DE2634306A1 - SMOKING FLAVORS - Google Patents

Description

D R. - I N G. H. FIMCKE

DIP L. - IN GH BOH Λ ,

DIPL. - ING. S. CTAEGER ^ό ° - ^Jlll -I 1976

ΏΡ .. Γ2Γ. nat. Γ. K.>! EiS ^ L M Cl LLERSTRASSE 31 OJOO MUNICH 5

Folder 2k O69 Case Dt. 28088/28620

IMPERIAL CHEMICAL INDUSTRIES LIMITED Imperial Chemical House, Millbank, London S.W.1., Great Britain

Smoke flavorings

The invention relates to substances that can be used as flavorings, especially as a smoke flavoring for Tobacco, reconstituted tobacco and tobacco substitutes are suitable,

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the latter being understood to mean materials which, although they do not originally come from tobacco, are in the same way Ways cigarettes, cigars, pipes, etc. can be smoked.

Tobacco substitutes have been proposed because tobacco smoke causes bronchial and lung diseases. the known substitutes are, despite some improved health characteristics compared to tobacco, from limited value because their smoke taste is not that of tobacco resembles. In order to achieve a noticeable tobacco taste, mixtures with large proportions of tobacco and / or tobacco extracts have hitherto been used necessary, through which attainable health benefits are diminished.

According to the invention, a substance is made available, that is a glycosyloxy derivative of 4- (2,6,6-trimethylcyclohexan-1-yl) butane compound the general formula

Formula X

contains, wherein either the carboxyl ring or the four-membered side chain or both are unsaturated, and the molecule may carry methyl groups, a keto group and / or a hydroxyl group as additional substituents.

The above and the following formulas are given in the usual way; unless unsaturated bonds and substitution otherwise indicated, each angle or free ending line represents a carbon atom, its

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»* 1 Μ

four valences are either ± n as indicated or are saturated with hydrogen.

An embodiment according to the invention is a substance which is a glycoside of the formula

Formula II

contains, in which the ring A contains a double bond in optional positions indicated by the dashed lines, and in which the four-membered side chain contains a double bond in optional positions, also indicated by the dashed lines, one of the radicals R_ and R. is a glycosyl oxy group (-OX), in which X is a mono- or disaccharide residue, R, R and Ru optionally -H, = 0 or -OH (provided that R_ and Rjl are not simultaneously = 0), and R ^ - optionally mean -H, -OH or nothing.

There is of course the restriction that the various possible compounds according to formula II must contain the carbon atoms have no value greater than 4. For example, if there is a double bond between the carbon atoms 1 and 2 is arranged in ring A, the radical R ^ nothing, and the ring carbon atom 1 is with the side chain atom 4 only connected with a single bond.

Another embodiment of the present invention is one Substance that is a glycoside of the formula

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Formula III

contains, in which one of the radicals Y is a mono- or disaccharide radical is.

Glucosides of the formula II and ITl (in which the glucosylresfce X and Y are glucosyl residues) were identified as tobacco components in which they are contained in extremely small amounts.

They are highly concentrated preparations that, for example, 25 Containing weight percent or more of the glucosides, obtainable from tobacco. A method for making such preparations consists in extracting tobacco with a low-boiling ketonic solvent, for example acetone, that one gradually from the extracts in aliphatic hydrocarbons, for example hexane, and then m a low-boiling chlorinated hydrocarbon, For example, chloroform, soluble components are removed and a water-soluble fraction is obtained from the residue that this can be obtained aqueous solution with ion exchange resins for removal Treated the basic and acidic fractions, so that a neutral residue remains that the residue with a lower alkanol, especially butane1, extracted and the Solution subjected to gel permeation and liquid chromatography, to separate them into factions rich in individuals

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Glu.cosld.en are.

The glucosides according to the invention are mainly used in the early fractions eluted from separation by gel permeation found; From these, individual pure glucosides can be isolated, if necessary, by liquid chromatography. the last fraction eluted from the gel permeation contains mainly Other types of glucosides, as described, for example, in GB-PA 32288/75 and 4745V75. The separation technology, which was used according to the invention is in individually described in the examples.

At each stage of the process, the produced tobacco taste more clearly.

In their final form, the glucosides are colorless solids, when they are practically pure. Their chemical structure was duiOh C -NMR spectroscopy (nuclear magnetic resonance) and by enzymatic hydrolysis to the corresponding aglycones, which contain ÜH groups instead of the glycosyloxy groups, and which were isolated as colorless oils, cleared up,

C-NMR spectroscopy and PMR spectroscopy (proton magnetic resonance) have also been used to determine the structure of aglycones, which are generally known compounds. In the aglycones, the gem-dimethyl group produces am Carbon atom 6 has a characteristic PMR resonance with two 3-proton singlets in the range of 0.95 to 1.30 ppm, based on on tetramethylsilane (TMS).

