DE1692941A1 - Use of additives to change the taste or aroma of tobacco products - Google Patents

Description

Use of additives to change the taste or aroma of tobacco products,

The invention relates to a tobacco product and advantageously proposes a composition and a method to improve the taste and aroma of tobacco and tobacco smoke. In the tobacco industry it is known that The taste and aroma of a tobacco product are very important considerations as far as the end user is concerned. Significant efforts are being made by tobacco product manufacturers to provide a product that is acceptable to the consumer, especially in terms of taste and aroma properties, it is so far it has been common practice in the tobacco industry to produce mixtures of domestic and oriental tobacco to produce a To deliver smoking tobacco with a pleasant taste and a'roma before and during smoking. However, one such procedure is

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expensive and can temporarily become inapplicable if certain types of tobacco are not available »Correspondingly, there is a Another object of the invention is to provide a new class of additives which can be used when added to tobacco products Improve and promote the taste and aroma of these products and the smoke they emit and thereby improve and improve the enjoyment and other values that the consumer derives from the use of these products raise"

Another object of the invention is a method for increasing or otherwise improving taste, Aroma and other properties of certain domestic, oriental, synthetic or substitute tobacco that contain this Not having sufficient taste, aroma and other properties.

An additional object of this invention is a method of making a smoking tobacco or product, which has an improved taste or aroma when smoked «

Another object of the invention is smoke products such as cigarettes, cigars or pipe tobacco and a method for producing the same, with taste and Aroma can be improved or increased before and during smoking

According to one embodiment of this invention, a tobacco product is proposed which contains a small amount one of the compounds with the following formulas is added

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■ »3—

was, or which was treated with it:

CH ₂ -CH = C-CHO

CH,

H ₂ COCH ₃

CH,

CH (CH ₃ ) ₂ £

IV

O
η

VI CH ₃ OOCh = CHOOCH (CH ₃ )

VII (CH ₃ ) ₂ C = CHCH ₂ CH ₂ CHOHCH ₃

-0

CH,

I!

C-I

VIII

IX

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In the links that go through. Formula IX are shown, R is hydrogen or methyl «If R is hydrogen, the tobacco additive is 5-methylfurfuraldehyde, R is through Replaced methyl, the compound 5 »^ lethyl-2-acetyl-furan ·

example 1

Synthesis and properties of 2,4-diphenylcrotonaldehyde

(Formula i)

This connection was made according to the procedure of

W. Treibe and K. Krumliolz, Chenu Ber _# , 85, 1116-19 (19525 prepared by the dropwise addition of 50 g of phenylacetylaldehyde to 2 ml of ethanol containing 90 mg of acetic acid and 0.125 g of piperidine, 18.8 g of 2.4 -Diphenylcrotonaldehyde with a boiling point of 202-5 ° C / 1 mm and a nuclear magnetic resonance spectrum "J ~ = 6.32 (2d) j 3.15 (1); 2.73 (10); and 0.33 (1) received.

fe example 2

The compound of formula II is the commercially available diphenyl ether having a melting point of 26-27 ⁰ C and a nuclear magnetic resonance spectrum ~ J '' = 2.70 (10).

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Example 3

Synthesis and properties of 2-acetonyl ~ 4 ~ methyltetrahydro pyran (lormel III)

1c Production of 2-hydroxy «4-tetrahydropyran:

To a solution of 20 g ß-ilethyl-o-vslerolactone (im Commercially available) in 50 ml of absolute ether was added dropwise a solution of 1.67 g of lithium aluminum hydride in 50 ml of ether added. After refluxing for 1 hour, the solution was hydrolyzed with water and the ether layer separated from the aqueous layer. The aqueous layer was extracted twice more with ether and the combined ether layers were dried and constricted; 11.3 g of 2-hydroxy-4-methyltetrahydro resulted pyran.

2. 2-Acetonyl ~ 4-methyltetrahydropyran:

Z * Hydroxy-4Haiethyltetrahydropyran (11.3 g) was added dropwise to a stirred solution of 36 ml of acetone, 36 ml of water and 3 g of a 3Q sodium hydroxide solution Acetic acid neutralized «The aqueous layer was extracted several times with ether and the residue of the ether layers was distilled, yielding 7.3 g of 2-acetonyl-4-methyltetrahydropyran, boiling point 56-63 ° C / i mm; nuclear magnetic resonance spectrum j T = 9.06 (3); 7.86 (3); 7.53 (2); and 6.37 (2) _O

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Example 4 Synthesis of the properties of 2-methyl ~ 5-iaopropylpyridine

(Formula IV)

Ethyl 6-methylniootinate, boiling point 113-16 ° 0/11 mm, was made according to the instructions of P.A. Plattner, ¥. Keller and A. Boiler, HeIv. Ohim. Acts .37, 1379-92 (1954). 5.5 g of the ester in 25 ml of ether were added dropwise 40 ml of ethylmagnesium dromide added to ethyl ether. To After the addition, the mixture was refluxed for 2 hours and decomposed with potassium hydroxide. The resulting Layers were separated. The aqueous layer was extracted with ether and the ether extract with the organic Layer combined, which was then dried over sodium sulfate «, after removal of the solvent in vacuo gave 4 g of crude o-methylpyridine-S-dimethylcarbinols.

