CH621928A5 - Seasoning and/or aromatising agent - Google Patents

Description

The invention is explained in more detail with the aid of the following examples, examples 1, 2, 4-8, 10, 11 and 13-15 illustrating processes for producing betacyclohomocitral. Example 9 shows that dimethylformamide cannot be used in the oxidation of β-ionone with peracetic acid for the purposes according to the invention. Example 3 shows that a reaction without a buffer, e.g. Sodium acetate, does not lead to the desired result. Example 12 shows that if a-ionone is used instead of β-ionone, the desired a-ionone ester is not formed. Examples 16-30 show the usefulness of the beta-cyclohomocitral itself and the Damascol-beta-cyclohomocitral and damascenone-beta-cyclohomocitral mixtures.

All quantities and percentages are parts by weight,

if nothing else is said.

example 1

(A) Preparation of / 3-ionone esters from / J-ionone

The following components were added to a 2 liter reaction flask equipped with a stirrer, thermometer, reflux condenser, filling funnel and cooling bath:

(i) solution of 96 g / 3-ionone in 300 cm3 chloroform;

(ii) 30 g sodium acetate.

95 g of a 40% peracetic acid were then slowly added over one hour with cooling at 10 ° C. The reaction mass was stirred for a further hour at 10 ° C. and then the solution was slowly warmed to room temperature. The reaction mass was then poured into 11 water and the organic and aqueous phases obtained were separated. The aqueous phase was extracted with 100 cm 3 of chloroform and the organic phases obtained were combined. After evaporation of the solvent from the organic phase, 99.5 g of an oil were obtained, which was deactivated on 1000 g of aluminum chromatography, with 5% w / w water and eluted as follows:

Volume solvent fraction Amount of eluted cm3 solute g

1 750 hexane 8.0

2,500 hexane 7/31

Volume solvent fraction Amount of eluted cm3 solute g

5 3

300 hexane

13.5

4th

250 hexane

7.0

5

250 hexane

1.9

6

240 hexane

1.6

7

600 25% diethyl

10th

ether- 75% hexane

15.6

8th

600 diethyl ether

15.3

Fractions 1 to 4 consisted essentially of / i-ionone ester.

is The spectral data of a purified sample of this material (obtained by preparative gas chromatography and mass spectrography as well as IR and NMR spectra) confirm the structural formula (6).

20 (B) hydrolysis to form betacyclohomocitral from / 3-ionone esters 60.2 g β-ionone esters, fractions 1 to 4 from step (A), were made into 280 cm 3 of 10% potassium hydroxide solution (in a 50:50 water / methanol mixture ) added at room temperature and stirred for 30 minutes. Then 1000 cc of water was added to the reaction mass which was then extracted with three 250 cc portions of diethyl ether. The combined ether extracts were washed twice with two 100 cm3 portions of saturated sodium chloride solution 30, dried over anhydrous magnesium sulfate and evaporated. 53 g of an oil which was betacyclohomocitral was obtained.

The crude beta cyclo-homocitral was distilled at 2 mm Hg pressure and the fraction boiling at 70-80 ° C was collected. It was 35.6 g.

Gas chromatography analysis indicated a product purity of approximately 85%. A pure sample of the beta cyclo homocitral was obtained by preparative chromatography. The conditions were: a 10 'x V4 "10% water-soluble 40 polyethylene glycols, known under the WZ Carbowax 20M-filled column made of stainless steel at 220 ° C. Isothermal. 1).

45 Examples 2 to 10

The same process steps as in Example 1 were used in the following examples. They show the results. which occur when parameters of the oxidation reaction of β-ionone with peracetic acid are varied, for example with regard to the buffer, the solvent, the temperature, the presence of organic base and the ratio of organic alkanoic acid to peracetic acid. The percentages were obtained by gas chromatography analysis of the reaction mixture after 30 minutes and do not represent the yield of isolated material.

Example% enol% initial% secondary reactants and

No. ester material products reaction conditions

2 47 24 29 acetic acid (150 cm3)

Sodium acetate (20 g) β-ionone (30 g) 40% peracetic acid (30 g), temperature: 25 ° C

3 12 52 36 acetic acid (150 g)

ß-ionon (30 g)

40% peracetic acid (30 g).

Temperature: 25 "C.

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Example No.

% Enol ester

% Starting material

% By-products

Reactants and reaction conditions

40

52

31

49

36

29

26

30th

21st

10th

55

17th

Example 11

Production of beta-cyclohomocitral by H202 peroxidation of β-ionone 12 ml of 30% hydrogen peroxide were added to 20 g / 3-ionone in 100 ml of methanol. The solution was cooled to 15 ° C and 6 molar aqueous sodium hydroxide was added over 30 minutes. The reaction mixture was kept at 15 ° C., then allowed to warm up to 30 ° C. and kept at this temperature with cooling from the outside. The exothermic reaction lasted about 60 minutes. An examination by gas chromatography showed that some ß-ionone was still present in the reaction product. An additional 12 ml of 30% hydrogen peroxide and 18 ml of 6 molar aqueous sodium hydroxide were added over 30 minutes while maintaining the temperature at 250 ° C. The exothermic reaction again took about 60 minutes and during this time the temperature was kept at 30 ° C. The reaction mass was then poured into an excess of water (500 ml) and the product extracted with three 150 ml portions of diethyl ether. The combined ether extracts were then washed with two 150 ml portions of saturated sodium chloride solution and dried over anhydrous MgSO4. The solvent was evaporated, leaving 16.8 g of a crude oil. Examination of this oil by gas chromatography showed 22% betacyclohomocitral.

The desired product was prepared by preparative gas chromatography (in a 10 'x 1/4 "10% water-soluble polyethylene glycol. WZ Carbowax 20M-filled column

Cyclohexane (150 cm3) sodium acetate (20 g)

ß -ionon (30 g) 40% peracetic acid (30 g), temperature: 25 ° C acetic acid (150 cm3) potassium acetate (35 g)

/ i-Ionon (30 g) 40% peracetic acid (30 g), temperature: 25 ° C formic acid (150 cm3) potassium acetate (50 g)

ß-lonon (30 g) 40% peracetic acid (30 g), temperature: 25 ° C acetic acid (150 cm3) potassium acetate (35 g)

ß-Ionon (30 g) 40% peracetic acid (33 g), temperature: 25 ° C acetic acid (150 cm3) potassium acetate (35 g)

β-ionone (30 g) 40% peracetic acid (33 g), temperature: 50 ° C dimethylformamide (150 cm3) β-ionone (30 g) 40% peracetic acid (33 g), temperature: 4 days at 18 ° C acetic acid ( 450 cm3) potassium acetate (105 g)

ß-ionon (96 g)

40% peracetic acid (105 g), temperature: 25 ° C

40 stainless steel at 220 ° C isothermal).

The structural formula (1) was confirmed by IR, mass spectrometry and NMR analyzes.

Example 12 (Comparative Example) 45 Formation of α-ionone epoxide from α-ionone

The following components were introduced into a 500 ml flask equipped with a thermometer, stirrer, filling funnel and reflux condenser in the order given:

31

22

39

45

43

91

^ -lonone epoxy

28

50.

