DE1792731A1 - USE OF ADDITIVES TO CHANGE THE FLAVOR OR FLAVOR OF A TOBACCO PRODUCT - Google Patents

Description

R 1274 PATcNTAWÄLTe

- 1

■;. ^ Sse65

R.J. Reynolds Tobacco Company, Winston-Salem, North Carolina,

V.St.A.

Use of additives to change the taste or aroma of a tobacco product

Elimination II from P 16 92 941.2-41 (R I] Al)

The invention relates to a tobacco product and proposes in advantageous V / a composition and a method for improvement the taste and aroma of tobacco and tobacco smoke. In tobacco technology it is known that taste and aroma are one Tobacco product are very important considerations as far as the end user is concerned. Significant efforts are made by ften Tobacco product manufacturers are striving to deliver a product that is acceptable to the consumer, especially what the taste and aroma properties are concerned. It has hitherto been common practice in the tobacco industry to use mixtures of and oriental tobacco to produce smoking tobacco

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to deliver with a pleasant taste and aroma before and during smoking. However, such a procedure is expensive and can be temporary become inapplicable if certain types of tobacco are not available. Accordingly, there is another object of the invention in providing a new class of additives which, when added to tobacco products, change the taste and aroma of those products and improve and promote the smoke emitted by them and thereby the enjoyment and other values that the consumer veto use of these products derive, improve and increase.

Another object of the invention is a method of enhancing or otherwise enhancing taste, aroma and others Properties of certain domestic, oriental, synthetic or substitute tobaccos that have this taste, aroma and other properties do not own to a sufficient degree.

An additional object of this invention is a method of manufacture of a smoking tea or smoking certificate issued at the Smoking has an improved taste or aroma.

Another object of the invention are smoking products such as cigarettes, Cigars or pipe tobacco and a method of making the same, with taste and aroma before and during smoking be improved or increased.

According to one embodiment of this invention, there is a tobacco product suggested which a small amount of one of the compounds

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BATH ORIGINAL

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with the following formulas was added, or which was treated with it became:

CH ₂ -CH = Q-CHO

CH-

III

0
ti

H ₂ COCH ₃

0
dd

V CH, CCH ₂ CH ₂ CCH (CHL) ₂

II CH,

IV

CH, COCH = CHCOCH (CH,),

VII (CHJ ₂ C = CHCH ₂ Ch ₂ CHOHCH ₅

CH

-R

VIII

IX

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In the compounds represented by Formula IX is R is hydrogen or methyl. If R is hydrogen, the tobacco additive is 5-methylfurfuraldehyde, if R is replaced by methyl, so the compound is 5-methyl-2-acetylfuran.

example 1

Synthesis and properties of 2,4-diphenylorotonaldehyde

(Formula i)

This compound was prepared according to the method of W. Treibs and K. Krumbholz, Chem. Ber., 8f5, 1116-19 (1952) by adding 50 g of phenylacetylaldehyde dropwise to 2 ml Ethanol containing 90 mg of acetic acid and 0.125 g of piperidine, wherein one 18.8 g of 2,4-diphenylcrotonaldehyde with a boiling point of 202-5 ° C / l mm and a nuclear magnetic resonance spectrum / = 6.32 (2d); 3.15 (1); 2.73 (10); and 0.33 (1).

Example 2

The compound of Formula II is the commercially available Diphe nylon ether with a melting point of 26-27 ° C and a nuclear magnetic resonance spectrum / = 2.70 (10).

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t A '

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Example 3

Synthesis and properties of 2-acetonyl-4-methyltetrahydropyran

(Formula III)

1. Preparation of 2-hydroxy-4-tetrahydropyran: To a solution of 20 g of ß-methyl-P-valerolactone (commercially available) a solution became dropwise in 50 ml of absolute ether of 1.67 g of lithium aluminum hydride in 50 ml of ether was added. After this Was refluxed for 1 hour, the solution was hydrolyzed with water and the ethereal layer from the aqueous Layer separated. The aqueous layer was extracted twice more with ether and the combined ether layers were dried and narrowed; 11.3 g of 2-hydroxy-4-methyltetrahydropyran resulted.

