DE2700688B2 - Carbonyl compounds, processes for their production and their use as seasoning for food, beverages, tobacco and / or perfumery items - Google Patents

Description

wherein the group C = f represents a cycloalkyl or a cycloalkenyl group with 6 carbon atoms, which in 3-position is dimethyl substituted and either

1) R21 is hydrogen and R22 is a carbon atom, that by one or two allyl or meihallyl groups or a group of the general formula

fC — R ₃

Lh

is substituted, in which R24 is the ethyl or isobutyl group,
or

2) R22 the methyl group or hydrogen and R21 an allyl or methallyl group

or

3) C = f represent an acyclic hydrocarbyl group, in which case the compound Is 2,4,7-trimethyl-2,6-octadienal.

2. A method for producing a compound according to claim 1 by reacting a substituted one Halide or aldehyde with a carbonyl compound in the presence of a reaction accelerator, a base or boron compounds, characterized in that a compound of the general formula

Il

C H

H C

Il ο

with an aldehyde or an allyl or methallyl halide of the general formula R12X11 in the presence a tertiary amine, toluene, t-butanol or a crown ether and in the presence of a base or a boron oxide-boric acid mixture and a compound of the general formula

A / "

R ₂₁ C

wins, where the groups f = C in the 3-position are dimethyl-substituted and each represent a cycloalkyl or a cycloalkenyl group with 6 carbon atoms or an acyclic hydrocarbyl group, in which Xn
Ru

in which R24 is the ethyl or isobutyl group,

and when C = f represents an acyclic hydrocarbyl group, the compound 2,4,7-trimethyl-2,6-octadienal is obtained.

3. Use of the carbonyl compounds according to claim 1 as a seasoning for food, Beverages, tobacco and / or perfumery.

The invention relates to new carbonyl compounds of the general formula

μ wherein the group C = f is a cycloalkyl or a Represents cycloalkenyl group with 6 carbon atoms, which is dimethyl-substituted in the 3-position and either

1) R21 is hydrogen and R22 is a carbon atom, the v, by one or two allyl or methallyl groups or a group of the general formula

■ Es- ¹ -]

is substituted, in which R24 is the ethyl or isobutyl group is, or

2) R22 is the methyl group or hydrogen and R21 is one Allyl or methallyl group or

3) C = f represent an acyclic hydrocarbonyl group, in which case the compound 2,4,7-trimethyl-2,6-octadienal is.

The invention also relates to a process for preparing these carbonyl compounds by reaction a substituted halide or aldehyde with a carbonyl compound in the presence of a reaction accelerator, a base or boron compounds, which is characterized in that one compound of the general formula

, 0

with an aldehyde or an allyl or methallyl halide of the general formula Ri ₂ Xu in the presence of a tertiary amine, toluene, t-butanol or a Kronälher and in the presence of a base or a boron oxide-boric acid mixture and a compound of the general

my formula

R "

I. ο

R ₁ R ₂

wherein Ri or one or both R2 and / or Rj allyl or Methallyl and the other R groups are hydrogen. These compounds, the l-acetyl-3,3-dimethyI-cyclohexane derivatives of the formula mentioned are suitable as condiments and they improve or intensify Orange seasoning and give the aroma of pineapple, allyl caproat, galbaniim, wood, fat, sweetness as well of fruits, citrus fruits with green notes and have rose-like, ionon-like, oriental, woody, sweet, fruity, citrus-spicy characteristics, especially with food, chewing gum and medical products. They also modify and intensify perfumery items by adding them a sweet, earthy, animal, green, herbaceous, melon-like and fruity aroma with pineapple-like, amber-like, galbanum-like, ginger-like and citrus-like nuances as well as tobacco / animal notes to lend.

The compounds are made by reacting acetyl-S.S-dimethyl-cyclohexane with a methallyl halide or an allyl halide of the general formula R12X11 in the presence of a base such as alkali metal hydroxide or potassium t-butoxide and a reaction accelerator that contains a tertiary amine, toluene, t-butanol or a crown ether or mixtures thereof.

The properties of the reaction product depend essentially on the reaction accelerator used with regard to the isomer ratios of the reaction products.

When crown ether of the general formula

wins, the groups f = C in the 3-position dimethylsubstituieri and and in each case a cycloalkyl or a cycloalkenyl group with carbon atoms or acyclic hydrocarbyl group represent where

Xu chlorine or bromine,

Ri2 is an allyl or methallyl group or a group the general formula

wherein Z is Cj-C ₄ lower alkylene, for example methylene or ethylene, η is a number from 3 to S, P and Q are the same or different C1-C4 alkylene or o-phenylene groups, such as compounds of the general formula

in which R ^ _{4 is} the ethyl or isobutyl group,

and when C = f represents an acyclic hydrocarbyl group, the compound 2,4,7-trimethyl-2,6-octadienal is obtained.

The carbonyl compounds according to the invention are suitable as seasonings for foods, beverages, Tobacco and / or perfumery.

In general, it is the invention: L-dimensions Compounds around 1-acetyl-1 (methallyl or allyl) -3,3-dimethylcyclohexane and 1 - (2-methaIlyl- or allyl) -5-methyl-1-pentenoyl-S.S-dimethylcyclohexane the general formula

(Dibenzo-18-crown-6) are used as the accelerator, the reaction product essentially consists from products in which the methallyl or allyl substituent is in the "1" position on the ring, namely

Crown ether

MOH

wherein R _{4 is} methyl or hydrogen and M is an alkali metal Γι. However, when a phase shifter is used as a reaction accelerator, several by-products are formed:

Phase converter

I.

X MOH

R4

+ MX

wherein R _{4 is} methyl or hydrogen and X is chlorine or bromine.

If a tertiary amine, or toluene, or t-butanol is used as a reaction accelerator, it will run the reaction as follows:

R ₄

where R <methyl or hydrogen and X chlorine or bromine mean. Examples of suitable tertiary amines are trimethylamines, triethylamines, and dimethylaminoethyldimethylamine.

These process steps are carried out in an inexpensive solvent which is (a) opposite to the reaction system is inert and (b) also serves as a reaction accelerator. Such solvents are toluene, benzene, o-xylene, m-xylene, p-xylene, ethylbenzene, η-hexane, cyclohexane, Methylene chloride-o-dichlorobenzene, t-butanol and Crown ethers, such as dibenzo-18-crown-6.

A temperature in the range from about 10 ° C. to about 150 ° C., preferably from 50 ° to 120 ° C., is used. The reaction time is inversely proportional to the reaction temperature, with lower reaction temperatures require longer response times. It is therefore with a response time of about 30 minutes up to about 10 hours can be expected.

No matter which reaction accelerator is used is the molar ratio of 1-acetyl-3,3-dimethylcyclohexane to allyl halide or methallyl halide 0.5: 1.5 up to 1.5: 0.5. preferably 1: 1 up to about 1: 1.2.

The molar ratio of base to allyl halide or base to methallyl halide can range from about 0.75: 1 up to about 1.5: 1, preferably 1: 1 up to about 1.2: 1 vary.

The method is preferably carried out at atmospheric pressure as this is the most convenient working condition is. However, it is also possible to use lower or higher pressures without reducing the desired yield Product would be adversely affected.

The base used is critical and it will be sodium hydroxide, potassium hydroxide or potassium t-butoxide preferred.

According to the invention it has been found that with 1-acetyl-3,3-dimethylcyclohexane derivatives the formula

Carbon single bond or a carbon-carbon double bond and the other dashed line a carbon-carbon single bond and R means hydrogen or methyl, a new seasoning for solid and liquid foods. Kaiignmml · medical Products, toothpastes and seasonings was created for this, the sweet, fruity, raspberry-like, woody, cilron-like, spruce-like, ion-like, blueberry-like and flowery aronia characteristics as well as sweet, raspberry-like, lemon-like, sweet-fruity, Has berry-like, spruce-like, flowery, ionone-like and nut-meat-like seasoning characteristics. Perfume compositions, colognes and perfumed articles give the compounds fruity, woody, spruce-like aromas with floral nuances and light chocolate undertones.

The l-acetyl-SS-dimethylcyclohexane derivatives are produced by reacting l-acetyl-SS
hexane with an aldehyde of the formula:

C "

I.
R.

produced, being a compound of the formula

is obtained in which one of the dashed lines is a Carbon-carbon double bond and the other dashed line is a carbon-carbon single bond. It is made in the presence of an inorganic Base or a mixture of boric oxide (B2Ojj and boric acid worked. The product obtained is either known as such due to its organoleptic properties used or it is reduced with hydrogen and a compound of the formula

formed, in which R is hydrogen or methyl. The first reaction with aldehyde of the formula

wherein one of the dashed lines is a carbon is carried out at a temperature of about 20 ⁰ C up to about 160 ⁰ C, if the catalyst is an inorganic base, such as an alkali metal hydroxide, for example potassium hydroxide, sodium hydroxide and lithium hydroxide, or an alkaline earth metal hydroxide, such as barium

hydroxide or lithium hydroxide is used. When the catalyst is a mixture of boric acid (HBO ₃ ) and boron oxide, the reaction temperature is about 100 ° C to about 200 ° C.

The response time is inversely proportional to the Reaction temperature. If a mixture of boric acid and boron oxide is used, the reaction time will vary between 2 and 10 hours. At higher temperatures, the reaction time is about 1 to 8 hours.