Components

amount

Acetic acid potassium acetate ss g-ionon

150 cm3 35 g 30 g

Then 33 g of 40% peracetic acid was added dropwise with stirring at 25 ° C over 45 minutes. The reaction was exothermic for one hour and then allowed to stand at room temperature for 15 hours.

The reaction mass was then poured into 500 ml of water and the product extracted with three 150 cm3 portions of diethyl ether. The ether extracts were combined and washed with two 100 cm3 portions of saturated sodium chloride solution and then dried over anhydrous magnesium sulfate. The oil obtained after stripping off the solvent was at 93 to 99 ° C and a pressure of

9

621 928

0.5 mm Hg distilled to give 28.3 g of a pure, colorless liquid.

The IR, mass spectral and NMR analyzes showed that the compound obtained was a-ionone epoxide of the formula (14).

5

EXAMPLE 13 Production of Betacyclohomocitral The following constituents were introduced into a 2 liter reaction flask equipped with a stirrer, thermometer, filling funnel and cooling bath in the order given: io

Ingredients quantities

Acetic acid potassium acetate ß-ionone

450 cm3 150 g 96 g

20th

Then 105 g of 40% peracetic acid was added dropwise with cooling while the reaction mass was kept at 25 ± 2 ° C for 2 hours. The reaction mixture was then stirred at 25 ° C for a further three hours. A slightly exothermic reaction was observed during the first hour.

The reaction mixture was then poured into 1000 ml of water and the product obtained was extracted with three 300 cm 3 to 25 volumes of diethyl ether. The ether extracts were combined and washed with two 150 cm3 portions of saturated sodium chloride solution. The washed ether extract obtained was evaporated to give 118 g of an oil. 30th

118 g of this oil were added to 400 cm 3 of 10% potassium hydroxide solution (50:50 mixture of water and. Methanol). The solution warmed slightly and was stirred for 45 minutes.

The solution was then poured into 500 ml of water and the mixture was extracted with three 250 cm 3 portions of diethyl ether. The diethyl ether extract was washed with 200 cm3 portions of saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. 89 g of a crude oil were obtained. This was distilled by in a 40 Vigreux distillation column at 70 to 75 ° C and 2.0 mm Hg pressure and gave 40.2 g of compound of formula (1) as determined by IR, NMR and mass spectral analyzes.

Example 14

Perpropionic acid was produced as follows:

A mixture of

45

160 ml propionic acid J herein as

1 ml of sulfuric acid (concentrated) J "Mixture A" 40 g 50% hydrogen peroxide J.

50

was left at room temperature for 20 hours.

The following compounds were introduced into a 500 ml reaction flask equipped with a stirrer and cooling bath: 55

140 ml propionic acid 75 g potassium acetate 60 g ß-ionone

I referred to herein as "Mix B" with water (three 100 ml portions) and then with a saturated sodium chloride solution (150 ml). The ether solution was dried over anhydrous magnesium sulfate and the solvent was evaporated. 78 g of a crude oil were obtained, which contained propionic acid and product. The crude product was hydrolyzed with a solution of 40 g of potassium carbonate in 300 ml of water by heating under reflux for 15 hours, with constant stirring. After cooling, the organic layer was collected and the aqueous layer extracted with 200 ml of diethyl ether. After the organic substances had been combined, the solvent was evaporated off, giving 57.5 g of an oil. This was distilled to give 19.5 g of beta cyclo-homocitral (yield: 37%).

Example 15

Performic acid was prepared as follows:

20 g of 50% hydrogen peroxide and 80 ml of formic acid were mixed with one another and this reaction mixture was left to stand at room temperature for 1 V2 hours.

The previously prepared performic acid was added dropwise over a period of 30 minutes to a mixture of 50 g of potassium acetate, 70 ml of acetic acid and 30 g of β-ionone. The mixture was stirred and the temperature was kept at 25 ° C. by external cooling. After the addition was complete, the mixture was stirred at 25 ° C for a further 90 minutes and then poured into 800 ml of water. This product was extracted with two 200 ml portions of diethyl ether, the combined extracts washed with two 150 ml portions of saturated sodium chloride solution and then dried. After evaporation of the solvent, 32.5 g of a crude oil remain. Gas chromatography showed:

4% compound of formula (1)

41% compound of formula (6)

32% compound of formula (4)

23% other products.

The following mixture was produced:

20 g of lithium carbonate, 200 ml of 50% aqueous methanol and then the crude enol ester added. This reaction mixture was then heated to 65-70 ° C until the hydrolysis of the enol ester to betacyclohomocitral was essentially complete. This was determined by gas chromatography. After adding water, the reaction mixture was extracted with three 200 cm 3 portions of diethyl ether. The combined ether extracts were washed twice with two 100 cm3 portions of saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated to give an oil, i. H. Obtain beta cyclo homocitral.

The crude product was distilled at 2 mm Hg pressure and the fraction boiling at 70 to 80 ° C was collected.

Gas chromatography analysis showed a purity of about 85%. A sample of pure beta cyclo homocitral was obtained by preparative chromatography. Formula (1) was confirmed by mass spectral, 1R and NMR analyzes.

Example 16 Raspberry Flavor The following basic mixture was produced for a raspberry flavoring:

Mixture A was added dropwise to this mixture B over 60 minutes and the reaction temperature was kept at 25 ± 2 ° C. by external cooling. After the addition was complete, the reaction mixture was stirred at 25 ° C. for a further 2 hours. 65

Then the reaction mixture was poured into 1000 ml of water and extracted with two portions of 250 ml of diethyl ether. The combined ether extracts were then first

Components

Parts by weight

Vanillin Maltol

Parahydroxybenzylacetone a-ionone (10% in propylene glycol) ethyl butyrate

2.0 5.0 5.0 2.0 6.0

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10th

Ingredients parts by weight

Ethyl acetate 16.0

Dimethyl sulfide 1.0

isobutyl acetate 13.0

Acetic acid 10.0

Acetaldehyde 10.0

Propylene glycol 930.0

Part A

Betacyclohomocitral was added to half of the above base mixture in an amount of 0.2%. This mixture was compared to the base mixture without beta cyclo-homocitral, with 0.01% (100 parts / mill.) In water and examined by a test bench committee.

It was found that the mixture containing betacyclohomocitral had a far more pleasant and better raspberry flavor than the preparation without this seasoning. It is the unanimous opinion of the committee that the chemical compound betacyclohomocitral rounds off the aroma, taste and fragrance, in short the spice, and contributes to a very natural, fresh aroma and taste, as can be found in ripe raspberries.

part B

Three portions of the above-mentioned basic mixture were made and the following compounds were added individually:

a. Damascenon, 0.01 parts / mill .;

b. Betacyclohomocitral, 0.1 parts / mill .; and c. Mixture of 0.01 parts / mill. Damascenon and 0.1 parts / mill. Betacyclohomocitral.

The mixture of damascenone and betacyclohomocitral as such is sweeter, fruity, fruity rose-like and more pleasant in taste and aroma than betacyclohomocitral or damascenone alone when the compounds are tested in a concentration of 10% in ethanol solutions.

