DE1517303A1 - Tobacco product and process for its manufacture - Google Patents

Description

DR. I. M. MAAS

PATENT ADVOCATE
MUNICH 23

UNGERERSFRASSE 25 1517303

A U 909

Dr. Expl.

Tobacco product and process for its manufacture

The invention relates to flavorings that are suitable for introduction into tobacco and 3?

of the tobacco product when smoking «™

It has long been customary to change and improve the smell and aroma of tobacco tobacco products by introducing a wide variety of flavorings and other ingredients in a wide variety of processes. Sugar, liquorice,

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Yakritz juices and other condiments are used for this purpose frequently used and it has also been suggested to apply less common flavorings to the leaf or even to inject into the living plant. The present However, the invention particularly relates to the introduction of volatile derivatives from the tobacco from Hatur own substances in order to improve the Rguchvraren in terms of taste and smell and others to achieve fc properties o you used according to the invention Flavorings can be introduced into the tobacco or applied to the filter or otherwise with the pack be united.

In the tobacco industry, a particularly desirable one is becoming The aim is to increase the sweetness of tobacco products. Attempts were made to target the sea by adding raw Sugar either as aolchen or in the form of high sugar Substances, e.g. molasses, to reach the tobacco o Such Substances change the aroma of the tobacco product, are, however, unsatisfactory because their intrinsic properties are mutually exclusive strongly differ from those of tobacco, especially if because of the degree of aromatization itself or for Supplementing other additives or flavorings contained in the Tobacco have been introduced, medium or higher

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Degrees of sweetness are desired, it has declined that the Loading the tobacco with large amounts of such sugars interfered with its combustion to an intolerable extent

It has now been found that particularly suitable for insertion into tobacco products sweetener made can be produced in tobacco leaf inherently contained substances · Bm has also been found that such derivatives, whether they are self-extracted from the tobacco or synthetic, the desired sweetness but do not interfere with the combustion of tobacco products "

It has also been found that certain other derivatives of natural substances occurring in tobacco, regardless of

the end
whether they are made from / tobacco-derived substances or synthetically, give the smoke other pleasant and very pleasing properties than StiSe ₀

It is therefore an advantage of the invention that sweeteners |

and other .Äromastoffe are made available, which even then do not interfere with the burning of the tobacco product, when present in relatively high amounts Sindo Thus srfindungsgemäßen flavorings are all volatile, by which is meant I3T ₉ that it the temperature at a temperature below the pyrolysis of the tobacco evaporate and before

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Distill off char, with nothing or nothing of these substances being removed by incineration. A further advantage of the invention is that new and delicate, pleasant aromatic substances which can be used in any desired combination and in any desired ratio are created for introduction into tobacco. According to one embodiment of the present invention, flavorings which are well suited and pleasant for introduction into tobacco products, which are characterized by volatility and a sweet aroma, are produced by alcoholysis of saccharides. Other pleasant and useful products which give the tobacco product desirable and characteristic smells before and during smoking are grounded by alcoholysis of organic acids or mixtures thereof and in particular by alcoholysis of organic acids naturally occurring in tobacco with the formation of products which volatilize under the pyrolysis temperature of the tobacco, obtained. ,

W The aroma-rich products lcönner? individually, be introduced with or without other commonly used flavoring agents, humectants, and other common additives in tobacco or you can combine selective and -vermischen in appropriate proportions to get au other make and pleasing qualities in the aroma of the pack and in the smoke au _ö

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The alcohols zweokmäfifeerweise used in the practice of the invention are U ₀ a · the lower alkyl alcohols, d.ho those having 1 to 6 carbon atoms "V / urther suitable. Alcohols can be determined by simple experiments, since only the requirement must be met that the product is volatile below the pyrolysis temperature of tobacco and has the desired properties with regard to smell and / or aroma,

In practicing the invention, anyone can possible saccharides can be used, e.g. Monosaccharides, Disaccharides, trisaecharides, totrasaccharides and polysaccharides, as long as their reaction products with alcohol are volatile and pleasant, as mentioned above. "In general the monosaccharides, disaccharides and polysaccharides are preferred, especially the hexoses, pentoses and dihexoses like sucrose and the polyhexoea like daxtrins, starches and

The organic acids which can be used with advantage are also those which are used in the reaction with the Alcohol or alcohol mixture result in volatile products with the desired properties. The preferred organic acids are those found naturally in tobacco