When using an inorganic base, the molar ratio of inorganic base to 1-acetyl-3,3-dimethylcyclohexane from 0.1: 1 to 2: 1, preferably 1: 1. When using a mixture of Boric acid and boron oxide, the molar ratio of boron oxide to l-acetyl-S.S-dimethylcyclohexane varies from 0.5: 1 to at 1.5: 1, preferably 1: 1. The concentration of boric acid in the reaction mass can range from 1 g up to 80 g per mole of aldehyde of the formula

20th

vary.

In all cases the molar ratio of aldehyde the formula

30th

H: 1 -acetyl-B ^ -dimethylcyclohexane

The reduction to form the compound

10 is preferably in the presence of inert solvents such as isopropyl alcohol, at Hydrierdrucken of between 3.43 and bar, at temperatures between 25 ° and 15O ⁰ C and using hydrogenation catalysts such as 5% palladium-on-carbon, rhodium, platinum and Raney -Nickel. The reaction time varies inversely with the reaction temperature and pressure. Lower pressures and temperatures require a longer reaction time, which can vary from 1 hour to 5 hours.

The reaction sequence can be represented as follows:

O O

vary from 1: 1 up to about 3: 1, with a molar ratio of 2: 1 is preferred. Examples and organoleptic properties of Both reactions are preferably carried out in the presence of 40 compounds made by the above procedure

carried out an inert solvent.

Table I.

are given in Table 1:

Structural formula

Organoleptic properties: Seasoning fragrance

Mixture of l- (3,3-di- \ /
methylcyclohexyl) - / \

4-methyl-cis-2-penten-l-one, [j j

l - ^ - dimethylcyclohexyl) - \ / \ / V \ ^ methyl-trans-l-pentene, ([

1-one, and l- (3,3-dimethyl- O

cyclohexyl) -4-methyl-3-penten-1-one

Mixture of l- (3,3-di-

methylcyclohexyl) -cis-

2-penten-l-one, l- (3,3-di-

methylcyclohexyl) -trans-

2-penten-l-one; and

l- (3,3-dimethyl) -3-pentene-

S \ sweet, woody, raspberry-like, lemon and
spruce-like aroma with
sweet, raspberry-like and lemon-like spicy character at 1.0 ppm

fruity woody, spruce-like aroma with St. John's wort-like, floral nuances and a slight chocolate undertone

sweet, raspberry-like, fruity, spruce-like, flowery, iononic Aroma with sweet, sweet-voluptuous, raspberry-like, redberry, spruce, floral and iononic flavoring characteristics

sweet, fruity woody (spruce) with pineapple-galbanum, hexalone notes

continuation

Structural formula

Organoleptic properties: Seasoning fragrance

3,3-dimethyl-1 - (4-methylvaleryl) cyclohexane

sweet, straightened, blueberry-like, woody aroma character with sweet,
spruce-like, fruity,
nut meaty
Characteristics.

low-voiced, sweet,
woody somewhat chocolatey.

It was also found that the compound 1-butanoyl-3,3-dimethylcyclohexane the formula

with good success for new perfume compositions, colognes and perfumed items can be used to give them a fruity, berry and herbaceous flavor To give aroma with green and tobacco nuances.

This compound is preferably made by reacting 1-acetyl-S.S-dimethylcyclohexane with acetaldehyde produced in the presence of an inorganic base or a mixture of boron oxide (B2O3) and boric acid, being a compound of the formula

(Mixture of "cis" and "trans" isomers) and a compound of the formula

solvent worked. In the case of an inorganic basic catalyst, a solvent such as methanol, ethanol or isopropanol is preferably used.
The reduction to the connection

can be obtained. The product obtained is reduced with hydrogen and a compound of the formula

educated

The first reaction with acetaldehyde is carried out in the same way as with aldehyde

The reactions can be carried out with or without an inert solvent be performed. When using boric acid or boron oxide, preferably without solvent

it is expediently carried out in the presence of inert solvents, such as isopropyl alcohol. The hydrogenation pressures are in the range between 3.43 and 10.30 bar and the temperatures between 25 ° and 150 ° C. 5% palladium-on-carbon, rhodium, platinum and Raney nickel are suitable as hardening catalysts.

The reaction sequence can be represented as follows:

+ CH ₃ -C

Reducing agent

wherein one of the dashed lines is a carbon-carbon double bond and the other dashed line represents a carbon-carbon single bond

The compounds according to the invention which are suitable as seasonings can be used as such or together with other, per se known and commercially available seasoning auxiliaries can be used. Furthermore can they with carrier substances, stabilizers, thickeners, wetting agents, conditioning agents and the like be combined. They can be incorporated into a carrier by conventional methods e.g. by spray drying,

Drum drying or the like. They can be encapsulated in a capsule material or in the form of emulsions be prepared using emulsifiers. By means of such carrier substances, the desired physical form of the seasoning.

It has been found that good results are achieved when flavoring with compounds according to the invention if the end product contains an amount of about 008 ppm up to about 250 ppm, it being ι ο also depends on the special connection.

So are of 2,4,7-trimethyl-2,6-octadienal on addition to food in an amount of about 0.15 ppm up to 50 ppm and the Seasoning characteristics increased or modified. In some cases, an amount from about 0.2 up to effects 10 ppm in the end product, positive citrus-like flavoring properties.

In general, the amount of the 2,4,7-trimethyl-2,6-octadienal used can be over a wide range vary. About 1 to 80 or 90% of the total amount of seasoning can be added, with about 2% to about 20% have proven to be particularly favorable.

In terms of perfume properties, this compound has an excellent lemon-citrus character, which also gives them perfume preparations and essential oils.

The effective effective amounts of 1-acetyl-3,3-dimethylcyclohexane derivatives can range from 0.5 ppm up to about 100 ppm based on total product to be seasoned, vary.

Concentrations of l-acetyl-S.S-dimethylcyclohexane derivatives are suitable for seasoning foods from about 0.1% by weight up to about 15% by weight based on the total weight of a combined Seasoning composition.

It has also been found that an amount as low as 0.01% - or even less (e.g. 0.005%) - of one l-acetyl-S.S-dimethylcyclohexane derivative is sufficient, * o around perfumery items such as soaps, cosmetics or other preparations, green, fruity, aldehyde-like notes with nuances of galbanum, ginger and citrus.

Tobacco and tobacco products are obtained by adding the compounds according to the invention green, sweet, fruity, floral nuances reminiscent of Virginia tobacco, which are easily varied and controlled in order to obtain the desired uniform flavoring characteristics. For flavoring tobacco l-acetyl-S.S-dimethylcyclohexane derivatives are used in Amounts of between 250 ppm up to 1500 ppm (0.025% to 0.15%), based on the active ingredients, added and thus achieved good results. Furthermore, amounts by weight between 0.25% and 1.5% (2500 ppm to 10 000 ppm) have proven to be beneficial, when these are used alone as a condiment. The addition to tobacco can be in any conventional Way to be done. The compounds according to the invention are particularly suitable for seasoning of smoking tobacco, such as cigarette, cigar and pipe tobacco. But it can also be used for other tobacco products made from compressed tobacco dust or from tobacco substitutes be used. Filter tips, seam pastes, packaging material and the like can be seasoned with the compounds.

The invention is illustrated by a few examples

explained

S e i s ρ i e 1

Reaction:

CHO

CK ₂ Cl

CHO CHO

Into a 12 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and filling funnel a solution of 720 g of sodium hydroxide and 720 g of water was added. To this mixture were 800 g of cyclohexane and 50 g of tricaprylmethylammonium chloride were added. While stirring it was brought to a temperature heated between 75 and 80 ° C and a solution of 2000 g for a period of 6 hours 2-methylpent-2-enal and 2100 g of prenyl chloride were added. After these 6 hours the reaction mixture was at 75 to 80 ° C stirred for a further 4 hours. The organic layer was then separated off and washed neutral and the solvent removed. The oil obtained was after the addition of 82.0 g of Primol and Subjected 6 g of Ionox to a rapid distillation and obtained the following fractions:

fraction Steam temp. Flow. Temp. vacuum weight No. (° C) ( ⁰ C) mm Hg (G) 1 42-65 100-100 120-95 24.7 2 75 100 87 34.8 3 80 102 87 41.7 4th 87 102 75 82.7 5 90 102 64 94.9 6th 88 105 59 121.1 7th 94 114 58 133.8 8th 108 125 58 179.4 9 120 130 56 165.2 10 122 132 57 161.5 11th 124 134 57 199.5 12th 125 136 57 197.4 13th 127 139 57 182.3 14th 129 145 57 198.5 15th 133 157 57 173.1 16 144 185 57 165.8 17th 172 212 57 99.0 18th 179 215 55 35.1

Fractions 4 through 17 were pooled and placed on a 45.72 cm long, wire mesh-filled column distilled again after addition of 5 g of Ionox and 63 g of Primol. A reflux ratio of 9: 1 was established used The distilled fractions were as follows:

Fraction steam temp. Flow. Temp.Vacuum Weight No. (° C) (° C) mm Hg (g)

1 49-55 96-97 50 14.2 2 59 100 50 273 3 60 104 50 40.6 4th 60 109 50 455 5 66 120 50 85.6 6th 100 124 50 56.5

continuation

Fraction dump temp. Flow. Temp. Vacuum weight; No. (X) ("C) mm Hg (g)

7th
8th
9
10
11th
12th
13th
14th
15th
16
17th
18th
19th
20th
21

113 125 118 125 118 125 95-100 110 108 113 100 109 99 109 99 109 104 110 108 113 106 113 105 111 105 112 105 112 105 112

50

50

50

25-27

30th

26th

26th

26th

26th

26th

26th

26th

25th

25th

25th

27.0 27.5 89.4 22.0 51.8 74.9 79.0 73.0 63.1 83.8 73.4 82.3 82.4 83.5 89.7 14

Fraction steam temp. Flow. Temp. Vacuum Weight No. ('C) ("C) mm Hg (g)

5 23 24 25 26

10 28 29 30 105
105
107
112
114
116
124
140
147

116 119 124 131 145 170 192 216 250

25 25 25 25 25 20 20 15 15

98.4 92.0 91.1 92.8 91.5 48.6 365 31.8 2Z7

15th

20 Fractions 24 to 27 were collected and after addition of 10 g Primol and 0.3 g Ionox on a 12 "Vigreaux column provided with a heating jacket and fraction separator, distilled The data of the fractions were as follows:

fraction
No.

