds for use as dienophiles include maleic anhydride and other closely related dicarboxylic acid derivatives, alpha, beta-unsaturated carbonyl compounds, acetylenic compounds, quinones and cyclic ketones.
• Particularly suitable dienophiles for use as flavorants in accordance with this invention include:
• alpha,beta-unsaturated aldehydes as cinnamic aldehyde, alpha-alkyl cinnamic aldehydes, cyclopenten-lal and cyclohexene-l-al.
• Such alpha,beta-unsaturated acids, esters, and carboxylic acid derivatives as maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dimethyl furnarate, diethyl fumarate, citraconic anhydride, itaconic anhydride, cinnamic acid, 3,4-dimethoxycinnamic aldehyde, methyl cinnamate and ethyl cinnamate, coumarin.
• Such alpha,beta-unsaturated ketones as cyclopentenone, cyclohexenone and benzalacetone.
• Such allyl compounds as allyl alcohol, allyl methyl ether, allyl ethyl ether.
• Such acetylenic compounds as acetylene dicarboxylic acid, propiolic acid, acetylene.
• Such vinyl compounds as ethylene, vinyl formate, vinyl acetate, vinyl stearate, vinyl acetic acid, vinyl ethyl ether, vinyl methyl ether, vinyl butyl ether, styrene, anethole.
• the diene and dienophile may be reacted to form the Diels-Alder adduct, either in the absence or in the presence of a solvent.
• Suitable solvents include Water, and organic solvents, either aqueous or anhydrous, such as benzene, dioxane, xylene, nitrobenzene, acetone, chlorobenzene, ethyl ether, toluene, cyclohexane, o-dichlorobenzene, acetic acid, acetic anhydride, propionic acid and ligroin.
• the temperature of the reaction may vary between wide limits, for example from 0 C. to 250 C.
• the time of the reaction may also vary over Wide limits, for example, it may be between about 5 minutes and several days.
• At least one of the Diels-Alder reactants should be a flavorant.
• flavorant as used throughout this specification, is meant a material which Will volatilize under the conditions of pyrolysis existing when tobacco is burned and which imparts a desired flavor to the tobacco smoke when it is present therein.
• the other Diels-Alder reactant may also be a flavorant or it may be an innocuous material which either remains in the ash in an inactive condition, imparting no flavor to the smoke, or volatilizes to form an innocuous gas which imparts no flavor to the smoke.
• the Diels-Alder adducts described above may be employed per se in tobacco compositions, their salts are also useful adducts.
• the sodium salt is the most preferred salt, but other salts such as potassium, calcium, barium, lithium, aluminum, magnesium or other non-toxic salts, may also be employed.
• Such salts may be prepared by reacting the adduct With the hydroxide or other base, such as the carbonate or bicarbonate of the metal desired. For example, the adduct is reacted at 0 to C. preferably at room temperature, With a sodium hydroxide solution, containing 0.5 to 1.5 mols of sodium hydroxide. The resulting solution is then evaporated to yield the sodium salt.
• the Diels-Alder adducts or their salts can be added to tobacco in a range of .05 to 5% by Weight of the total tobacco composition, depending upon the amount of volatile flavorant which is desired in the smoke.
• Example 1 Anethole and maleic anhydride were reacted according to the procedure of Cookson and Wariyar, J. Chem. Soc., 1956, 2302.
• the adduct, 6.57 g., in 50 ml. of water was stirred at room temperature while 2 N sodium hydroxide was added dropwise until a permanent pink color with phenolphthalein Was observed. 38.2 ml. of sodium hydroxide was required. Evaporation of the resulting solution gave the tetra-sodium salt as an odorless, hygroscopic solid which did not melt below 320.
• the tetrasodium salt 0.20 g., was heated to 750 C. in a stainless steel needle for 60 seconds. During the heating, 500 ml. of air was drawn through the needle and then through a Cambridge filter. The filter was extracted first with 10 ml. of ether, then with 25 ml. of Water. Gas chromatography of the ether extract on a 2 meter Col. R column at 190 C. showed 9.1 mg. of anethole in the extract. No other components were present. The residues from evaporation of the aqueous and ethereal extracts were examined separately by paper chromatography, using Whatman 3MM paper and an ether-formic acid-water (5:2:1) solvent system. No maleic acid or other acids were detected. Chromatography of known acids in this system showed that as little as 20 micrograms of acid could have been detected. Any maleic anhydride present would have been converted to maleic acid and identified as such under the conditions used.
• Example 2 Menthofuran, 1.0 g., in 3.0 ml. of benzene was treated with 1.0 g. of maleic anhydride. After 3 hours the crystalline adduct was filtered off and recrystallized from benzene, giving 0.52 g. of the adduct, MP. 133.5-134.0 C. The adduct was converted to the disodium salt by suspending it in 25 ml. of water, adding 20 ml. of 0.2 ml. of 0.2 N sodium hydroxide, and stirring the mixture for 4 hours. Evaporation of the resulting solution gave the salt as an odorless, white solid which did not melt below 320 C.
• the disodium salt 0.10 g., was pyrolyzed at 750 C. by the method described in Example 1, and the products examined in the same manner. 8.2 mg. of menthofuran, observed by gas chromatography (Col. R, 150 C.) was the only volatile product. No maleic acid was found in the aqueous or ethereal extracts of the pyrolysate.