The three blends were examined by members of an audit committee, each 100 parts / mill. in water. The majority of the committee members preferred the seasoning composition containing the mixture of damascenone and betacyclohomocitral and referred to it as the natural raspberry flavoring since it is the only composition that has the characteristic off-flavor note of ripe raspberries.

The addition of the mixture of damascenone and betacyclohomocitral to the base seasoning results in an unexpected and surprising effect, since only 50% of each of the constituents of the mixture are required to obtain the same level of taste and aroma notes that is expected if only the starting compounds even be examined organoleptically.

Similar results were obtained with the following weight ratios of Damascenon and Betacyclohomocitral:

Parts / mill. Parts / mill. Weight

Damascenon betacyclohomocitral ratio

0.05 1.0 1:20

0.15 1.0 1: 6.7

0.20 1.0 1: 5

0.25 1.0 1: 4

0.4 1.0 1: 2.5

0.6 1.0 1: 1.7

1.0 1.0 1: 1

Example 17

2 parts / mill. A 1: 1 mixture of damascenone and betacyclohomocitral was added to Burgundy ("Selected California", red wine from the Christian Brothers of Napa) and compared with an unseasoned wine by an examination board. The spiced wine was preferred because it had several top notes and a richer aroma, which gave the impression of a "round" and "aged" wine.

Example 18

A mixture of 3 parts by weight of betacyclohomocitral and 1 part by weight of damascenone was added to distilled white vinegar in an amount of 0.01% and compared in water (in an amount of 1%) with unseasoned vinegar. The seasoning mixture gave the distilled white vinegar natural top notes similar to wine vinegar and rounded them off, which improved the aroma and taste of this product.

Example 19 Part I.

(A) powder flavoring

20 g of one of the seasoning compositions from Example 16, Part A or Part B, each containing betacyclohomocitral, was emulsified in a solution of 300 g acacia resin and 700 g water. This emulsion was spray dried (using a Bowen Lab Model dryer: air flow with an inlet temperature of 260 ° C and an outlet temperature of 93 ° C and 50,000 rpm).

(B) paste mixture

The following mixture was then prepared:

Ingredients parts by weight

Liquid seasoning composition according to

Example 16 (Part A or Part B) 48.4

Silicic acid (manufactured and sold under the trademark Cab-O-Sil der

Cabot Corp., Boston) 3.2

Characteristics:

Surface area: 200 m2,

Nominal size of the particles: 0.012 / (,

Density: 0.01068 g / cm3

The silica was dispersed in one of the liquid seasoning compositions mentioned with vigorous stirring. 48.4 parts by weight of the powder prepared in part (A) of this example 19 were stirred into the resulting viscous liquid at 25 ° C. for 30 minutes. The result was a thixotropic paste that evenly gave off a seasoning.

Part II

chewing gum

100 parts by weight of chicle were mixed with 4 parts by weight of one of the seasoning compositions according to Part I of this Example 19 and then 300 parts of sugar and 100 parts of cereal syrup were added and the whole was mixed intimately. The chewing gum mixture was cut into strips. It had a pleasant, long-lasting raspberry taste.

Part III

Toothpaste

The following separate groups of mixtures were produced:

Group «A»

30,200 glycerin

15,325 distilled water

.100 sodium benzoate

.125 saccharin sodium

.400 stannofluoride

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

11

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Ci group "B" 12,500 37,200

Group "C" 2,000

Group «D» 1,200

100.00 (total)

Calcium carbonate dicalcium phosphate (dihydrate)

Sodium n-lauroyl sarcosinate (foaming agent)

One of the seasoning compositions from Part I

method

1. The constituents from group «A» were stirred in a vessel provided with a steam jacket and warmed to 71 ° C.

2. The mixture was stirred for a further 3 to 5 minutes until a homogeneous paste was formed;

3. The powders from group "B" were added to the gel and the whole was mixed to a homogeneous mass;

4. The seasoning compositions from group “D” and finally the sodium n-lauroyl sarcosinate (“C”) were added with stirring;

5. The slurry obtained was then mixed for 1 hour. The finished paste was homogenized and finally filled into a tube.

The toothpaste obtained in this way had a pleasant raspberry taste with constant strong intensity during normal use.

Example 20 Tobacco Composition A tobacco blend was made from the following ingredients:

Components

Parts by weight

Bright Burley Maryland Turkish

Sten (fire dried)

Glycerin

water

40.1 24.9

1.1 11.6

14.2 2.8 5.3

Cigarettes were made from this tobacco. The seasoning composition for this consisted of:

Components

Parts by weight

Ethyl butyrate ethyl valerate maltol

Cocoa extract Coffee extract Ethyl alcohol Water

0.05 0.05 2.00 26.00 10.00 20.00 41.90

Part A

This seasoning composition was added in an amount of 0.1% to all cigarettes made from the above tobacco blend. Half of the cigarettes were then 500 or 1000 parts / mill. Betacyclohomocitral, prepared according to Example 1 or 13, treated. These cigarettes and those without betacyclohomocitral were compared in pairs: it was found that the experimental cigarettes were more full, were smoother, richer, tobacco-like and less strict when smoking and had woody, damascenon-like notes.

The tobacco of the experimental cigarettes had a sweet, floral, fruity, earthy and fresh green note before smoking. All cigarettes were fitted with a 20 mm cellulose acetate filter.

5 Betacyclohomocitral, manufactured according to Example 1 or

13, enhances the tobacco-like taste and aroma and "gives the cigarette made with it a woody, damascenon-like note.

io part B

The tobacco wort described above was added in an amount of 0.1% to all cigarettes produced from the tobacco mixture mentioned. Half of the cigarettes were then at 250 or 500 parts / mill. treated with a mixture of 0.1 15 parts damascenone and 1 part betacyclohomocitral. These cigarettes were compared to unseasoned cigarettes.

The cigarettes containing the seasoning composition had more volume and were smoother, richer, 20 tobacco-like and less severe when smoked than the unseasoned cigarettes and had an intense woody and fruity note.

The cigarettes tested were all fitted with a 20 mm cellulose acetate filter.

The spice mixture of beta cyclo-homocitral and damas-25 cenon thus enhances the natural tobacco-like taste and aroma of a cigarette and gives it woody and fruity notes when smoking.

30th

Example 21 Petitgrain composition

Components

Parts by weight

Betacyclohomocitral, produced 35 according to Example 1 or 13 Linalool Linalylacetat Dimethylanthranilat Terpineol 40 Geraniol Terpinylacetat Geranylacetat Ocimen Limonen 45 Pinen Nerolidol

20 500 600 2 20 30 10 5 20 50 20 10

50

The Betacyclohomocitral gave the Petitgrain the necessary green, earthy note.