Steam temp. CQ

Flow. Temp.

ro vacuum
mm Hg

Weight (g)

Reflux ratio

1 83-85 98-98 15-14 2.0 14: 1 2 86 99 14th 9.0 14: 1 3 86 99 12th 10.5 14: 1 4th 86 99 12th 8.1 14: 1 5 86 99 12th 8.5 14: 1 6th 88 99 12th 14.4 14: 1 7th 85 99 12th 7.3 14: 1 8th 85 99 12th 6.2 14: 1 9 85 99 12th 11.3 14: 1 10 85 99 12th 11.3 14: 1 11th 85 99 12th 14.1 14: 1 12th 85 99 12th 15.4 14: 1 13th 85 102 12th 14.5 14: 1 14th 83-85 99-101 10-10 4.8 12: 1 15th 90 104 12th 8.3 12: 1 16 89 104 13th 9.9 12: 1 17th 82 104 12th 7.0 12: 1 18th 87 105 12th 12.8 12: 1 19th 90 105 11th 11.2 12: 1 20th 92 105 11th 9.6 12: 1 21 94 105 11th 8.6 12: 1 22nd 94 105 11th 11.9 12: 1 23 94 105 11th 15.8 12: 1 24 94 105 11th 16.9 12: 1 25th 94 105 11th 14.6 12: 1 26th 94 105 11th 15.8 12: 1 27 94 105 11th 14.4 12: 1 28 94 119 11th 8.4 12: 1 29 100 140 11th 5.7 12: 30th 108 220 11th 5.7 12: 1

Fraction 26 of the distillate was analyzed on a gas-liquid chromatography column (Conditions:

6.35 mm 3 m; 5% water-soluble polyethylene glycols; Column programmed at 10 "C / minute from 80-220 ° C) chromatographs and a major component of 90% purity determined. The NMR, mass spectrum and IR analyzes showed that this major component Was 2,4,7-trimethyl-2,6-octadienal.

The NMR S ⁿ ektrum for the fraction 26, the main peak is in F i g. 1 shown. The IR spectrum for fraction 26, main peak, is shown in FIG. 2 shown.

Example 2 Mandarin Orange Seasoning Composition

An orange seasoning was made by mixing the following ingredients:

16

Components

Parts had the formula

Natural orange oil

acetaldehyde

Ethyl acetate

Ethyl butyrate

Propanal

Trans-2-hexenal

Ethyl alcohol (95%)

Fusel oil

Propylene glycol

13.00 1.50 0.10 0.50 0.10 0.10

60.00 0.05

24.65

This mixture was designated as wort "A". A second mixture - wort "B" - was produced, by adding 2,4,7-trimethyl-2,6-octadienal, prepared according to Example 1 (1% in ethanol) to a portion of the Wort "A" was added.

Each seasoning mix "A" and "B" was made in an amount of about 57 g per 3.7851 from 32 ° Baume Sugar syrup is added to make a syrup that, when diluted with water, makes a drink with The drink added to the seasoning mixture "A" was an acceptable orange drink of good character, good flavor and intensity

The drink mixed with the seasoning mixture "B" had a much better orange character new tangerine, orange and lemon nuances.

Example 3

Production of 1-acetyl-3,3-dimethyl- (2-propenyI) -cyclohexane

Reaction:
O

Cl

NaOH

Tricaprylmethyl

ammonium chloride

toluene

To a slurry of lycyclohexane (462 g, 3 mol), granulated sodium hydroxide (180 g, 4.5 mol), tricaprylmethylammonium chloride (24 g) and toluene (200 g) were added over a period of 15 minutes with stirring and at a temperature from 70 ^° C. 222 g (3.8 mol) of allyl chloride were added. The mass was heated to reflux for 7/2 hours, at the end of which time the temperature rose to 83 ° C. After the mass had cooled, 1 liter of water was added with a stirrer. The organic phase of the reaction mixture was washed twice with water and distilled through a 30.48 cm χ 1.27 cm column which was filled with a wire mesh and equipped with an automatic reflux head. The reflux head was set at 19: 1 (85 ° C, 2.7 mm Hg). There were 275 g of a compound of the formula

Yield) and 147 g of 1-acetyl-S.S-dimethylcyclohexane.

If sodium hydride is used instead of sodium hydroxide, a compound of the form!

educated.

The NMR spectrum of the compound

is in Fig. 3 and its IR spectrum in FIG. 4 shown.

The NMR analysis is as follows:

Explanation

0.74 (s, 3) 0.90 (s, 3) 2.14 (s, 3) 4.8-5.1 (m, 2) 5.4-5.8 (m, 1)

Methyl groups "A"

CH3 group "B" CH ₂ group C

H _D

The IR analysis is as follows:

C = O; 1690 cm- ¹ .

C = C; 1660. The mass spectral analysis is as follows:

m / e = 95, 94, 69, 41, 109, 55, 194 (starting peak). The NMR spectrum for the compound:

obtained (56% conversion), 40 g of the compound

is in Fig. 5 shown. The NMR analysis is as follows

<5, ppm

Explanation

0.90 (s, 3) methyl groups "A" 0.93 (s, 3)

2.2 ^ 2.65 (m, 5) CH ₂ 's "B" and H _c

4.60-5.12 (m, 2) CH ₂ "D"

5.50 to 5.95 (m, 1) _E H

The mass spectral analysis is as follows:

m / e = 69, 111, 55, 41, 83, 139, 194 (starting peak). The NMR spectrum of the compound with the formula

O (stereo structure unknown)

(made using sodium hydride) is shown in FIG. 6 and the IR spectrum in FIG. 7 shown. The NMR analysis is as follows:

(Stereo structure unknown)

(5, ppm

Explanation

0.83-0.93

2.08 (d, 1) small link

Scattered Allyl H resonances

Methyl groups "A" J = (Hz) CH ₃ "B" Hd

The IR analysis is as follows:

1600 cm- ¹ ; C = C.

1700; C = O.
The mass spectral analysis is as follows:

m / e = 111, 69, 55, 41, 43, 57, 290 (starting peak).

Example 4

A perfume composition was prepared by mixing the following components:

by

Components

lot
(G)

n-decylaldehyde

n-dodecylaldehyde

Methylnonylacetaldehyde

Linalool

Linalyl acetate

Phenylethyl alcohol

Petitgrain SA

Bergamot oil

alpha-methylionone

l-acetyl-3,3-dimethyl- (2-propenyl) -

cyclohexane, prepared according to

Example 3
Cyclized bicyclo C-ΐ 2 compound,

produced according to Example 4 of

CA-PS 8 54 225 (20.10.70)
Isobornylcyclohexyl alcohol J.
Benzyl acetate
2 n-heptylcyclopentanone

0.5
50
70
100
20th
30th
25th
10

10

25th

353.3

This mixture has been evaluated and found to have a high level of body and aftertaste in its new natural amber quality. The basic composition can be mixed with aqueous Alcohol can be mixed, chilled and filtered to make a finished cologne. This has one Ambra aroma that tends towards a woody amber note. The basic composition can also be used for perfuming used by soap or other toilet articles, such as lotions, aerosols, sprays and the like will.

Example 5
Manufacture of a cosmetic powder preparation

In a ball mill, 100 g of talcum powder were mixed with 0.25 g of 1-acetyl-S.S-dimethyl-p-propeny ^ cyclohexane (Example 3) mixed. This powder mix had an excellent woody, earthy, amber flavor.

Example 6
Perfumed liquid detergent

Concentrated liquid detergents with woody, earthy and amber-like aromas (the detergents prepared from the lysine salt of n-dodecylbenzenesulfonic acid according to US Pat. No. 3,948,818 had been) containing l-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane (Example 3) produced by homogeneously mixing the two ingredients. By increasing concentrations of 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane the woody, earthy, amber aroma has been intensified.

Example 7

Making a cologne and
Handkerchief perfumes

1-Acetyl-3,3-dimethyl- (2-propenyl) cyclohexane (Example 3) were in a concentration of 2.5% 85% aqueous ethanol is added to a cologne. The concentration for the handkerchief perfume was 20% (in 95% aqueous ethanol). Both the cologne and the handkerchief

füm received a clear and definite woody, earthy, amber aroma.

Example 8

Making a cologne and a
Handkerchief perfumes

The compound 2-methyl-2-benzyl-pent-3-enal became a cologne at a concentration of 23% in 85% aqueous ethanol and one Handkerchief perfume was added at a concentration of 20% in 95% aqueous ethanol. The connection 1-Acetyl-33-dimethyl- (2-propenyl) cyclohexane in the compound of Example 4 gave a distinct and certain strong woody, earthy, amber aromas, both in the colognes and the handkerchief perfume.

