EP1231848A2

EP1231848A2 - Smoking products

Info

Publication number: EP1231848A2
Application number: EP00989871A
Authority: EP
Inventors: Thomas Pienemann; Gunther Peters; Hans Noe
Original assignee: Reemtsma Cigarettenfabriken GmbH; HF and PhF Reemtsma GmbH and Co
Current assignee: Reemtsma Cigarettenfabriken GmbH; HF and PhF Reemtsma GmbH and Co
Priority date: 1999-11-23
Filing date: 2000-11-22
Publication date: 2002-08-21
Also published as: DE19957487A1; HK1048418A1; JP2003517822A; AU2667401A; WO2001037685A2; DE19957487B4; TW557202B; WO2001037685A3

Abstract

The invention relates to smoking products whose wrapper, consisting in particular of paper or tobacco, contains a furaneol glycoside which gives the environmental tobacco smoke a previously unknown aroma.

Description

Smokable items

The present invention relates to smokable articles which contain special flavoring substances in their wrapping in order to aromatize the sidestream smoke, as well as a wrapping for smokable articles.

When using smokable items, such as cigarettes, cigars and cigarillos, the so-called by-pass smoke arises from the smoldering of the tobacco during breaks. This is often perceived - especially by non-smokers - as unpleasant and annoying.

Numerous ways have been proposed to overcome this problem. In the case of conventional cigarettes, these methods are based either on a reduction in the amount of sidestream smoke or an improvement in odor by aromatizing the sidestream smoke. The aroma substances required for the latter method are preferably applied to the wrapping of the tobacco certificate. This application is preferable to an aroma treatment of tobacco, since it leads to a more effective transition of the aroma substances into the by-pass smoke and to less influence of the smoke taste. Because of the volatility of most of the effective aroma substances, it has proven to be advantageous to use them in chemically or physically bound form. This avoids loss of aroma during storage and a noticeable smell of the unlit smokable article. The bond must be thermolytically cleavable so that the aroma component is released by the heating when smoking.

For example, US Pat. No. 4,804,002 proposes treating the wrapping of a smokable article with glycosides of an aroma component, only glucosides of ethyl vanillin, altol and menthol being specifically examined. When the article is burned off, the aroma component is released from the glucoside and can thereby have a positive effect on the smell of the side-stream smoke without the taste impression of the main-stream smoke being changed appreciably. Among the suggested glucosides, the ethylvanillyl-ß-D-glucopyranoside shows primarily

(Ethylvanillinglucosid) the desired effect. The glucosides of maltol and menthol, which are also described, on the other hand only have a weak effect.

A cigarette is also known from US Pat. No. 4,941,486, the wrapping of which is in close contact with a bound flavoring agent. Ethylvanillin glucoside is used primarily as a bound flavoring agent. Impregnation, application of a film, introduction via a size press, electrostatic deposition, printing and incorporation into the seam glue of the cigarette are mentioned as possible methods for applying flavor to the wrapper.

However, the disadvantage of ethyl vanillin glucoside, which is known as a flavoring substance, is that the ethyl vanillin released from it produces an aroma which, although certainly pleasant, is clearly perceived as being foreign to tobacco. In addition, it is also desirable to have flavorings available which produce a different smell than previously known flavorings. The invention is therefore based on the object to provide smokable articles with flavoring in their wrapping for aromatizing the sidestream smoke, wherein this flavoring does not produce a smell unfamiliar with tobacco when the article is smoked and provides a different aroma than previously known aroma substances and thus that Spectrum for changing the odor of the sidestream smoke expanded.

This object is surprisingly achieved by the smokable articles according to the invention. The smokable articles according to the invention have an envelope which contains at least one aroma substance for aromatizing the sidestream smoke, and they are distinguished by the fact that the aroma substance is a furaneyl glycoside.

The invention also relates to a casing for smokable articles, which is characterized by a content of furaneylglycoside.

Glycosides of furaneol with maltose, lactose or cellobiose are preferably used. A particularly preferred furaneyl glycoside is furaneyl glucoside, i.e. a glycoside of furaneol with glucose. The chemical name of furaneol is 2, 5-dimethyl-3-hydroxy-4-oxo-4, 5-dihydrofuran.

The prior art only describes ethyl vanillin as an effective flavoring substance which, at doses above the threshold, leads to a clearly identifiable vanilla note in the bypass smoke. Although this is often perceived as pleasant, it is also perceived as foreign to tobacco. In contrast, the furaneol released from the furaneyl glycoside used when smoking has a completely different odor characteristic. While sweet, caramel-like and bready notes are predominantly perceived in high doses, its smell in low doses is perceived as pleasant, but difficult to identify. The articles of the invention preferably contain tobacco as a smokable material. They are therefore especially in the form of cigarettes, cigars and cigarillos.