Example 22 Lily of the Valley Perfume The following ingredients were mixed:

55 components

Parts by weight of indole 2

Hexylcinnamyl aldehyde 400

Rhodinol 40

60 terpineol 30

Tetrahydro-2-pentylpyran-4-yl acetate 10

Cinnamyl acetate 5 4- (4-hydroxy-4-methylpentyI) -3-cyclohexene

1-carboxaldehyde 20

65 Hydroxycitronellal 280 absolute violet leaves (10% in

Diethyl phthalate) 4

Phenylethyl alcohol 45

621 928

12

Components

Parts by weight

Tetrahydromuguol n-undecylenaldehyde (10% in diethyl phthalate) n-decanal (10% in diethyl phthalate) n-nonanal (10% in diethyl phthalate) benzyl acetate

Dimethylphenylethylcarbinol p-t-butyl-a-methylhydrocinnamyl-

aldehyde

Methyl cinnamate (10% in diethyl phthalate) benzyl cinnamate

20 5 5 4 10 10

4 2 4

940

40 parts by weight of a 10% solution of betacyclohomocitral (according to Example 1 or 13) in diethyl phthalate were added to the above mixture. The beta cyclo homocitral improved the flower nuance and significantly increased the rose character of this lily of the valley fragrance.

In another experiment, 80 parts by weight of a 10% solution of the beta cyclo homocitral was added. The floral nuance was further improved considerably and the rose character was enhanced.

Example 23 Flower Perfume A mixture of

Ingredients parts by weight

Lavender, type Barreme 60

Linalool 370

Phenylethyl alcohol 500

Benzyl acetate 120

Linalyl acetate 520

Hydroxycitronellal 600 4- (4-hydroxy-4-methylpentyl) -

3-cyclohexene-1-carboxaldehyde 100

Eugenol 230

a -Isomethylionon 1000

Sandalwood oil 120

Ylang oil 50

Amborne Musk 100

Benzyl salicylate 1350 6-oxa-l, 1,2,3,3,8-hexametal-

2,3,5,6,7,8-hexahydro-lH-benze [fJ-indene 550 4'-t-butyl-2 ', 6'-dimethyl-3'-5'-

dinitroacetophenone 450 p-t-butyl-c.-methylhydrocinnamyl-

aldehyde 20

Diethyl phthalate 90

6230

35 parts by weight of a 10% solution of betacyclohomocitral (according to Example 1 or 13) in diethyl phthalate were added. This compound gave the mixture a rose effect, which was significantly enhanced by adding an additional 35 parts by weight of the 10% beta cyclo-homocitral solution. A further improvement in the rose effect was achieved by an additional 35 parts by weight of the solution.

Example 24

Scent of roses

Components

Parts by weight

Components

Parts by weight

Linalool

30.0

5 terpineol

30.0

Phenylethyl alcohol

12.0

Terpinenol

5.0

Linalyl acetate

1.5

Citronelly acetate

15.0

io geranyl acetate

10.0

Eugenol

30.0

Citral

15.0

Phenylethyl acetate

20.0

Rose oxide

8.0

15 Guaicol

30.0

Citronellyl

93.0

Nerylacetate

3.0

Clove bud oil

1.0

Cadinen

2.0

20 guaien

1.0

French resin turpentine

12.0

a -pin

1.0

purified myrcene

5.0

Lime

2.0

25 p-cymes

1.0

687.5

Part A

30 parts by weight of a 0.1% solution of betacycloho-30 mocitral in diethyl phthalate was added to a portion of the above mixture. This preparation had a much more lively rose top note than the mixture without beta cyclo-homocitral.

part B

35 To a portion of the above mixture was added 30 parts by weight of a 0.1% solution of betacyclohomocitral in diethyl phthalate and 15 parts by weight of a 0.01% solution of damascenone in diethyl phthalate. This preparation also had a much more lively rose top note and was 40 more fruity and richer when it dried out than the mixture without the addition of seasoning.

/

45

Example 25 Rose Essence The base substance was a mixture of the following

Components

Parts by weight

Phenylethyl alcohol as Geraniol Citronellol a-Ionon

Hydroxy-Citronellal

55

1040 390 390 130 130

2080

Rhodinol nerol

270.0 90.0

(A) 208 parts of 4-Damascol (2,5-dimethyl-5-phenylhexanone-4) were added to a sample.

(B) For a second sample, 208 parts of 4-Damascol 60 and 52 parts of a 10% betacyclohomocitral solution in

Diethyl phthalate added.

(C) To a third sample, 104 parts of 4-Damascol and 52 parts of a 10% betacyclohomocitral solution in diethyl phthalate were added.

65 (D) To a fourth sample, 208 parts of Damascol (2,5-dimethyl-5-phenylhexen-1-one-3) were added.

(E) To a fifth sample, 208 parts of Damascol and 52 parts of betacyclohomocitral were added.

13

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(F) To a sixth sample, 104 parts of Damascol and 52 parts of a 10% beta cyclo-homocitral solution in diethyl phthalate were added.

Betacyclohomocitral was found to significantly improve the character of roses when used with 4-Damascol (samples (B) and (C)).

The combination of betacyclohomocitral and Damascol in samples (E) and (F) intensified the rose character considerably.

Example 26 Preparation of Soap Compositions 100 g of soap chips were homogeneously mixed with 1 g of one of the seasonings according to the invention and examined. The results are summarized in the following table.

10th

Table 1

Seasoning composition result

Composition from Example 21 (Petitgrain)

Betacyclohomocitral

Composition from Example 22 (Lily of the Valley Perfume)

Composition from Example 23 (floral perfume) Rose fragrance from Example 24 (Part A)

Rose fragrance from example 24 (part B)

Mixture of Betacyclohomocitral and Damascenon:

(a) 1: 0.1 weight ratio

(b) 1: 0.2 weight ratio

(c) 1: 1 weight ratio

(d) 1: 1 weight ratio

(e) Weight ratio 2: 1 mixture of Damascol and Betacyclohomocitral:

(a) 2: 1 weight ratio

(b) Weight ratio 1: 1 mixture of 4-Damascol and beta cyclo-homocitral:

(a) 3: 1 weight ratio

(b) 4: 1 weight ratio

(c) Weight ratio 1: 1 rose essence from Example 25

(a) Sample B

(b) Sample C

(c) Sample E

(d) Sample F

excellent petitgrain character with green and earthy notes.

excellent woody, green, earthy aroma with a rose nuance. Lily of the valley character with excellent floral notes.

distinctive and strong rose aroma.

excellent rose aroma.

fruity rose aroma with earthy and green notes. Rose aroma with woody, green and earthy notes.

Rose aroma with woody, green and earthy notes.

Rose aroma with woody, green and earthy nuances.

Rose aroma with woody, green and earthy notes.

Example 27

Preparation of a wetting agent (cleaning agent) 100 g of cleaning agent powder were mixed homogeneously with 0.15 g of one of the compositions from Table 1. The aroma of the detergent mixture corresponded to the information of the respective seasoning composition.

Example 28

Preparation of a cosmetic powder 100 g of talcum powder was homogeneously mixed with 0.25 g of one of the seasoning compositions from Table 1. The fragrance and aroma of the powder corresponded to the information for the respective seasoning compositions.

Example 29 Perfumed Liquid Cleaning Agents Concentrated liquid wetting agents or cleaning agents were mixed 55 homogeneously with seasoning compositions according to Table 1, the addition amount of the seasoning agent being 0.10%, 0.15% and 0.20%. The mixtures had the specified aroma and fragrance notes, with higher concentrations increasing the intensity.