One possible definition of the compounds according to the invention consists of them as glycosides, which are enzymatically hydrolyzable to aglycones, and the PMR-spectroscopic described Have characteristics.

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BATH

Glycosides according to the invention can be produced synthetically by using as starting compounds a mono- or disaccharide (especially glucose) and a hydroxy derivative of the ίΐ, -ο suitable Lon h- (2, 6, 6-trimethylcyclohoxan-1-yl) butane compound (aglycon ) used. Accordingly, the mono- or disaccharide can be O-acylated and converted into a functional derivative, for example a halide, which is reactive towards hydroxyl groups and is then reacted with the hydroxy compound, and whose O-acyl groups are hydrolyzed. For example, glucose can be converted into the _s Tetraacetoxyglucosylbromid mi L hydroxy - ^ - (2,6,6-trimethyleyelohexan-1 "pyl) is condensed butane; the acetyl groups are hydrolyzed to form the glucoside.

Preferred glycosides are obtained from hexoses or pentoses, glucosides are particularly preferred.

Examples of the preferred glucosides are the compounds according to the following formulas

Formula IV

Formula V

Formula Vx Formula VXI

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BATH ORIGINAL

* - 7 -

Formula VIII Fgrmel IX

Formula X Formula XI

Formula XII

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in which G stands for a ß-D-glucosyl group.

The substances according to the invention give the smoke of tobacco substitutes, which otherwise would practically not taste of tobacco, a clear and definite tobacco taste. Only small amounts, for example 1 percent by weight, are necessary to achieve such a effect. This is most remarkable because the substances themselves are not volatile. In addition, the aglycones, from which they are obtained, tobacco substitutes with little or no tobacco taste,

Although the synthetic glycosides have a special inventive Execution, the invention also relates to flavorings in the form of concentrates, which are isolated from tobacco, these concentrates, for example, at least 25% of the glucosides described contain.

The substances according to the invention can optionally be used for To improve or enhance the tobacco taste, especially of reconstituted tobacco or mixtures of tobacco with tobacco substitutes.

According to another embodiment of the invention Smoking materials such as tobacco, (including reconstituted tobacco), tobacco substitutes, or mixtures of tobacco provided with a tobacco substitute product that is low in weight, for example $ 1, one of those described Contains added substances.

Tobacco substitute products can be based on, for example, materials with a carbohydrate origin, for example according to GB-PS 1,055-73 and 1,143,500 and US-PS 3,106,209, viz Cellulose, oxidized cellulose or lettuce leaves

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be. Cellulose ethers can also be used. Modified Carbohydrates are preferred, where "modified" is intended to mean chemically modified and the starting carbohydrate has been chemically altered in its nature.

The tobacco substitute product can advantageously be a thermal be degraded carbohydrate, which was produced, for example, by the fact that a carbohydrate (especially cellulose) a catalytic degradation process at about 100 C (for example 100 to 250 ° C) according to GB-PS 1 113 979 or above 250 ° C according to GB-PS 1 415 893) is subjected until the weight of the degraded Carbohydrates less than $ 90> the weight of the original carbohydrate. An equal substance is made according to GB-PS 1 289 354 by acid-catalyzed or base-catalyzed condensation a compound of the formula

R ¹ COCH ₂ CH ₂ COR ² (il)

1 2

obtained in which R and R, which may be the same or different, represent a hydrogen atom or an alkyl, hydroxyalkyl or formyl group; a precursor of the compound (il) is also suitable.

The substances according to the invention can be converted into those according to the invention Smoking materials are introduced in the usual way. Other known additives to smoking materials can also be used be introduced in order to convey the corresponding physical properties and burning properties. For example, can the smoke materials catalyst for glow control, materials to improve the coherence of ash and color, nicotine, other flavors, medicines, paint, film-forming agents or agents for regulating humidity. keep.

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In particular, the smoking materials according to the invention according to GB-PS 1,312,483 and 1,312,786 contain protein. Appropriately the smoking materials according to the invention are in the form of sheets or webs that form a film Agents, for example a natural gum or pectin or a cellulose ether, in particular carboxamethyl cellulose or contain its salt. To produce such sheets or webs, the ingredients of the Smoking material, preferably together with tobacco or tobacco substitute product in finely divided form mixed with sufficient water to form a slurry which is then applied to a surface and dried will. Web material made from the slurry can crushed into a form suitable for smoking.