2. 2-Acetonyl-4-methyltetrahydropyran:

2-Hydroxy-4-methyltetrahydropyran (11.3 g) was added dropwise to a stirred solution of 36 ml of acetone, 36 ml of water and 3 g of one 30) sodium hydroxide solution was added. After six hours The solution was left stirring for 16 hours and then neutralized with 10% acetic acid. The aqueous layer was extracted several times with ether and the residue of the ether layers is distilled, yielding 7.3 g of 2-acetonyl-4-methyltetrahydropyran, Boiling point 56-63 C / l mm; nuclear magnetic resonance spectrum / = 9.06 (3); 7.86 (3); 7.53 (2); and 6.37 (2).

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Example 4

Synthesis and properties of 2-methyl-5-isoproHä.pyridin

(Formula IV)

Ethyl-6-methyl nicotinate, boiling point II3-I6 ⁰ C / ll ram, was by the method of PA Plattner, W. Keller and A. Boiler, Helv. Chim. Acta 2L, 1379-92 (1954). 5.5 g of the ester in 25 ml of ether were added dropwise to 40 ml of methyl magnesium bromide in ethyl ether. 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 combined with the organic layer, which was then dried over sodium sulfate. Removal of the solvent in vacuo gave 4 g of crude δ-methylpyridine-S-dimethylcarbinol.

The crude carbinol was mixed with 35 g of hydrogen iodide and 1 g of red Mixed phosphorus. The mixture was boiled for 10 hours and then filtered. 2 g of zinc dust were added to the filtrate. After 4 10 hours potassium hydroxide was added and the mixture was extracted with ether. The ether layer was over sodium sulfate dried and the ether removed in vacuo. The residue was distilled to give 1.5 g of 2-methyl-5-45opropylpyrldine, boiling point 73-74 ° C / 15 mm; nuclear magnetic resonance spectrum / = 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 Y)

35 S Äthyllevulinatäthylenglykolketal were in 76 ml of absolute Dissolve ether and place in a 500 ml 3-neck flask fitted with a magnetic stir bar, reflux condenser, nitrogen inlet tube and a pressure equalizing addition funnel. Isopropyllithium (160 ml, 1.33 m in pentane) was added under nitrogen pressure transferred to the addition funnel and added dropwise over 1.5 hours. The stirring was continued for an additional hour and then slowly and carefully added v / ater. The developing organic Layer was separated and the solvent removed in vacuo. The residue was mitlOO ml 10 ^ iger sulfuric acid and 60 ml Mixed ethanol. After refluxing for 1/2 hour, the reaction mixture was diluted with water and with ether extracted. 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, ^ 0 (5).

Example 6

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

(Formula Vl)

A mixture of 10 g of 6-methyl-2,5-heptanedione, 6 g of selenium dioxide and 200 ml of water was heated to 75 ° C for 12 hours. The mixture was filtered, the filtrate was saturated with ammonium sulfate and extracted with ether. The residue after removal of the ether u.i VaI -lurj, was distilled and gave 5 g of G-Mothyl-.v-hopton-2, ^ -

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dion, boiling point 98-100 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 VIl)

The compound 6-methyl-5-hepten-2-ol is commercially available and has the following properties: boiling point 80 ° C./25 mm; Infrared spectrum \ ^ - 3300, 1620 and 1115 cm; nuclear magnetic resonance spectrum ^ ** = 4.83 (1, triplet), 6.15 (l, quadruplet), 7.92 (2), 8.30 (3), 8.37 (3) and 8.83 (3 , Doublet); Mass spectrum: "parent peak" at 128 mass units.