The crude Garbinol was with 35 g of hydrogen iodide and 1 g of red phosphorus mixed. The mixture was boiled for 10 hours and then filtered. 2 g of zinc dust were added to the piltrate joined. After 4 hours, 10 # potassium hydroxide was added and the mixture was extracted with ether. the The ether layer was dried over sodium sulfate and the ether removed in vacuo. The residue was distilled and gave 1.5 g of 2-methyl-5-isopropylpyridine, boiling point 73-74 ° C / 15 mm j nuclear magnetic resonance spectrum T = 8.80 (3); 8.70 (3); 7.52 (3); 7.06 (1); 2.96 (1); 2.60 (1); and 1.65 (1).

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Example 5 Synthesis and properties of 6-methyl-2,5-heptanedione

(Formula V)

35 g Äthyllevulinatäthylenglykolketal were in 76 ml dissolved in absolute ether and placed in a 500 ml 3-neck basket, equipped with a magnetic stir bar, reflux condenser, nitrogen inlet tube and a pressure equalizing Addition funnel., Given. Isopropyllithium (160 ml, 1.33m in pentane) was transferred into the addition funnel under nitrogen pressure and added dropwise over 1.5 hours The mixture was stirred for a further hour and then water was slowly and carefully added to the organic which formed Layer was separated and the solvent removed in vacuo. The residue was washed with 100 ml of 10% sulfuric acid and 60 ml of ethanol mixed. After refluxing for 1/2 hour, the Omeetzgemisch was with Water diluted and extracted with ether. The ether extract was dried, the ether removed in vacuo and the residue distilled «14 g of 6-methyl ~ 2,5-heptanedione were obtained, Boiling point 88-89 C / 15 mm, nuclear magnetic resonance spectrum T = 9 »0 (3); 8.88 (3); 7.90 (3); and 7.40 (5).

Example 6
Synthesis and properties of 6-methyl-3-hepten-2,5-dione

(Formula VI) A mixture of 10 g of 6-methyl-2,5-heptanedione, 6 g

oelendioxid and 200 ml of water was heated to 75 ⁰ C for 12 hours. T h e mixture was filtered, the Piltrat with ammonium

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Saturated sodium sulfate and extracted with ether »The residue, after removal of the ether in vacuo, the mixture was distilled and gave 5 g of 6- * iethyl-3-hepte.n-2.5-dione, boiling point 98400 ° C / 2 mm, nuclear magnetic resonance spectrum 8.90 (3); 8.78 (3) | 7.64 (3); 7.10 (1); and 3.13 (2).

Example 7 6-Methyl-5-hepten-2-ol (Formula YII )

The compound 6-methyl-5-hepten-2-ol is commercially available and has the following properties: boiling point 80 ^° O / 25 mm; Infrared spectrum V? - 3300, 1620 and 1115 cm " ¹ 'nuclear magnetic resonance spectrum *}" «= 4.83 (1, triplet), 6.15 (1, quadruplets, 7.92 (2), 8.30 (3), 8, 37 (3), and 8.83 (3, doublet); mass spectrum parent peak "at 128 mass

Il

Units.

Example 8

Synthesis and properties of 2,5,5,8a-tetramethyl-3 _> 5,6 _> 7, - 8,8a-heiahydro-2H-1-benzo pyran-7-one.

1. 5-Oxo-a-ionon

The method of V. Prelog and M. Osgan, HeIv. Chinu Acta 35., 986-92, (1952) or modifications thereof has been used for Used for representation of 5-oxo-a-jonon. 100 g of a-ionone was

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treated with t-butyl chromate in carbon tetrachloride (325 g of t-butyl alcohol, 220 g of chromic anhydride, 30 ml of acetic anhydride and 2 1 CCl.). The mixture was ^{kept in the dark at 0} ° C. for 16 days, then worked up in the manner described. The obtained substance was chromatographed, and 40 g of α-ionone, 1.5 g of 4-oxo-β-ionone, and 12 g of 5-oxo-α-ionone were obtained as pure compounds. The 5-oxo-a-ionone was recrystallized from pentane-ether solutions and melted at 71-73 ⁰ C (theor. Melting point 66-67 ⁰ C).

2 · Addition and cyclization of 5-oxo-a-ionone.