Example 9
Manufacture of a soap composition

100 g of soap chips were mixed with 2 g of the compound from Example 4 until an essentially homogeneous one Mass was formed. The soap perfumed in this way had an excellent amber aroma with intense woody and earthy nuances.

Aroma notes and a sweet raspberry, raspberry seed-like and had sweet macho taste and mouthfeel. Properties that the basic mix lacked. From this it followed that the 1-acetyl-S ^ -dimethyl - ^ - propenyljcyclohexane rounds off the spice and contributes to a very natural fresh aroma and taste, as found in fully ripe raspberries. The seasoning mixture with the seasoning additive according to the invention is therefore much better than the basic mixture without additives.

Example 12
A powder-seasoning mixture

20 g of seasoning mixture from Example 22 were emulsified in a solution of 300 g of acacia and 700 g of water and the emulsion having a "Bowen" dryer (LabormodeU) (736 mV M in. Air and an inlet temperature of 260 ⁰ C, an outlet spray-dried at 93 ° C and a speed of 50,000 rpm.

B Persistent aromatic blend of spices
The following mixture was prepared

Example! 0
Preparation of a detergent composition

100 g of a detergent powder (lysine salt of n-dodecalbenzenesulfonic acid known from US-PS 39 48 818) were mixed with 0.70 g of the compound from Example 4, until a homogeneous mass was formed. This composition had an excellent amber flavor with intense earthy and sweet woody nuances.

Example 11
Raspberry seasoning mix

The following basic mixture of a raspberry seasoning was made:

Components

Parts by weight

Components Weight
share Vanillin 2.0 Maltol 5.0 p-hydroxybenzyl acetone 5.0 alpha-ionon (10% in propylene glycol) 2.0 Ethyl butyrate 6.0 Ethyl acetate 16.0 Dimethyl sulfide 1.0 Isobutyl acetate 13.0 acetic acid 10.0 acetaldehyde 10.0 Propylene glycol 930.0

2.0% of 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane was added to half of this mixture and compared this mixture with a mixture without 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane. 0.01% (100 ppm) of each of the two test mixtures was added to water and examined.

It has been found that the seasoning mixture with 1-acetyl-3,3- (2-propenyl) cyclohexane is considerably sweeter Liquid raspberry seasoning

from example 11
Propylene glycol

Silica

Physical Properties:
Surface area 200 m - '/ g
Nominal particle size: 0.012 μ
Density: 0.037 g / ccm

20th
9

5.00

The silica was in the liquid raspberry seasoning mixture from Example 11 dispersed with vigorous stirring until a viscous liquid was formed. the Seasoning Mix A was then added to the viscous liquid in an amount of 71 parts by weight and this was stirred at 25 ° C. After 30 minutes a dry free flowing seasoning powder was obtained which persisted was spicy.

Example 13

10 parts by weight of 50 Bloom pig skin gelatin were added to 90 parts by weight of water at a temperature of about 65 ^° C. and the mixture was stirred until the gelatin was completely dissolved. After cooling the solution to about 48 ° C., 20 parts by weight of the liquid seasoning mixture from Example 11 were added, which was then homogenized and an emulsion was formed, the particle size of which was in the range of 2-5 μm. This mixture was kept at about 48 ^° C. so that the gelatin did not gel.

A coacervate was made by adding 40 parts by weight of a 20% strength solution of sodium sulfate educated. The addition was slow and even. The gelalinmoleküje were evenly around each oil droplets deposited as a core.

Gelling was carried out by pouring the heated coacervate mixture into 1000 parts by weight of a 7% aqueous sodium sulfate solution at 18 ° C causes. The obtained thickened coacervate could be filtered and washed with water at temperatures below the Melting point of the gelatin can be washed to remove the salt.

The filtered cake in this example was made by washing with 200 parts (weight) of a 37% Formaldehyde solution hardened in water. The cake was then washed to remove the remaining formaldehyde to remove.

procedure

Be is pi e! 14th

100 parts by weight of chicle were mixed with 4 parts by weight of the seasoning mixture from Example 13. to 300 parts of sucrose and 100 parts of corn syrup were added to this mixture. It was mixed in a ribbon blender with insulated sidewalls, such as those sold by Baker Perkins Co. was sive.

The resulting chewing gum was cut into strips 2.54 cm wide and 0.254 cm thick, and the Length was 7.62 cm. While chewing, this gum had a pleasant, long-lasting raspberry flavor.

1. The constituents of group "A" were agitated and heated to 7TC in a steam-jacketed kettle.

2. Stirring was continued for 3 to 5 minutes to form a homogeneous gel.

3. Group "B" powders were added to the gel while continuing to mix until easy homogeneous paste was formed.

4. The seasoning mixture "D" was added while stirring and finally the sodium n-lauroyl sar conisat.

5. The resulting slurry was mixed for 1 hour. The finished paste was made into a three whale zen mill brought, homogenized and filled into a tube to cut off.

The toothpaste obtained gave a pleasant raspberry flavor with normal use, which lasted for a while of the entire cleaning process (IV2 minutes) very inten

Example 17

B e i s ρ i e 1 15

chewing gum

100 parts by weight of chicle became 18 parts by weight mixed the seasoning mixture from Example 14 and added 300 parts of sucrose and 100 parts of corn syrup. Mixing was carried out as in Example 14.

The chewing gum cut into strips had a pleasant, long-lasting raspberry flavor.

Chewable vitamin tablets

The seasoning mixture from Example 13 was added to a chewable vitamin tablet preparation, unc although in an amount of 10 g / kg. The vitamin tablets preparation was made by mixing in a Hobart-Mi made of the following components:

g / 1000 tablets

Components 100.00 (total) Example 16 Toothpaste preparation Glycerin The following separate groups from different distilled water which components are made: Sodium benzoate Parts by weight Sodium saccharine Group "A" Stannous fluoride 30,200 15325 Calcium carbonate .100 Dicalcium phosphate (dihydrate) .125 .400 Sodium N-Lauroyl Sarcosinate Group "B" (Foaming agent) 12300 37,200 Seasoning mixture from example 23 Group "C" 2,000 Group "D" UOO

50

55

60

65

Vitamin C (ascorbic acid) as 70.0 Ascorbic acid sodium ascorbate Mixture 1: 1 Vitamin Bj (thiamine mononitrate) 4.0 Vitamin B2 (riboflavin) 5.0 Vitamin B ^ (pyridoxine hydrochloride) 4.0 Niacinamide 33.0 Calcium pantothenate 11.5 Vitamin B12 (cyanocobalamin) 3.5 Vitamin E (dl-alpha-tocopheryl 6.6 acetate) as dry vitamin E acetate d-biotin 0.044 Approved opaque dye 5.0 Seasoning mixture from example 13 (as above specified) Sweetener - sodium saccharin 1.0 Magnesium stearate as a lubricant 20.0 Mannitol q. see up to 500.0

The preliminary tablets were produced by means of flat punches. These tablets were made then ground through a 5 DIN sieve and 13.5 g dry Vitamin A acetate and 0.6 g of vitamin D were added in the form of beads. The whole mix was pressed with a concave punch to give 0.5 g tablets

When chewing, the result was a pleasant, long-lasting, steadily strong raspberry taste for one Time span of 12 minutes.

Example 18

Preparation of 1-acetyl-1-methyIaHyI-3,3-dimethylcyclohexane and 1- (2-methylallyl-5-methyI-

4-pentep.oy!) - 3,3-dirnethy! Cyc! Ohexane
Reaction:

+
O Cl

Tricaprylmethylammonium chloride
toluene

(Main product)

(By-product)

(By-product)

A slurry of i-acetyl-SS-dimethylcyclohexane (624 g, 4 mol), granulated sodium hydroxide (240 g, 6 mol), tricaprylmethylammonium chloride / 35 g /, methallyl chloride (432 g, 4.8 mol) and 400 ml of toluene were 4 Heated under reflux for ^{1 A hours.} Then 1 liter of water was added to the cooled reaction mixture. The aqueous layer was discarded and the organic layer was rapidly distilled through a short column to give 203 g of regenerated 1-acetyl-S ^ -dimethylcyclohexane, 500 g of i-acetylO ^ -dimethyl-1-methallylcyclohexane and 73 g of 3,3- Dimethyl 1- (2-methallyl-5-methyl-4-pentenoyl) cyclohexane) (1-4 °, 3.0 mm Hg) containing 5% 3,3-dimethyl-1- (4-methyl-4-pentenoyl ) to win. A portion of the latter compound was determined by gas-liquid chromatography (30.48 cm 6.35 mm 80% SE-30 packed column; 200 ° C isothermal) and showed the following fragrance and flavoring properties:

Fragrance properties:
green;
herbaceous;
melon-like;
fruity;
galbanum-like;
gingery and
citrusy.

Seasoning properties:
greasy;
Sweet;

fruity;
citrusy;
green;

vegetable-like and
waxy

The NMR analyzes of the compounds showed the following:

"A"

ppm

Explanation

0.92 (s, 3)

0.94 (s, 3)

1.70 (s, 6)

3.02 (quintet, 1, J = 6H)

4.76 (d, 4, J = 8 H)

Methyl groups "A"

Methyl groups "C" H ₀ methyl groups "B"

The IR analyzes gave the following data: C = O 1695 cm- '.
C = CH ₂ 1635 cm- '.

