DE1792656A1 - Process for influencing the taste of tobacco smoke - Google Patents

Description

4690 Herno, 8030 Munich 23,

Frelllgrathstrasse 1 »Elienacher Strasse 17

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PaL-Anw. Herrmann-Tr.nl.polil DlBl.-PhVS. Ed USTdBOtZIoT Telephone: J? 8011

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- β «« 2 Dipl.-Ing. V /. Herrmann-Trentepohl ³⁹⁸ ° «

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Process for influencing the taste of tobacco smoke

The invention relates to a method for influencing the taste of tobacco smoke by adding the tobacco smoke flavoring substances for tobacco or a tobacco mixture.

The brand awareness of the modern consumer is increasingly the tobacco products and especially the cigarette manufacturing industry is faced with the task of keeping their products in to always offer consistent quality. Naturally, this is particularly true for the taste Properties of a specific brand that has been established on the market.

The difficulty in terms of this task

Solving tobacco products are obvious. The raw material 209811/0730 _ ₂ _

is subject to seasonal fluctuations, various influences on the cultivation areas, poor harvests, etc. The tobacco processing industry tries to compensate for these qualitative fluctuations by making their own Products are based on complicated mixing recipes, within which one tries to avoid partial fluctuations Compensate for mix changes. However, this can only be attempts to override the task of constant quality to maintain for longer periods of time.

The object of the invention is to treat tobacco, tobacco products, tobacco foils or other substances suitable for smoking, for example in cigarette form, with small amounts of chemical compounds so that the taste properties of the material to be treated are influenced in the desired manner during smoking. This influencing is intended to change the smoke taste of the material to be treated, which for the sake of simplicity is to be referred to as tobacco in the following, in a targeted manner, without depriving the tobacco of its own taste note, falsifying it or covering it up. In particular intended by the method according to the invention aroma poor tobacco aroma in their strong flavor ¹ characteristics, ie be approximated as a rule also expensive tobaccos.

It is already known, if necessary, to add certain substances to the tobacco or tobacco mixture: or to add certain substances to parts thereof, which give the tobacco product the missing flavor

- 3 209811/0730

_ "5 -

should convey nuances. Substances are already known with a peppery-spicy note such as 4- (2-butenylidene) -3,5,5 -trinetliyl-2-cyclohexen-i-one or also as a tobacco flavoring agent known 4- (4-oxo-2,6,6-trimethyl-2-cyclohexen-1-yl) -1,3-butadiene. Attempts have also been made to convey cedar-like deaths, for example through tobacco treatment with dodecahydro-3a, 6,6,9a-tetranethylnaphtho- (2,1-b) -furan or 2-hydroxy-2,5,5,8a-tetramethyl-1- (2-hydroxyethyl) decahydronaphthalene. Furthermore, pruchtic acid derivatives have been or have been used as substances to improve tobacco aronia Furanones and pyranones. Other chemical compounds are (γ-lactones or γ-lactols), (2-acetyl-5-methylpyrene) and (IT-methyl-2-formylpyrene). Attempts have also been made to improve the one Tobacco unsaturated alcohols such as Solanesol, polycarboxylic acid derivatives such as truxilic acid and carboxylic acid esters lower aliph. Add alcohols such as malonic acid, malic acid, succinic acid, ΐ / monoic acid, citric acid, etc.

All these proposals to influence the taste of tobacco with chemical substances have in common that the used Substances are known in terms of their aroma properties and these known properties of the tobacco to be improved communicate in a more or less specific way. Some of these taste properties are so foreign to tobacco, that in many cases it does not succeed in incorporating them into the flavor bouquet to be classified according to the tobacco mixture to be improved.

In addition, the substances described, such as 4- (2-butenylidene) -3,5,5-trimethyl-2-cyclohexen-1-one, are in the Production is so complex that the cost

209811/0730 _ _3a _

establish use as a tobacco flavoring agent forbids.