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Occurring, such as aliphatic polycarboxylic acids, in particular the aliphatic di- and tricarboxylic and hydroxycarboxylic acids, ZoBo malonic acid, malic acid, succinic acid, tartaric acid and citric acid · Aroma-giving substances which serve the purpose are, for example, the lower allyl esters of malic acid and citric acid, tartaric acid ₀

Other well-suited substances imparting a sweet smell or a sweet aroma include, inter alia, the lower alkyl derivatives of oxymethylfurfurol and the lower allyl esters of levulinic acid _{or the like}

The amount of flavoring substance introduced into the Tebek according to the invention is largely left to one's discretion. At least an amount should be introduced that is effective for achieving a distinct aroma and odor in the product or its smoke. All amounts exceeding this depend on the desired character W and the extent of the Verboseerung, whereby it has been shown that its effect is most pleasant when it is fine and tender. Ss was also found that the flavoring substances according to the invention each other and the super-.

see below
Aroma sets used wisely can srgänaan and that by varying the proportions and amounts in a manner known per se, extraordinarily pleasant and beneficial effects

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can be achieved. The flavorings can be sprayed, Dipping or other customary measures to be introduced into the tobacco.

Mr the production of the flavoring substances used according to the invention suitable processes and devices are readily apparent to the aehmann and do not form part of it the; Invention. The following examples serve to explain 'without limiting the invention. Unless otherwise specified, parts are by weight.

ι «

example 1

3500 ml of absolute methanol and 138.5 ml concentrated aqueous SalLsänre \ ferden in a 5 1-Dreihalekolben at 40 ⁰ C is heated, after the addition of 400 g of sucrose, the temperature is raised to about 80 ^e C. The fleaktionsteilnehmer be held for 4 hours with occasional stirring at this temperature, "after which the reaction mixture is distilled at a temperature of 86 ⁰ C. The distillate is then broken down into two fractions by vacuum distillation. According to the analytical method, the first fraction consists practically entirely of methyl levulinate, which is characterized by a fruity odor. the

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2. Fraction consists essentially of methoxymethylfurfurol and has a smell reminiscent of Maraechinokirsohen Die Total yield is $ 25.3.

Example, 2

15 liters of anhydrous ethanol, 457 ml of concentrated HCl and 2000 g of sucrose are placed in a balloon with a capacity of about 19 liters (5 gallons), which is shaken occasionally and then left to stand overnight Hours in a bath with constant temperature at 50 ⁰ C, with constant stirring to achieve the complete dissolution of the sugar, The bath is then heated to 75 ° C and the contents of the balloon is kept at this temperature for 24 hours. The mixture is then cooled and neutralized with 391 ml of 41% sodium hydroxide solution to a pH of 6.5.

The reaction mixture becomes excess on removal Alcohol distilled under constant water jet vacuum.

The syrupy residue v / d * is in 2 parts in a continuously operating Plüssig-Plüsaig-Bxtraktor with ethyl ether extracted, after which the ether Durah moderate heating FCEI atmospheric pressure is removed ₀ The 2 parts extracted material was 1 to 2 mm Hg

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subjected to vacuum distillation. Part 1 is broken down into 4 fractions and Part 2 into 3 fractions. Fractions 1 and 4 of fraction 1 and fractions 1 and 3 of fraction 2 are identified by gaachromatography as Laevullns & ureäthyleater (Kpg ^ ^β 51 to 64 ⁰ O) or as Äthoxymethylfurfurol. ! The middle fractions are mixtures of the two "The yield of Laevulinsäureäthylester is 6.25 $>% of the ethoxy - me thy furfural 9 '0 fi and Geaamtausbeute 23» 5 $> ·

Example 3

12 ml of concentrated aqueous hydrochloric acid and 500 ml of n-propyl alcohol are introduced into a 11 three-necked flask equipped with an air-driven stirrer and a fractionation column. The flask contents are brought by means of a Glascol coat at 60 ⁰ C and 50 g sucrose are sieved with constant stirring to the flask. The sugar dissolves in about 1 to 11/2 hours. The reaction is accompanied by color changes from clear and colorless through yellow, orange and red to finally black

Then the solution is at a head temperature of 37 to 97 ° C distilled, whereby about 200 ml ^ distillate are obtained, which mainly consist of the azeotropic mixture of water with consist of n-propanol "

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The fractions remaining in the flask are under Stirring continuously for H hours at 95 ° C under RüokfluS and then until a head temperature of 95 ° C is reached distilled, at the softest point the distillate is dry (in the sense that it does not dissolve a sodium chloride crystal). About 250 ml of product distillate are obtained.