The preferred smoking materials of the present invention are manufactured on the basis of tobacco substitute products and in particular on the basis of the thermally degraded ones described above Carbohydrates. Such smoking materials produce smoke that contains relatively small amounts of pollutants; since they themselves have a distinct tobacco taste, they can be mixed with tobacco in relatively large quantities, so that mixtures accepted by habitual smokers of tobacco cigarettes.

The invention is illustrated in more detail by means of the following examples. All parts and percentages relate to weight.

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EXAMPLE-

The following is the isolation and characterization of 4- (2,6, o-trimethylcyclohexan-i-yl) butane glycosides FCV tobacco described.

An acetone extract made from 200,000 parts of hot air dried Virginia Tobacco (FCV) was fractionated by sequentially the portions soluble in hexane and then in chloroform were removed. The residue was then extracted with water.

The water soluble portion (8,000 parts) was then treated with ion exchange resins to (a) bases (under "Use from Amberlit IRC-50 (H) / ethanol), (b) to remove acids (using Amberlit IRA-45 (OH) / water); the neutral residue was treated with n-butanol. The butanol soluble The fraction (400 parts) was separated into 4 main bands during gel permeation (using LH 20 / water). These bands were further identified by preparative liquid chromatography under pressure (phase! Silica; solvent system : Dichloroethane (85) j acetonitrile (8.5) "ethanol (8.5)" and water 0.6) dissolved; the following were obtained Substances obtained as colorless freeze-dried solids.

a glycoside with the designation G1 (20 parts) a glycoside with the designation G2 (40 parts) a fraction rich in a glycoside designated with G3 (5 parts) is a fraction containing glycosides designated as G4, G5 and g6 (15 parts) a fraction rich in glycoside ₃ referred to as G7 (1 part).

band 1 (I) band 2 (H) (in) B _a nde 3 (IV) band 4th (V)

13th

C-NMR spectroscopy and enzymatic hydro-

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lysis were important in characterizing these glycosides Methods. All 5 fractions were easily eliminated by β-glucosidase hydrolyzed, thereby reducing the ß-D-glucoside character of this Glycoside was confirmed. The corresponding released aglycones, A1, A2, A3, A4, A5, Λ6 and A7 were purified and characterized.

Aglycone A1 was obtained as a colorless oil with the following characteristics isolated:

MS: M ⁺ 224 CH O _20; m / e 168, 124 ($ 100), 122, 111, 79, 45, 43.

IR (CDCl): 36IO, 345Ο, I66O, 1630, 16ΟΟ, 978 cm "" ¹ UV: X (MeOH) max 239 nm (£ 11,500)

PMR (CDCI): 1.01 (3H, s); 1.08 (3H, s); 1.30 (3H, d, J =

7Hz); 1.90 (3H, d, J = 1Hz); 2.34 (2H, AB-quartet J = 16.5 Hz); 4.39 (1H, m); 5.9 (3H) ctppm.

These data are sufficient to classify Aglycon A1 as 4- (1-hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) -but-3-en-2-ol (Vomifoliol) to identify.

Aglycon A2 was obtained as a colorless oil with the following characteristics isolated:

MS: M ⁺ 208 CH _2Q 0 ₂ ; m / e 193, 152, 134, 123, 109, 108 ($ 100), 107, 95, 91, 84, 81, 79, 77, 69, 45, 43, 41

IR (CCIj ^): 3610, 3400, 1660

UV: X (MeOH) max. 237 nm (£ 9000)

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PMR (CDCI): 0.95 (3H, s); 1.02 (3H, s); 1.28 (3H, d, J

= 7Hz); 1.89 (3H, d, J = 1.5 Hz); 4.33 (1H, m); 5.60 (2H, m); 5.88 (iH, broad s). <f ppm

These data are sufficient to classify aglycone A2 as 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) -but ~ 3-en-2-ol (3-Oxo- OC -ionol) to identify.

Aglycone A3 was obtained as a colorless oil with the following characteristics isolated:

MS: M ⁺ 210 C ₁₃ H ₃₂ O ₂ ; m / e 195, 192, 177, 164, 150, 135, 123, 109, 108, 95, 93, 79, 67, 45, 43 ($ 100), 41.

IR (CCl ^): 36IO, 3420, 1660 cm " ¹

UV: Λ (meOH) max 237 nm (f 98ΟΟ)

PMR (CDCl ₃ ): 1.03 (3H, s); 1.09 (3H, s); 1.25 (3H, d, J-7Hz); 2.00 (3H, d, J ~ 1Hz); 3, 80 (1H, m); 5.84 (1H, expanded s) ctppm.

These data are sufficient to classify aglycone A3 as 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) -butan-2-ol to identify.