The invention solves the problem of tobacco flavoring agents to procure that the tobacco processing industry is cheap in sufficient quantities and so in classify the natural tobacco smoke flavor bouquet that for the consumer this through the newly added ! Dead appears more rounded and qualitatively and quantitatively raised, i.e. a real improvement in smoking properties the tobacco mixture treated according to the invention is achieved.

The treatment of tobacco according to the invention for influencing the tobacco smoke taste also leads to the full smoke aroma those tobaccos that are inherently poor in aroma. The invention can therefore add the natural overall aroma of a cigarette approximately the same proportion of the mixture component responsible for this improved, as well as the proportion of the amount of expensive components within the tobacco mixture are reduced or eliminated at all without this adversely affects the aroma of the smoke

209811/0730

Me invention solves this problem in that the tobacco mixture to be improved or individual components of the same small amounts one or more substances are added which correspond to the following structural formula;

in the

R = H, CH ₃ , C ₂ H ₅ , C ₂ H ₃ , C ₃ H ₇ , C ₄ H ₉ , C ₅ H ₁₁ , C ₅ H ₉ , C ₆ H ₅ ,

Means C ₆ H ₁₃ , C ₇ H ₁₅ , C ₇ H ₇ , C ₄ H ₅ O, C ₅ H ₅ O ₉ : C ₆ H ₇ O _or C ₈ H ₉ .

It has been found that these derivatives of pyrazine are found in tobacco smoke Develop new, surprising taste properties that round off the overall taste impression as desired lead without being disturbing or masking other flavor notes that are inherently associated with the tobacco. The novelty in the The mode of action of the use of these substances according to the invention is not least that the tobacco treated with them does not This group of substances has its own taste and smell nuance grafted onto it gets, but that these substances in connection with the natural pyrolysis products of tobacco have new taste properties to develop.

1 / 073Ö

1732656

The amounts of flavoring agent required in this sense depend on the type of tobacco mixture to be improved, taking into account the overall flavor note to be aimed for. In addition, all flavoring components must be taken into account in their mutual influences. Furthermore, it is not without significance whether the entire tobacco mixture on which a certain cigarette is based or only individual constituents of this mixture are treated for the purposes of this invention. It has been shown, however, that an effective influence on the tobacco smoke taste is indicated when 0.005-510 fo its dry weight of pyrazine derivatives are added to the tobacco mixture.

The use of pyrazines according to the invention does not lead to undesirable effects Changes in tobacco smoke with regard to its taste or physiological properties. Because of their low Vapor pressure, the substances added to the tobacco according to the invention survive even long storage times without any significant Loss of aroma can be registered. A taste shift within that of the respective tobacco composition, that with pyrazines individually or has been treated in a mixture with one another, the underlying taste bouquets are extremely small or at all due to storage influences undetectable.

They come because of their sometimes quite high water vapor volatility Compounds of the group of substances to be used according to the invention only in the mainstream smoke for full taste development.

The substances belonging to the group of substances mentioned can alone or in admixture with one another in any way of the tobacco mixture or a part thereof, whose stomach taste is influenced should be admitted.

209811/0730

Bas can be done, for example, by immersing the tobacco to be treated in solutions of the substances used in suitable, highly volatile solvents or by spraying such solutions onto the tobacco. This can be done at any process step in, for example, cigarette manufacturing. It has proved to be expedient to spray the cut tobacco prior to feeding to the cigarette maker with a 1-5 ^c / o ethanolic solution of the taste of the tobacco smoke affecting substances.

The subject of the invention and its mode of operation are described below are explained in more detail using examples:

example 1

Methylpyrazine (commercially available product)

For organoleptic assessment of the influence of the tobacco smoke taste the tobacco mixture of a commercial cigarette that contains no artificial or natural additives such as essential oils, etc., was a two follow ethanolic solution of methylpyrazine sprayed. The amount of solution was chosen so that the treated tobacco contained 0.3 or 1.0 $, based on its dry weight, more methylpyrazine than an untreated comparison sample of the same tobacco mixture. From the two treated

209811/0730

Tobacco samples and an untreated control sample were each made cigarettes that its taste characteristics were evaluated during smoking by an expert panel with respect to a storage time of 72 hours at 2O ⁰ C and 67 fo relative humidity. The sample cigarettes from the tobacco mixture that had been treated with methylpyrazine were rated better than the comparison cigarettes from the same but untreated tobacco mixture. The cigarettes from the treated tobacco blend had a Dunkelsüß aromatic enhanced flavor, in which the containing 1.0 $ methylpyrazine, appeared more marked than in those whose mixture was sprayed with 0.5 i ° of the tobacco weight in methylpyrazine.

