US2995476A - Organoleptic materials and method of production thereof - Google Patents

Organoleptic materials and method of production thereof Download PDF

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Publication number
US2995476A
US2995476A US843947A US84394759A US2995476A US 2995476 A US2995476 A US 2995476A US 843947 A US843947 A US 843947A US 84394759 A US84394759 A US 84394759A US 2995476 A US2995476 A US 2995476A
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United States
Prior art keywords
tobacco
reaction
organoleptic
lower alkyl
mineral acid
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US843947A
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English (en)
Inventor
John D Hind
Frank H Crayton
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Philip Morris USA Inc
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Philip Morris USA Inc
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Publication date
Application filed by Philip Morris USA Inc filed Critical Philip Morris USA Inc
Priority to US843947A priority Critical patent/US2995476A/en
Priority to GB33426/60A priority patent/GB908773A/en
Priority to CH1105560A priority patent/CH401792A/de
Application granted granted Critical
Publication of US2995476A publication Critical patent/US2995476A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • A24B15/305—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances of undetermined constitution characterised by their preparation
    • 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
    • A24B15/42—Treatment of tobacco products or tobacco substitutes by chemical substances by organic and inorganic substances

Definitions

  • Th1s invention relates to organoleptic materials derived from tobacco, methods for their preparation, and tobacco products embodying such materials.
  • organoleptic materials as used herein includes substances prepared in accordance with our invention, which are pleasing to the senses of taste and smell.
  • Another object of this invention is to provide means for deriving economic value from tobacco leaf or stems or other portions of the tobacco plant which are commonly considered inferior or Waste.
  • the characteristic flavors and aromas of the organoleptic products obtained in accordance with this invention may be varied according to the alcohols or mixtures thereof which are employed.
  • Lower alkyl alcohols containing up to 8 carbon atoms have been found to give pleasing and useful products, although alcohols of higher molecular weight may also be employed.
  • Lower alkyl alcohols containing from 1 to 6 carbon atoms are. generally preferred. Alcohols useful.
  • the mineral acid catalyst is essential in the practice of our invention. In its absence any reaction which may occur is, at a rate so slow as to be substantially useless.
  • the organoleptic materials are formed directly in and on the leaf or other part of the plant.
  • the tobacco leaf may be suspended or otherwise ex posed to the atmosphere of a room. or chamber and lower alkyl alcohol vapors introduced therein.
  • an appropriately high temperature or low pressure depending on the particular reagents used, must be maintained. Selection of proper reaction conditions to maintain the alcohol in vapor phase will be routine to those skilled in the art. Temperatures in the range of 20 to 70 C. are preferred.
  • the amount of alcohol employed is not critical but a ratio of 4 to 16 parts by weight of tobacco to 1 part of alcohol has been found satisfactory.
  • the novelty and desirability of the enhanced tobacco flavorings may be improved by employing mixtures of such alcohols as the reagent.
  • a substantial amount of mineral acid should be employed, limited principally by a concentration of acid vapor which would char or discolor the leaf.
  • a preferred amount of acid is about 0.03 to about 0.20 gram equivalent per grams of tobacco.
  • the reaction will be promoted by circulating the atmosphere within the reaction chamber to increase the exposure of the surface of the tobacco to the alcohol and acid vapors.
  • the leaves or other portions of the plant should be disposed so as to permit the greatest contact with the vapors within the chamber.
  • the reaction may proceed for three hours or less to three weeks or more, depending upon the concentration of reagents, temperature, flavor or aroma desired, and other variables apparent to one skilled in the art.
  • the alcohol and acid vapors may be removed from the tobacco by exposure to a current of fresh air. This may be done either by ventilating the system or by removing the tobacco from the chamber and blowing air over it. If desired the vapor phase operation may be conducted as a continuous or semicontinuous process, the tobacco entering the chamber and slowly traversing a path therein for a suflicient time to permit production of organoleptic material, and finally leaving the room and being exposed to the atmosphere or a current of air which serves to remove residual vapors.
  • the reacted tobacco may be directly fabricated into a greatly enhanced smoking tobacco, either singly, or blended with other tobaccos.
  • organol'eptic product by the reaction between tobacco and a lower alkyl alcohol in liquid form, in the presence of a dissolved mineral acid catalyst. This process is particularly advantageous in making possible a very broad range of pleasing and novel smoking products and generally requires less time than for reaction in vapor phase.