60 Example 30

Preparation of a colognes and handkerchief perfume The respective seasoning composition was added to colognes in a concentration of 2.5% in 85% aqueous ethyl alcohol and to a handkerchief perfume in a concentration of 20% in 95% aqueous ethyl alcohol. The result corresponded to the information in Table 1.

S

3 sheets of drawings

Claims (11)

621 928 2nd 1. The seasoning and / or flavoring agent, characterized in that it contains 2,6,6-trimethyl-l-cyclohexen-l-yl-acetaldehyde of the formula (1) with a peralkanoic acid of the formula (5) .0 R - C (5) \ (1) contains as a component. 2. Composition according to claim 1, characterized in that it also 2,6,6-trimethyl-l-crotonyl-l, 3-cyclohexadiene of the formula (2) 0-0 H in which R is the hydrogen atom or the methyl or ethyl group, the oxidation of the / 3-ionone (4) with the perloalkanoic acid (5) by mixing the components to form a / 3-ionone ester of the formula (6) QCY (6) (2) contains. 3. Composition according to claim 1 or 2, characterized in that it is also at least one PhenyI-C6 ketone of the formula (3) and hydrolyzing the enol ester (6) to form the compound of formula (1). 20 9. Process for the preparation of 2,6,6-trimethyl-l-cyclo-hexen-l-yl-acetaldehyde of the formula (1) 25th (1) (3) characterized by oxidation of / 3-ionone of the formula (4) 30th contains, in which the broken line represents a C-C single bond or a C-C double bond. 4. Composition according to one of claims 1-3, characterized in that it also contains at least one adjuvant. 5. Composition according to claim 4, characterized in that the adjuvant is at least one food flavoring additive from the following group: p-hydroxybenzyl acetone, malto], benzyl acetate, methyl cinnamate, geraniol, ethyl methyl phenyl glycidate, vanillin, methyl anthranilate, a-ionone, y- Unde-calactone, ethyl pelargonate, isoamyl acetate, acetaldehyde, dimethyl sulfide, isobutyl acetate, acetic acid, ethyl butyrate, diacetyl, anethole, cis-3-hexenol-l, naphthyl ethyl ether, ethyl acetate, isoamyl butyrate, 4-methyl acid, 2-methyl-2-p-2 Hydroxy-4-methylpentyl) norbornadiene, 4-allyl-l, 2,6-trimethoxybenzene and 4-propenyl-l, 2,6-trimethoxybenzoI. 6. Composition according to claim 4, characterized in that the adjuvant is at least one perfume auxiliary from the following group: natural or synthetic perfume oils, alcohols, aldehydes, ketones, esters and lactones. 7. Composition according to claim 4, characterized in that the adjuvant is at least one tobacco seasoning additive from the following group: ethyl butyrate, ethyl valerate and maltol. 8. Process for the preparation of 2,6,6-trimethyl-l-cyclo-hexen-l-yl-acetaldehyde of the formula (1) (1) characterized by oxidation of β-ionone of the formula (4) ÖC ^ (4) 35 with hydrogen peroxide, the oxidation of the / 3-ionone (4) with hydrogen peroxide by mixing the hydrogen peroxide with an inorganic base and the / 3-ionone (4). 40 10. Use of 2,6,6-trimethyl-l-cyclohexen-l-yl-acetaldehyde of the formula (1) 45 (1) to change the organoleptic properties of food, luxury goods or consumer goods. 50 (4) 55 From CH-PS 520 479 a compound also known as “damascenone” (see formula 2 of the formula sheet) with organoleptic properties is known which make damascenone suitable as a seasoning and flavoring agent or as a component of such agents. 60 It has been found that a new compound, namely 2,6,6-trimethyl-l-cyclohexen-l-yl-acetaldehyde of the formula (1) given below, is also referred to below as / 3-cyclohomocitral or betacyclohomocitral referred to, alone or optionally together with compounds such as 2,5-di-65 methyl-5-phenyl-hexen-l-one-3 ("Damascol", formula 3b), 2,5-dimethyl-5-phenyl-hexanone -3 ("Damascol-4", formula 3a), 2,6,6-trimethyl-l- (but-2'-en-l'-oyl) -l, 3-cyclohexadiene ("Damascenon", formula 2) and / or with adjuvants for 3rd 621 928 Changing, modifying or enhancing the taste and / or aroma of consumables, such as foods, food condiments, perfume preparations, perfumed articles, tobacco, tobacco condiments, chewing gums and chewing gum flavors, is outstandingly suitable and new seasoning and / or flavoring agents in solid or liquid form and with offers fruity, woody or tea-like aroma or woody-tea-like and fruity-tobacco-like taste; Such agents are also suitable for or as perfume compositions with woody, camphor-like, green, earthy, flowery and rose-like fragrance notes, and for or as tobacco seasoning preparations with sweet, rich tobacco-like, flowery, fruity, green, woody, "damascenon-like" and earthy notes. The patent therefore relates to a seasoning and / or flavoring agent, which is characterized in that it contains 2,6,6-trimethyl-1-cyclohexen-1-yl-acetaldehyde (“β-cyclohomocitral”) of the formula (1) contains as a component. The patent also relates to the use of the compound of formula (1) to change the organoleptic properties of food, luxury goods or consumer articles including, for example, food products, chewing gums, medical products, perfume compositions, perfumed articles, colognes, tobacco and tobacco substitutes. With the agent according to the invention or through the use according to the invention, new perfume compositions and perfumes with very intense and nature-like rose fragrance notes as well as new perfumed articles with an intense rose aroma, which can optionally have woody, green and earthy notes, can be obtained, in particular by Use of mixtures which, in addition to the / J-cyclohomocitral (formula 1), contain at least one phenyl-C6-ketone of the formula (3). A compound of formula (3) is the 4-damascol already mentioned above (formula 3a, see formula sheet); Another compound of the formula (3) is the above-mentioned Damascol (formula 3b, see formula sheet). It was found that the organoleptic effect of the combination of one or both of the phenyl-C6-ke-tone (3) and β-cyclohomocitral (1) mentioned is stronger than the sum of the individual organoleptic properties of each phenyl-C6-ketone and des / 3-cyclohomocitral (1), ie that these preferred blends have a synergistic effect. Seasonings and / or flavoring agents according to the invention can be used for solid and liquid products to be seasoned. By using mixtures of / i-Cycloho-mocitral (1) and Damascenon (2), foods, chewing gums and medicinal preparations can create rose-like, fruity, woody and tea-like aroma notes and woody-tea-like and fruity-tobacco-like flavors, perfume compositions of rose-like, woody , camphor-like and so-called «green» notes are awarded; In addition, such mixtures can be used to impart sweet, rich tobacco-like, floral, fruity, fresh-green, woody and earthy notes to various types of tobacco. Even when ß-cyclohomocitral (1) and damascenone (2) are combined, the organoleptic effect of the combination is stronger than the sum of the organoleptic properties of the individual components. β-Cyclohomocitral is preferably obtained by an oxidation process, either (A) in a two-stage process, initially with / 3-ionone with peralkanoic acid of the formula (5) (see formula sheet), i.e. with performic acid, peracetic acid or perpropionic acid, preferably in the presence of buffer by preferably intimately mixing the components, oxidized to / ionic ion (formula 6, see formula sheet) and then this ester, e.g. B. with a base (aqueous or alcoholic), hydrolyzed to form the / j-cyclohomocitral, or after (B) a one step process; Here, / 3-ionone (4) is oxidized with hydrogen peroxide by mixing the hydrogen peroxide with an inorganic base and the / 3-ionone β-cyclohomocitral. Process (A) is preferably carried out without dimethylform amide. Surprisingly, the reaction according to (A) in the absence of dimethylformamide does not form the expected β-ionone epoxide, which has one of the formulas (11) or (12). As a buffer in synthesis (A) z. B. an alkali metal salt of a lower alkanoic acid or an alkali metal carbonate with a lower alkanoic acid, such as propionic acid, acetic acid