Example 2 ethyl pyrazine

To 10 g of sodium amide in 250 ml of liquid ammonia, 23.5 S of commercially available methylpyrazine dissolved in 50 ml of absolute ether were added dropwise at -35 ° C. (dry ice + acetone as coolant) with vigorous stirring over a period of 25 minutes, and then the reaction mixture remained constant Temperature of -35 ° C for 30 minutes further stirred. To the blood-red solution, 2 g of methyl iodide dissolved in absolute ether precooled to the reaction temperature of -35 ° C. were then added dropwise over a period of 50 minutes, then stirring was continued for 1 hour, and 15 g of solid ammonium chloride were added. After dilution with a further 3OO ml of absolute ether became

209811/0730

slowly warmed to room temperature and the ammonia evaporated. That Ice water was then added to the reaction mixture, the mixture was acidified with concentrated hydrochloric acid and the acidic aqueous phase was separated off alkalized from the ethereal phase and repeated washing with fresh ether with sodium hydroxide solution and exhaustively extracted with dichloromethane. This methylene chloride extract was concentrated and the residue was distilled. The yield of ithylpyrazine was 13.1 g equivalent to $ 77

For organoleptic examination of those influencing tobacco smoke Properties was as described in Example 1, the procedure. The verdict of the panel of experts drew the test cigarettes the comparison cigarettes made from untreated tobacco of the same mixture before with the reference to an aromatic, earthy taste depth.

Example 3 Propylpyrazine

V ^ ' ° 7 ^H 10 ^N 2

'IT

Propylpyrazine can be obtained from methylpyrazine by alkylation as in Example 2. In contrast to Example 2, however, 17 »5 S ethyl bromide were used instead of methyl iodide.

-9- 209811/0730

The reaction resulted in 13 »8 g corresponding to a yield of approx. 70 / J of propylpyrazine, which is used for organoleptic testing its mode of action on influencing the taste of tobacco smoke, as described in Example 1, in 2 $ iger Ethanol solution was sprayed onto tobacco ". The result of this Treated tobacco-made cigarettes were in their change in taste compared to comparison cigarettes made from untreated Tobacco of the same mixture assessed as follows:

"In comparison to the untreated tobacco mixture, it is dull and aromatic with a dull sweetness "

Example 4 Isopropylpyrazine

was made from ethyl pyrazine by reacting it with methyl iodide obtained according to Example 1. The reaction proceeded in 68% yield.

According to the expert opinion, tobacco treatment with isopropylpyrazine leads to a change in the smoke taste compared to untreated comparison tobacco, which is described with a burley-like shift and pronounced power of smoking pleasure.

209811/0730

Example 5

Cyclopentylpyrazine

Oyilopeiitylpyrazine was obtained by the basic method of preparation described in Example 1, albeit with a lower yield. The specified molar ratio of 5 * 5 ^! However, 3 was changed to 1: 2: 2 with the starting materials methylpyrazine, sodium amide and 1,4- ^ ichlorobutane.

The organoleptic assessment of treated with cyclopentylpyrazine Tobacco in terms of the change in the taste of its smoke Compared to untreated but otherwise identical tobacco, the treated samples showed a clear superiority, with a special note to the more intensive emphasis of the Burley tobacco within the tobacco blend with a weak amine character without obtrusiveness .

The examples given gave good yields Butylpyrazine, isobutylpyrazine, (2-butyl) pyrazine, pentylpyrazine, Phenylpyrazine, furylpyrazine, 5-methylfurylpyrazine and 2- (i- (furyl-2-) ethyl-2 -) pyrazine depicted and applied to tobacco.