Aglycones A4 and A5 were isolated as colorless oils with the following characteristics: (the MS and IR spectra of these compounds were identical and are reproduced below)

MS: M ⁺ 208 CH ₂₀ O ₃ ; m / e 164, 149 (i00 $), I36, 122, 108, 105, 91, 77, 45.

" ¹

XR (CCl ₂ ^) s 362Ο, I67O

cm

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UV: A4 A- (MeOH) max 288 nm (ξ. 51Οθ)

A 5 Λ (MeOH) max 286 nm (£ 5000)

PMR (CDCI): Ak 1.17 (OH, s) ;, 1.25 (3H _f d, J ~ 6Hz);

2.20 (3H, s); 3.85 (1H ₁ m); 5.70 (1H, t, J-7Hz); 5.90 (1H, s) Ζ ppm

A5 1.25 (3H, d, J ~ 6Hz); 1.30 (6h, s);

2.30 (3H, s); 3.90 (1H, m); 5.90 (iH, s); 6.00 (1H, t, J ~ 7Hz) cf ppm

Based on these data, the aglycones A4 and A5 were identified as the two geometric isomers of 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-ylene) -butan-2-ol identified.

Aglycon a6 was produced as a colorless oil with the following Ch.ara.kteristika isolated:

MSs M ⁺ 208 C ₁₃ H ₂₀ O ₂ ; m / e 193, 175, 159, 1 47, 133, 131, 119, 105, 91, 77, 55, 43 ($ 100), 41, 39.

IR (CCl ^): 36IO, 3450, 2210 (w), cm " ¹

PMR (CDCl ₃ ): 1.10 (3H, s); 1.15 (3H, s); 1.48 (3H, d, J =

7Hz); 1.87 (3H slightly broadened S); 4.67 (1H, q, J = 7Hz); 4.06 (1H, m) _{; c} fppm

The acetylenic moiety was determined by Raman spectroscopy confirmed. The data led to the identification of aglycone a6 as 4- (4-hydroxy-2,6,6-trimethyl-i-cyclohexen-1-yl) -but-3-yn-2-ol.

Aglycon A7 was obtained as a colorless oil with the following characteristics isolated:

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MS: M ⁺ 208 C ₁₃ H ₂₀ O ₂ ; m / e 193, 175, i49, - 147, 139, 133, 121, 105, 91, 79, 77, 69, 41 (100/0).

): 3620, 3480, 3020, 1676, 1648, 1620, 1060, 975 cm " ¹ UV: Λ (MeOH) max 227 nm (£ 11 700)

PMR (CDCl ₃ ): 0.98 (3H, s); 1.14 (3H, s); 1.55 (3H, s);

ABX_ system (a centered at 6.19 »B 6.67 and X 1.93); 4.03 (1H, m) <fppm.

These data are sufficient to classify aglycone A7 as 4- (4-hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl) -but-2-en-4-one (4-hydroxy-ß-damascone) to identify.

1 3
The 13 C-NMR data of the chemical shift in the case of the free glucosides G1 and G2 are shown in Table 1 and confirm the structural assignment, based on investigations on the aglycon.

This analysis consequently has to identify certain GIy co siderr, - either free or in selected fractions, in FCV tobacco. These are the ß-D-glucosides from

(i) 4- (1-Hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexen-1 yl) -but-3-en-2-ol

(II) 4- (4-Keto-2,6,6-trimethyl-2-cyclohexen-1-yl) -but-3-en-2-ol (G2)

(ill) 4- (4-Keto-2,6,6-trimethyl-2-cyclohexen-1-yl) -butane-2-0I (G3)

(iV) and E and Z 4- (4-keto-2,6,6-trimethyl-2-cyclohexene-1- (V) ylen) -butan-2-ol (g4 and G5)

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(VI) 4- (4-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl) -but-3-yn-2-ol (g6)

(VII) 4- (4-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl) -but-2-en-4-one (υ?).

The synthesis of G2, G3 and G7 from the corresponding AgIykonen A2, A3 and A7 are in Examples 5> 7 or 8 be written.