  • organoleptic materials By selection and blending of organoleptic materials and by controlling the amount of such material used, flavors and aromas of desirable may also beused.
  • the amount of acid used may be calculated as at least equivalent to the alkalinity of the stern ash. This value is determined by reducing a small representative sample of the ground tobacco to ash in a muffle furnace. An excess of 0.2 N HCl is added to the ash and after warming to 60 C.,.the mixture is backtitrated with 0.2 N and NaOH to a phenolphthalein end point. Alkalinity of bright stems is commonly in the range of 0.l7 to 0.21 equivalent per 100 grams. The preferred range of acid is from 10 to 30% in excess of this value. In runs where a 20% excess of HCl has been used, the pH ofthe alcoholic reaction liquor has ranged from 0.1 to 0.9.
  • the mineralacid selected as the catalyst should be capable of bringing the reaction mixture to the desired ether, tetrahydrofuran, dioxane, Freons, methylene pH, and salts of such acids having the requisite acidity Hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acids, and acidic salts such as those of aluminum, iron or magnesium, for example the chlorides, sodium and potassium acid sulfates, and sodium and potassium acid phosphates are exemplary of suitable catalysts.
  • the rate of reaction will be increased by elevating the temperature and, subject to the volatility of the reactants, a temperature in the range of 40 to 78 C. is preferred.
  • the time required for the reaction will of course vary with the reactants and conditions. It has been found that the variety of tobacco also influences the rate, due in part, it is believed, to differences in mineral content.
  • the pH of the mixture is adjusted to a point on the acid side of neutral.
  • Sodium hydroxide or other common base may suitably be used for this purpose.
  • Organic solvents generally are useful forextnaction of the tobacco.
  • mineralacid such as that used in catalyzing the esterification reaction
  • the acid need not bepresent in the amounts appropriate in esterification, and the extracting medium may have a pH in the range of 2.0 to 4.0.
  • the tobacco may be' extracted with solvent containing a small amount of acid to provide a liquor containing substance esterifiable to the organoleptic products of this invention.
  • lower alkyl alcohol or mixture of lower alkyl alcohols has been used to preparetheextract theesterification reaction can be conducted following extraction merely by the addition, if necessary, of sufficient mineral acid catalyst to attain the desired pH below 3.5, andpreferably below about 1.5, as previously described in connection with the liquid phase reaction.
  • the extract may be concentrated, if desired, and blended with a suitable lower alkyl alcohol or alcohols, as described above, and a suitable mineral acid catalyst.
  • a suitable lower alkyl alcohol or alcohols as described above
  • a suitable mineral acid catalyst At completion of the reaction the pH of the reaction mix is adjusted to a slightly acid level as described above and the organoleptic material may be recovered by conventional methods.
  • Asignificant advantage of liquid phase and extract modes of porducing organoleptic material by this invention is that stems and other portions of the plant which are waste or are generally considered inferior or suitable for useonly after reprocessing in manners known to the art may now be processed to providea useful product.
  • the organoleptic matcrialfmlay' be isolated and embodied in the tobacco product as" a flavoring or odor-enhancing attribute or constituent by spraying or other suitable means. ofapplication. It is possible to isolate organoleptic ma tenial formed in the-vapor phase by washing or extraction, but. for reasons of convenience we prefer to employ this m'odeprincipally for reaction of leaf.
  • the amount of recovered organoleptic material employed tobacco product in which they may be incorporated is affected by the pH to which the reaction mix is brought. Useful material will be derived if the pH is brought within the range of about 6 to 7, with the sweetest flavors obtained in the preferred range of about 6.3 to about 6.8;
  • the mix may be filtered to remove the exhausted tobacco and the organoleptic materialmay be recovered, as by distillation or other conventional methods.
  • Example II Example I was repeated using 50 ml. of alcohol-acid reagent and reaction for 18 hours. The product was more acidic (the pH of a 2% dispersion of product in distilled'water was 3.5) and more strongly flavored. ⁇ It was shredded, blended in equal parts with cut bright tobacco, and used to make cigarettes. On smoking, a sweet, fruity flavor was imparted to the smoke.
  • Example III 227 grams of regular tobacco leaf cigarette filler but additive-free were placed in a 4-liter flask which was deeply immersed in a Dry Ice-acetone bath. After the contents of the flask had been brought to the temperature of the bath, a low vacuum was drawn on the flask. Use of the low-temperature bath avoided loss of volatile tobacco constituents upon application of the vacuum.
  • the flask was opened and the contents removed.
  • the tobacco had a very fruity, raisin-apple aroma which was discernible also in the smoke of cigarettes made from it as noted hereinafter.
  • Example IV cally to maintain a constant level of liquid. This process was carried out on two consecutive working days, and 600 m1. of azeotropic mixtures which boiled below 78 C. were removed from the system. By this time, all benzene had been removed as distillate, along with a substantial amount of water of reaction.