20981 1/0730

Jl

Example 6 Vinyl pyrazine

6.1 Preparation of ß-dimethylaminoethylpyrazine

A mixture of 5.6 g of methylpyrazine and 6.6 g of dimethylamine hydrochloride was heated to the onset of boiling and
then 5.0 g of 35% strength formalin solution were added dropwise over a period of 2 hours, with constant stirring, and the mixture was refluxed for a further 2.5 hours at the boiling point. After cooling to room temperature, the mixture was diluted with 10 ml of water, made alkaline with sodium hydroxide solution and exhaustively extracted with dichloromethane. After evaporating the solvent on the water bath, the residue became at
Distilled 18 Torr and gave at 106-122 ⁰ C in 77 $ iger yield 6.9 g of ß-dimethylaminoethylpyrazine.

6.2 Preparation of ß- (pyrazyl-ethyl) -trimethylafflmonium iodide

4.5 g of ß-dimethylaminoethylpyrazine (from 6.1) were allowed to react overnight with 4.7 g of methyl iodide in 50 ml of ether. The white, hygroscopic precipitate formed was extracted with 30 ml of water and processed further without drying to:

2098 1 1/0730

6. 5 Preparation of vin? / - lpyrazine

The aqueous solution of β- (pylacyl-ethyl) -trimethylani-ionium iodide (from 6.2) was kept at the boiling point with 1.2 g of sodium hydroxide for 2 hours and, after cooling to room temperature, extracted with dichloromethane. The extract was dried over potassium carbonate and up. freed from the solvent in the water bath. The remaining residue was fractionated at 15 torr and gave 2 g of vinylpyrazine at 54-56 ° C. in a fixed yield of 64%.

Table 1 shows those characteristic of mcmosubstituted pyrazines Data and in Table 1 a the properties characteristic of these substances in terms of the application according to the invention for influencing the tobacco smoke taste shown as an example.

209Ö1 1 / Ö730

I.
No ^KP Torr ° ^C MS Berec
\ t / τ hnet
H " Found
\ ι IO Π / 0 ι 6.4 Retention time
*) 1 737 ¹³³ ■ 34 / 94,67,39,40 63.8 6.4 63.9 7.3 43 2 ^170101-102 108 / 107,108.80 66.6 7.5 66.4 8.1 64 3 23 67-68 122 / 94,107,122,
39.121 68.9 8.2 68.6 8.1 103.5 4th 22 ⁵⁸ ~ ⁶¹ 122 / 107,108,122,
121,94,53,80 68.9 8.2 68.7 9.1 79.5 5 20 ⁸⁴ " ⁸⁶ 136 / 94.95,107,121
39.41 70.6 8.9 71.0 9.0 182.5 SJ 6th 20 72-73 136 / 94,95,121,
136 70.6 8.9 70.9 9.1 132 IO 7th ₁₇ 68-72 136 / 108,107,121,
94.136 70.6 8.9 70.9, 9.2 126 - * 8th 16 ⁹⁴ " ⁹⁶ 150 / 94,107,121.39
41,150,135 72.0 9.4 71.8 5.7 322 i * s Q 15th 106 / 106.79.53,
52.105 67.9 ' 5.7 68.0 8.1 83 10 ₁₅ 11O-119 148 / 107,148,119,
120.147 73.0 8.2 72.8 5.1 86 11 ₂ 122-132 156 / 156,103,76,51
157,104,102 71.9 5.1 71.8 4.2 266 12th ₂ 101-105 146 / 93,146,117,
118 66.7 4.2 66.5 5.1 123 13th 1.25 ⁿ ° ⁷ 160 / 160,131.81,
159,53,117, 68.4 5.1 68.6 178.5 ^ 107.145 5.7 0.4 ⁹⁶ " ⁹⁷ 174 / 81,174,53,14
131,172,118,
94 69.8 5.8 69.5 CD ? m, 126 ⁰ G ,. 1 a + ü He, paper template chub cm / τη j 185 ISJ p
CD
cn
cn ti Methylpyrazine Ethyl pyrazine Propylpyrazine Isopropylpyrazxn Butylpyrazine Isobutylpyrazine Sec-butylpyrazine Pentylpyrazine Vinyl pyrazine Cyclopentylpyrazine ' Phenylpyrazine Purylpyrazine (5-MethyIfury1) -pyrazine 2 (i- (Furyl-2 -) - ethyl-2 -) - pyrazine *) Gas column ί

No.