The preparation of the preferred furaneyl glucoside, its thermogravimetric analysis and the sensory evaluation of the sidestream smoke from cigarettes treated with it are described in the exemplary embodiments.

The evaluation of the sidestream aroma showed a significantly different characteristic than in the case of ethylvanillinglycosides. While the use of the latter led to a general decrease in the perceived aroma intensity and smoke density, when using a furaneyl glycoside, undesirable odors such as "musty", "sour" or "rancid" were perceived significantly reduced. By using furaneyl glycosides completely different aromatization effects can be achieved than was possible with the glycosides known for this purpose.

It has also proven to be advantageous to use furaneyl glycoside in combination with at least one other glycoside of a sugar and an aroma component other than furaneol. In these combinations the released furaneol is able to remove the aroma which is sometimes perceived as tobacco-like, e.g. of ethyl vanillin, without diminishing its positive effects, such as less irritating or stale smoke.

This other glycoside is, in particular, a glycoside of a double or multiple sugar, since such glycosides can be used even in the form of concentrated solutions without undesired crystallization occurring during their processing. This means that these glycosides can even be applied to the coating in the form of warm solutions using nozzles. Maltose, lactose or cellobiose is preferably used as the double or multiple sugar and thus the sugar component of this other glycoside. With the exception of furaneol, all flavoring compounds which can be linked to the double or multiple sugar via a glycosidic bond can be used as aroma components of this glycoside. Preferred aroma components are vanillin, ethylvanillin, eugenol, menthol or maltol.

It is preferred that the amount of all glycosides present in the coating is 0.1 to 5% by weight, based on the weight of the coating.

The wrapping of the articles according to the invention has in particular paper or tobacco. It is particularly advantageously made of paper or film tobacco. The wrapping can also be multi-layered, whereby combinations of paper and tobacco can also be used. A natural cover sheet can also be used as the outer layer.

The use of wrapping materials, such as e.g. of papers that contain substances to reduce the particle mass of the sidestream smoke. As such, special fillers, e.g. cigarette papers provided with magnesium hydroxide, magnesium oxide or a mixture thereof.

Usually, when using cigarette paper as wrapping, it is used in one or two layers. The furaneyl glycoside is advantageously applied directly to the paper in the case of a single-layer form and to the outer layer in the case of a two-layer form. In the latter embodiment, it is preferred to use the bypass-reducing paper for the inner layer and conventional cigarette paper for the outer layer. Furthermore, the wrapping of the smokable articles according to the invention can in particular also consist of one or two layers of film tobacco. If two-ply film tobacco is used, it is preferred that the outer ply contain the furaneyl glycoside. Accordingly, in the case of cigars and cigarillos, the cover sheet is usually provided with the furaneyl glycoside.

In general, the smokable articles according to the invention can be produced by providing the coating, in particular in the form of a web, with the furaneyl glycoside and any glycoside present in a sugar and an aroma component other than furaneol.

The glycosides are applied in particular by

(a) spraying a solution of the glycosides on the outside or inside of the casing,

(b) using a size press, or

(c) Direct application of a solution of the glycosides using nozzles.

In addition to the methods listed in US Pat. No. 4,941,486 for impregnating wrapping materials for smokable articles with glycosides, the following two methods can also be used in particular:

1. Wrapping materials for smokable articles, such as cigarette paper or foil tobacco, are usually manufactured according to common paper manufacturing processes. Such methods often provide for one-sided spraying of the paper or tobacco fleece with the aid of a spray bar, which can be used to apply a solution of furaneyl glycoside. The possible one-sided application of the glycoside either on the inside or outside of the casing also permits more targeted control of the pyrolytic decomposition. 2. A very flexible way of impregnation is also to apply a solution of the furaneyl glycoside in the form of traces to the wrapping directly on the cigarette machine. A device required for this is offered, for example, by the company KAYMICH, Sheffield, UK, under the designation FAS or MAS, which is why this process is also referred to as the KAYMICH process. The device works with a series of nozzles, which are supplied with the solution by a dosing pump.

In addition to using the impregnation processes mentioned above for paper or film tobacco, wrappings of film tobacco can also be produced using the so-called slurry process. Here, finely ground tobacco dust is mixed with an aqueous solution of binders, scraped onto a heated belt and then dried. In this case, the furaneyl glycoside can be added to the aqueous binder solution, which results in film tobacco impregnated with it.

