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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/72—Hydrazones
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/20—Synthetic spices, flavouring agents or condiments
  • A23L27/202—Aliphatic compounds
  • A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
• • 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
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  • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
  • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
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  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
  • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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  • C07C45/78—Separation; Purification; Stabilisation; Use of additives
  • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
  • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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  • C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
  • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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  • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups

Definitions

• ABSTRACT Assigneel Llggett & Myers Incorporated New The base-catalyzed self-condensation of isovaleral- York dehyde yields a mixture of threoand erythro-2- 22 Filed; June 16, 7 isopropyl-S-methyl-3-hydroxyhexanal.
• the reaction conditions can be so chosen as to favor predominance [21] Appl' 153,900 of one isomer over the other.
• aldehydes are the i z z and 73,194 Sept" parent members of a class of compounds composed of l an one 2-isopropyl-S-methylhexanal, 3-hydroxy-2-isopropyl- S-methylhexanal, 2-isopropyl-5-methyl-2-hexenal, and [52] US. Cl ..131/17 R, 99/140,131/144 the alcohol and carboxylic acid derivatives ofthese ab [51] Int. Cl.
• Field is h 131/17 140 99/140 dehydes, the ester and ether der1vat1ves of the al- 0 earc cohols and acids, as well as certain other alcohol and [56] References Cited ketone derivatives.
• This invention relates to novel aldehydes, alcohols, acids, ethers and esters as tobacco flavorants. More particularly, this invention is concerned with 3-hydroxy-2-isopropyl-5-methylhexanal, 2-isopropyl-5-methyl-2 -hexenal and 2-isopropyl-5-methylhexanal, the corresponding primary alcohols and their ethers and esters, the corresponding carboxylic acid derivatives and esters of the acids, 3-iso-propyl-6-methylheptan-2- ol, 3-isopropyl--methylheptan-Z-one and their corresponding unsaturated derivatives as tobacco additives to modify the flavor of the tobacco smoke.
• Y is hydrogen, hydroxyl, lower acyloxy, or lower alkoxy
• X is hydroxymethyl, lower acyloxymethyl, lower alkoxymethyl, 2-hydroxyethyl, formyl, acetyl, carboxyl or lower alkoxycarbonyl and y is or I.
• a solution of isovaleraldehyde in an organic solvent is admixed with aqueous base at reduced temperatures, preferably 0 to 5C., and then the reaction mixture vis maintained at room temperature for about 6 to about 120 hours or more, depending upon the desired product, with dehydration being favored by longer reaction times.
• the resulting acids are then esterified in known manner, as by acid-catalyzed reaction with a low molecular weight alcohol of the formula ROI-l, wherein R is lower alkyl.
• a preferred method comprises the use of perchloric acid or sulfuric acid and methanol.
• the methyl ester is obtained by reaction of the acid with diazomethane.
• the 3-hydroxy-2-isopropyl-S-methylhexanal and the 2-isopropyl-5-methyl-2-hexenal are also readily reduced, as by treatment with sodium borohydride in conventional manner, to the corresponding primary alcohol, i.e., 2isopropyl-5-methylhexane-l,3-diol and 2- isopropyl-S-methyl-2-hexen-l-ol.
• the hexenal compound can be hydrogenated under mild conditions, e.g., over a palladium catalyst, to yield 2- isopropyl-S-methyl-hexanal, or under more severe con- I ditions, e.g., over platinum oxide and ferrous chloride,
• the saturated hexanal may be oxidized to the corresponding acid as describe above, and the acid converted to a lower alkyl ester.
• All of the alcohols may be fully or, in the case of the derivatives of Formula IA, partially esterified or etherified in known manner.
• the amount of the compound which is added to the tobacco will vary with the compound and the effect desired. In general, however, amounts of at least about 0.02 milligrams per gram of tobacco are employed. Normally amounts exceeding 0.5 mg per gram of tobacco are undesirable because of harshness. When employed in filter cigarettes higher amounts are required to achieve the same effect obtained with non-filter cigarettes.