Task *

Influence on the taste of smoke

T / 92656

10

0.3 1.0

0.3 1.0

0 ", 3 1.0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 .1.0

Dark 1 sweet, aromatic.

Aromatic earthy jxesclimackstiefe

Dull aromatic., Dull sweetness Burley-like shift, power

earthy herbaceousness, aromatic, mild, dull, power

Somewhat dull, soft, aromatic note

Expressive depth

Rounded, deepened taste impression, somewhat earthy character

Weakly aminig, "Burleynote, unobtrusive

*) Feed quantity on tobacco in "/ ■> of the tobacco residue weight

209Ö 1 1/0730

Table no «1a ( continuation). U

Aufgf Rauchgeschmaekseinfluesung

, N,

"0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 1.0 Dull aromatic, spicy Frisehe spiciness

Expressive spiciness with ger Frisciie

Full

, refreshing note

0.3 1.0 Expressive rounding with an aromatic note

*) Feed quantity on tobacco in ^ of the tobacco dry weight

209811/0730

The preparation of disubstituted pyrazines used as the starting material commercially available dirnethylpyrazine. The method of the examples 1-4 could also be used without difficulty on the representation of the Use 2-methyl-5-alkyl-pyrazine. G-aschromatographisch could it can be demonstrated that a small part of the 2,5-dialkylpyrazines was always formed with the same substituents in the 2 and 5 position.

For the organoleptic assessment of these substances for tobacco smoke, this was accepted and therefore a separation of the Mixtures waived, especially for the practical application of the object of the invention anyway the simultaneous use of Mixtures of different types of pyrazine derivatives, which are therefore different from one another, to further improved results leads.

The 2-alkyl-5-vinylpyrazines are used according to Example 6 of the corresponding starting products accessible.

Table 2 below contains examples of the 2,5-disubstituted pyrazines shown, their organoleptic results are compiled in Table 2 a.

209811/0730

Table No. 2

Kr , 5-dimethylpyrazine 2m ^KP Torr ° ^C 156 MS 42, 59.40 136 135 108
39 , 121, Berec
π rf 6th them
F i- t Found
\ ι / O 5 äen 4th Reten + i on time 1792656 1 -Methyl-5-ethylpyrazine 758 105-108 108/108, 122 / 122,121,39,
56.94.42 15O / 108, "121
66.41.1 136
08 107
39 , 135,
22, .15C 66 9 7, 5 66 2 7, 1 62 ^ _-— jl 2 2-methyl-5-propylene pyrazine 120 75 136/108,
39 150/108,
39 120 / 120.52,
79.93 88
39 , 150, 68, 6th 8th, 2 69 0 8th, 7th 96 3 2-methyl-5-butylpyrazine 17th 95-99 136/121,
39.1 150 ⁷ 122,
135 92,
131
Hey , 135, 70 2 8th, 9 71 1 8th, 4th 155 4th 2-methyl-5-isobutylpyrazine 17th 89-90 150/122,
135 54.39, 72, 0 9, 4th 72, 8th 9, 3 276 2091 5 2,5-diethylpyrazine 19th 74-81 188 / 81.1
108
145 , 121,
150 72, 6th 9, 4th 71 2 9, 9 197 6th 2-methyl-5-vinyipyrazine 25th 68 160/160,
161,
;, 1 atü , 150, 70 0 8th, 9 70 2 8th, 8th 148 O 7th 2-Methy1-5-s ec.-butylpyrazine 15th 85-89 159
53 70 0 ⁶ ' 7th 70 2 6, 6th 127 <*>
O 8th 2-ethyl-5-propyIpyrazine 18th 93,
, 63
Papie 72, 0 9, 4th 72, 0 9, 3 156 - 9 2-methyl-5-furylethylpyrazine 105-107 72, 4th 9, "4 ⁷² ' 3 9, 3 239 10 2-methy1-5-furylpyrazine
*) Gaschr. 0.4 O, 83-86
Column, 126 ° 70 67.6
rvors 6, 4th 70 67.0
cm / mi 6, 1 243 11 5,
; hul: 0
) 1 5,
1 163.5