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TABLE 1

Chemical shift in the ^ C-NMR spectrum of natural and synthetic glucosides

G = ß-D-glucosidyl residue (carbon atoms denoted by

a-f)

well ^ 3, i Ch ₁ R FrVT * "for Vi fitis n" h e 1 Kpimcr
2 II Coals
material
number 1 1 1 R - H 35.7 35.8 Mixture d,
Buckets Ring 6 R = H R = OH ** 7.i * itf.if 35.7 5 35-8 1 * 1.0 198.O 198.0 i * 8.5 1* 1 * 7.2 W. ** 125.O 125oO 201.6 3 198.2 197.5 162.O 162.3 12i * .9 2 125.O 125.7 5 **. 6 54.6 169.6 1 162.3 16I * .1 129.7 127Λ 51. if Be k 5 »*. 6 77.9 135. »* 136.9 25.1 ten- 2
chain 127.3 130. i * 72.3 74.8 35-7 & 33o5 2 136.8 133. »* - 22.1 - 20.8, 72 "9 & 67.7 -1" - 7i * .8 7i * .7 23.O
27.5
26.8 23-0
27.5
26.8 20.2 2-methyl
6.6 - according to
Dimethyl ( 20.8 20.8 99.7 101.1 22.1
29.3
27.5 a 23.O
27.5
26.8 18.9
21 * .1
23.0 73.1 * 73 * 8 101.6 & 97.3 b 101.1 100.9 77.1 76o9 7i * .2 C. 73.8 73.9 70.2 7QoO 77.0 d 76.9 76.9 77.1 76o9 70.8 e 7O.I 70.1 61.2 61 “ο 77.0 f 76.9 76.9 61.8 61.1 61.1

- 17 - ■ 709807/1182

EXAMPLE 2

In the following example, the taste of isolated 4- (1-hydroxy-4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) but-3-en-2-ol (G1) examined.

18 parts of a material which was produced by thermal degradation of cellulose by heating at 250 ° C. in the presence of 5/0 ammonium sulphamate to a weight loss of more than 10 $ was mixed with 60 parts of water and ground in a disintegrator. 1.2 parts of glycerine and 0.4 parts of ammonium sulphate in 20 parts of water were added. Then a dry mixture consisting of 3> 3 parts calcium carbonate and 1.0 part bentonite was added; then 3t0 parts of sodium carboxymethyl cellulose, 5.72 parts of magnesite and 0.2 part of 4- (1-hydroxy- ■ '"= keto-2, 6, 6-trimethyl-2-cyclohexen-1-yl) -but-3- en-2-ol £ = B «= glucoside added The resulting slurry was stirred for at least 1 hour and then placed on a dryer to form a film having a dry weight of 48 to 52 g / m 2.

The film was crushed; the product turned into cigarettes produced and rated them in terms of their taste. A tobacco taste was detected when the cigarettes were smoked.

Example 2 was repeated with the following changes:

(a) β-D-glucoside has been omitted;

(b) instead of the ß-D-glucoside was o, 2 parts of the corresponding Hydroxy compound used.

In either case, very little taste was observed when smoking the cigarettes.

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26343Ol

EXAMPLE 3

In the following example, the taste of isolated 4- (4-keto-2, 6, ö-trimethyl ^ -cyclohexen-i -yl) -b-ut ~ 3-en ~ 2-ol (G2) lint requested.

5.18 parts of a material which was produced by thermal degradation of cellulose by heating at 250 ° C. in the presence of 5% ammonium sulphamate to a weight loss of more than 10 $ were mixed with 60 parts of water and ground in a disintegrator. 1.2 parts of glycerin and 0.4 parts of ammonium sulphate in 20 parts of water were added. A dry mixture consisting of 3.3 parts calcium carbonate and 1.0 part bentonite was added; then 3> 0 parts of sodium carboxymethyl cellulose, 5 ', 7 parts of magnesite and 0.2 parts 4_ (4-keto-2, 6-trimethyl o - ^ - cyclohexen-1-yl) -but ~ 3-en-2-ol ß-D-glucoside added. The resulting slurry was stirred for at least 1 hour and placed on a dryer, so

2 that a film with a dry weight of 48 to 52 g / m 2 is formed became.

The film was crushed and the crushed product was made into cigarettes, the taste of which was evaluated. At the Smoking the cigarettes was found to have a tobacco taste

Example 3 was repeated with the following changes:

(a) the ß-D-glucoside has been omitted altogether.

(b) Instead of the ß-D-glucoside, 0.2 parts of the corresponding Hydroxy compound used.

When smoking the cigarettes, only a very slight taste was found in each case.

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EXAMPLE k

The taste evaluation of the tobacco fractionon according to bands 1, 2, 3 and h according to example 1 under the conditions which were described in example 2 and in example 3 shows that a tobacco taste occurred in all cases.

EXAMPLE 5

In the following the preparation of 4 - (^ - keto-2,6,6-trimethyl 2-Cyclohexen-1-yl) -but-3-en-2-ol-ß-D-glucoside (Formula V) (G-2) be honored.