or formic acid, can be used. The synthesis (A) is preferably carried out under the following conditions: (i) Temperatures between 15 and 75 ° C: lower temperatures slow the reaction, which moreover does not proceed completely; higher temperatures result in a lower yield and significantly higher proportions of by-products. The most appropriate temperature is around 25 ° C. (ii) A small molar excess (e.g. from about 10 to 15%) of peralkanoic acid, especially peracetic acid; this enables a slightly higher yield; a large excess (about 200%), on the other hand, causes the formation of dihydroacetinodiolide of the formula (13) in an amount of about 30 to 35% yield if no buffer, for example potassium acetate, is present in the reaction mass. (iii) Potassium carbonate as a buffer instead of potassium acetate gives essentially the same yield; (iv) On the other hand, the yield becomes somewhat lower if sodium acetate is added as a buffer instead of potassium acetate; (v) If formic acid is used in the reaction mass instead of acetic acid, the yield is reduced; (vi) In this first oxidation reaction with alkanoic acids, any solvent inert to peralkanoic acids can be used. For example, cyclohexane or chloroform as a solvent has no noticeable effect on the yield; (vii) If no buffer is used, i.e. if the reaction is carried out under strongly acidic conditions, the reaction remains incomplete, the yield is reduced and a larger amount of by-products is formed: (viii) When using dimethylformamide as solvent, only β-ionone epoxide of the formula (12) is formed in an amount of about 70 to 75%, so that care must be taken to ensure that the reaction proceeds without dimethylformamide; (ix) The use of monoperphthalic acid (which is formed in situ from phthalic anhydride and hydrogen peroxide) gives 60 to 70% / 3-ionone epoxide. Perbenzoic acid also leads to the formation of the epoxide. It has been found that a percetic acid, such as peracetic acid, in a slight excess in the presence of a buffer system, preferably of acetic acid / potassium acetate, is a suitable route for the oxidation of / 3-ionone at 25 ° C. and for the formation of the corresponding enol acetate. The / j-ionone ester is preferably hydrolyzed with 10% alkali metal hydroxide (for example potassium hydroxide, lithium hydroxide or sodium hydroxide) mixed with 50% aqueous methanol. On the other hand, it is also possible to work under other mild hydrolysis conditions, such as aqueous potassium carbonate, sodium carbonate or lithium carbonate solution. The desired betycyclohomocitral is formed by this hydrolysis. The reaction product obtained is crude beta cyclo 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 621 928 4th mocitral. which can be purified by standard procedures, for example by preparative gas chromatography, extraction, distillation and the like methods. (B) When hydrogen peroxide (in the presence of an inorganic base) is used as the oxidizing agent, the beta-cyclohomocitral is formed from the / 5-ionone in one step. It works with an approximately 10 to 50% hydrogen peroxide. The inorganic base can be an alkali metal hydroxide or alkali metal carbonate, such as sodium, potassium or lithium carbonate, or sodium, potassium or lithium hydroxide. Sodium hydroxide is preferred. The molar ratio of hydrogen peroxide to β-ionone is about 1.1: Ibis 3: 1. The above methods are aimed at ß-ionon. Experiments have shown that when using a-ionone (instead of ß-ionone) epoxide is formed under the specified conditions and neither a significant amount of enol acetate nor isomers of betacyclohomocitral are obtained. With the 2,2,6-trimethyl-l-cyclohexen-l-yl-acetaldehyde according to the invention, which is referred to herein briefly as betacyclohomocitral, taste and aroma notes of a wide variety of products can be modified, changed, improved or even awarded and / or enhanced . The seasonings according to the invention have better spice properties than many of the known fruit and berry aromas and tobacco spices. In addition, the beta cyclo-homocitral according to the invention can be used to impart certain fragrance notes which are usually absent in many perfume substances, for example petitgrain fragrance, rose fragrance, lily of the valley fragrance and floral fragrance. Furthermore, mixtures of damascenone and 2,2,6-trimethyl-1-cyclohexen-1-yl-acetaldehyde (betacyclohomocitral) form a seasoning which is superior to known seasonings and is capable of imparting new flavors and aromas to these seasonings and of existing ones supplement or improve. This subheading includes fruit, wine and fermenting spices as well as tobacco spices. In addition, these mixtures are also suitable for perfumes or perfumed articles in order to give them missing scent notes, for example a rose scent. The weight ratios of damascenone to betacyclohomocitral can be 1:99 to 99: 1, but in practice a ratio of damascenone to betacyclohomocitral from about 1:20 to about 1: 1 is preferred. The most economical and organoleptically useful range is from about 1:20 to about 1:10. If betacyclohomocitral or mixtures of damascenone and betacyclohomocitral are used as seasoning additives for food, the nature of the other ingredients must also be taken into account when manufacturing the finished food. The terms "change" and "modify" as used herein mean that mild, relatively tasteless substances impart certain taste and characteristic aroma notes or that existing, but in a certain way insufficient, naturally or artificially produced spice notes are strengthened, or that an existing one is enhanced Spice note added and thereby the quality, character and / or taste of the product to be seasoned modified. The term “strengthened” means that one or more taste and / or aroma nuances that already determine the organoleptic impression of a product, such as food, tobacco, chewing gum, medical product, perfume composition or perfumed article, are intensified without, however, this Quality type of aroma or taste is changed. The term "food" includes both solid and liquid edible products that do not necessarily have to be nutritional. Such foods are soups, ready meals, beverages, dairy products, sugar confectionery, vegetables, grain products, non-alcoholic beverages, small snacks and the like. “Chewing gum” is understood to mean a product which consists of an essentially water-insoluble, chewable, plastic gum base, such as chicle or a substitute, such as io Jelutong, guttakay gum and / or certain natural or synthetic resins or waxes and plasticizers, such as glycerin and consists of a seasoning. Betacyclohomocitral or a mixture of this compound with damascenone is suitable as a seasoning. Other ingredients are natural or artificial sweeteners and possibly other additives. The term “medical preparations” encompasses both solid and liquid products to be taken orally, for example cough syrups, cough drops, toothpastes, aspirin and 20 chewable medical tablets. Substances that can be used as additives or seasoning aids are known and are sufficiently described in the relevant literature. They are “edible” and are neither toxic nor harmful in any other way. 25 However, it is also important that such additives are organoleptically compatible with betacyclohomocitral or with mixtures of damascenone and betacyclohomocitral. Furthermore, these additives must be inert to Damascenon 30 and Betacyclohomocitral under storage conditions and when used at room temperature. In the broadest sense, such additives, which can generally be referred to as seasoning auxiliaries or carrier substances, include stabilizers, thickeners, wetting agents, conditioning agents and other seasonings and seasoning enhancers. The seasoning adjuvants can be either solid or liquid, their consistency depending on the desired state of matter of the end product. In any case, they must be such that they are homogeneously dispersible or miscible with the beta cyclo-homocitral or its mixture with Damascenon. The selection and the proportions of the seasoning auxiliaries depend on the desired organoleptic character of the end product. The amount of beta cyclo-homocitral used or its mixture with damascenone can vary within a relatively wide range and depends on the desired organoleptic effects depending on the nature of the product. Larger quantities are needed where the food to be seasoned is relatively mild. On the other hand, comparatively small amounts are sufficient if the natural taste and aroma of the substances to be seasoned is inadequate and should only be intensified. The addition of the seasoning must be coordinated, since an insufficient amount does not give the desired result, 55 while an excessive amount causes unnecessary costs and in extreme cases disturbs the taste-aroma balance. A rule for the amount to be used cannot be given, but must be determined on a case-by-case basis. 