. Table No. 2a

Aufgi

Influence on the taste of smoke

'Ή'

0.3 1.0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 .1.0

0.3 1.0

0.3 1.0

0.3 1.0

0.3 1.0

• Friendly earthy note

Tobacco friendly, dull depth

Dark-colored taste impression, strong note

Slightly roasted character, dark sweetness

Bread-like impression with a light burley note

Weak amine sweetness with an intensified smoky character

Dark amber impression with increased strength

Burleynote with a light roasted character

Increased smoke impression with power

Slightly amine burleyn note with a slightly fruity character

*) Feed quantity on tobacco in $> of the tobacco dry weight

209811/0730

Table no.2a (continued)

Aufgauclige s chmaokeb e inf Ittesung

0.3 1.0 Pleasantly early Rauöhnot © with a slightly amiable sweetness

*) Feed quantity on tobacco in "/> of the tobacco roken weight

209811/0730

To prepare the 2-methyl-6-alkylpyrazine, the starting product was 2,6-Diinethylpyrazine used. The way of representation of the Example 2 was followed while changing the crude ratios. The ratios were 2 moles of I sodium amide, 2 moles Dimethylpyrazine and 1 mole of alkyl halide. To represent 2-Kethyl-6-äthylpyrazine, I'-methyl iodide was used for all other examples the alkyl bromides required in each case.

^T , as noted for the 2,5-disubstituted pyrazine derivatives, in addition to the desired 2-methyl-6-alkylpyrazines, 2,6-dialkylated pyrazines with the same ligands were also obtained from this group of 2,6-disubstituted pyrazines, upon their special separation here as there was waived.

The 2-alkyl-6-vinylpyrazines were according to Example 6 taking into account of the corresponding starting materials.

The following table 5 characterizes the examples used 2,6-disubstituted pyrazines and in table 5a are the results of the organoleptic examination are compiled.

-20- '

2098 11/0730

Table No. 3

No 2,6-dimethylpyrazine I. . · • ^KP Torr ° ^C MS 42, . ■ Berec
π 4, 6th ; hnet
TT 4, Found
Π 4> , 5 the ti Retention time • CC 1 2-methyl-6-ethylpyrazine *) Gases! - 08/108, 40.39 66 9 7.5 6th , 6 7, 6th 63 ? 656 2 2-methyl-6-propylpyrazine ₆₂ 89-91 39
109 68 »6 8.2 8th , 9 8th, O 92 3 2-methyl-6-furylpyrazine 16 ⁶³ ~ ⁶⁷ 36/108,
121,
135 92,
63 136
.66, 70 , 6 8.9 O , 3 9, 1 147 4th 209811 0.3 ⁸³ ~ ⁸⁶ 60/160,
131, 1 93,161, 67 Papi 5.0 37 4, 9 163.5 O Lr. 2m column , 126 ⁰ C atü he srvors UJ-
O, •

Table no. 3a

Task *

Influence on the taste of smoke

T792656.

0.3 1.0

0.3 1.0

0.3 ■ 1.0

0.3 1.0

Dark herb sweetness

Tart sweet ITote, a little more resinous character

Coniferous note, soft

Fruity and resinous impression, v / oak sweetness

*) Feed quantity on tobacco in ° /> of the tobacco dry weight

209811/0730

Example 7

2,5-bimethylpyrazine

To 37 g of ethylenediamine monohydrate in 4CO ml of ither, a solution of 40 g of diacetyl in 36Ο ml of ether was added dropwise with vigorous stirring and the mixture was stirred until the reaction mixture was completely clear. The mixture was then refluxed on the water bath for about 0 minutes at the boiling point and, after cooling to room temperature, the aqueous phase was separated off. The remaining ether phase was dried over potassium carbonate and the ether was then evaporated. The residue was then distilled at 13 Torr and 51 »5 - 53 C and produced 4 ^, 5 S 2,3-dimethyl-5,6-dihydropyrazine, which was dehydrated over solid potassium hydroxide under normal pressure, with a yield of 85% 2 , 3-dimethylpyrazine was obtained.