Example 8

Synthesis and properties of 2,5,5,8a-tetramethyl-3,5,6,7,8,8ahexahydro-2H ~ 1-benzopyran-7-one.

1.5-oxo-

The method of V. Prelog and M. Osgan, HeIv. Chim. Acta 25, 986-92, (1952) or modifications thereof were used to prepare 5-0xo-oC.-ionone. 100 g of j ^ ionone were treated with t-butylehromat in carbon te trachloride (3 ^ -5 g t-butyl alcohol, l.L \) ^

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Chromic anhydride, jQ ml acetic anhydride and 2 1 CCl ^) treated. The mixture was kept in the dark at 0 ° C. for 16 days, then worked up in the manner described. The material was chromatographed, and 40 g OC, ionone, 1.5 g 4-0xo-ßjonon, and 12 g of 5-oxo & - ~ j Onon were obtained as pure compounds. The 5-OxO-OC-J ⁰³¹⁰¹¹ was recrystallized from pentane ether solutions and melted at 71-73 ° C (thenr. Melting point 66-67 ° C).

2. Rearrangement and cyclization of 5-oxo-OC -ionone.

25 g of crude 5-OxO-OCrJ ⁰¹¹⁰¹¹ were in 100 ml of methyl alcohol / water

1: 1 containing 8 g of potassium hydroxide dissolved and left to stand overnight at room temperature. The solution was neutralized, diluted with water, extracted with ether and the ether removed in vacuo. The crude dione (A) was dissolved in 25 ml of ethanol and

2 g of sodium borohydride were added. After standing for 2 hours, the mixture was 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 dissolved in 25 ml of benzene containing 0.2 g of p-toluenesulfonic acid, dissolved and the resulting solution refluxed for 1 hour. The cooled solution was mixed with water and 5 Washed aqueous sodium carbonate solution. After removing the benzene the residue was distilled in vacuo, and 1.2 g of 2,3,6,7 * 8,8a- -Hexahydro-7-oxo-2,5,5 * 8a-tetramethy1-5H-1-benzopyran were obtained Boiling point 87-89 ° C / 2 mm; nuclear magnetic resonance spectrum 7 * = 8.87 (3); 8.77 (3); Doublet 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.I. Shucikin and I.F. Bel'skii, J. Gen. Chem. (U.S.S.R.) £ 2, IO66-IO68 (1959) * from 41 g methyIfuran, 76.5 g acetic anhydride and 3 ml of phosphoric acid. 17 g of 5-methyl-2-aoetylfuran were obtained, Boiling point 75-76 C / 9 mm; nuclear magnetic resonance spectrum / = 7 * 68 (3); 7 * 58 (3); 3.82 (1); and 2.84 (1).

Example 10

Synthesis and properties of 5-methylfurfuraldehyde

This compound was synthesized according to the method of VJ Traynelis, JJ Miskel, Jr., and JR Sowa, J. Org. Chem. 22, 1269-70 (1957) from 26 g of dimethylformamide, 54 g of phosphorus oxychloride and 25 g of 2-methylfuran. This gave 25 g of 5-Methylfurfuraldehyd, boiling point 70 ⁰ C / ll mm; nuclear magnetic resonance spectrum

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= 7.52 (3); 3.68 (1); 2, γ4 (1); and 0.37.

It has been found that the tobacco additives of the invention, when incorporated into tobacco products, impart a taste and aroma to them before and during smoking, which many smokers consider desirable tobacco products. However, it should be noted that the methods for defining and characterizing the value properties of taste and aroma in tobacco technology are almost purely subjective in nature, and that different smokers can assess the same taste very differently. Also, the compounds within the broad scope of the invention can impart different flavor and aroma directions depending on their substituents. Thus, based on subjective experimentation, the compounds of the invention impart characteristic taste properties which are desirable in tobacco products, although the precise properties cannot be described on the basis of known standards. The tobacco additive of Example 1 imparts a sweet floral aroma or taste reminiscent of geraniums, which many smokers consider desirable in a tobacco product. The tobacco additive of Example 2 imparts what some refer to as camphor-mathol-like flavor; the tobacco additive of Example 3 has a mild rose odor and imparts a banana-like spicy aroma; the tobacco additive of example k 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. Of the

