DE2418335C2 - New cyclohexene-keto derivatives and their use for odor and aroma modification - Google Patents

Description

COCH ₃

COCH ₃

10

15th

If)

COCH ₃

COCH ₃

If)

2. The use of the connections of the Formulas Ia and / or Ib according to claim 1 for modifying the smell or aroma in perfumes, perfumed products, artificial flavors, foodstuffs, animal feedstuffs, beverages, pharmaceutical preparations or tobacco products.

30th

With regard to the flavoring of foodstuffs and tobacco products, special attention was given to it pointed out that it is of the utmost need for to find a substitute for certain compounds that are dangerous for the human and animal organism and that are contained in various aromatic compositions. Most developed countries today have regulations that prohibit the use of chemical additives in Food regulates. In addition, a list of those considered "dangerous" has been drawn up in many countries Connections Established therein are any use of these compounds as flavor-modifying Components prohibited in the manufacture of food or tobacco products

One of the numerous compounds identified in a number of scientific publications as a toxin defined and described is coumarin. For this reason it must not be used as a flavoring component in the above-mentioned products be used. The following references are given herein: J. Pharmacol. Exp. Therapy 118,348 (1956), Yakugaku Zasshi 83, 1142 (1963), Food cosmet Toxicol. 2,37.7 (1964) and 5,141 (1967), and Arzneimittel Forsch. 17.97 (1967).

In fact, coumarin is a natural component of certain plants, such as B. from Tonka beans, Lavender, woodruff and clover. All of these plant species contain a relatively high amount of coumarin Concentration. Coumarin has a bitter note, but its taste changes as soon as the called compound is tasted organoleptically in a diluted state and then a sweetish and has a grass-like aroma. In very strong dilution, coumarin develops a typical, fresh look mowed hay or even tobacco-like aroma. Because of its particular organoleptic properties, this compound was formerly widely used both produced as flavor-modifying ingredients can be.

The subject matter of the invention is defined by the preceding claims

One of the compounds claimed herein, namely 1. ^ dimethyl-cyclohex-S-enyl-methyl-ketone later also found in nature. It could be made from juniper oil (Juniperus Communis L.) with the help of a very complex and costly process. For this purpose, various fractional distillations were first carried out using a column with high Fractionation power, such as B. the spinning band column A fraction obtained thereby having a K.p. from 82-88 ° C / 13.3 mbar, which is practically only 0.1% the total weight of the treated material was then separated by column chromatography (silica gel-benzene / CHCh 1: 1) and the isolated cyclohexene keto derivatives by preparative Purified gas chromatography

The analytical data of the spectral analysis of the so obtained connection are listed here:

NMR: 1.3 (3H, s); 1. 66 (3H, broad); 2.15 (3H, s); 537

(IH, broad m) cfppM MS: M + - 152 (6); m / e: 137 (24), 109 (100), 95 (20), 81 (16), 67 (51), 55 (16), 43 (60), 41 (21).

The above compound is found in only one essential oil used as the starting material Concentration of about 0.001% by weight, i.e. only in extremely small amounts.

In view of its particularly interesting organoleptic properties, the above cyclohexene-keto derivative is found in pure form both in the Aroma as well as in the perfume industry a further area of application than the natural essential oil.

The new synthesis described below is from an industrial and economical point of view seen far more advantageous than the isolation process, in which the above keto derivative from natural Juniper oil was obtained. So today there is the option of a perfumer or aromatizer pure M-dimethyl-cyclohex-S-enyl-methyl-ketone for Available to sullen. This compound, as well as its isomer, the U-dimethyl-cyclohex-3-enyl-methyl ketone, can be described below without difficulty method illustrated.

Scheme A Manufacture of the Starting material:

3OCH ₃

COCH ₃

COCH ₃

The great advantage of the synthesis described above is that cheap and easily accessible starting material, namely 3- and * -Methyl-cyclohex-3-enyI-methyl-ketone made from isoprene and vinyl ketone to be able to use.