The mass spectral analysis showed:

MW-262 (confirmed by GC-MS). The NMR spectrum is shown in FIG. 8 for 1-acetyl-3,3-dimethyl-1-methallylcyclohexane; the IR spectrum is in Figure 9 for l-acetyl-S.S-dimethyl-l-methallylcyclohexane shown.

The NMR spectrum for 3,3-dimethyl-1- (2-methallyl-5-methyl-4-pentenoyl) cyclohexane is in Fig. 10 and the IR spectrum in FIG. 11 shown.

Example 19

Reaction:

A slurry of 1-acetyl-S.S-dimethylcyclohexane (156 g, 1 mol), potassium hydroxide (86 g, 1.5 mol) and toluene (300 ml) was heated to reflux Methallyl chloride (135 g, 1.5Mol) was added to the concentrated reaction mixture, whereupon the mass became liquid became. The mixture was heated to reflux for 6 1/2 hours. It was then cooled to room temperature and 500 ml of water are added. The aqueous layer was discarded and the organic layer distilled to make regenerated l-acetyl-33-dimethylcyclohexane (86 g), 1-acetyl-S ^ -dimethyl-1-methallylcyclohexane (67 g, containing 2% 3,3-dimethyl-1- (4-methyl-4-pentenoyl) cyclohexane) (NMR spectrum Fig. 8; IR spectrum Fig. 9) and 3,3-dimethyl-1- (4-methyl-4-pentenoyl) cyclohexane (12 g) to win.

Example 20 Example 22

Reaction:

Production of l-acetyl-3,3-dimethyl- (2-methyl-2-propenyl) cyclohexane

Reaction:

Cl

A mixture of 1-acetyl-S.S-dimethylcyclohexane (156 g, 1 mol), sodium hydroxide (60 g, 1.5 mol), methallyl chloride (135 g, 1.5MoI) and triethylamine (10 g) was stirred for 12 hours and heated to 80 to 84 ° C. It was then cooled to room temperature and water was added with stirring. The aqueous layer was discarded and the organic layer was distilled. 1-Acetyl-S.S-dimethylcyclohexane was obtained (62.4 g); 1-acetyl-S.S-dimethyl-1 - (2-methyl-2-pro-

penyl) cyclohexane (80g), (NMR spectrum Fig. 11; IR spectrum Fig. 9); and 3,3-dimethyl-1- (4-methyl-4-pentenoyl) cyclohexane (8 g).

18-crown-6- (dibenzoderivative)

A slurry of potassium hydroxide (84 g, 1.5MoI), 1-acetyl-S.S-dimethylcyclohexane (156 g, 1 mole), dibenzo-18-crown-6 (3 g) of the formula

Example 21

Reaction:

35

KO-t-Bu

t-BuOH

A fresh solution of potassium t-butoxide was made by adding potassium metal (28 g, 0.72 mol) to 500 ml of anhydrous t-butanol under a nitrogen blanket became. For this purpose was l-AcetylO ^ -dimethylcyclohexane was added and the resulting mixture was stirred at room temperature for 1 hour Methallyl chloride (74.4 g, 0.8MoI) added and that The reaction mixture was stirred for a further hour. It was then filtered in order to remove potassium chloride. The t-butanol was removed by evaporation in a rotary evaporator. The remaining oil was distilled to give a mixture of l-acetyl-3,3-dimethylcyclohexane, 1 - Acetyl-33-dimethyl-1 - (2-methyl-2-propenyI) cyclohexane (NMR spectrum Fig. 7; IR spectrum F i g. 9) and 3,3-dimethyl-1- (4-methyl-4-pentenoyl) cyclohexane.

and toluene (150 ml) was heated to reflux while the reaction mixture was thickened. Nar '~ cooling to 70 ⁰ C and addition of methallyl ^ ^ id ₁ (135 g, 1.5 mol) was added, the reaction mixture liquid. The mixture was heated under reflux for a further 9 hours and then cooled and water was added. The aqueous layer was decanted and the organic layer was distilled and 1-acetyl-S ^ -dimethylcyclohexane (62 g) and 1-acetyl 1-3,3-dimethyl-1 - (2-methyl-2-propenyl) cyclohexane (83g - NMR spectrum Fig. 8; IR spectrum Fig. 9) obtained.

Example 23

A tobacco blend was made from the following ingredients:

55 components by weight

Bright Burley Maryland 60 Orient Stem Glycerin Water 40.1

24.9

1.1

11.6

14.2

2.8

5.3

65 This tobacco mixture was used to make cigarettes in which the following preparation was incorporated:

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

8:00 pm

41.90

The seasoning mixture was placed in sample "filter" cigarettes in an amount of 0.1%. A third of these test cigarettes were used in the tobacco sector with the mixture of 1-acetyl-1-methallyl-3,3-dimethylcyclohexane and 1- (2-methallyl-5-methyl-4-pentenoyl) -3,3-dimethylcyclohexane from Example 18 treated in an amount of 100 ppm per cigarette. Another third of the sample cigarette was prepared by treatment of the filter with said mixture, and χ in an amount of 2 10 ~ ⁵ g and 3xl0 ^"5 g. Comparison tests have shown that the cigarettes which have been treated in the tobacco and the filter , in the smoked wort had a green, sweet, fruity, flowery nuance of spice and aroma reminiscent of Virginia tobacco both in the main stream and in the side stream, but also had these nuances before smoking.

Example 24

The tobacco mixture was produced as in Example 23 and sample “filter” cigarettes formed therefrom were treated with an amount of 0.1% of the seasoning mixture according to Example 23. One third of the test cigarettes in the tobacco sector were treated with 1-acetyl-1-methallyl-3, 'himethylcyclohexane, from Example 22, in an amount of 100 ppm per cigarette. Another third of the sample cigarettes was treated in the filter material, and g in an amount of 2χ 10 ~ ⁵ g and 3 χ 10 ^-5 of said compound. It was found that the cigarettes treated in the tobacco and filter had a green, sweet, fruity, floral and spice and aroma nuance reminiscent of Virginia tobacco both in the main stream and in the secondary stream, but also before smoking had.

Example 25

The same tobacco mixture as in Examples 23 and 24 was made into cigarettes and with a also treated in these examples seasoning mixture, which is added in an amount of 0.1% Sample "filter" cigarettes were added.

One third of the sample cigarettes was 1-acetyl-methallyl-SS-dimethylcyclohexane, prepared according to Examples 30, 21 or 22 in the tobacco area in an amount of 100 ppm per cigarette amount of 2 χ 10- ⁵ g and 3 χ 10 ~ ⁵ g. Comparative tests have shown that the cigarettes treated in the tobacco and filter had a green, sweet, fruity, flowery and spice and aroma nuance reminiscent of Virginia tobacco in the main stream as well as in the side stream, but also before smoking had.

Example 26
Orange seasoning

The same ingredients as in Example 2 were mixed together

This seasoning mix was designated "A".

A seasoning mixture "B" was made by adding 1-acetyl-1-methallyl-S.S-dimethylcyclohexane (1% in Ethanol) to the seasoning mixture "A", with "B" added in an amount of 2 parts per 100 parts of "A" became.

Each of the seasonings "A" and "B" was made into a tree in an amount of 56-57 g per 3.81 Given sugar syrup, which together with water made a drink. The seasoning mix "A" gave that Drink a decent orange character.

The drink treated with the seasoning mixture "B", however, had better seasoning. The through the 1-acetyl-1-methaHyl-S.S-dimethylcyclohexane Improvement is due to the following reasons:

1. Increasing the natural character of freshly squeezed oranges,

2. greater depth of orange juice flavor.

Example 27
Perfume composition

25 components Parts Linalool 30th Linalyl acetate 10 Terpineal-coeur 5 jo Nerol-coeur 10 Terpinylacetate 2 Geranyl acetate 2 Nerylacetate 2 Methyl anthranilate 1 j-, Cilral 10 n-decyl alcohol 1 n-dodecyl alcohol 5 n-dodecanal 15th n decanal 30th 40 n-nonanol 3 n-nonanal 5 n-decyl acetate 5 n-dodecyl acetate 3 1-acetyl-1-methallyl-SJ-dimethylcyclohexane 5 -n (produced according to example 18)

The 1 -acetyl-1-methallyl-3.3-dimethylcyclohexane gave this terpeneless orange perfume a natural, bitter orange character.

Example 28

Reaction:

toluene

KOH

A slurry of 1-acetyl-S ^ -dimethylcyclohexane (156 g, 1 mol), potassium hydroxide (86 g, 1.5 mol) and

Toluene (300 ml) was heated to reflux. Allyl chloride (114 g, 1.5MoI) was added to the thickened reaction: Given reaction mass, whereupon this became more fluid. This mixture was refluxed for six and a half hours and then cooled to room temperature and added with 500 ml of water. The aqueous layer was discarded and the organic layer distilled, with 74 g of regenerated 1-acetyl-33-dimethylhexane, 53 g 1 - Acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane, and 35 g of 3,3-dimethyl-1- (4-pentenoyl) cyclohexane obtained became.

The NMR spectrum of the 1-acetyl-S.S-dimethyll- (2-propenyl) cyclohexane is in Fig. 12 and the IR spectrum in Fig. 13 shown.