In the event that the articles according to the invention are cigarettes or cigarillos provided with a natural cover sheet, they can be applied either by spraying the cover sheet with an aqueous solution of the glycoside, or else by dissolving the glycoside in that for the gluing between transfer and Cover sheet used glue.

The invention is explained in more detail below with the aid of examples. Examples

Example 1 ; Manufacture of furaneyl glucoside

Furaneylglucoside was according to a literature specification by R. RÖSCHER et al. , Phytochemistry 43 (1), 155 (1996).

The obtained furaneyl glucoside ((2,5-dimethyl-4-oxo-dihydrofuran-3-yl) -ß-D-glucopyranoside) showed the following nuclear magnetic resonance spectra:

^X H NMR (400 MHz, D-, 0) δ = 4.82-4.73 (m, 2 H, Hl, furaneyl H-5), 3.87 (dd, 1 H, H-6a), 3.74 (dd, 1 H , H-6b), 3.52 (dd ~ t, 1 H, H-3), 3.49-3.39 (m, 3 H, H-2, H-4, H-5), 2.35 (s, 3 H, furaneyl 2-CH ₃ ), 1.46 (d, 3 H, furaneyl 5-CH ₃ ) ppm.

' ₂ , 3 = 8. 6; J _{3 ι4} = 8. 6; J _3ι6b = 5. 1, J ', 6a, 6b = 12. 2 Hz

¹ C-NMR (100.6 MHz, D-, 0) S = 203.30 (furaneyl C-4), 188.68 (furaneyl C-2), 136.08 (furaneyl C-3), 106.00 (Cl), 84.71 (furaneyl C-5 ), 78.88 (C-5), 78.23 (C-3), 75.75 (C-4), 71.95 (C-2), 63.11 (C-6), 18.16, 18.06 (furaneyl 5-CH ₃ ), 16.56 ( furaneyl 2-CH ₃ ) ppm.

Beis ^p iel 2: Thermogravimetrisc-ie investigation

Fig. 1 shows the (ufheizrate _A: 5 ° C / min) by means of the thermogravimetric curve of the decomposition Furaneyl- obtained glucoside. The thermolytic cleavage of the glycosidic bond with the release of furaneol results in a theoretical mass loss of 44%. A corresponding mass loss of 42% was found using the curve in a temperature range of 125-270 ° C.

During the measurement, the smell of the furaneol released was clearly perceptible in the decomposition area.

Fig. 1: Thermogravimetry of furaneyl glucoside m / m ₀ [% J

200 4Q0 600 800 1000 where m - mass at measuring temperature m ₀ - initial mass (initial weight)

TG - thermogravimetry

DTG - differential thermogravimetry (1st derivative of TG) Examples 3 to 5; Production and sensory evaluation of the

Side stream smoke from cigarettes with furaneyl glucoside

Example 3: The furaneyl glucoside was applied to a commercial cigarette paper (basis weight 25 g / m 2, porosity 40 CU) in a dosage of 0.3 mg per cigarette during the paper production in the size press. The paper was used as a strand wrapper for a commercially available Ultralights cigarette (KS format, 25 mm filter, strand length 59 mm, mixture type: American blend, filter ventilation 72%, smoke data according to ISO standard with a number of puffs of 7.3: 1, 2 mg dry condensate and 0.13 mg smoke nicotine).

Example 4: In this example, cigarettes were produced with a two-layer strand wrapping, the inner layer being a special paper from ECUSTA, Pisgah Forest, NC, USA (basis weight 28 g / m2, porosity 15 CU) to reduce the visible sidestream smoke and as outer layer the paper according to Example 3 was used. Format, mixture and filter system corresponded to the cigarettes according to example 3. The smoke data according to ISO resulted in a dry condensate of 1.0 mg / cigarette and a smoke nicotine of 0.11 mg / cigarette at a train number of 7.1.

The sensory evaluation of the sidestream smoke of the test samples was carried out by a trained panel of smokers and non-smokers in comparison to similar cigarettes without flavoring glycoside in the cigarette paper. The test samples were machine-smoked in a room of known size and defined equipment (eg 5 cigarettes in a room with a volume of 20 m). The evaluation was made immediately on the fresh smoke and also after 6 hours on the aged smoke. The subjects had to be scaled Specify questionnaire, among other things, how intense the smell of the aroma (here furaneol) and how strongly the unpleasant properties associated with cigarette smoke, such as burning in the eyes, are perceptible. The evaluation was carried out according to the statistical methods customary for sensor-related tests.