Scheme B

Invention:

Oa)

COCH ₃

If)

COCH,

20 The compounds Ia and Ib may be prepared in the same manner with a relatively high yield in a one-step synthesis according to the following reaction scheme.

: also ₃

COCH ₃

45

50

The compounds Ia and Ib were made more preparative by careful fractional distillation or by means of Gas chromatography separated from each other and obtained in pure form.

The method of preparation of the compounds Ia and Ib is described in detail below.

Scheme A

Production of the starting material
(see DE-PS 7 55 875 example 6)

a) 3- and 4-methyl-cyclohex-3-enyl-methyl-ketone.
A mixture of 34 g of isoprene and 35 g of methyl vinyl ketone was heated in a sealed tube for 1 h at 80 ⁰ C. The reaction mixture gave, after fractional distillation, 54 g (about 80%) of the desired product with the Kp of 82 ^e C / 133 mbar.

invention

b) 13- and M-dimethyl-cyclohex-S-enyl-methyl ketone.

5 g of the above mixture was a solution of 2.4 g of metallic potassium in 30 ml of anhydrous tert-Butanol added. After keeping the reaction mixture at room temperature for 15 min left, it was cooled to 10 ° C. and then 10.5 g of methyl iodide were added. That Whole was first refluxed and added to neutral with a further amount of Treated methyl iodide. After filtering, the reaction mixture became under reduced pressure evaporated, the residue obtained is diluted with ether, washed, dried and

COCH ₃

Qb)

finally evaporated by the generally conventional methods. Fractional distillation of the isolated product gave a 60:40 (parts by weight) (Ia: Ib) mixture of isomeric ketones (boiling point 82-84 ° C./133 mbar).
Their semicarbazone derivatives had a melting point of 146-148 ° C.

Pure 1 / ♦ -Dimethyl-cyclohex-S-cnyl-methyl-ketone was prepared by slow distillation in a reflux distillation process in a ratio of 14: 1 (boiling point 208-212 ° C./1.01 bar). The analytical data obtained in this way agreed with those of the naturally occurring compounds (see above).
Pure U-dimethyl-cyclohex-S-enyl-methyl-ketone was isolated from an enriched fraction by means of preparative gas chromatography. (PoIypropylenglykol -160 ⁰ C).

MS: M + - 152 (l); / 77 / e: 137 (5), 119 (3), 109 (100), 95 (10), 81 (10), 67 (40), 55 (12), 43 (37).

Scheme B

A mixture of 42 g of isopropenyl methyl ketone and 68 g of isoprene was added dropwise with stirring a cold (0-5 ⁰ C) suspension of tin chloride - added and benzene (SnCl 5 H2O). After stirring for 18 hours at room temperature, the reactin mixture was diluted with 500 ml of water and then extracted with ether. The organic phase obtained was first _{washed neutral with saturated aqueous NaHCO 3} solution and then with water. After drying and evaporation of the essential phase according to the generally conventional methods

20 g (26%) of the product, 90% of which consisted of the mixture of isomers described above, Κ, ρ. 82 ° C / 13.3 mbar).
If anhydrous tin chloride was used instead of tin chloride pentahydrate in the above synthesis, the same mixture of isomers was obtained in 60% yield.

b) A mixture of 49 g methyl isopropenyl ketone and 40 g of isoprene was heated hours in a sealed tube at 90 ⁰ C. 3 After cooling, the reaction mixture was fractionally distilled and then gave 25 g of a product (class 72-85 ° C./133 mbar) which consisted of 35% of the desired mixture of isomers. After repeated distillation of the product obtained, a pure mixture of 1,4- and l ^ -dimethyl-cyclohex-S-enyl-methyl-ketone (boiling point 84 ° C./133 mbar) in a ratio of 70:30 was found.
The isopropenyl-methyl-ketone used as the starting material in the above synthesis is a readily available commercially available compound.
The above-mentioned methyl-cyclohex-S-enylmethyl-ketone has valuable organolepsy properties that are reminiscent of some of the typical odorous and flavorful characters of coumarin. As has been found according to the invention, both isomers or even any mixture of the above ketones developed analogous organoleptic effects.