The odor of the product, a pecan or black walnut note, indicates that esterification has occurred. The distillation range of the product corresponds to the boiling points of xaevulinic acid n-propyl ester and n-propoxymethylfurfurol, which shows that these expected compounds have formed. The product is separated into two fractions by vacuum distillation and the calculated total yield is 16.7 $ fruity odor, namely a peach-sweet odor with superimposed nuances of pecan nut.

Ex iel 4

500 ml of 99% strength isopropanol are poured into one ait one 1 1 three-neck flask equipped with an air-driven stirrer and a fractionating column. 12 ml concentrated aqueous hydrochloric acid are added and

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the temperature is increased to 60.degree. Kaefc sine sieves of 50 g of sucrose, the mixture is constantly stirred while the sugar is dissolved in about 1 1/2 hours. The contents of the flask are then distilled to remove the water. Then, the content is hot o maintained for about 14 hours under continuous Hühren 80 to 82 ° in Rüekflußsieden and then distilled at a head temperature of 82 ⁰ C.

About 220 ml of product are withdrawn from the flask « The odor is that of the Iiaevulinaäure-n-propyleeter and n-Propoxyme thylf urfur oils prepared according to Example 3 similar, but slightly different from it. It is reminiscent of nuts, but does not have the distinct peeanut note, which characterizes the n-propoxomethylfurfurol »

By vacuum distillation that product is obtained in a yield of 19.95 i>. Ea has a sweet ethereal odor ₀

Example 5

50 g of sucrose, 500 ml of isobutyl alcohol and 12 ml of concentrated aqueous hydrochloric acid are reacted with one another according to the procedure described in Example 3. A yield of 17 _t 45 $> obtained

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Due to their distillation temperatures, the products are classified as isobutyl levulinate and isobutoxyine thy! Furfurol identified. Their smell is stronger and more pronounced ale the smell of the from the lower limbs of the Products manufactured by alkyl alcohol series ο

Example 6

50 g of sucrose and 500 ml of n-butyl alcohol are introduced into a flask equipped with an air driven stirrer and a fractionating column 1 1 three-necked flask "The! Temperature is increased by means of a Glaseol-Mantele gradually at 60 ⁰ C» The mixture is stirred for 3 hours and then left to stand over the weekend. The temperature is again kept at 60 ° 0 for 1 hour with stirring, further water being added in order to dissolve the sugar completely ₀ Then 12 ml of concentrated hydrochloric acid are added.

The work-up is carried out as described in Example 3, a yield of 16.1% being obtained. The products are distilled in vacuo and, on the basis of their distillation temperatures, all laevulinic acid n-butyl ester and n-butoxymethylfurfural are identified. The levulinic acid butyl ester has a woody ethereal odor that is quite pungent ₀ The n-butoxymethylfurfural has a sweet but woody odor

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Example 7

10 g of sucrose, 100 ml of n-hexanol and 0.3 ml of concentrated hydrochloric acid are placed in a squeeze bottle. The bottle is closed and partially immersed in a thermostatically controlled water bath. The reactants are kept at 77 ^° C. for 72 hours and for 24 hours. 84 ⁰ C, after which the bath is allowed to cool down with the bottle still immersed

An aliquot of the dark-colored reaction product is neutralized with sodium hydroxide to a pH of 7, evaporated to a semi-dry state and evaluated with regard to its odor by several test persons. The following fine fetuses are found: sweet and spicy, nutty (a smell of green walnut), fruity. All of these notes are different from those found for sucrose or hexanol and it is evident that their presence is a direct result of the conversion _e

Example 8

5 g sucrose, 10 g acid potassium sulphate (KHSO.) And 100 ml neutral ethyl alcohol are introduced into a pressure bottle. The bottle is loosely capped and ^{immersed in a 7O 0} O water bath for 2 hours, with occasional shaking ₀

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The reaction vessel is then placed in a 60 ° C forced air oven introduced and left in it for 16 hours. When taking out from the oven, the contents are bright yellow in color and have a very pleasant smell, very similar to that of alcohol is different »from which it can be seen that the desired Implementation has taken place «Test subjects determine the following odor notes in the sample: apple, fruit aroma, coconut o