25 g of crude 5-oxo-a-ionone were dissolved in 100 ml of methyl alcohol / water 1: 1 containing 8 g of potassium hydroxide dissolved and left to stand overnight at room temperature Solution was neutralized, diluted with water, extracted with ether and the ether removed in vacuo Dione (A) was dissolved in 25 ml of ethanol and 2 g of sodium borohydride was added. Naoh 2 hours of standing was the Mixture acidified, diluted with water and extracted with ether. Removal of the ether in vacuo gave crude Keto alcohol (B).

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The keto alcohol (B) was contained in 25 ml of benzene 0.2 g of p-toluenesulfonic acid, dissolved and the resulting solution Boiled under reflux for 1 hour. The cooled solution was washed with water and 5% sodium carbonate solution » After removal of the benzene in vacuo, the residue was distilled and 1.2 g of 2,5,5,8a-tetramethyl-3,5,6,7-8,8a-hexahydro-2H-1-benzopyran-7-one were won; Boiling point 87-89 ° C / 2 mm; nuclear magnetic resonance spectrum 7 "= 8.87 (3); 8.77 (3); D 8.76 (3); 8.51 (3); 7.64 (2); 7.42 (2); 6.15 (1); and 4.27 (1).

Example 9
Synthesis and properties of 5-methyl-2-acetylfuran

This compound was synthesized according to the method of N ₀ I · Shucikin and I.] ?. Bel'skii, J _e Gen. Chem. (USSR) 29., 1066-1068 (1959), from 41 g of methylfuran, 76.5 g of acetic anhydride and 3 ml of phosphoric acid. 17 g of 5-methyl-2-acetylfuran, boiling point 75-76 ° C./9 mm; nuclear magnetic resonance spectrum T = 7.68 (3); 7.58 (3); 3.82 (1); and 2.84 (1).

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Example 10 Synthesis of properties of 5-M ethylfurfuraldehyde

This compound was synthesized according to the method of VJ, Traynelis, JJ Miskel, Jr., and JRSowa, J.Org » Chem.2g, 1269-70 (1957) from 26 g of dimethylformamide, 54 g of phosphorus oxychloride and 25 g of 2-methylfuran. 25 g of 5-M ethylfurfuraldehyde, boiling point 70 ° C./11 mm; nuclear magnetic resonance spectrum ^ = 7.52 (3)} 3.68 (1); 2.74 (1); and 0.37

It has been found that the tobacco additives of the invention when they are incorporated into tobacco products, give them a taste and aroma before and during smoking, which many smokers consider desirable tobacco products · However, it should be noted that the methods to define and characterize the value properties of taste and aroma in tobacco technology almost pure subjective in nature, and that different smokers can judge the same taste very differently «Also the compounds can fall within the broad scope of the invention depending on their substituents give different flavors and aromas. Thus, the compounds of the invention confer, based on subjective Attempts to find characteristic taste properties that are desirable in tobacco products, although the exact properties not based on known dimensions

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rods can be described. The tobacco additive of Example 1 imparts a sweet floral aroma or flavor Taste that is reminiscent of geraniums, which many smokers consider desirable in a tobacco product. Of the The tobacco additive of Example 2 gives what some refer to as camphor-menthol-like aroma; the tobacco additive of Example 3 has a mild odor of roses and gives a banana-like, spicy aroma; the tobacco additive of Example 4 has a sweet potato odor; the compounds of Examples 5 and 6 impart a sweet taste; and the tobacco additive of Example 7 is somewhat reminiscent of camphor. The additive of Example 8 imparts an iononic taste and aroma during smoking. The compound of Example 9 gives an aromatic, spicy aroma and the tobacco smoke a strong tobacco-like taste, while the Additive of Example 10 imparts an aroma and taste that some describe as similar to bitter almonds.

. According to the invention of the above compounds or a mixture of these compounds tobacco, a smoking article or its components in amounts of from about 0.0001 to 2.0 percent is - $> of the product added. The amount used, however, will depend on the intensity of flavor and aroma desired and the particular compound or mixture of compounds used. Of the

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Additive can be added to the tobacco at any stage of its treatment, but preferably after aging _t roasting and cutting and before the tobacco is made into cigarettes. Likewise, it is obvious that only a part of the tobacco needs to be treated, and the tobacco so treated can then be mixed with other tobacco before cigarettes or other tobacco products are manufactured. In this case, the treated tobacco can contain the additive in greater quantities Amount as stated above, so that the end product after mixing with other tobacco has a percentage in the specified range _e

According to a further embodiment of the invention, an aged, roasted and shredded tobacco is made with a 1 # solution of 2,5 »5,8a-tetramethyl-3,5,6,7, -8,8a-hexahydro» 2H-1-benzopyran-7 ~ one sprayed in ethyl alcohol in an amount that a tobacco with 0.1 wt .- ^ des Additive, based on the dry substance, provides »Then the alcohol is removed by evaporation and the Tobacco is made into cigarettes in the usual way. It was found that the so produced Cigarettes have a desirable and pleasant taste.