Smoke density measurement with a piezo scale showed a 45% reduction in particle mass compared to example 3.

Example 5: Furthermore, cigarettes according to Example 3 were produced with a single-layer special paper from ECUSTA (basis weight 48 g / m, porosity 12 CU). The furaneyl glucoside was also given in a dose of 0.3 mg / cigarette.

The smoke density was reduced by 60% compared to example 3,

For the samples with furaneyl glycoside produced according to the three examples 3, 4 and 5, the panel did not find any independent or tobacco-related odor notes during the olfactory evaluation, as was clearly perceived when higher doses of ethylvanillin glycosides were applied. The sidestream smoke was described as more pleasant overall, specific notes such as "musty", "sour" or "rancid" were reduced in intensity.

For the samples according to Examples 4 and 5, the test room was also felt to be less smoky. Example 6: Preparation of ethyl vanillin maltoside

A solution of 332 mg (2.0 mmol) of ethyl vanillin in 4.4 ml of a 0.45 molar solution of potassium hydroxide in absolute methanol slowly becomes a solution of 1.54 g (2.2 mmol) of acetobromomaltose in 9 ml of absolute dichloromethane dropwise. The mixture is stirred for 13 hours at room temperature and then poured into 20 ml of ice water. The aqueous phase is extracted twice with dichloromethane and the combined organic phases are dried over magnesium sulfate. The solvent is removed and the residue is purified by column chromatography on silica gel (mobile phase: petroleum ether / ethyl acetate 1: 1). Yield: 341 mg (0.43 mmol, 22%) of ethylvanillin maltoside protected with acetyl groups.

For deacetylation, 982 mg (1.25 mmol) of the protected maltoside are suspended in 15 ml of absolute methanol and 1.5 ml of a 1% sodium methoxide solution are added. After stirring for ten minutes, the maltoside is completely dissolved and neutralized with Amberlite IR-120 (H ⁺ ). The ion exchanger is filtered off and the solvent is removed in vacuo. The purification is carried out by recrystallization from 95% ethanol. 520 mg (1.06 mmol, 85%) of ethylvanillin maltoside are obtained as a white solid.

f 4-Formyl-2-ethoxyphenyl) -4-0-α-D-qlucopyranosyl-ß-D-qlucopyranoside (ethylvanillin maltoside):

C ₂₁ H ₃₀ O ₁₃ (490.46 g / mol)

, 20 [α] 7 ₅₇₈ = + 1 - 2 ° (c 0.1, H ₂ 0) mp. : 199 ° C Elemental analysis calculated: C 51.43 H 6.17 found: C 50.97 H 6.22

Mass spectrum: MALDI-TOF-MS: m / z = 513.2 [M + Na] ⁺ , 529.2 [M + K] ⁺

^X H NMR (400 MHz, D, Q. Δ = 9.67 (s, 1 H, CHO), 7.49 (dd, 1 H, aryl H-5), 7.43 (d, 1 H, aryl H-3), 7.21 (d, 1 H, aryl H-6), 5.38 (d, 1 H, H-l '), 5.19 (d, 1 H, Hl), 4.08-4.17 (, 2H, 0-CH ₂ - CH ₃ ), 3.62-3.89 (m, 10 H, H-2, H-3, H-4, H-5, H-6a, H- 6b, H-3 ', H-5', H-6 ', H-6'b), 3.53 (dd, 1 H, H-2 '), 3.37 (dd ~ t, 1 H, H-4'), 1.36 (t, 3H, O-OL _j -CH _j ) ppm ,

J., 2 ⁼ 7.6, Jι «, ₂ ' ⁼ 4.1, J ₂ ', ₃ ' ⁼ 9.7, J' _t4 <= 9.7, J _ή ', ₅ ' = 9.7,

Jar-3, ar-5 ⁼ "-'S, J _a r-5, ar-6 ⁼ 8.1, J _0Et = 7.1 Hz.

¹³ C NMR (.100.6 MHz, d, -MeOH. Δ = 195.11 (CHO), 151.62, 148.36 (2 x C, aryl C-1, aryl C-2), 131.31 (aryl C-4), 126.94 ( aryl C-5), 115.34 (aryl C-6), 112.99 (aryl C-3), 100.07 (C-1 '), 99.78 (C-1), 76.74 (C-5), 76.21 (C-3) , 75.24 (C-4), 73.23 (C-2), 73.11 (C-5 '), 72.86 (C-3'), 72.06 (C-2 '), 69.69 (C- 4'), 65.68 (0 -CH ₂ -CH ₃ ), 60.85, 60.80 (2 x C, C-6, C-6 '), 15.37 (0-CH _z -CH ₃ ) ppm.

