CH549955A - Tobacco, food and beverages - aromatised by treatment with amides, esters, ketones and phenol derivs - Google Patents

Abstract

The organoleptic props. of tobacco and other prods. are improved or modified by adding (i) a cpd. of formula (I): R-C(O)NHR1 (where R and R1 are 1-6 alkyl or H); (ii) cycloaliphatic esters and ketones; (iii) phenol derivs.; (iv) heterocyclic ketones of formula (II): with a double bond in the posn. of 1 of the dotted lines, where X is H or OH if the double bond is in the ring, or O if the double bond is outside the ring; R2 and R3 are lower alkyl and Z is O or S; (v) caryophyllene derivs. or (vi) epoxy-beta-ionone, 6-methyl-hepta-3,5-diene-2-one, 3-isopropylcyclopent-2-ene-1-one, octa-3,5-diene-2-one, nonane-2,5,8-trione, 2-methyl-5-(alpha-methyl-alpha-hydroxyethyl)cyclohex-2-ene-1-one, or 4-methylthiobutan-2-one. Food, fodder, drinks and pharmaceuticals may be treated, as well as tobacco. The taste of tea, coffee and lime-flower tea can be modified; the additives may be used in meat, esp. smoked meat, and cocoa.

Description

  

  
 



   The present invention relates to a flavoring composition for strengthening, improving or modifying the organoleptic properties of tobacco.



   It is well known that the tobacco used for the manufacture of cigarettes is essentially composed of a mixture of different types of tobacco which thus give the smoke the particular flavor which is desired. Thus, ordinary cigarettes contain mixtures of tobacco from Virginia, Maryland or Kentucky and oriental or Turkish tobacco, the respective proportions varying according to the particular flavor desired. It is also common to use flavoring substances and humectants, in order to improve the aroma of said tobacco mixtures.



   One of the objects of the present invention consists of a composition intended to strengthen, improve or modify the organoleptic properties of tobacco smoke (natural tobacco or tobacco replacement product, of natural or synthetic origin), said flavoring composition being characterized by that it contains at least one of the compounds belonging to the group of the following alkyl derivatives: a) 3,5,5-trimethyl-2,3-epoxycyclohexa-1,4-dione cn



  b) 4,4, Strimethylcyclohexa-2,5-diene-2-ol-1-one c.n.



  c) 3,5,5-trimethylcyclohex-2-en-2-ol-1-one J. Org. Chem.



   24, 719 (1959)
 Following the designation of each product appears the literature reference mentioning a method for their preparation.



  In the case of new compounds, the synthesis methods are mentioned in the description which follows. Such compounds are designated by the abbreviation c.n. .



   The results of the organoleptic evaluation tests are given in the specific examples.



   Another object of the present invention relates to the use of the flavoring compositions defined above as agents for modifying the taste and aroma of tobacco smoke.



   The flavoring compositions which are the subjects of the present invention can be used in various forms. The nature, solubility and stability of their constituents will determine the form in which the composition is to be used. It is, however, preferable to use said compositions in the form of solutions. A suitable method of flavoring tobacco is by sprinkling the tobacco with an alcoholic solution of the flavoring product or composition. Mixtures of alcohol and propylene glycol can also be used as solvent.



   The proportions for the use of the alicyclic compounds mentioned in flavoring compositions. or the use of said compositions according to the invention, can vary within wide limits. These proportions vary according to the desired organoleptic effect and according to the origin of the tobacco to which the above-mentioned flavoring compositions are added. For example, interesting flavoring effects can be obtained with amounts of the order of 1 to 1000 ppm, amounts based on the weight of the alicyclic compounds mentioned in the finished flavored products. More particular effects, however, can be obtained with proportions of 5 and even 10%. Amounts of between 10 and 200 ppm are preferably used. In all cases, the limits given above can of course vary according to the flavoring effect sought.



   The present invention will be better illustrated by the following example.



  Example:
 7 g of a 1% solution of 3.5,5-trimethyl-2,3-epoxycyclohexa- 1, 4-dione in 95% ethyl alcohol were dispersed over 100 g of a mixture of tobacco of the American type blend. The tobacco thus flavored was then used for the manufacture of test cigarettes, the smoke of which was subjected to an organoleptic evaluation, after comparison of the latter with the smoke of control cigarettes, unflavored, the tobacco of which had been previously treated with 95% ethyl alcohol.



   The requested expert group unanimously declared that the smoke of the test cigarettes had a milder character and had a grassy note reminiscent of the taste of cigar smoke.