In particular, it has been found that the compounds Ia or Ib and any of these Compounds existing mixture in most cases successfully applied as a substitute for coumarin can be. Using the above products it is possible to produce various flavor determinants Notes, e.g. B. sweet, lactone-like, caramel-like and slightly grass-like, fatty or even woody Develop grades.

These fragrances were used to flavor solid and liquid foods such as syrups, Jams, milk beverages, puddles, ice cream or even baked goods and confectionery products from great benefit. In addition, the compounds Ia and Ib or any mixture consisting thereof can be used can be used to flavor various tobacco products.

This means that all products, such as coffee, tea or chocolate, are broadly defined as »food« meant.

The compounds Ia or Ib and any mixture consisting of these compounds are in the Perfume industry valuable odor-modifying ingredients and are used for the manufacture of concentrated or diluted perfumes, from perfumed products such as soaps, washing powders, waxes, cleaning agents or cosmetic preparations used In addition, those compounds find a special one Area of application for the reconstitution of certain essential oils such as B. Juniper Oil. In particular, the compounds Ia or Ib, as well as any of these compounds, can be used Mixture in this type of product is a grass-like, reminiscent of caraway or artemisia oil Develop grade.

The concentrations of the new compounds to be used in the preparations can vary widely Limits vary. They depend in particular on the nature of the flavored product and on the special organoleptic effects that one wishes to achieve. So you can z. B. interesting Flavor effects with amounts between 0.5 to 100 ppm, based on the weight of the to be flavored Product. Are the compounds Ia and Ib or any of these compounds Mixture used as a flavoring ingredient for the production of artificial flavoring preparations, so their proportion can be in a range between 1 and 10 or even from 15 to 20 wt .-%, based on the Total weight of the aroma composition.

V / ground the compounds according to the invention or any mixture consisting of these as Perfuming ingredients for making perfume compositions is used, you can achieve interesting odor-bearing effects with amounts between 03 to 10% of the total weight of the composition.

In all cases, depending on the particular odor-carrying effect that one is about desires to achieve, the ranges given above can be varied.

The present invention is illustrated in detail by the following examples

example 1

Z'vei base buttery nut type flavor compositions were prepared by mixing the following ingredients (Parts by weight) produced:

so The "test" basic composition stands in contrast to the "control" basic composition with a better defined one Karameil-like character as well as a fatty, sweet lactonic and woody note. in the On the whole, the two basic compositions of taste and aroma were those flavored with coumarin Similar products, but in contrast to these, lacked the typical properties of coumarin floral note.

Both mixtures A and B were then used to prepare the following preparations in the form below specified proportions, used:

Sweetened milk:

10 g of the flavoring composition per 1001

Ice cream:

10-15 g of the flavoring composition per 1001

A. B. (Test- (Control Comp.) Comp.) Methyl cyclopentenolone 50 50 Furfuryl alcohol 50 50 Furfural 10 10 Diacetyl 5 5 Acetyl methyl carbinol 30th 30th Benzyl alcohol 100 100 Propylene glycol 755 705 1,4-dimethyl-cyclohex- 3-enyl-methyl-ketone - 50 All in all 1000 1000

Cake: 20 g

the flavoring composition per 100 kg
Pudding:

10-15 G of flavoring composition per 100 kg ί

Chocolate:

25 g of the flavoring composition per

100 kg _{| 0}

Sweetened milk: a liquid food base was made by diluting 4 g of sugar in 100 ml Milk was made and then the aroma was added. π

Ice cream: A basic mixture of one liter of milk, 5 egg yolks and 250 g of sugar was prepared as follows: first the milk was warmed. Sugar and

Milk was then poured in while stirring. With further stirring the mass thickened and was finally frozen in the usual way.