185 parts of freshly prepared silver carbonate and 180 parts of Drierit were added to a solution of 80 parts of 3-oxo- <A -ionol (a mixture of the two C-9 epimers according to US Pat. No. 3,21,718) in 1,000 dioxane in a three-necked flask ; the mixture was stirred for 15 minutes while dry nitrogen gas was bubbled through the vessel. At this stage, 7 parts of iodine and then a solution of 480 parts of 2,3> 4,6-tetra-o-acetyl-ot -D-glucopyranosyl bromide (λ-aceto-bromonglucose) in 300 parts of dioxane were added dropwise over one hour. The mixture was stirred in the dark for 20 hours, filtered and the filtrate plus dioxane wash of the material removed by filtration, evaporated at 25-30 ° C under reduced pressure (1-2 cm) to remove the dioxane, leaving 550 parts of an oily residue which resulted in 25 parts of the tetraacetate as an oily liquid. When examined by gas chromatography, this material gives a doublet, probably due to the presence of two diastereoisomers. The epimeric mixture of the tetraacetates was purified by gel permeation chromatography and subsequently processed further without separating the epimers.

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A solution of 54 parts of the tetraacetates in 11,000 parts anhydrous methanol was treated with a solution of 5> 2 parts of barium methoxide in 147 parts of anhydrous methanol; the mixture was left to stand at 0 ° C. for 12 hours. The barium was then added by adding a light Excess aqueous 10% sulfuric acid precipitated; the Solution was just made alkaline by adding dilute aqueous ammonium hydroxide »using a Centrifuge, the solids were removed from the reaction mixture; the supernatant liquid became constant Weight evaporates at a pressure of 1 to 2 cm and temperatures of 25 to 30 C; this left a residue, the 31 parts of 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) -but-3-en-2-ol-β-D-glucoside an epimeric mixture of 2 epimers in approximately equal amounts would contain the individual Epimers were identified by preparative high speed liquid chromatography (hSLC) on silica with a solvent system from dichloroethane (85) 1 acetonitrile (8.6), Ethanol (8.5) and water (0.6) isolated.

The epimers were obtained as a colorless freeze-dried solid · = body preserved; an epimer (epimer 2) was according to HSLC analysis

1 3
analysis and 13 C-NMR analysis with material that is isolated from tobacco

1 3 was identical. The entire 13 C-NMR spectroscopic

Data are summarized in Table I » EXAMPLE 6

In the following the production of 4- (4-keto-2,6,6-tri « methyl-2-cyclohexen-1-yl) butan-2-ol.

A portion of 4- (4-keto-2 , 6 , 6-trimethyl-2 = cyclohexene «-1 ° -yl) -but-3-en-2-one (manufactured according to US Pat. No. 3,21-18) was Hydrogenated in the presence of 5io palladium on charcoal (0.1 part) in 100 parts of absolute ethanol »Immediately found fasserstoffaufnähme

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instead, and the reaction was terminated after one equivalent of hydrogen was consumed. The ethanol solution was filtered and the solvent removed, whereby 0.9 parts of crude 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) butan-2-one revealed.

The crude product was dissolved in 200 parts of aqueous methanol (1: 1), and sodium borohydride (1.3 parts) was added. The reaction mixture was left to stand overnight at room temperature and worked up in the usual manner; by the following column chromatography, 0.6 parts of 4- (4-keto-2,6, 6- trimethyl-2-cyclohexen-1-yl) -butan-2-ol, the NMR data is characterized by the following:

PMR (CDC1 "): 1.00 (3H, s); 1.07 (3H, s); 1.21 (3H, d, J =

7Hz); 1.99 (3H, d, J-IHz); 3.77 (iH, m); 5 »83 (1H, broadened s); cfppm

^{6 3} C NMR (CDCl3): 199.4, 16.5.5, 125.2, 68.2 and 68.0, 51.2,

47.2, 38.2, 36.4, 27.2, 26.3, 24.7, 23.8, cf ppm

The signals at 68.2 and 68.0, which are assigned to the carbinol carbon, had the same intensity and showed thus indicates the presence of an equimolar mixture of the two C-2 epimers.

EXAMPLE 7

The following describes the preparation of 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) butan-2-ol-β-D-glucoside (Formula VI) (G3) described.

While stirring, a solution of 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) butan-2-ol (0.21 parts) in 25 parts of dry 1,2-dichloroethane freshly made pulsed

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added silver carbonate (0.9 parts). The system was purged with nitrogen and refluxed. The volume of the reaction mixture was halved by distillation; then a crystal of iodine was added. Over a period of 3 hours, while stirring the solution, 2,3, h, 6-tetra-o-acetyl-oC-D-glucopyranosyl bromide (1.13 parts) in 150 parts of 1,2-dichloroethane was added dropwise while stirring during this time the solvent was allowed to distill off at approximately the same rate. Another 100 parts of 1,2-dichloroethane were added dropwise while being removed by distillation. The reaction mixture was filtered and the solvent removed; 1.1 parts of a syrupy residue were obtained.