The NMR analysis showed:

Example 29

8. ppm

Explanation

0.74 (s, 3)
0.90 (s, 3)
2.14 (s, 3)

Methyl groups »A« CH3 group »B«

8. ppm

Explanation

4.8-5.1 (m. 2)
5.4-5.8 (m, 1)

CH2 group "C" H ₀

The IR analysis showed:
C = O; 1690 cm- '.
C = C; 1660.
The mass spectral analysis showed:

m / e = 95, 94, 69, 109, 55, 194 (starting peak). The NMR analysis for 3,3-dimethyl-1- (4-pentenoyl) -cyclohexane is in Fig. 14 and looks like this: A.

Explanation

0.90 (s, 3)
0.93 (s, 3)
2.2-2.65 (m, 5)
4.60-5.12 (m, 2)
5.50-5.95 (m, 1)

Methyl groups "A"

CH ₂ 's "B" and H _c

CH ₂ »D«

H _E

The mass spectral analysis gave: m / e = 69, 111, 55, 41, 83, 3S, 194 (starting pack).

20th

25th

3 (1 A mixture of 1-acetyl-SS-dimethylcyclohexane (156 g, 1 mol), sodium hydroxide (60 g, 1.5 mol), allyl chloride (114 g, 1.5 mol) and triethylamine (10 g) was stirred and The mixture was heated for 12 hours to 80 to 84 ° C. After the mass had cooled to room temperature, water was added with stirring and then the aqueous layer was discarded, the organic layer was distilled and 119 g of 1-acetyl-SS-dimethylcyclohexane, 31 g of 1-acetyl -SS-dimethyl-1 - (2-pentenyl) cyclohexane and 5 g of 3,3-dimethyl-1 - (4-pentenoyIJcyclohexan obtained.

The NMR spectrum for 1-acetyl-S.S-dimethyll- (2-propenyl) cyclohexane is in Fig. 12; the IR spectrum in Fig. 13 and the NMR spectrum for 3,3-dimethyl-1- (4-pentenoyl) cyclohexane in Fig. 14 shown.

B e i s ρ i e 1 30

Reaction:

Cl

KO-t-Bu

t-BuOH

A fresh solution of potassium t-butoxide was made by adding potassium metal (28 g, 0.72 mol) to it 500 ml of anhydrous t-butanol prepared under a nitrogen blanket. To this reaction mixture was l-acetyl-S.S-dimethylcyclohexane given and then the whole stirred at room temperature for 1 hour. Then allyl chloride (63.2 g, 0.8 mol) was added and stirred for another hour. The reaction mixture was filtered to remove potassium chloride. The t-butanol was evaporated in a rotary

bo evaporator driven off. The oil obtained was distilled and 78 g of a 13: 1 mixture of 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane and 3,3-dimethyl-1- (4-pentenoyl) cyclohexane. The relationship was created by the intetragion of a gas-liquid

b5 chromatography chromatogram determined. (Gas-liquid chromatography conditions: 3 m 6.35 mm 10% SE-30 packed column, 200 ⁰ C isothermal). 41 g of volatile substances

I "I U. f

UkIItUlM MH.

The NMR spectrum for
1- (2-propenyl) cyclohexane is shown in FIG. 12 and the IR spectrum in FIG. 13. The NMR spectrum for 3,3-dimethyl-1- (4-pentenoyl) cyclohexane is shown in FIG .

Example 31

Production of
1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane

Reaction:

Example 32

Production of l- (33-dimethylcyclohexyl) -4-methylciy- and trans- (2 and 3) -pent-1-one

Reaction:

CHO

15th

NaOH

MeOH

KO-t-Bu

18-crown-6 (dibenzoderivative)

A slurry of potassium hydroxide
1.5 mol), 1 - acetyl-3,3-dimethyl) cyclohexane (156 g, '
Dibenzo- 18-K.ronen-6 (3 g) of the formula

A solution of 474 g of 1-acetyl-S.S-dimethylcycIohexane, 500 ml of methanol, 40 g of NaOH and 50 ml of toluene were heated to reflux. During a period of time over 45 minutes, 240 g of isobutyraldehyde was added dropwise. The reaction mixture was then heated under reflux for a further 90 minutes, then cooled to room temperature and with (84 g, 25 hydrochloric acid neutralized. Methanol was replaced by Destil-MoI), lation and the aqueous layer from the resulting two-phase system was removed by discarding. the organic layer was washed once with water and quickly distilled through a short column, a mixture of l- (3,3-dimethylcyclohexal) -4-methyl-cis- and trans- (2 and 3) -penten-l-one (360 g, 58%) / l 12 to 117 ° C, 2.8 mm / and higher boiling products was obtained as

and toluene (150 ml) was heated to reflux, the mass becoming thick. It was cooled to 70 ⁰ C and allyl chloride (114 g, 1,5MoI) was added and the reaction mixture was liquid. The mixture was refluxed for a further 9 hours, then cooled, and water was added. The aqueous layer was discarded and the organic layer was distilled to give 24 g of 3,3-dimethylcyclohexane, 48 g of 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane and 90 g of non-volatile materials.

The NMR spectrum for 1-acetyl ^ -dimethyll- (2-propenyl) cyclohexane is shown in FIG. 12 and the IR spectrum in FIG.

and

OMe

45

have been identified.

Redistilling this mixture through a 3.80 cm by 30.48 cm column filled with wire mesh resulted in the following fractions:

fraction Steam temp. Flow. Temp. vacuum weight 'Reflux 1 No. ("C) ( ⁰ C) mm Hg (E) relationship 1 1 85-101 128 2.8 6.fc 9: 2 112 128 2.8 10.6 9: 3 112 128 2.8 16.6 9: 4th 112 132 2.8 12.9 9: 5 112 128 2.8 28.3 9: 6th 112 128 2.8 12.0 9: 7th 112 128 2.8 24.2 9: 8th 112 128 2.8 27.3 9: 9 114 134 2.8 27.1 4: 10 115 135 2.8 22.7 4: 11th 115 137 2.8 26.9 4: 12th 115 140 2.8 25.7 4: 13th 116 149 2.8 25.0 4: 14th 116 149 2.8 26.9 4:

33 27 00 688 34 weight Reflux (G) relationship continuation Steam temp. 16.9 4: fraction ro Flow. Temp. vacuum 16.9 4: No. 117 ro r.in ed 23.9 4: 15th 122 155 2.8 265 4: 16 128 160 2.8 243 4: 17th 128 165 2.8 23.1 4: 18th 130 176 2.8 255 Tf 19th 130 205 2.8 255 4: 20th 130 214 2.8 11.7 Tf 21 138 219 2.8 22nd 149 241 2.8 23 250 Z8

Fractions 5 to 13 contained more than 99% of the desired product of the form:

and

The following fractions contained the following percentages of this mixture:

freed from the inorganic salts by filtration and washed three times with 10% hydrochloric acid. the Distillation gave 319 g of 1-acetyl-SJ-dimethyl-cyclohexane and 138 g l ^ S-DimethylcyclohexylJ ^ -methylcis- and trans- (2 and 3) -penten-l-one (22%, based on the added l-acetyl-SJ-dimethylcyclohexane.

Das! - (SJ-Dimethylcyclohexyl ^ -methyl-cis- and trans- (2 and 3) -penten-l-one was determined by NMR and IR analyzes to be a mixture is:

fraction

No.

% of what you want

% of ge product

5-13
14th
15th
16
17th
18th

60 90 > 99 98 96 90 60 20

With regard to the fragrance properties, fractions 5 to 13 had fruity, woody, spruce-needle-like Aroma notes with St. John's wort-like, floral nuances and a light chocolate undertone.

In terms of flavoring properties, this material had a sweet, fruity, raspberry-like, woody, Lemon-like, spruce needle aroma with a sweet, raspberry and lemon-spicy character.

Example 33

Production of! - (SJ-DimethylcyclohexylJ ^ -methylcis- and trans- (2 and 3) -pent-1-one

CHO

HBO. ,, B ₂ O., \ /

A mixture of i-acetyl-JJ-dimethylcyclohexane (462 g), isobutyraldehyde (108 g). Boric acid (6.2 g) and boron oxide (52 g) was stirred for 5 hours in an autoclave and erwärml to 150 ⁰ C. The solution was (ice and trans)

The NMR spectrum for this mixture is shown in FIG. 15 4 · and the 1R spectrum are shown in FIG.
The NMR analysis is as follows:

ppm Explanation 1.85 (s) Methyl groups "A" 1.87 (s) 2.62 (d, J = 1 Hz) Methyl groups "C" 2.76 (d, J = 1 Hz) 2.03 (s) Methyl groups "B" 2.1 (S) 2.3-2.8 (broad multiplet) H ₀ 3.14 (d,] = 7 Hz) CH ₂ group »Ε« 5.28 (wide t, J = 7 H ₂ ) Mr 6.0 and 6.28 (two multipletles) Ed 6.68-6.92 (two multiplettes) Hm The IR analysis showed: 1665 cm- ¹ . 1710C = O. 1690 (sh). 1720 (sh). 1620 cm- 'C = C.

35 36

Example 34 Synthesis of l-P.S-dimethylcyclohexylJ-cis- and trans- (2 and 3) -penten-l-one

Reaction:

+ C-C-CHO B ₂ O ₅
H ₃ BO ₃

I! c—

—C—

A mixture of 462 g of l-acetyl-S ^ -dimethylcyclohexane, 87 g of propionaldehyde, 52 g of boron oxide and 6.2 g of boric acid were heated to 150 ° C. in an autoclave for 8 hours warmed up. After cooling down to room! temperature, the solution was filtered and the inorganic salts removed, the filtrate washed with aqueous sodium carbonate once and with saturated saline solution twice. Distillation through a short column gave a mixture of 367 g of 1-acetyl-a ^ -dimethyl-cyclohexane and 60 g l-p ^ -DimethyicyclohexylJ-cis- and trans- (2 and 3) -penten-l-one (20%, based on the added propionaldehyde.