Cake: The following ingredients were mixed with stirring: 100 g of vegetable margarine, 1.5 g of NaCl, 100 g of sugar, 2 eggs and 100 g of flour. After the aroma adding the flavored mass was 40 min. Baked in the oven at 180 ⁰ C.

Pudding: A mixture of 60 g sugar and 3 g pectin was stirred into 500 ml hot milk. This mixture was heated to the boil for a few seconds, whereupon the aroma was added and the mass was allowed to cool. ^j1

Chocolate: A commercially available chocolate mass was heated to 44 ° C. and then pumped through a heated pipe into a temperature control machine. In order to achieve the correct final temperature, the mass was first cooled slowly to 18-22 ° C, then cooled rapidly and finally reheated to 32-33 ⁰ C. After the flavoring had been added to the pasty mass, the whole was poured into molds and allowed to cool.

The foods flavored in this way were organoleptic by a panel of experts rated. All declared unanimously that all tasted flavored samples were opposed the unflavoured material with a more defined caramel-like note, which on the whole had a very pleasant lactone-like character.

Was used instead of l / l-Dimethyl-cyclohex-S-enylmethyi-ketone 13-dimethyl-cyclohex-3-enyl-methyl ketone or any of these compounds If an existing mixture is used, analogue taste effects are obtained.

Example 2

0.5 g of a 1% solution of 1,4-dimethyl-cyclohex-3-enyl-methyl-ketone in 95% ethanol was sprayed onto 100 g of a tobacco mixture of the "American blend" type. Then the so-flavored Tobacco "test" cigarettes are produced, the smoke of which is subjected to an organoleptic evaluation by a panel of experts was subjected. It was unanimously declared that the smoke of the "test" cigarettes compared to the Smoke from the "control" cigarettes whose tobacco had previously been treated with 95% ethanol. a had a sweet character and had a very pleasant grass-like note on the whole.

Similar effects were achieved as 1,3-dimethyl-cyclohex-3-enyl-methyl-ketone instead of M-dimethyl-cyclohexO-enyl-methyl-ketone or a mixture consisting of these compounds was used.

Example 3

By mixing the following ingredients (parts by weight) a basic perfume composition of an »Eau de Toilette« type was produced:

Methyl nonyl acetaldehyde 10 Undecanal 20th jO% 'ges absolute oak moss *) 40 Mnschus ambrette 30th Coumarin 50 Decanal 10 Sweet orange oil 40 Synthetic bergamot 160 Petitgrain Bigarade 100 Λ-iso-methylionone 100 Geraniol 40 Phenylethyl alcohol 60 Synthetic jasmine 50 Synthetic rose oil 50 10% muscon *) 50 Vetiver bourbon oil 50 Patchouli oil 30th Galbanum oil 20th Synthetic amber 10 Allspice oil 10 Benzyl alcohol 30th Methyl 3-oxo-2-pent-2-enyl- cyclo-pentyl acetate 10 all in all 970 *) In diethylphthalel

3 g of l ^ -dimethyl-cyclohexO-enyl-methyl-ketone were added to 97 g of the above basic composition, then the new perfume composition had a very natural and original grass-like character.

Similar effects were achieved when, instead of M-dimethyl-cyclohex-S-enyl-methyl-ketone, 1,3-dimethyl-cyclohex-3-enyl-methyl-ketone or a mixture consisting of these compounds was used.

Claims (1)

Claims; 1. 1,4- and / or l ^ -dimethyl-cydohex-a-enylmethyl-ketone of the formulas Ia and Ib Used for flavor modification and as a perfume ingredient It has now been found, surprisingly, that certain organoleptic notes of coumarin also well using at least one of the new cyclohexenketo derivatives of the formula Ia or Ib