  • reaction liquor was separated from the stems, and the latter were washed carefully with 500 ml. of absolute ethyl alcohol. Washings and liquor were combined and reduced to a volume of about 600 ml. .by distillation at atmospheric pressure.
  • the material' was adjusted toa pH of 5.5, using 285 m1. of water containing about 13 grams of sodium bicarbonate, as the flask was cooled in an ice bath. I
  • the mixture was made up with water to about 3% liters and transferred to a 4-liter continuous extractor and extracted with ether for 24 hours.
  • the ether ex tract was dried with anhydrous sodium sulfate. After removing excess ether and ethyl alcohol, the residue was vacupm distilled at 2 to 3 mm. to yield 33.2 grams of organoleptic material which boiled over the range 76 to 123 C.
  • Example V The esterification of bright stemextract solids with higher boiling alcohols was carried out in the apparatus and following the procedure described in Example IV, heating the reactor in a glycerine bath.
  • the reaction mixture was neutralized to pH 6.3 with about 150 m1; of 10% NaOH and the stems removed and washed with four ml. portions of water.
  • the isobutanol was removed under vacuum, and the residue was taken up in 300 ml. of ether and centrifuged to remove solids. After removing ether, 184 grams of material remained; This was.distilled in a Claisen flask at 2.5 mm. Hg and 49 grams, of products was obtained (B.P. 60- 0.).
  • the odor was described as woody, like pine oil and distinctly camphoraceous.
  • the saponification equivalent weight was about 141, and the theoretical amount of isobutanol was recovered from a saponified sample.
  • Example VI The esterification reaction of Example V was carried out using n-hexanol'in place of isobutanol. The method used was essentially the same, except that 114 ml. of 37 /2%.-l1ydrochloric acid was used in place of sulfuric acid, and benzene was used to reduce temperatures in the later stages of cooking, permitting removal of most of the water at temperatures well below the boiling point of hexanol. At2' to 4 mm. Hg, the n-hexyl esters distilled up to about 137 C. About 40 g. of organoleptic material was obtained. It had an odor of low intensity which was distinctly pleasant and nutty, at lower dilutions.
  • Organoleptic material prepared in accordance with the foregoing examples was incorporated into cigarettes.
  • the smoke from these cigarettes was compared with that from cigarettes containing filler from the same batch but not containing organoleptic material. It was found that the smoke of those containing the organoleptic material was noticeably enhanced, having interesting and pleasing qualities of taste and aroma. The alteration of these characteristics of the smoke was not dramatic, but rather pleasing and definitely discernible. By combining the products of the examples differing flavors and aromas were obtained. It was further found that a s'ub'stantiallY linear relationship existed betweenthe ameunt or ergang leptic material incorporated in the cigarette andtlie-apparentness of its presence.
  • a method of preparing organoleptic material from tobacco which comprises reacting said tobacco with low'er alkyl alcohol in the presence of mineral acid catalyst.
  • a method of forming organoleptic material in tbacco which comprises reacting said tobaccowith vaporous lower alkyl alcohol in the presence of vaporous mineral acid catalyst.
  • a method of preparing organoleptic material from tobacco which comprises reacting said tobacco. with liquid lower-alkyl alcohol in the presence of suflicient mineral acid catalyst to reduce the pH of said. tobacco, liquid lower alkyl alcohol and mineral acid catalyst below about 3.5, adjusting thepH after" reaction to betweenabout 6 to 7, and recovering the reaction product.
  • a method of preparing organoleptic material from tobacco which comprises reacting "said tobacco” with lower alkyl alcohol in the presence of mineral acid cat'- alyst, the amount of said catalyst being from10%' to 30% in excess of the stoichiometric equivalent required to neutralize the combustion ash of said tobacco, adjusting the pH after reaction to between about 6m 7', and recovering the reaction product.
  • a method of preparing organoleptic'material from tobacco which comprises extracting said tobaccowith organic solvent extracting medium, reacting the resultant extract with lower alkyl alcohol in the presence of sufficient mineral acid catalyst to reduce the pH of the mixture of said extract, said lower alkyl alcohol and said mineral acid catalyst below about 3 .5, adjusting thepH of the mixture after reaction to between about 6 to 7, and recovering the reaction product.
  • brg-anic solvent extracting medium contains suflicientmineral acid to bring the pH thereof between about 2 to 4.
  • a method of preparing organoleptic material from tobacco which comprises extracting said tobacco with a lower alkyl alcohol extracting medium, acidifying the resultant extract with mineral acid catalyst in an amount sufiicient to reduce thepHbelowabout 3.5, whereby reaction takes place between the alcohol and tobacco, adjusting the pH after reaction'to between about 6 to 7, and recovering the product.
  • a composition of matter which comprises (a) tobacco, and (b) organoleptic material which is the reaction product prepared by reacting tobacco with lower alkyl alcohol in the presence of mineral acid catalyst.