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Additive of Example 8 imparts an iononic flavor and a such "aroma during smoking. The compound of Example 9 imparts an aromatic, spicy aroma and tobacco smoke strong tobacco-like taste, while the additive of Example 10 imparts an aroma and taste that some consider to be similar to the 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 wt -.% Of the product was added. The amount used, however, will depend on the intensity of flavor and aroma desired and the particular compound or mixture of compounds used. The additive can be added to the tobacco at any stage of its treatment, but preferably after aging, roasting and cutting and before the tobacco is made into cigarettes. It is equally obvious that only 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 made. In this case, the treated tobacco can contain the additive in a larger amount than stated above, so that the end product after mixing with other tobacco has a percentage content in the stated range.

According to a further embodiment of the invention, an aged, roasted and crushed tobacco with a 1 ^ igen solution

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of 2,5,5,8a-tetramethyl-3,5,6,7,8,8a-hexahydro-2H-l-benzopyran-7- -on sprayed in ethyl alcohol in an amount that delivers a tobacco with 0.1 wt .- ^ of the additive, based on dry substance. The alcohol is then removed by evaporation and the tobacco is made into cigarettes in the usual way. The cigarettes thus produced have been found to have a desirable and pleasant taste.

According to a further special embodiment of the invention becomes an aged, smoke-roasted and cut tobacco with a 1 # solution of 5-Methy1-2-acetyIfuran (Formula IX) sprayed in ethyl alcohol in an amount that provides a tobacco with 0.1 wt .- ^ of the additive, based on the dry substance. The alcohol is then removed by evaporation and the tobacco is processed into cigarettes in the usual way. It found that the cigarettes prepared in this way had a desirable and pleasant taste. The additives that are in the area of this invention can be added to the tobacco by spraying, dipping, or otherwise using suitable slurries or solutions of the additive are used. So water or volatile organic solvents such as alcohol, ether, acetone, volatile hydrocarbons and the like, are used as a carrier medium for the additives while they are added to the tobacco will. Also other flavor and aroma-producing additives, such as U.S. Patents 2,766,145, 2,905,575, 2,905,576, 2,978,365 and 3,041,211 shown can be added to the tobacco.

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While the invention is primarily useful in the manufacture of cigarettes, it can also be used in connection with the Manufacture of pipe tobacco, cigars or other tobacco products can be used. Furthermore, the compounds can 'certain tobacco substitutes of natural or synthetic origin are added. With the term "tobacco" as used herein is means any composition intended for human consumption by smoking or otherwise, whether it is made from parts of tobacco plants or substitutes or both. '

The invention has also been described in particular with regard to the direct addition of the compounds to tobacco. However, it is Obviously, the compound can also be added to the cigarette paper or the cigar wrapper. Likewise, it can the filter tip or the to. Gluing the cigarette paper used to be incorporated. This is how a tobacco product becomes which includes the special additives and tobacco, although the compound does not match the tobacco in every case as above must be added as described *.

- patent claims -

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Claims (4)

- 15 - R 1274 claims: 1. Use of 2-methyl-5-isopropylpyridine in sufficient quantities Amount to change the taste or aroma of the tobacco product. 2. Use according to claim 1, characterized in that the additive in an amount between about 0.0001 and 2.0 wt -.% Of the product is present. 3. Use according to claim 2, characterized in that the additive in an amount between about 0.01 and 1 wt -.% Of the product is present. 4. Use according to claim 2 or j5, characterized in that the additive in an amount between about 0.01 and 0.5 wt. ~% Of the product is present. Dr. Pa. / Br. "" " 2098B2 / Ü129 ORIGINAL INSPECTED