The organoleptic assessment with regard to the influence of tobacco smoke Effect was carried out according to Example 1. Thereafter, the tobacco smoke receives from treated with 2,3-dimethylpyrazine Tobacco has a bread-like note that enriches the taste with a light character reminiscent of roasted peanuts. Of the treated tobacco was said to be stronger with a raised taste level.

209811/073 (1

About the 2,3-dimethylpyrazine are used according to Example 2

ν corresponding halogen compounds other 2 - disubstituted pyrazines available, of which Table 4 shows a selection whose taste-influencing properties are summarized on tobacco smoke in Table 4 ^a.

That in it under Mr. 6 exemplified 2-methyl-3- "vinylpyrazine was prepared according to Example 6.

BATH ORIGINAL

20981 1 / Ö73Ö

Table No. 4

MS

Calculated Found Π < ι Π < Π <& t H °

Retention time

2,3-dimethylpyrazine

2-methyl-3-ethylpyrazine

2-methyl-3-propylpyrazine

2-methyl-3-butylpyrazine

2-methyl-3-isobutylpyrazine

2-IvIe thy 1-3-vinylpyrazine

2-methyl-3-phenylpyrazine

2-liter-diethyl-3-phenylethylpyrazine

2-methyl-3-furylpyrazine

^ 168-171

21

21

₂₂ 97-105 95-97

24

15th

66-69

105-108

"114-116" ^

1 »5

*) Gas no. 2m column

108 / 108,67,40, 42

122 / 42,122,39, 81,54,121

136 / 108,136,135, 42,54,121

150 / 122,150,135, 39.42

150 / 108,135,107, 67,41,39, '150,149

120 / 120,119.67, 79.52

170 / 169,170,103, 67,76,42

198 / 91,198,197, 183,121,65, 39

160 / 160,93,67, 131

126 ⁰ C, 1 atmosphere,

• 7.5 8.2 8.9 9.4 9.4

6.7 5.9 7.1

5.0

66.4

68.5

71.0

71.5 72.0,

69.8 77.8

78.1

67.2

7.5

8.3

9.0

9.3

9.3

6.8

5.8 6.8

4.7

66

98

150.5

232-265

187

135

248

492

147.5

Paper rvors

hub

cm / mi:

CjO

ro

CT)

cn

CD

Table No. 4a

No.

Task *

Influence on the taste of smoke

O, 3 1, 0 ο, 3 1, 0 ο, 3 ■ 1, 0 ο, 3 ιί 0 ο, 3 1, 0 ο, 3 1, 0
Γ7

, 3 1.0

P, 3 1.0

0.3 1.0

Bready, toasted

. Roasted, nutty ITote deepening the flavor

Erenus-like character '

Baked dark, softly rounded, slightly raised overall

Dark coloring of the overall impression, raised level

Fresh roasting impression, somewhat dull and softly tinted

Dark nut character, deepening of the Own taste

Baked dark roasting impression

Somewhat dull and fruity tint, Elevated overall impression

*) Feed quantity on i'abak in "/ ■> of the iCabak dry weight

209811/0730

Example 8 2 ο, 5-trimethylpyrazine

113-123 ° C

₁₀₀

MS 122 / 42,122,39,81,121,54 RZ *) 98

The 2, ^, 5-trimethylpyrazine was made from propylenediamine accordingly Example 7 by reacting with diacetyl in an ethereal solution and dehydrating the resulting 2,3> 5 ~ ^ imsthyl - 5> 6-dihydropyrazine over solid potassium hydroxide in ethanol in 79% yield obtain.