.. Example 9

In each of 3 Erlenmeyer flasks, 300 g of dried light-colored stems (approx. 8 # reducing sugar) are covered with 700 ml of anhydrous ethanol each time. The alcohol in flask 1 is acidified with 58 ml of HCl, that in flask 2 with a mixture of 29 ml of HCl and 10 ml of concentrated H ₂ SO, and that in the 3 flask with 20 ml of concentrated H ₂ SO ₄ . All 3 flasks contain stoehiometrically identical acid equivalents _{or the like}

The flasks are placed in a 75 ° C water bath for 15 hours and their contents are then neutralized. Samples are then taken and diluted. It appears, that smell and aroma of the produced with HgSO ^ catalysis Product best, read the product made with the mixed acid as in the 2 * place and dee ait HCl obtained products rated as in 3 position will.

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Beiapicl 10

100 g of starch (dry weight) and 500 ml of ethanol with a content of 7 # HGl are placed in a 1 liter flask and refluxed for 5 hours. By vacuum distillation of the reaction products, 11 g of ethyl laevulinate and 3.9 g of thoxymethyl furfural are obtained.

Example 11

In a flask, 5 g of molasses, 200 ml of anhydrous ethanol and 7.3 ml of concentrated H ₂ SO. brought in. The reactants are heated to 75 ° C. for 18 hours. The aroma notes indicate that the implementation of the type described above has taken place ₀

Example 12

5 g fructose, 150 ml SDHr. 30 alcohol and 7.3 ml concentrated

HgSOi 96 hours at temperatures between 50 and 70 ⁰ C.

reacted A sample is made with an equal volume

Diluted water and with HaOH to a pH value of 6.5 Ä

A sweet smell that neutralized the smell very much is similar to that of the same implementation with bright

Stems was obtained, can be determined and can

even if the reaction can still be perceived mixture is diluted to 1: 2000 o

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40 g of DL malic acid, 1000 ml of anhydrous ethanol and 70 ml of acidified alcohol (16.2 g of HCl / 100 ml of ethanol) are introduced into a 1! Flask. The flask is connected to an ascending air condenser and a descending water condenser and the contents of the flask are heated for 6 hours and 43 minutes, during which time 4-74 ml of alcohol is removed. The Kolbanin contents are then neutralized to pH 7.0 with 41 # NaOH. A 40.04 g (73 $) making up Doatillat yield of the expected boiling point is obtained when the residue at 2.5 mm Hg vacuum distillation is subjected _o The product can be identified as SiOH gaschromatographiseh Äpfelsäurediäthylester.

Following the procedure described in Example 13, from n-butanol and succinic acid di-n-butyl succinate fe, which has a Goruchenote of butyric acid and has a sweet smell of relatively low overall intensity

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Example 1 g>

Place in a 19 liter (5 gallon) v / earth 5 _ton pyrex glass balloon (12.5 pounds) of tobacco (dried pale stems) and covered with a mixture of 12 liter of ethanol and 1000 ml of concentrated hydrochloric acid. The piston v / ird 1? Held at a constant temperature of 68 ⁰ G for 1/2 hour. The temperature is then increased to 75 ^° C. and left at this fourth for 4 1/2 hours. The liquid contents of the balloon are diluted to 12 liters with fresh ethanol and acid in the same proportions and poured into a 2, balloon, which contains 5-66 kg of fresh, dried light-colored stems Way and is implemented with stems in a 3 * balloon.

The product fluid obtained from the 3rd balloon of the counter-current series is neutralized with Matriumhydroxyd to pH 6.3 and to remove excess alcohol g of sine water jet pump is connected »The residue is transferred to a continuously operating extraction apparatus and extracted for about 18 hours with ether" The ether v / ird bsi Atmosphärendruok evaporated and any remaining traces of ether are removed in vacuo to a water jet pump "The product is subjected in a Claisenkolben 2 to 3 Seih Hg vacuum distillation ₀

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To an alcoholic solution of part of the light yellow distillate becomes a reagent solution of 2,4-nitrophenylhydrazine given, whereby 4 derivatives are obtained o 2 of these derivatives melt at the one for Iiaevulineäureathylestar and ethoxymethylfurfurol applicable point,

The gas chromatography separation / products of the distillate shows that they are mainly made from apple acid diethyl ester, Succinic acid diethyl ester, laevulinic acid ethyl ester and Ethoxymethylfurfurol consist., These ingredients are also by mass spectrometry and infrared spectrophotometry identified

The fired components can be used individually or in desired Mix with Ü? Abak mixed.