   Other samples were also evaluated according to the method of the example above. The following table gives the list of products thus evaluated and mentions the quantities used for the desired flavoring, as well as the developed flavor.



   Board
Compound Quantity [g] l Organoleptic evaluation2 a) 1.010.0 sweet, phenolic, flue-cured character, nutty, chocolate b) 7.0 sweet, oaky, anise note, more pleasant c) 1.010.0 sweet, grassy
 The amounts indicated refer to amounts of 1% alcoholic solutions (95% ethyl alcohol).



  2 The characteristics mentioned refer to the organoleptic properties of the compounds tested on tobacco and compared with unflavored tobacco.



   4,4,6-trimethylcyclohexa-2,5-diene-2-ol-1-one, a new alicyclic compound, can be prepared as follows:
 a) An equimolecular mixture of isophorone (13.82 g; 0.1 mol) and N-bromo-succinimide (17.80 g; 0.1 mol) in the presence of a trace of a, '-azodiisobutyronitrile a was refluxed in 500 ml of CCl4 for 15 min. After cooling, about 500 ml of petroleum ether (30-50 ° C) was added to the reaction mixture and the precipitated succinimide filtered off. Evaporation of the volatile parts gave 3,5,5-trimethyl4-bromo. crude cyclohex-2ene-one.



   NMR (CCl4): 1.16 (3H, s); 1.25 (3H, s); 2.11 (3H, s); 2.07 (1H, d,
J = 16cops); 2.53 (1H, d, J = 16 cps); 4.45 (1H, s); 5.78 (1H, s) 6 ppm.



   b) 43.4 g of 3,5,5-tnmethyl4-bromo-cyclohex-2-ene-one were added over 30 min to a solution maintained at 40 ° C of anhydrous trimethylamine-N-oxide (32 g) in 100 ml of anhydrous chloroform.



  The reaction was slightly exothermic and the temperature of the mixture was maintained at about 4550 ° C throughout the addition. After being kept at reflux for 20 min, the reaction mixture was cooled and poured onto 110 ml of H2SO4 diluted to 10%.

 

  The organic phase was then separated, washed with water (3x), 10% sodium carbonate (3x) and again with water (3x).



   Evaporation of the volatiles gave a residue which, on distillation, gave a product to eb. 47-60 C / 0.001 Torr. This product was taken up in petroleum ether (30-50 C), washed with a 5% aqueous solution of sodium carbonate (2 x) then with 2% caustic soda in water (5 x ). The caustic soda washes were acidified and immediately re-extracted with sulfuric ether.



   After washing, drying over MgSO4 and evaporation of the volatile parts, the ethereal extracts gave 8 g of crystalline product having a purity of 95%, according to the analysis carried out by gas chromatography.



   The following purification, carried out by sublimation at 70-80 "C / 10
Torr, gave 6 g of 4,4,6-trimethyl-cyclohexa-2,5-diene-2-ol-1 -one.



  The product gave a positive test by treatment with a solution of ferric chloride (violet blue coloration). F. 46 "C.



     IR (CCl4): 1630, 1650, 3440 cm-l
 UV: ta XH = 205, 249, 310 me = 5650, 7880, 2420 respective
 is lying)
 MS: M + = 152, m / e: 109
 NMR (CCl4): 1.27 (6H, s); 1.92 (3H, s); 5.97 (1H, pseudo d, J = about 2.5 cps); 6.34 (1H, m); 6.65 (1H, m); 8 ppm.



   Under the analytical conditions used, the structure of this compound was defined according to the formula
EMI2.1

 However, it is to be expected that under other conditions a keto-enolic balance will develop as follows:
EMI2.2

 keto-enol diketone
 If, instead of trimethylamine oxide, other oxides of a tertiary aliphatic or cycloaliphatic amine are used, analogous results are obtained. Likewise, as the halogenating agent, apart from the mentioned N-bromo-succinimide, halogenating agents capable of providing a positive halogen can be used.



   3,5,5-trimethyl-2,3-epoxy-cyclohexa-1,4-dione can be prepared as indicated below:
 2 ml of a 6N aqueous solution of NaOH were added over 15 min, at 15 ° C., to a mixture of 3.7 g of 3,5,5-trimethyl cyclohex-2-ene-1,4-dione and 8.3 ml of a 30% solution of hydrogen peroxide in 27 ml of methanol. The reaction mixture was then stirred for 3 hours at 20-25 ° C, then treated with water and extracted with l. 'ether. The combined organic extracts were washed with water until neutral, dried over MgSO4 and evaporated to dryness. In this way 3.33 g (82%) of the desired product is obtained, eb.