• Example 3 The literature procedures were followed for the preparation of maleic anhydride adducts 'from alpha phellandrene (Diels and Alder, Annalen, 460, 98 (1928)), myrcene (Goldblatt and Palkin, J. Am. Chem, Soc. 63, 3517 (1941)), and sorbic acid (Farmer and Warren, J. Chem. Soc. 1929, 897).
• the adducts were converted to their disodium salts by allowing them to react with the calculated amount of 1 N sodium hydroxide in aqueous solution for 4 hours (8.6 ml.
• Example 4 The adduct from furan and acetylenedicarboxylic acid was prepared by the method of Diels and Alder, Annalen 490, 243 (1931). Neutralization of the adduct to a phenolphth-alein end point with normal potassium hydroxide and evaporation of the resulting solution yielded the dipotassium salt, a white, odorless infusible solid.
• a solution of .03 g. of the dipotassium salt in 1 ml. of water was sprayed onto 10 g. of tobacco, which was then made into cigarettes.
• One of these cigarettes was smoked on a constant pressure smoking machine having a constant putt volume of 35 ml. Seven puffs were taken.
• the gas phase smoke after passage through a Cambridge filter, was injected into a 300 foot squalane-coated capillary column having a flame gauge ionization detector.
• the furan resulting from the added dipotassium salt was identified by comparing the intensity of the furan peak at 11.28 minutes with the intensity of the same peak in the chromatographic pattern of gas phase smoke from an untreated control cigarette smoked in the same manner.
• the amount of added furan was estimated at 106 micrograms per cigarette.
• Example 5 The adduct from acetylenedicarboxylic acid and cyclopentadiene was prepared by the literature procedure (Diels and Alder, Annalen 490, 236 (1931), and was converted to its disodium salt by neutralizing with normal sodium hydroxide to a phenolphthalein end point and evaporating the resulting solution.
• the disodium salt was an odorless, white solid.
• Example 1 The method given in Example 1 was used to pyrolyze 0.10 g. of the salt at 750 C.
• the only volatile product was cyclopentadiene, 7.9 mg, identified by gas chromatography. No acetylenedicarboxylic acid or other volatile acids could be detected by paper chromatography, using the system described in Example 1.
• Example 6 Isoprene, 20.4 g., and cinnamaldehyde, 26.4 g., were heated in a sealed tube at 200 C. for 17 hours. Distillation of the crude reaction mixture gave 23.1 g. of the Diels-Alder adduct, 1-methyl-S-phenylcyclohexene-4- carboxaldehyde, as a colorless, odorless, oil having a boiling point of 1101l1 C. at 1.5 mm. Hg.
• Example 7 Cyclopentadiene, 49.5 g., and vinyl acetate, 74.1 g, were sealed in a heavy walled Pyrex tube and heated at 185 C. for 12 hours.
• This adduct was pyrolyzed under conditions similar to those occurring in a burning cigarette.
• the experimental procedure for the pyrolysis was the same as that given in Example 6.
• the pyrolytic products from this adduct were analyzed by vapor phase chromatography and by the mass spectrometer. The products were cyclopentadiene and vinyl acetate. In addition, traces of acetaldehyde, acetone, and benzene were found.
• a tobacco product containing a member selected from the group consisting of non-volatile, flavor-containing Diels-Alder adducts and their salts.
• a tobacco composition comprising tobacco and a member selected from the group consisting of non-volatile flavor-containing Diels-Alder adducts and their salts.
• a tobacco composition comprising smoking tobacco and a member selected from the group consisting of non-volatile Diels-Alder adducts and their salts, which decompose to yield a flavorant upon smoking of the tobacco.
• a tobacco product containing a non-volatile, flavorcontaining Diels-Alder adduct 4.
• a tobacco product comprising tobacco and a nonvolatile, flavor-containing Diels-Alder adduct.
• a tobacco product comprising smoking tobacco and a non-volatile Diels-Alder adduct which decomposes to yield a flavorant upon smoking of the tobacco.
• a tobacco product comprising tobacco and a nonvolatile salt of a flavor-containing Diels-Alder adduct.
• a tobacco product comprising smoking tobacco and a non-volatile salt of a Diels-Alder adduct which decomposes to yield a flavorant upon smoking of the tobacco.
• a tobacco product containing the disodium salt of the Diels-Alder adduct of maleic anhydride and alphaphellandrene 12.
• a tobacco product containing the dipotassium salt of the Diels-Alder adduct of furan and acetylenedicarboxylic acid containing the dipotassium salt of the Diels-Alder adduct of furan and acetylenedicarboxylic acid.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Cited By (23)

Citations (4)

• 1961
  • 1961-10-19 US US146372A patent/US3047433A/en not_active Expired - Lifetime
• 1962
  • 1962-10-01 GB GB37056/62A patent/GB986553A/en not_active Expired
  • 1962-10-04 NL NL283991D patent/NL283991A/xx unknown
  • 1962-10-04 DE DE19621517304 patent/DE1517304A1/de active Pending
  • 1962-10-04 NL NL283991A patent/NL124805C/xx active
  • 1962-10-05 FR FR911374A patent/FR1335462A/fr not_active Expired
  • 1962-10-10 DK DK437562AA patent/DK113556B/da unknown
  • 1962-10-10 CH CH1188962A patent/CH447914A/de unknown

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