Example 16

The pleasing, distinct and feihai nuances that daa Incorporation of exemplary flavorings according to the invention in smoking products are achieved by the the following example illustrates. 3 parts of a common cigarette material ^ / on each 10g with a Mixture of ithoxymethylfurfurol, ethyl levulinate, Malic acid diethyl ester, succinic acid diethyl ester and Lemon acid diethyl ester sprinkles »half of the mixture

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consists of the ethoxymethylfurfurol and iaevulinic acid ethyl ester prepared according to example 2 and the other half consists of practically the same parts of the other three compounds mentioned (all files relate to the weight) 3 wt. -F *, amounts in the range from 0.1 to 1 wt.-Ja have been found to be satisfactory, with 0.2 to 0.4 $ being preferred.

The treated material is dried and used for evaluation The smell and taste are processed into cigarettes. the so produced cigarettes and untreated control cigarettes 3 evaluators are presented who use an intensity level ranging from 0 to 10 for the evaluation «

The evaluators point out that the cigarettes which receive the aromatic additives according to the invention are distinguished by a fruity feces in the taste when drawn in the uninflamed state and in the taste of the puff and can be easily distinguished from the control cigarettes. It is found that the flavoring the taste and smell of the tobacco used to fill considerably improve the Datsn obtained in this experiment are shown in the following ι

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Cigarettes with control flavoring eggarettes

Evaluation of the odor 7.0 0.0 Overall rating 2.33 0.0 Average
Rating / evaluator Evaluation of the taste when you are not sinful State 3.0 0.0 Total value 1.0 0.0 Average
Rating / evaluator Assessment of smoke taste 7.0 0.0 Overall rating 2.33 0.0 Average
Rating / evaluator

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Claims (1)

-21-claims Process for improving the smell and aroma of a tobacco product, characterized in that an effective amount of at least one aromatic substance is introduced into the tobacco product which is the reaction product of an alcohol and a saccharide or such an organic acid inherent in tobacco and below The pyrolysis temperature of tobacco is volatile % 2. The method according to claim 1, characterized in that a reaction product from a lower one is used as a flavoring substance Alkyl alcohol and an aliphatic di- or trioarboxylic acid or hydroxycarboxylic acid, which is volatile below the pyrolysis temperature of tobacco, is used » 3. Method according to claim 1 or 2, characterized in that that by introducing an effective amount of the - ! Reaction products from an alcohol and a saccharide in a tobacco product, the smoke of the same gives a sweet aroma gives ,,. 909837/0524 4β Method according to one of the preceding claims, characterized characterized in that an effective amount of the reaction products of at least 1 lower alkyl alcohol and at least 1 representative of the class of hexoses, pentoses, Dihexoses, dextrins, starches or pructosans in the Tobacco product introduces «ί 5. Tobacco product containing a flavoring substance which is characterized by its volatility below the pyrolysis temperature of tobacco and which represents the reaction product of an alcohol and a naturally occurring in tobacco acid or such an organic acid _o 6. Product according to claim 5, characterized in that the flavoring is the Heaktiönsprodukt from a lower one Alkyl alcohol and a saocharide. Product according to claim 5 or 6, characterized in that the flavoring is the reaction product from a lower Alkyl alcohol and a hexoee, pentose, dihexose, a Dextren, a starch or a pructosan is " 8. Tobacco product according to one of claims 5 to 7, containing a lower alkyloxymethylfurfurol or a lower alkyl ester of laevulinic acid as a flavoring agent 909837/0524 9 «Product according to claim 8, characterized» that the low alkyloxymethylfurfur oil is atlioxymethylfurfurol «, 10. Product according to claim. 8 _f characterized in that the lower alkyl ester of laevulinic acid is ethyl levulinic acid eater » 11.Product according to claim 5 »characterized! that the Flavor the reaction product from a lower Allyl alcohol and an aliphatic di- or tricarbonoic Hydroxycarboxylic acid is » 12, product according to claim 5 _f containing a lower alkyl ester of malic acid, succinic acid, citric acid, malonic acid or tartaric acid as a flavoring substance » 9 0983 7/0524