     40 "C / 0.001 Torr.



   IR: 1715cm-1; MS: M + = 168; m / e: 56
 NMR (CCl4): 1.05 (3H, s); 1.25 (3H, s); 1.50 (3H, s); 2.08 (1H, d,
J = 13 cps); 3.09 (1H, d, J = 13 cps); 3.47 (1H, s) 8 ppm.



   3,5,5-trimethylcyclohex-2-en-1,4-dione, used as a starting material in the above preparation, can be obtained according to the method described in Tetrahedron, Suppl. 8 / I, p. 1 (1966).

 

      CLAIM I
 Composition intended to strengthen, improve or modify the organoleptic properties of tobacco smoke, characterized in that it contains at least one of the compounds belonging to the following group of alicyclic derivatives: a) 3,5,5-trimethyl-2,3 -epoxycyclohexa-1,4-dione, b) 4,4,6-trimethylcyclohexa-2,5-diene-2-oî-1 -one, c) 3,5,5-trimethylcyclohex-2-en-2-ol -1 -one.



   CLAIM II
 Use of a composition as defined in claim I, as an agent for modifying the taste and aroma of tobacco smoke.

** ATTENTION ** end of DESC field can contain start of CLMS **.



   

 

Claims (1)

** ATTENTION ** start of field CLMS can contain end of DESC **. a purity of 95%, according to the analysis carried out by gas chromatography. The following purification, carried out by sublimation at 70-80 "C / 10 Torr, gave 6 g of 4,4,6-trimethyl-cyclohexa-2,5-diene-2-ol-1 -one. The product gave a positive test by treatment with a solution of ferric chloride (violet blue coloration). F. 46 "C. IR (CCl4): 1630, 1650, 3440 cm-l UV: ta XH = 205, 249, 310 me = 5650, 7880, 2420 respective is lying) MS: M + = 152, m / e: 109 NMR (CCl4): 1.27 (6H, s); 1.92 (3H, s); 5.97 (1H, pseudo d, J = about 2.5 cps); 6.34 (1H, m); 6.65 (1H, m); 8 ppm. Under the analytical conditions used, the structure of this compound was defined according to the formula EMI2.1 However, it is to be expected that under other conditions a keto-enolic balance will develop as follows: EMI2.2 keto-enol diketone If, instead of trimethylamine oxide, other oxides of a tertiary aliphatic or cycloaliphatic amine are used, analogous results are obtained. Likewise, as the halogenating agent, apart from the mentioned N-bromo-succinimide, halogenating agents capable of providing a positive halogen can be used. 3,5,5-trimethyl-2,3-epoxy-cyclohexa-1,4-dione can be prepared as indicated below: 2 ml of a 6N aqueous solution of NaOH were added over 15 min, at 15 ° C., to a mixture of 3.7 g of 3,5,5-trimethyl cyclohex-2-ene-1,4-dione and 8.3 ml of a 30% solution of hydrogen peroxide in 27 ml of methanol. The reaction mixture was then stirred for 3 hours at 20-25 ° C, then treated with water and extracted with l. 'ether. The combined organic extracts were washed with water until neutral, dried over MgSO4 and evaporated to dryness. In this way 3.33 g (82%) of the desired product is obtained, eb. 40 "C / 0.001 Torr. IR: 1715cm-1; MS: M + = 168; m / e: 56 NMR (CCl4): 1.05 (3H, s); 1.25 (3H, s); 1.50 (3H, s); 2.08 (1H, d, J = 13 cps); 3.09 (1H, d, J = 13 cps); 3.47 (1H, s) 8 ppm. 3,5,5-trimethylcyclohex-2-en-1,4-dione, used as a starting material in the above preparation, can be obtained according to the method described in Tetrahedron, Suppl. 8 / I, p. 1 (1966). CLAIM I Composition intended to strengthen, improve or modify the organoleptic properties of tobacco smoke, characterized in that it contains at least one of the compounds belonging to the following group of alicyclic derivatives: a) 3,5,5-trimethyl-2,3 -epoxycyclohexa-1,4-dione, b) 4,4,6-trimethylcyclohexa-2,5-diene-2-oî-1 -one, c) 3,5,5-trimethylcyclohex-2-en-2-ol -1 -one. CLAIM II Use of a composition as defined in claim I, as an agent for modifying the taste and aroma of tobacco smoke.