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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)
US843947A 1959-10-02 1959-10-02 Organoleptic materials and method of production thereof Expired - Lifetime US2995476A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US843947A US2995476A (en) 1959-10-02 1959-10-02 Organoleptic materials and method of production thereof
GB33426/60A GB908773A (en) 1959-10-02 1960-09-29 Organoleptic materials derived from tobacco and method of production thereof
CH1105560A CH401792A (de) 1959-10-02 1960-09-30 Verfahren zur Herstellung von organoleptischen Stoffen aus Tabak

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3132651A (en) * 1961-08-23 1964-05-12 Julius E Kiefer Smoking products and manufacture of the same
US3704714A (en) * 1971-06-16 1972-12-05 Liggett & Myers Inc 2-isopropyl-5-methyl-2-hexenal, 2-isop-ropyl-5-methylhexanal,3-hydroxy-2-isopropyl-5-methylhexanal, and derivatives thereof as tobacco flavorants
US3762423A (en) * 1971-06-16 1973-10-02 Liggett & Myers Inc Methyl trans-2-isopropyl-5-methyl-3-hexenoate and derivatives thereof as tobacco flavorants
US4967771A (en) * 1988-12-07 1990-11-06 R. J. Reynolds Tobacco Company Process for extracting tobacco
US5005593A (en) * 1988-01-27 1991-04-09 R. J. Reynolds Tobacco Company Process for providing tobacco extracts
US5148819A (en) * 1991-08-15 1992-09-22 R. J. Reynolds Tobacco Company Process for extracting tobacco

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6769437B2 (en) 2002-04-08 2004-08-03 Philip Morris Incorporated Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette
US8701681B2 (en) 2003-10-27 2014-04-22 Philip Morris Usa Inc. Use of oxyhydroxide compounds in cigarette paper for reducing carbon monoxide in the mainstream smoke of a cigarette

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US747081A (en) * 1903-02-25 1903-12-15 Alfredo Nauwelaers Process of treating tobacco.
DK6481A (da) * 1979-05-08 1981-01-08 Babington Robert S Forbedringer i forbindelse med braendere til flydende braendstof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US747081A (en) * 1903-02-25 1903-12-15 Alfredo Nauwelaers Process of treating tobacco.
DK6481A (da) * 1979-05-08 1981-01-08 Babington Robert S Forbedringer i forbindelse med braendere til flydende braendstof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3132651A (en) * 1961-08-23 1964-05-12 Julius E Kiefer Smoking products and manufacture of the same
US3704714A (en) * 1971-06-16 1972-12-05 Liggett & Myers Inc 2-isopropyl-5-methyl-2-hexenal, 2-isop-ropyl-5-methylhexanal,3-hydroxy-2-isopropyl-5-methylhexanal, and derivatives thereof as tobacco flavorants
US3762423A (en) * 1971-06-16 1973-10-02 Liggett & Myers Inc Methyl trans-2-isopropyl-5-methyl-3-hexenoate and derivatives thereof as tobacco flavorants
US5005593A (en) * 1988-01-27 1991-04-09 R. J. Reynolds Tobacco Company Process for providing tobacco extracts
US4967771A (en) * 1988-12-07 1990-11-06 R. J. Reynolds Tobacco Company Process for extracting tobacco
US5148819A (en) * 1991-08-15 1992-09-22 R. J. Reynolds Tobacco Company Process for extracting tobacco

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Publication number Publication date
CH401792A (de) 1965-10-31
GB908773A (en) 1962-10-24

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