A portion of the distillate rich in desired products was cut through a 3.8 cm χ 30.48 cm Wire mesh-filled column is distilled and the following fractions collected:

fraction
No.

Steam temp. CQ

Flow. Temp. CC vacuum mm Hg

Weight (g)

Reflux ratio

1
2
3
4th
5
6th
7th
8th
9
10
11th

55-52

105-103

109

126

138

138

140

140

144

154

181

220 2.5 2.2 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0

10.2 11.1 5.5 6.6 3.0 5.3 6.7 6.7 6.5 7.0 2.6

Fraction No. 7 had a sweet, raspberry-like, fruity, pine-needle-like, floral, iononic aroma and a sweet, sweet-fruity, red berry, raspberry and spruce needle-like, flowery, ionon-like seasoning. The mixture 1- (3,3-dimethylcyclohexyl) -cis- and trans- (2 and 3) -pent-1-one became evaluated by preparative gas-liquid chromatography and had the structural formula

(ice and trans)

The GC-MS profile of this mixture is shown in Fig. 17, the NMR spectrum in FIG. 18 and the IR spectrum in FIG. 19 shown.

The NMR analysis showed:

Λ. ppm

Explanation

<). ppm

Explanation

1.95 (s, 6H)
2.08 (1. 3,) = 8Hz)

CH! Groups »A« CHj groups »B«

4) 2.25 (quintet, 2 H, J = 8 Hz) CH ₂ groups "C" 2.7-2.9 (broad multiples, IH) Hd 6.05 and 6.22 (two _{multipettes) H E} 6.75-7.05 (m, 1 H) Hf

The IR analysis showed: C = O 1665 and 1685 cm- '. C = C 1620.

B e i s ρ i e 1

Hydrogenation of l- (3,3-dimethylcyclohexyl) -4-methylcis- and trans- (2 and 3) -penten-l-one

Reaction:

H, / Pd

Into a 250 cc pair shaker was placed 107 grams 1- (3,3-Dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) -penten-l-one - prepared according to Example 1 -. 1 g a 5% palladium-on-carbon catalyst and

Introduced 125 g of isopropyl alcohol. The pusher was sealed and heated to 125 ° C at 50 to 150 psig (hydrogen) pressure. In this pressure range and at this temperature the

Reaction mixture held for about IV2 hours. Thereafter the reaction product was filtered and distilled on a 122 cm Vigreaux column. The data of the Distillation were the following:

fraction Steam temp. Flow. Temp. vacuum weight Reflux 1 No. CC) ( ⁰ C) mm Hg (G) relationship 1 1 67-89 118-126 2.2 3.8 9: 1 1 2 91 137 2.2 3.7 9 . *
1 3 91 129 2.2 7.4 4th 1 4th 91 129 2.2 8.6 4th 1 5 91 129 2.2 13.4 4th 1 6th 91 129 2.2 14.0 4th 1 7th 91 131 2.2 15.2 4th 1 8th 91 156 2.2 14.7 4th 9 94 187 2.2 8.2 4th 10 98 240 2.2 3.5 4th

With regard to a food seasoning, fraction No. 6 had a sweet, pine-needle-like, fruity, Blueberry-like, woody aroma with a sweet, pine-needle-like, fruity, nut-like character.

From a perfumery standpoint, the pooled fractions # 2 through 9 were 10% Solution in pure alcohol creates a dark, liquorice-like aroma with chocolate-like nuances.

Fraction No. 7 was determined by NMR, IR and mass spectrum analyzes and the formula

determined. Explanation The NMR analysis showed: CH3 groups ό, ppm Methylene "A" 0.82-0.98 (m, 12H) 2.43 (t, 2 H, J = 8 Hz) The IR analysis showed: 2950 cm- ¹ . 2870. 1700. 1560 (C = O). 1390. 1360.

The mass spectral analysis showed:

111,41,43, 69, 55 and 27.

The NMR spectrum of this compound is shown in FIG. 20th and the IR spectrum in FIG. 21 shown

Example 36 Raspberry seasoning

As in Example 11, a raspberry seasoning was produced from the ingredients

2.0% of the l-ßS-dimethylcyclohexylH-methyl-cis- and trans- (2 and 3) -penten-l-one (prepared according to Example 43) was added. The two comparative mixtures were in an amount of 0.01% (100 ppm) in water and evaluated.

The seasoning l- (3,3-dimethylcyclohexy!) -4-methyl-cis- and sample containing trans- (2 and 3) -penten-l-one had much sweeter flavor notes and one sweet raspberry seed-like and sweet aftertaste and mouthfeel, properties that make the Basic mixture of raspberry spice did not have. There is no doubt that the compound l- (3,3-dime thylcyciohexylH-methyl-cis- and trans- (2 and 3) -pent-1-one rounds off the spice and contributes to a very naturally fresh aroma and taste, like it can be found in fully ripe raspberries. Hence isi

j5 the basic mixture mixed with this compound or raspberry seasoning better than the one without the added seasoning.

Example 37
Raspberry seasoning

The same ingredients as in Example 11 were mixed together.
1- (3,3-Dimethylcyclohexylj-cis- and trans- (2 and 3) -penten-l-one prepared according to Example 45 was added in an amount of 2.0% to half of this mixture. The two comparison products were each added dissolved in water in an amount of 0.01% (100 T / M ill.) and the beverages produced in this way compared with one another. The l- (3,3-dimethylcyclohexyl) -cis- and trans- (2 and 3) - Containing penten-l-one seasoning mixture had much sweeter aromas and a raspberry and raspberry seed-like, sweet aftertaste and a corresponding mouthfeel which was not found in the simple raspberry seasoning.It is obvious that the seasoning additive l- (33- dimethylcyclohexyl) -cis - and trans- (2 and 3) pentene-l-on, of course fresh aroma and fresh Ge natural taste rounds and contributes both to cause the Aromi as well as the taste of full ripe raspberries ii artificial flavoring.

B e i s ρ i e 1 38 A. Powder seasoning mix

20 g of the seasoning mixture from Example 36 was emulsified in a solution of 300 g of acacia gum and 700 g of water. The emulsion was emulsified with a Bowen

Dryer (laboratory model) spray-dried, with 7.36mVMin. Air, an inlet temperature of 26O ⁰ C, an outlet temperature of 93 ⁰ C and a speed of 50 000 rev / min were used.

B. Persistent aromatic flavor

A seasoning mix with delayed release of the aroma was made from ingredients as in Example 11 and worked in the same manner as in Example 12. ι ο

After 30 minutes a dry, free flowing powder was formed which was persistently flavorful; H. one exhibited delayed release of the wort.

Example 39

The same starting materials as in Example 13 were used. After cooling the solution to about 48 ° C, 20 parts by weight of the liquid seasoning mixture from Example 37 were added and then the Solution homogenized to form an emulsion, the particle size of which ranged from 2 to 5 μ. the The emulsion was kept at around 48 ° C, a temperature at which the gelatin would not gel.

By slowly and evenly adding 40 parts by weight of a 20% aqueous solution Sodium sulfate formed a coacervate. During this process, the gelatin molecules became uniform deposited around each oil droplet as a core. The procedure was continued as in Example 13.

Example 41
chewing gum

40

The procedure was as in Example 14, but using a seasoning mixture from Example 37. The chewing gum obtained had a pleasant, long-lasting raspberry flavor when chewed.

Example 42

Toothpaste

50

The same separate groups as in Example 16 were prepared and processed as there and treated, but the seasoning mixture from Example 36 was used. The toothpaste made in this way had a pleasant raspberry flavor, the intensity of which throughout the entire brushing process (1 to Ii / 2 minutes) remained constant.

Example 43
Chewable vitamin tablets

The seasoning mixture from Example 37 was added to a preparation for chewable vitamin tablets, and although in an amount of 10 g / kg. The vitamin tablets were prepared as in Example 17

When chewed, these tablets had a pleasant, long-lasting strength that was constant over 12 minutes Raspberry seasoning.

Example 44

30th

Example 40
chewing gum

The procedure was as in Example 14, but using the seasoning mixture from Example 36. That chewing gum obtained was cut into appropriate strips, which during chewing a pleasant, had long-lasting raspberry flavor.

60

65 The ingredients were mixed as in Example 4 to form a perfume composition, with the exception of the seasoning substance according to the invention, the l- (3,3-dimethylcyc! Ohexy!) - 4-methy! -Cis- and trans- (2 and 3) - penten-1-one according to Example 33 was.

This mixture has been found to have a rich and sustained natural amber quality. The base composition can be mixed with aqueous ethanol, cooled, and filtered to give a to form finished cologne. A cologne produced in this way has an amber aroma, which to a woody amber note, with an excellent St. John's wort nuance. The basic composition can also be used to perfume soaps and other toilet articles such as lotions, aerosols, Sprays and the like can be used.

Example 45
Manufacture of a cosmetic powder mixture

In a ball mill, 100 g of talcum powder with 0.25 g of l- ^ S-dimethylcyclohexyl ^ -methyl-cis- and trans- (2 and 3) -penten-l-one from Example 33 mixed. This mixture had an excellent, pine needle-like, woody, floral and fruity aroma.