• EXAMPLE 1 To a cooled (C. solution of isovaleraldehyde 100 g.) in 100 ml. of ether was added with stirring 200 ml. of aqueous 15 percent potassium hydroxide solution over a period of 45 minutes and at such a rate that the'temperature did not rise above 5C. After cooling at 0C. for an additional minutes, the cooling bath was removed and the mixture was stirred for 24 hours. The liquid layers were separated; the aqueous layer was washed with ether and the combined ether solutions were washed successively with 2 N acetic acid, saturated sodium bicarbonate solution, water and saturated sodium chloride solution.
• EXAMPLE 11 The unsaturated aldehyde recovered in Example 1 was purified further by fractionation using a semimicro spinning-band column and a manostat to regulate the pressure at 200 mm. Four fractions were collected between 135 and 136l200 mm. Hg.
• the 2,4- dinitrophenylhydrazone was prepared and recrystallized from methanol, orange-red crystals, m.p. 129-13 2C., and showed one spot on thin layer chromatography using several solvent systems. Analysis. Calcd. f0! CmHggN 4041C, H, N, Found: C, 57.44; H, 6.67; N, 16.68.
• Example 1 The aldol of Example 1 was converted to 3-hydroxy- 2-isopropy1-5-methy1hexanoic acid by allowing the higher-boiling fraction of Example 1, 3-hydroxy-2- isopropyl-5-methylhexanal, to stand for several weeks, or by bubbling air through the viscous liquid for several days, whereupon crystals of the acid separated. Recrystallization from cold methylene chloride-carbon tetrachloride gave white needles, mp. 88-89. The mass spectrum gave the molecular ion at m/e 188, with major peaks at 170, 131, 113, 102, 87, 85, 71, 69, 43, 41, 29, 27.
• the IR spectrum (CH Cl shows acid and hydroxyl OH bands at 3300-3000 and 3600-3500 cm, and has three carbonyl bands, for dimer (1700 cm), intramolecularly hydrogen-bonded form (1726 cm"), and nonbonded form (1752 cm"). By the use of dioxane as a solvent the band at 1700 cm'l reverts to the bonded form 1726 cm'l thus indicating that the hydroxyl on carbon 3 is hydrogen-bonded to the carbonyl oxygen.
• EXAMPLE 1V Methyl 3-hydroxy-2-isopropyl-5-methylhexanoate was prepared from the acid of Example 111 using excess ethereal diazomethane. Quantitative conversion was indicated by thin layer chromatography (Silica gel G, benzene-ethyl acetate, 9:1). The compound was chromatographed on grade [11 neutral alumina (-200 mesh), using benzene as the eluent. An analytical sample was obtained by gas liquid chromatography on a 10 ft. X '16 in stainless steel column packed with 10 percent GE-SF-96 on Gas Chrom RZ, 100-200 mesh, flow rate 40 ml. Helmim; column temp. 68 initial hold/4 min, program 4lmin.
• a 70-80 percent yield of the ester was also obtained by treatment of the acid of Example 111 with perchloric acid in methanol; i.e., l g. of acid, 25 ml. methanol and 0.1 ml. 70 percent perchloric acid was refluxed on the steam bath overnight. The methanol was evaporated and the residue taken up in ether. The ether solution was washed with dilute sodium bicarbonate solution, water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and evaporated. The IR spectrum was identical to that of the ester prepared using diazomethane.
• EXAMPLE V 2-Isopropyl-5-methyl-2-hexanoic acid was prepared from the unsaturated aldehyde of Example 1 as follows: A solution of 3.5 g. of 2-isopropyl-5-methyl-2-hexenal in 400 ml. of acetone was cooled to l015C. and stirred while bubbling nitrogen through the mixture, and 4-5 ml. of Jones reagent was added dropwise until the orange color just persisted. The cooling bath was removed during this time. The solution was filtered; 50 ml. of water was used to wash the flask and added through the filter to the solution. The acetone was evaporated in vacuo and the mixture extracted with ether.
• the ether solution was extracted with 15 percent potassium hydroxide solution, and the basic extract was acidified with 10 percent sulfuric acid, followed by a final ether extraction.