This residue was dissolved in 150 parts of ethanol and washed with a solution of 1.1 parts of potassium bicarbonate in 50 parts Treated water. The reaction mixture was purged with nitrogen and then allowed to stand at room temperature for 5 days. The solution was concentrated to remove methanol; the aqueous phase was extracted repeatedly. Fractions containing the desired glucoside were pooled and analyzed by preparative liquid chromatography cleaned under pressure; 0.09 part of 4- (4-keto-2,6,6-trimethyl-2-cyclohexen-1-yl) -butan-2-ol-β-D-glucoside became (Total yield $ 24). The structure was created by the

C-NMR spectroscopic data according to Table I (structure II) confirmed.

EXAMPLE 8

The following example describes the preparation of 4- (4-hydroxy-2,6,6-trimethyl-i-cyclohexen-i-yl) -but-2-en-4-onrß-D-glucoside (Formula Vliqc) (G7).

709807/1182

4- (4-Hydroxy-2, 6, 6-trimethyl-1-eyelohexen-1-yl) -but-2-en-4-one was prepared according to Helvetica Chimica Acta 56, 1 503 (1973). The product was purified by column chromatography and gave a colorless oil with the following spectral data:

MS: M ⁺ 208 C ₁₃ H ₃₀ O ₂ ; m / e 193, 175, 149, 109, 105, (10056), 43, 41, 39

UV: Λ (MeOH) max 225 nm (6 13 4θθ) IR (CCl ^): 3620, 3030, 1640, 970 cm " ¹

PMR (CDCl ₃ ): 0.99 (3H, s); 1.16 (3H, s); 1.55 (3H, s);

ABX system (A centered at 6.15, B 6.75 and X 1.93); 4.09 (1H, m) <f ppm

13 C-NMR spectroscopic data are assigned in

Table IJ reproduced. The mappings were made using the "off-resonance" and selective decoupled proton spectra carried out. A solution of 4- (4-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl) -but-2-en-4-one (0.21 parts) in 25 parts of dry 1,2-dichloroethane freshly made powdered silver carbonate (0.9 parts) added. The system was purged with nitrogen and refluxed. The volume of the reaction mixture became halved by distillation; then a crystal of iodine was added. 2,3,4,6-Tetra-o-acetyl-oC -D-glucopyranosyl bromide (1.13 parts) in 150 parts of 1,2-dichloroethane were added dropwise added to the solution with stirring over 3 hours; during the addition time the solvent was left with about Distill off at a constant rate. At the same time Removal by distillation, a further 100 parts of 1,2-dichloroethane were added. The reaction mixture was filtered; then the solvent was removed to give 1.1 parts of a syrupy residue. This

709807/1182

Residue was dissolved ± n 150 parts of methanol and with a Solution of 1.1 parts of potassium bicarbonate in 50 parts of water treated. The reaction mixture was purged with nitrogen and then allowed to stand at room temperature for 5 days. The solution was concentrated to remove methanol, then the aqueous phase was repeatedly extracted. the Fractions containing the desired glucoside were pooled and subjected to preparative liquid chromatography Pressure cleaned; 0.05 parts of 4- (4-hydroxy-2,6,6-trimethyl-i-cyclohexen-1-yl) -but-2-en-4-one-β-D-glucoside were obtained (Ge

1 T
total yield $ 13). The 13 C NMR spectroscopic data of this material are given in Table II.

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TABLE 2

13 C NMR spectroscopic data of the chemical shift for synthetic 4- (4-hydroxy-2,6,6-trimethyl-i-cyclohexen-1-yl) -but-2-en-4-one and its corresponding β-D-glucoside

Carbon number Aglycon Glucoside Ring 6 36.If 34.6 5 47.9 44.6 If
3
2 64.9
41.0
140.1 under the
solvent
138.3 1 128.2 127.2 Page 4
ten- _
chain·*
2 201.8
134.6
146.3 199.6
133.1
146.2 1 18.3 17.3 2 methyl 21.3 22.5 6.6-like ( 29.1 28.it Dimethyl * 29.6 28.O

Aglycone and glucoside spectra were recorded in CDC1 "and D ^ -DMSO measured.