Example 46
Perfumed liquid detergent

Concentrated liquid detergents (lysine salt of n-dodecylbenzenesulfonic acid - described in U.S. Patent 39 48 818) with a pine needle-like, woody fragrance with a content of 0.10%; 0.15% and 0.20% of the compound l-p ^ -dimethylcyclohexyl ^ -methyl-cis- and trans- (2 and 3) -penten-l-one from Example 33 were prepared by homogeneously mixing the ingredients. The intensity of the pine needle-like, woody scent was increased with increasing concentrations of 1- (3,3-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) -pentene-l-or. elevated.

Example 47

Making a cologne and
Handkerchief perfumes

The compound l- (33-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) -penten-l-one from Example 33 was at a concentration of 2.5% in 85% Aqueous ethyl alcohol added to a cologne and a handkerchief perfume. To the latter at a concentration of 20% in 95% aqueous ethyl alcohol. Both the cologne as well as the handkerchief perfume this connection gave a clear and definite spruce needle-like, woody spicy note.

Example 48

Production of a Könischwasser and
Handkerchief perfumes

The compound l- (3,3-dimethylcyclohexy]) -4-methyl-cis- and trans- (2 and 3) -penten-l-one from Example 44

became at a concentration of 2.5% in 85% ethyl alcohol to a cologne and in a Concentration of 20% in 95% ethyl alcohol added to a handkerchief perfume. The additive gave both products a clear and distinct strong amber aroma with pine-needle-like, woody ones Grades.

Example 49 Manufacture of a perfumed soap

1 g of the compound l-p.S-dimethylcyclohexyiH-methyl-cis- and trans- (2 and 3) -penten-l-one from Example 33 and the two constituents are largely homogeneous with one another mixed. The soap produced in this way had an excellent woody, pine needle-like aroma.

B e i s ρ i e 1 50 Preparation of a detergent composition

100 g of a detergent powder (lysine salt dodecylbenzenesulfonic acid - Described in US-PS 39 48 818) were with 0.15 g of the compound 1- (3,3-dimethylcyclohexyl) -4-methyl-cis- and trans- (2 and 3) -penten-l-one mixed until a homogeneous substance was educated. This had an excellent woody, pine needle-like aroma.

Example 51

Synthesis of l-p.S-dimethylcyclohexylJ-cis and trans- (2 and 3) -butene-1-one

A mixture of 616 g of 1-acetylO.S-dimethylcyclohexane (4 mol), 132 g of acetaldehyde (3 mol), 105 g of boron oxide (1.5 mol) and 12 g of boric acid (0.2 mol) were in one

Autoclave heated to 150 ^° C. for 3 hours. After cooling to room temperature, the solution was filtered and the organic salts were removed. The filtrate was washed once with aqueous sodium carbonate and twice with saturated saline. The distillation

through a short column gave 127.2 g of 1-acetyl-3,3-dimethylcyclohexane and 127.2 g of a mixture of! - (S.S-dimethylcyclohexylJ-cis- and trans-2-buten-l-one and ί -p.S-Dimethylcyclohexyty-S-buten-1-one.

A portion of the distillate rich in the desired products was cut through a 2.54 χ 30.48 cm Distillation column, which was filled with a wire mesh, distilled and the following fractions collected:

fraction

No.

Steam temp. CQ

Flow. Temp. ( ⁰ C)

Vacuum mm Hg weight
(G)

Reflux ratio

10

11th

12th

The combined fractions 6 to 10 had a cedarwood-like in a concentration of 2 Aroma and a sweet, red berry-like, cedarwood-like spice.

The mass spectral analysis found: 180/69, 41, 39, 55, 165, 27.

The NMR spectrum for fraction 9 is shown in Figure 22 and the IR spectrum in Figure 23 The NMR analysis gave the following data:

67-70 89-91 4.4-4.7 70 95 4.9 70 103 5.0 74 113 5.0 100 116 5.4 102 123 4.8 102 125 5.0 112 131 8.2 106 139 5.7 104 154 5.2 104 179 5.3 100 202 5.2

2.74 (m)

55

0.94 ppm (s) acc
1.74-1.08 (m)

1.90 (duplicate with
Allyl bond

Dimethyl protons 6 H

b0

-CH ₂ -

8H 7.04-6.70 (m)

37.9 2: 1 HC Il
-—C— H 40.9 2: 1 O -C-C = C- 40.1 2: 1 Il H 29.9 2: 1 -C-C = C- 16.7 9: 1 O 17.1 9: 1 29.2 9: 1 20.7 9: 1 22.8 9: 1 13.3 9: 1 11.3 9: 1 6.7 9: 1 O
Il slette)

-C = C-IH

-C = C-IH

65

CH ₃ -C = CC- 3 H The IR analysis showed:

960 cm- ', 1290, 1360, 1380, 1440, 1625, 1670, 1690, 2860, 2940.

Example 52

Hydrogenation of l-p ^ -dimethylcyclohexylJ-cis- and

trans- (2 and 3) -buten-l-one reaction:

O \ / O

H ₂ / Pd

Into a 250 cc pair shaker was placed 107 grams [6 mol) l - ^ - DimethylcyclohexyO-cis- and trans- (2 and

3) -buten-l-one, 1 g of 5% palladium-on-carbon catalyst and 125 g of isopropyl alcohol were introduced. The shaker was tightly closed and heated to 125 ° C. at a pressure of 3.43 to 10.30 bar hydrogen and held under these conditions for 11/2 hours. The reaction product was then filtered, the solvent was evaporated off in vacuo and the oil obtained was distilled on an 8-plate Vigreaux column.
The dates of the distillation were as follows:

fraction Steam temp. Flow. Temp. vacuum weight Back nut I. No. CQ ( ⁰ C) mm Hg (G) relationship 1 86-89 100 4.6 9.0 11: 2 90 102 4.7 12.0 Π: 3 90 102 4.6 8.8 11: 4th 90 102 4.7 11.5 11: 5 90 105 4.6 14.0 11: 6th 90 no 4.6 13.5 Π: 7th 90 113 4.6 8.4 11: 8th 90 141 4.6 11.1 Π: 9 90 205 4.6 4.4 11:

From the point of view of perfumery, the group had No. 7 at a concentration of 10% in pure alcohol with a fruity, berry, herbaceous aroma green, tobacco-like nuances.

The mass spectral analysis showed: 71527

The NMR analysis resulted for fraction 8: O
Ij 3 H 0.90 ppm (t) CH ₃ - CH ₂ - - CH ₂ -CH ₂ -C- 6H 0.91 ppm (S) Dimethyl protons O
Il 1OH 1.95 -11.6 (m) -CH ₂ - Il
HC-C - 2H 2.49 U) IH 2.69-2.31 (m)

The NMR spectrum of fraction 8 is in Fig. 24 and the IR spectrum in FIG. 25 shown.

Example 53

A perfume composition was prepared as in Example 44, but with that from Example 52 derived compound 1- (33-dimethylcyclohexyl) -butan-1-one was moved.

. This mixture resulted in a perfume with a rich and sustainable natural amber quality This Base composition can be used as in Example 44.

Example 54 Manufacture of a cosmetic powder mixture

In a ball mill, 100 g of talcum powder were added 0.25 g of l- (33-dimethylcyclohexyf) -butan-l-one from example 52 mixed This composition had an excellent fruity, berry, herbaceous aroma with green and tobacco-like nuances.

Example 55 Perfumed Liquid Detergent

Concentrated liquid detergents (lysine salt from 3 ·, n-dodecylbenzenesulfonic acid - described in the US-PS 39 48 818) with an herbaceous scent were by mixing each with 0.10%; 0.15% and 0.20% of the Compound 1- (3,3-dimethylcyclohexyl) -butan-l-one from Example 52 prepared. These mixtures all had one herbaceous spice with green and tobacco-like nuances. The intensity of the scent was increased by increasing concentrations elevated

Example 56

^4> Making a cologne and

Handkerchief perfumes

1 - (3,3-Dimethylcyclohexyl) -butan-l -one prepared according to Example 52 was in a cologne in a so concentration of 2.5% in 85% aqueous ethanol; and at a concentration of 20% in 95% aqueous ethanol introduced. The two products received a distinct appearance from the addition of the seasoning and certain herbaceous spices.

Example 57

Production of a cologne and handkerchief perfume

«, Ο The compound l- (3 ^ -Dimethylcyclohexyl) -butan-1-one from Example 53 was at a concentration of 2 ^>% in 85% aqueous ethanol to a cologne and in a concentration of 20% in 95% ethanol to make a handkerchief perfume

give o5. This seasoning additive, together with one Mixture from Example 28 has a clear and definite strong amber aroma with herbaceous and tobacco-like Grades.

Example 58
Manufacture of a soap composition

100 g of soap chips were mixed with 1 g of the compound 1- (3,3-dimethylcyclohexyl) -butan-1-one from Example 52 mixed intimately until the product was essentially homogeneous. The soap thus perfumed had an excellent one fruity, berry, tobacco-like aroma with green and tobacco-like nuances.

Example 59
Preparation of a detergent composition

100 g of a detergent powder (lysine salt of n-dodecylbenzenesulfonic acid - described in US-PS 39 48,818) were with 0.15 g of the compound 1- (3,3-dimethylcyclohexyl) -butan-l-one from Example 52 mixed until homogeneous This product had an excellent, fruity, berry, herbaceous aroma with green and tobacco-like nuances.

14 sheets of drawings

Claims (1)

Patent claims: 1. Carbonyl compound of the general formula
f Chlorine or bromine, an allyl or methallyl group or a Group of the general formula