Example 7 Production and sensory evaluation of the secondary flow smoke of cigarettes with a mixture of furaneyl glucoside and ethyl vanillin maltoside

Filter cigarettes with a diameter of 7.9 mm and a total length of 84 mm (king size format) were produced (21 mm monoacetate filter, 63 mm strand length, tobacco weight 750 mg, mixture type: American blend, filter ventilation 20%, smoke data according to ISO -Normal with a train count of 8.0: 11.8 mg dry condensate and 0.86 mg smoke nicotine).

A commercial cigarette paper was used as the strand wrapper, which was provided with a mixture of 0.15 mg of ethyl vanillin maltoside and 0.3 mg of furaneyl glucoside per cigarette.

The evaluation of the cigarettes was carried out as described in example ₍ 4). The sidestream smoke was perceived to be significantly more pleasant with reduced irritation (fresh smoke) and less stale (aged smoke) compared to that of a commercially available comparative cigarette. A smell or taste unrelated to tobacco was not found.

Example 8: Production and sensory evaluation of the secondary flow smoke of cigarillos with a mixture of furaneyl glucoside and ethyl vanillin maltoside

Filter cigarillos with a diameter of 7.9 mm and an overall length of 84 mm were produced. The cover sheet consisted of film tobacco produced by a paper process, which was impregnated with the mixture of furaneyl glucoside and ethylvaniline maltoside mentioned in Example 7. This aroma mixture was applied during the production of the cover sheet in the size press.

The cigarillos obtained were evaluated as described in Example 4. By using the aroma mixture on the outer wrapper, the more pronounced olfactory notes "cigararry" and "alkaline" than cigarettes were perceived as significantly reduced.

Claims

claims

1. Smokable article with a covering which contains at least one flavoring agent for aromatizing the bypass smoke, characterized in that the flavoring agent is a furaneyl glycoside.

Article according to claim 1, characterized in that the furaneyl glycoside is a glycoside of furaneol with maltose, lactose or cellobiose.

Article according to claim 1, characterized in that the furaneyl glycoside is furaneyl glucoside.

Article according to one of claims 1 to 3, characterized in that the coating additionally contains at least one other glycoside from a sugar and an aroma component other than furaneol.

5. Article according to claim 4, characterized in that the sugar is a two or multiple sugar and in particular maltose, lactose or cellobiose.

6. Article according to claim 4 or 5, characterized in that the flavor component is vanillin, ethyl vanillin, eugenol, menthol or maltol.

Article according to one of claims 1 to 6, characterized in that the wrapping comprises paper or tobacco.

8. Article according to claim 7, characterized in that the paper contains substances for reducing the particle mass of the sidestream smoke.

Article according to one of claims 1 to 8, characterized in that the amount of all glycosides present in the casing is 0.1 to 5% by weight, based on the weight of the casing.

10. Article according to one of claims 1 to 9, characterized in that the wrapping consists of a layer of paper.

11. Article according to one of claims 1 to 9, characterized in that the wrapping consists of two layers of paper and the outer layer contains the furaneyl glycoside and any other glycoside which may be present.

12. Article according to claim 11, characterized in that the inner layer has fillers for reducing the particle mass of the sidestream smoke.

13. Article according to claim 12, characterized in that magnesium hydroxide, magnesium oxide or a mixture of these is present as a filler.

14. Article according to one of claims 1 to 9, characterized in that the covering consists of a layer of film tobacco.

15. Article according to one of claims 1 to 9, characterized in that the covering consists of two layers of film tobacco and the outer layer contains the furaneyl glycoside and any other glycoside which may be present.

16. Article according to one of claims 1 to 9, characterized in that the covering consists of an inner layer of film tobacco and an outer layer of paper and the outer layer contains furaneyl glycoside and any other glycoside which may be present.

17. A method for producing smokable articles according to one of claims 1 to 16, characterized in that the coating is provided with furaneyl glycoside and any other glycoside which may be present.

18. The method according to claim 17, wherein the furaneyl glycoside and any other glycoside present

(a) spraying a solution of glycoside on the outside or inside of the casing,

(b) using a size press, or

(c) Direct application of a solution of glycoside using nozzles

is applied.

19. The method of claim 17, wherein the coating is produced in sheet form by mixing ground tobacco dust with an aqueous binder solution which contains furaneyl glycoside and any other glycoside which may be present.

20. Wrapping for smokable articles, characterized in that the wrap contains furaneyl glycoside.