According to a further special embodiment of the invention, an aged, smoke-roasted and cut tobacco with a 1 follow solution of 5-methyl-2-

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acetylfuran (formula IX) sprayed in ethyl alcohol in an amount _{that delivers a tobacco with 0.1 wt. e} - # of the additive, based on the dry substance. The alcohol is then removed by evaporation and the tobacco is made into cigarettes in the usual manner. The cigarettes thus prepared were found to have a desirable and pleasant taste. The additives which fall within the scope of this invention can be added to the tobacco be added by spraying, dipping or otherwise, using suitable slurries or solutions of the additive. Thus, water or volatile organic solvents such as alcohol, ether, acetone, volatile hydrocarbons and the like can be used as a carrier medium for the additives as they are added to the tobacco. Other flavor and aroma-producing additives, such as those shown in U.S. Patents 2,766,145, 2,905,575, 2,905,576, 2,978,365 and 3,041,211, can also be added to the tobacco at the same time as the additives of this invention.

While the invention is primarily useful in the manufacture of cigarettes, it can also be used in Used in connection with the manufacture of pipe tobacco, cigars or other smoking products. Furthermore can the compounds are added to certain tobacco substitutes of natural or synthetic origin. With the The term "tobacco", as used here, is any addition

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Composition meant that is intended for human consumption through smoking or otherwise, whether it is made from parts of tobacco plants or substitutes or both is composed "

The invention is also described in particular with regard to the direct addition of the compounds to tobacco been. It is obvious, however, that the compound is also attached to the cigarette paper or the cigar wrapper It can also be incorporated into the filter tip or the paste used to glue the cigarette paper "So a tobacco product is obtained which includes the special additives and tobacco, although the Compound does not have to be mixed with the tobacco as described above in every case.

- patent claims -

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Claims (1)

Patent claims: 1. Use of 2,4-diphenylcrotonaldehyde, Diphenylether * 2-Acetonyl ~ 4 * 4nethyltetrahydropyran, 2-methyl-5 ~ isopropylpyrldine, 6- # ethyl-2,5 ~ heptanedione, 6-methyl-3-hept en-2,5-dione, 6-M ethyl-5-hepten-2-ol, 2,5 »5,8a-Tetramethyl-3» 5,6,7,8,8a-hexahydro ~ 2H-1-benzopyran-7-one, 5-methylfurfuraldehyde, or 5-methyl-2- acetylfuran in a tobacco product in an amount sufficient to change the taste or aroma of the tobacco product. 2β Use according to claim 1, characterized in that that the tobacco product contains a sufficient amount of 2,4-diphenylcrotonaldehyde contains to change its taste or aroma " 3 · Use according to claim 1, characterized in that the tobacco product contains a sufficient amount of diphenyl ether contains to alter its taste or aroma. 4. Use according to claim 1, characterized in that that the tobacco product contains a sufficient amount of 2-acetonyl ~ 4- * iethyltetrahydropyran to its Change the taste or aroma 5. Use according to claim 1, characterized in that that the tobacco product contains a sufficient amount of 2-methyl-5-isopropylpyridine to maintain its taste or change its aroma, 209817/1074 6β Use according to claim 1, characterized in that the _y tobacco product contains a sufficient amount of 6-methyl-2,5 ~ heptanedione, to alter its taste or aroma · 7e use according to claim 1, characterized in that that the tobacco product contains a sufficient amount of 6-methyl-3-hepten-2,5-dione to maintain its taste or to change its aroma. 8 · Use according to claim 1, characterized in that the tobacco product has a sufficient amount of Contains 6-methyl-5-hepten-2-ol to alter its taste or aroma 9 · Use according to claim 1, characterized in that the tobacco product has a sufficient amount of 2,5,5,8a-Tetramethyl-3,5,6,7,8,8a-heiahydro-2H-1-benzopyran-7-one contains to change its taste or aroma « 10. Use according to claim 1, characterized in that that the tobacco product contains a sufficient amount of 5-methylfurfuraldehyde to make its flavor or to change its aroma " 11. Use according to claim 1, characterized in that that the tobacco product has a sufficient amount of 5-methyl-2-acetylfuran contains to alter its taste or aroma. 12. Use according to one of claims 1-11, since 209817/1074 characterized in that the additive in an amount is between 0.0001 and 2.0% by weight of the product. 13β Use according to claim 12, characterized in that that the additive is present in an amount between about 0.01 and 1% by weight of the product, 14 · Use according to claim 12 or 13, characterized in that the additive in an amount between is about 0.01 and 0.5 wt. # of the product. 209817/1074