The smoke finding according to Example 1 gave a clear comparison of cigarettes made from treated tobacco compared to those made from untreated tobacco, with particular reference to the strong rounding the burley-like taste components without obtrusiveness combined with soft-sweet mildness.

Example 9 Tetramethylpyrazine

Kp ₂₀ ■ 80-9O ⁰ C

MS 136 / 54,136,42,53

RZ *) 150

*) Gaschr. 2m column, 126 ⁰ C, 1 atm, paper feed 1 cm / min

209811/0730 " ^2? "

«J

Ί792656

20 g of diacetyl was hydrogenated for 5 Rait S ßaney-ITickel at 70 C and 100 atm Hp for 5 hours in 170 ml of 13 ^ methanolic! IH ₇ solution. After filtering off the catalyst, the solvent was distilled off in a vacuum on the water bath and the remaining residue was fractionated at 20 torr.

The organoleptic evaluation was carried out as in the preceding Sepieleen and resulted in regard to the influence on taste of tobacco smoke a positive judgment with reference to the taste-enhancing and flavor-enhancing properties of the Tetramethylpyrazine with cautious rounding off the overall impression.

As far as the substances according to the invention as a component of tobacco or tobacco products due to the change on tobacco and tobacco products (Tobacco Ordinance) of December 19, 1959 (BG31 I 2Tr. 52 of December 22nd, 1959 p. 7p0 especially appendices No. 5) currently not permitted , they may only be used / ended for tobacco products or tobacco products that are intended for deliveries outside the area of validity of the Food Act are determined.

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Literature taken into account

2,905,575

3,124,140 3,159,888 3.Ι85.7Ο8 3,211,157 3,217,718 3,232,295 3,251,366 3,280,824

GBP Ι.7.7ΙΟ 1'. 072.946

Dunn et al., J. Chem. Soc. (1949): 2586, White et al., Bacterxol. ^, 433 (1943) and Winter Dutscher Steiner, J. Biol. Chem. 15, 5 "359 (1944) JH Goldmann et al., Helv. Chim. Acta J5J), 694 (1967)

J. Flament et al., HeIv. Chin. Acta J5J3, 2233 (1967) MB Mason et al., J. Agric. Food Chem. V ^, 66 (1967) HS Pattee et al., J. Food Sci. _3_p_, 388 (1965) JD Behun et al., Org. Chem., 2_6, 3379 (1961) MH Kamal et al., Org. Chem., 2J, 1355 (1962) ME Kamal et al., Org. Chem. , 2] _, I363 (1962)

^r 'π ο η) ι' π 7 T Π

Claims (1)

Patent claims: Tobacco smoke by adding flavoring tobacco smoke Substances for the starting tobacco or a starting tobacco mixture, in particular "in the production of cigarettes, characterized in that the tobacco or at least individual components of the tobacco mixture contain small amounts of substances with the following Structural formula to be added; 2.) Process according to claim 1, characterized in, in the structural formula wherein R are protons or alip ^ s ^ cal, alicyclic and / or aromatic Hydrocarbons .. "offradic ^ ie with an A _n number of 1-9 carbon atoms per radical. 5 ·) Method according to Ar ^ pruch 1, thereby marked-Z ^. Inet that S in the structural formula is a heterocyclic Radical is with 4 - 9 carbon atoms «.nd t. ^ N Heteroc. .on. - 30 20981 1/0730 BATH ORIGINAL 4 ·) Method according to claim 1, characterized that the ligands denoted by R ■ in the structural formula are the same. 5.) The method according to claim 1, characterized that the ligands denoted by R in the structural formula are different from one another. 6.) Method according to claims 1-5, characterized that they influence the taste of smoke applied to the starting tobacco in amounts of 0.05 5.0 ^, based on the dry weight of the tobacco will. 7.) Process according to claim 6, characterized in that the R _a uchgeschmaok substances influencing on the output of tobacco in amounts of 0.02 - 2.0 # are based on the Tabaktrookengewioht applied. 209811/0730