60 In general, the amounts of betacyclohomocitral or its mixture with damascenone in food are in the range of 0.2 parts / mill. up to about 50 parts / mill. based on the total weight of the composition. Concentrations over 50 parts / mill. in most cases 65 do not have an improving effect on the organoleptic properties. It is where betacyclohomocitral or its mixture with damascenone is added to the food as an integral component of a seasoning composition 5 621 928 it is important that the total amount of the seasoning according to the invention is present in a sufficient concentration in the food. Seasoning compositions for food produced according to the invention contain the beta-cyclohomocitral or its mixture with damascenone in concentrations of about 0.1 to 15% by weight, based on the total weight of the seasoning composition. The seasoning mixes or seasoned products can be produced according to conventional working methods, as are known in batter making and in the fruit beverage industry. In general, the ingredients are simply mixed in an appropriate mixer to obtain the desired consistency, homogeneity of the dispersion, etc. On the other hand, seasoning compositions in the form of comminuted solids can be produced by mixing betacyclohomocitral, or its mixture with damascenone, with, for example, gum arabic, fragant gum, and the like, and then spray drying. Prefabricated seasoning mixtures in powder form, for example fruit-spicy powder mixtures, are prepared by mixing the dried solids, such as starch, sugar and the like, with betacyclohomocitral or its mixture with damascenone, this mixture being mixed in a dry mixer until the required degree of uniformity is achieved. The following seasoning auxiliaries are suitable for combination with betacyclohomocitral or its mixture with damascenone: p-hydroxybenzyl acetone; Geraniol, acetaldehyde, maltol, ethyl methylphenyl glycidate, benzyl acetate, dimethyl sulfide, vanillin, methyl cinnamate, ethyl pelargonate, methyl anthranilate, isoamyl acetate, isobutyl acetate, a-ionone, ethylbutyrate, ethyl acetate, ethyl ethylactyl ethyl acetate, ethyl ethylactyl ethyl acetate Hexenol-l, 2-methyl-2-pentenoic acid, elemecin (4-allyl-l, 2,6-trimethoxybenzene), isoelemecin (4-propenyl-l, 2,6-trimethoxybenzene), and 2- ( 4-hydroxy-4-methylpentyl) norbornadiene. The seasonings according to the invention are also suitable for improving the organoleptic properties of smoking tobacco and the additives provided therefor. The production of smoking tobacco improved in this way is simplified compared to conventional methods, so that certain problems that have arisen up to now are eliminated, specifically when certain wood-spicy characteristics of natural tobacco are to be produced or improved. With the seasonings according to the invention, the seasoning character can easily be checked and kept at the desired uniform level, irrespective of the differences and variations of the tobacco components in the mixture. In addition, tobacco additives can also be produced by improved processes, giving the tobacco products desired wood-spicy characteristics with sweet, floral, fruity, earthy and green notes, which can be varied slightly and kept at a uniform level. An aroma and seasoning additive is added to the smoking tobacco or a corresponding substitute (for example dried lettuce leaves), which as active component contains either (i) betacyclohomocitral alone or (ii) a mixture of damascenone and betacyclohomocitral. In addition to betacyclohomocitral or its mixture with damascenone, other seasoning and aroma additives can be added to the smoking tobacco or its substitute either separately or together with the seasoning according to the invention. Such additives are: I. Synthetic substances: ß-ethyl cinnamaldehyde, eugenol, dipentene, damascenone, maltol, ethyl maltol, ó-undecalactone, ó-decalactone, benzaldehyde, amyl acetate, ethyl butyrate, ethyl valerate, ethyl acetate, 2-hexenol-l, 2-methyl-5-isopropyl-l, 3-nonadien-8-one, 2,6-dimethyl-2,6-undecadien-10-one, 2-methyl 5-isopropylacetophenone, 2-hydroxy-2,5,5,8a-tetrame-thyl-l- (2-hydroxyethyl) -decahydronaphthalene, Dodeca-5 hydro-3a, 6,6,9a-tetramethyl-naphtho- (2, Ib) -furan, 4-hydro-xyhexanoic acid, gamma-lactone, polyisoprenoid hydrocarbons, described in Example V of US Pat. No. 3,589,372. II. Natural oils: celery seed oil, coffee extract, bergamot oil, cocoa extract, nutmeg oil, dosten oil. A flavor and seasoning concentrate containing betacyclohomocitral or a mixture of damascenone and betacyclohomocitral and, if desired, one or more of the additional seasoning additives mentioned above can be added to smoking tobacco, the filter or the sheet or paper wrapper. The smoking tobacco can be shredded, pickled, packaged, or a mixed or some form of tobacco composition or a tobacco substitute (e.g., lettuce leaves) or mixtures thereof. The proportions of the seasoning additives can be varied according to the taste, provided that natural and / or sweet notes are to be improved or imparted. It has been found that satisfactory results are obtained when the weight ratio of the total of betacyclohomocitral or its mixture with damascenone is seen between 125 parts / mill. and 1500 parts / mill. (0.0125% to 0.15%) of the active components of the smoking tobacco. It has also been found that satisfactory results are obtained when the weight ratio of the total of betacyclohomocitral or its mixture with 30 damascenone as a seasoning is between 1000 and 10,000 parts / mill. (0.10% to 1.5%). The seasoning can be incorporated into the tobacco product in any conventional manner. For example, betacyclohomocitral or its mixture with damascenone alone or together with other seasoning additives is dissolved in an appropriate solvent, such as ethanol, pentane, diethyl ether and / or other volatile organic solvents. The solution obtained is either distributed over the prepared tobacco or the tobacco is immersed in the solution. 40 Under certain conditions, the corresponding solution can be applied to the wrapping paper or wrapping sheet of the smoking product by means of applicators, such as a brush or a roller, or either sprayed on, or immersed or coated on the filter. 