709807/1182

Claims (1)

Pat exempt Substance in concentrated form, consisting essentially of a glycosyloxy derivative of a 4- (2,6,6- Trimethylcyclohexan-1-yl) butane compound of the formula in which either the carbocyclic ring or the four-membered side chain or both are unsaturated, and the molecule can carry a keto group and / or a hydroxyl group as additional substituents. 2. Substance according to claim 1 in concentrated form, consisting essentially of a glycoside of the formula in which the ring A has a double bond optionally in the positions indicated by dashed lines and the four-link side chain a double bond optionally in the positions indicated by the dashed lines 709807/1182 where one of the radicals R and R. is a glycosyloxy group (OX), in which X is a mono- or disaccharide radical, in which II, R and R. each independently
of each other are -H, = 0 or -OH (provided that R
and R. are not simultaneously = 0), and Rx- for -H, -OH
or nothing stands. 3. Substance according to claim 1 in concentrated form, consisting essentially of a glycoside of the formula OY in which at least one of the groups Y is the remainder of a mono- or disaccharide and the other is optionally hydrogen can be. 4. Substance according to claim 1, in which the glycosyloxy compound is derived from a hexose. 5. Substance according to claim 4, in which the glycosyloxy compound is a glucoside. 6. Substance according to claim 5, in which the glycoseloxy compound is a β-D-glucoside. 7. Substance according to claim 1 containing a glycosyloxy compound the formula 709807/1182 in which G stands for a ß-D-glucosyl group, 8. Substance according to claim 1 containing a glycosyloxy compound the formula 1st floor in which G stands for a ß-D-glucosyl group. 9. Substance according to claim 1 containing a glycosyloxy compound according to formula in which G stands for a ß-D-glucosyl group , 7098 07/1182 10, substance according to claim 1 containing a glycosyloxy compound according to formula in which G stands for a ß-D-glucοsylgruppe. 11. Substance according to claim 1 containing a glycosyl oxy compound according to formula in which G stands for a ß-D-glucosyl group. 12. Substance according to claim 1 containing a glycosyloxy compound according to formula in which G stands for a ß-D-glucosyl group. 709807/1182 Substance according to claim 1 containing a glycosyloxy compound according to formula in which G stands for a β-D-glycosyl group. 14. Substance according to claim 1 containing a glycosyloxy compound according to formula ■ OH in which G stands for a ß-D-glucosyl group « 15 · Substance according to claim 1 containing a glycosyloxy compound according to formula 1st floor in which G stands for a ß-D-glucosyl group. 709807/1182 16. Substance after. Claim 1 in essentially pure, colorless form. 17. Substance according to claim 1, characterized in that it enzymatically to an aglycon with a PMR spectrum with two characteristic 3 "proton singlets in the area from 0.95 to 1.3 ppm, based on teiramethylsilane, is hydrolyzable. 18. Smoking material containing tobacco, reconstituted tobacco or a tobacco substitute product or mixtures thereof with from 0.02 to 2 percent by weight added flavoring substance according to claim 1. 19. Smoking material according to claim 18 with 0.1 to 1 percent by weight added flavoring substance. 20. Smoking material according to claim 18 containing a tobacco substitute, in which the essential smoke producing ingredient is a modified carbohydrate. 21. Smoking material according to claim 20, in which the modified Carbohydrate is a cellulose ether. 22. The smoking material of claim 21, wherein the cellulose ether is sodium carboxymethyl cellulose. 23. The smoking material of claim 20, wherein the modified carbohydrate is a thermally degraded carbohydrate. 24. Smoking material according to claim 23> in which the thermally degraded carbohydrate is thermally degraded cellulose. 709807/1182 25 · smoking material after. Claim 18 with additional salary of protein with a ratio of protein to smoke-producing raw material in the range of 1: 1 to 1g6O, 26. Process for the preparation of a glycosyloxy derivative according to claim 1, characterized in that an O-acylglycosyl halide with a hydroxy derivative of a 4- (2,6,6-trimethylcyclohexan ~ 1-yl) butane compound the formula condensed, with either the carbocyclic ring or the four-membered side chain or both being unsaturated are, and the molecule as additional substituents a keto group or another hydroxyl « group, and by then the 0-acyl groups hydrolyzed to hydroxyl groups in the product. 27. The method according to claim 26, characterized in that tetraacetoxyglucosyl bromide is used as the O-acylglucosyl halide used. 28. The method according to claim 26, characterized in that a compound of the formula .. ^ R ·? ^R l used, in which the ring A has a double bond in 709807/1182 the optional ones through which knitted. Positions indicated by lines and the four-membered side chain have a double bond in the optional positions indicated by dashed lines, one of the radicals R ₂ , R 1 and R being a hydroxyl group and the others independently of one another -H, = 0 or -OH (provided that R and R. are not simultaneously = 0), and R ^ - stands for -H, -OH or nothing. PATENT LAWYERS BIPl! "IIM έ STa'p ^ pI- ^DtP '- ^ING - H- BOHR DIPL-IfW. S. STAEGER, DR. Rer. Nat. R. KNEISSL 709807/1182