• the ether solution was dried over anhydrous sodium sulfate an purified by preparative gas liquid chromatography on a 10 ft. X 96 in. copper column packed with 17 percent Carbowax 20M on Chromosorb P, 60-80 mesh, flow rate 70 ml. Pie/min; column temp. 240. Under these conditions the clear liquid had a retention time of 18 minutes.
• EXAMPLE Vl Methyl 2-isopropyl-5-methyl-2-hexenate was prepared from the acid of Example V using diazomethane in a manner identical to that of Example IV.
• the ester was also prepared as follows: 33 g. of crude 2-isopropyl-5-methyl-2-hexenoic acid was dissolved in 300 ml. of dry methanol containing 3, ml. concentrated sulfuric acid, and the mixture refluxed for 24 hours. Solid sodium bicarbonate was used to neutralize the solution, and 200 ml water added. The methanol was evaporated in vacuo, and the whole extracted 4 times with ether. The ether extracts were combined, washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate.
• the ester (18 g.) was distilled through a semi-micro distillation apparatus which included a foam-trap and Claisen-head. The material distilling at 534/l.5 mm Hg weighted 13 g. The forerun and pot-residue also consisted largely of the ester.
• EXAMPLE VII Aliquots of 10 11.1 of a solution of 0.5 mg of 2- isopropyl-5-methyl-2-hexenal in 1 ml 95 percent ethanol were injected uniformly along a path of 55 mm length in experimental cigarettes manufactured from a commercial blend of tobaccos. The sample cigarettes were equilibrated at 60 percent relative humidity for lO-l 2 hrs. before smoking.
• EXAMPLE vur A solution of 10 mg of 2-isopropyl-5-methyl-2-hexenal in 4 ml of percent ethanol was applied by spraying to 200 gm of a cased and cut commercial blend of tobaccos, and the treated tobacco was made into cigarettes (Sample A).
• the cigarettes of Sample -A and B exhibited a complex and interesting aroma which had notes of sour, dried fruit, honey and licorice.
• the smoke from these cigarettes produced a dominant bitter-woody taste'and, especially those of Sample B, produced some throat irritation.
• the cigarettes of Samples C and D exhibited unpleasant astringency and irritation on smoking.
• EXAMPLE IX A solution of 25 mg of 2-isopropyl-5-methyl-2-hexenal in 4 ml of 95 percent ethanol was applied by spraying to 200 gm of a cased and cut commercial blend of tobaccos. The thus treated tobacco was made into cigarettes and cellulose acetate filters were attached. A second sample was prepared in a similar manner, except that three-piece filters consisting of cellulose acetate-charcoal-cellulose acetate were attached instead of the cellulose acetate filter. Cigarettes having attached cellulose acetate filters showed slightly enhanced tobacco fragrance and more fullness, whereas cigarettes having attached three-piece cellulose acetate and charcoal filters gave no improvement over the control on smoking.
• EXAMPLE X A solution of 20 mg of 2-isopropyl-5-methyl-3- hydroxyhexanoic acid in 4 ml of 95 percent ethanol was applied by spraying to 200 gm of a cased and cut commercial blend of tobaccos, and the thus-treated tobacco was made into cigarettes. The cigarettes produced more amplitude, more blended tobacco fragrance, and more sweet taste than the control when smoked. in addition a alight pepperiness was observed.
• EXAMPLE Xl A solution of 10 mg methyl 2-isopropyl-5-methyl-3- hydroxyhexanoate in 4 ml of 95 percent ethanol was applied by spraying to 200 gm of a cased and cut commercial blend of tobaccos. The thus-treated tobacco was made into cigarettes (Sample A). In a similar manner samples were produced employing solutions of 20, 30 and 50 mg. of methyl 2-isopropyl-5-methyl-3- hydroxyhexanoate in 4 ml of 95 percent ethanol (Samples B, C and D, respectively).
• the cigarettes of Sample A were not significantly different from the control, but those of Samples B produced a more balanced flavor spectrum than the control when smoked, with a higher level of sweet taste, less bitter taste, less drying and a low-level woody character.
• the cigarettes also produced a smoother, smoke, and a modest taste improvement over the control.