45 Furthermore, it is possible to treat only a part of the tobacco or the substitute and the tobacco so seasoned can be mixed with other tobacco components before the end product is produced. In these cases, the treated tobacco portion contains an excess of seasoning, the concentration being selected so that the stated percentages of seasoning are present in the end product. According to a particular example of the invention, an aged, pickled and chopped house tobacco is coated with a 10% ethyl alcohol solution of a 1: 1 mixture of Dass mascenon and betacyclohomocitral in an amount sufficient to obtain a tobacco composition that is 400 parts / mill. , based on the weight of the betacy clohomocitral damascenone mixture on a dry basis. The alcohol is then removed by evaporation 60 and the tobacco is processed into cigarettes by conventional working methods. A cigarette produced in this way has a desired and pleasant aroma which can be recognized in the main and side streams when smoking. This aroma can be described as sweet, rich, less severe, more tobacco-like and has excellent woody, "cigarette box" notes. Another preparation is that an aged, pickled and shredded house tobacco with a 20% 621 928 6 Ethyl alcohol solution of Betacyclohomocitral is coated in an amount that the tobacco composition contains 800 parts / ml, based on the weight of Betacyclohomocitral on a dry basis. The alcohol is then removed by evaporation and the tobacco is processed into cigarettes using conventional methods. A cigarette treated in this way has a desired and pleasant aroma, which is noticeable when smoking in the main stream and the secondary streams. This aroma is described as sweet, rich, less severe, tobacco-like with woody and damascenon-like notes. The seasonings according to the invention are particularly suitable for producing smoking tobacco, such as cigarette, cigar and pipe tobacco. However, other tobacco products made from covered or compressed tobacco dust or tobacco abrasion can also be treated successfully. Furthermore, the seasoning according to the invention can be added to the filter tip material, the seam paste, the packaging material and the like substances which are used in the preparation of a smoking article. Certain tobacco substitutes of natural or artificial origin (e.g. dried lettuce leaves) and other than smoking tobacco can also be improved with the seasoning. Another group of products that can be improved with the seasonings according to the invention are perfumes and perfume articles. Betacyclohomocitral can be mixed with one or more perfume additives, for example alcohols, aldehydes, nitriles, esters, cyclic esters and natural essential oils, so that the combined fragrance notes of the individual components result in a pleasant and desired fragrance, in particular flowers, roses, Lily of the valley or petit gray scent. Such perfume compositions usually contain (a) the main note, flower or the "bouquet" or the cornerstone of the composition; (b) modifiers that round off and accompany the main note; (c) fixatives, which include fragrance substances that give the perfume a special note during all stages of evaporation, and substances that delay evaporation; and (d) top notes, which are usually low-boiling, freshly scented substances. In perfume compositions, the individual components contribute their own olfactory characteristics, but the overall effect of the perfume composition is the sum of the effects of each individual component. For example, beta cyclo-homocitral can be used to alter the aroma characteristics of a perfume composition, for example, by exploiting or mitigating the olfactory response of another component of the composition. The effective amount of beta cyclo homocitral in perfume compositions depends on many factors, particularly on other ingredients present, their amount and the desired effect. It has been found that perfume compositions containing only 0.1% or less (e.g. 0.05%) betacyclohomocitral are already sufficient to give earthy, woody, green, floral and rose notes to soaps, cosmetic and other products to rent. In addition, it was found that perfume compositions with a content of only 0.05% betacyclohomocitral can be used to change, modify or modify earthy, woody, fresh green, floral and rose notes already present in soaps, cosmetic or other products to reinforce. The amount used can be up to 10% of the fragrance component and depends on the cost, the nature of the end product, the desired effect and the particular fragrance sought. The beta cyclo homocitral can be used either alone or in perfume compositions as an odor component in wetting agents and soaps, room sprays, deodorants, perfumes, colognes, toilet water, bath preparations such as bath oils and bath salts, hair preparations such as hair sprays, brilliantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions and sunscreens, powders such as talc, dusting powder, face powder and the like can be used. 1% betacyclohomocitral is enough to give petitgrain preparations a fresh green, earthy note, 4% betacyclohomocitral is enough to give rose or lily of the valley preparations a rose note or to intensify it. In general, no more than 10% betacyclohomocitral based on the final finished product is required for perfume compositions. Furthermore, a mixture of Damascol (phenyl-C6-ke-15 ton) and betacyclohomocitral and one or more perfume auxiliaries, for example alcohols, aldehydes, nitriles, esters, cyclic esters and natural essential oils, can be mixed in, so that the combined fragrances Individual components create a pleasant and desired fragrance, 20 especially and preferably in rose, lily of the valley and other «flower» fragrances. Of course, such additional auxiliaries must be organoleptically compatible with both the phenyl-C6-ketone and the beta-cyclohomocitral and must be inert to these compounds under the conditions of use at room temperature and storage conditions. As with the use of beta cyclo homocitral alone, the effective amount of the mixture of damascol and beta cyclo homocitral in perfume compositions depends on many factors, including other ingredients, their amount and effect. It has been found that an amount as low as 0.01% and even less (e.g. 0.005%) is sufficient to give a rose or lily of the valley fragrance to cosmetic or other products. The seasoning mixture can be added in an amount of up to 10%. The mixture of Damascol and Betacyclohomocitral can be used alone or in perfume compositions as an odor component in the same way and for the same cosmetic preparations and hygiene articles as Betacyclohomocitral 40. As an odor component, 1% of the Damascol-Betacyclohomocitral mixture is enough to give Petitgrain preparations a green, earthy note. Generally no more than 3% of the mixture, based on the final finished product, is required in the perfume compositions 45. It was found that Damascol (phenyl-C6-ketone): Betacyclohomocitral weight ratios of 1; 1 to 5: 1 can be used. In practice, ratios of about 2: 1 to about 4: 1 have proven to be expedient, so it is also possible to add one or more perfume auxiliaries to the damascenone and betacyclohomocitral mixture in order to achieve the desired fragrance. As already described above, such auxiliaries are, for example, alcohols, aldehydes, nitriles, esters, cyclic esters and natural ethereal oils. Of course, even in the case of the damascenone and betacyclohomocitral mixture, the amount effective in perfume compositions depends on many factors, for example those described above. In this case, too, it was found that 60 already 0.01% and even less (e.g. 0.005%) of the Damasce-non-Betacyclohomocitral mixture gave soaps, cosmetic or other preparations a rose aroma with earthy and fresh green notes . The addition of the seasoning can be up to 10%. 65 The Damascenon-Betacyclohomocitral mixture can also be used alone or in perfume compositions as an odor component in the preparation of the toilet, cosmetic and hygiene articles mentioned above. As a Ge 7 621 928 Fragrance components already suffice 1% of the Damascenon-Beta-cycIohomocitral mixture to give lily of the valley preparations an intense rose scent. Generally no more than 3% of the seasoning mix is required. The perfume or fragrance compositions may contain a carrier or nutrient for either (i) betacyclohomocitral alone or (ii) the phenyl-Q-ketone-betacyclohomocitral mixture, or (iii) the damascenone-betacyclohomocitral mixture. The carrier can be a liquid such as an alcohol, a non-toxic alcohol, a non-toxic glycol or the like. However, it can also consist of an absorbent solid, such as rubber (e.g. gum arabic), or a substance suitable as a capsule, such as gelatin.