• the cigarettes of Sample C and D produced a bitter, pipe-stem taste and a high level of pepperiness and sting.
• EXAMPLE x11 A solution of 20 mg of 2-isopropyl-5-methyl-2-hexenoic acid in 4 ml of 95 percent ethanol was applied by spraying to 200 gm of a cased and cut commercial blend of tobaccos. and the thus-treated tobacco was made into cigarettes.
• Cigarettes prepared in this manner exhibited increased fullness and interest in the smoke, but there were no flavor or taste differences from the untreated control.
• EXAMPLE XIII EXAMPLE XIV A solution of mg of 2-isopropyl-5methyl-2-hexenal and 20 mg of methyl 2-isopropyl-5-methyl-3- hydroxyhexanoate in 4 ml of 95 percent ethanol was sprayed onto 200 gm of a cased and cut commercial blend of tobaccos and the blend was made into cigarettes.
• the cigarettes exhibited enhanced tobacco fragrance which was described as having cocoa-burley character. There was also a more complex flavor spectrum characterized by a woody-Turkish note.
• EXAMPLE XV 2-lsopropyl-5-methyl-2-hexen-l-ol was prepared by reduction of the corresponding aldehyde with sodium borohydride in ethanol. After appropriate work-up, the product was obtained by distillation at 6l6 2C/ 1-2 Aliquots of 10 ,ul of a solution of 20 mg 2-isopropyl- 5-methyl-2-hexen-l-ol in 2 ml of 95 percent ethanol were injected uniformly along a path of 55 mm length in experimental cigarettes manufactured from a commercial blend of tobaccos. The solvent was removed from each cigarette by a gentle stream of air.
• the cigarettes contain ing the 2-isopropyl-5-methyl-2-hexen-l-ol exhibited moderate burnt, green, and sweet notes, while drying and coating were low to moderate as were mouth and throat irritations. Bright tobacco-like notes in the aftertaste were intensified.
• EXAMPLE XX 3-Isopropyl-6-methyl-2-heptanol was prepared from 2-isopropyl-5-methylhexanai by treating 5 g. of the aldehyde with 24 ml. of 1.66 M methyl lithium in 25 ml. anhydrous ether at l0l5C under an atmosphere of nitrogen. After addition of the methyl lithium was complete, the solution was stirred under reflux for 1 hour, cooled to 0C, and hydrolyzed with 15 ml. of icecold 15 percent sulfuric acid. The layers were separated and the organic layer was washed with saturated sodium bicarbonate solution, water, and saturated sodium chloride solution. dried over anhydrous sodium sulfate.
• EXAMPLE XXl 3-Isopropyl-6-methyl-2-heptanone was prepared by reacting 2-isopropyl-5-methylhexanoic acid with ethyl lithium as follows: A solution of 2 g. of the acid in 25 ml. anhydrous ether was treated with 16 ml. of 3.5 M methyl lithium in ethyl ether at 10C under a nitrogen atmosphere. The reaction solution was then refluxed with stirring for 2 hours, cooled to 0C, and hydrolyzed with 10 ml. of percent sulfuric acid.
• the layers were separated and the organic layer was washed sequentially with saturated sodium bicarbonate solution, water, and saturated sodium chloride solution, dried over sodium sulfate, and evaporated on the rotary evaporator.
• the additives of this invention may be applied to the tobacco by spraying, dipping or otherwise, utilizing suitable suspensions or solutions of the additive.
• the additives are also suitable for use in connection with the manufacture of pipe tobacco or other tobacco products.
• a tobacco composition including in an amount sufficient to modify the organoleptic characteristics of the tobacco at least one compound of the formula:
• Y is hydrogen, hydroxyl, lower alkoxy or lower acyloxy
• X is hydroxymethyl, lower alkoxymethyl, lower acyloxymethyl, 2-hydroxyethyl, formyl, acetyl, carboxyl or lower alkoxycarbonyl
• y is 0 or 1, with the proviso that X is acyloxymethyl or alkoxymethyl only when y is l.
• composition according to claim 1 wherein y is 1 and Y is hydroxyl.
• a tobacco smoking article including a tobacco composition according to claim 1.

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