CH630597A5 - Process for the preparation of a mixture containing lyral - Google Patents

Description

The invention relates to a process for the preparation of a mixture which can be used in particular for perfumery purposes, as is known by the abbreviation Lyral and 4- (4'-methyl-4'-hydroxyamyl) -A3-cyclohexenecarboxaldehyde of the formula (Ia) specified in claim 1 contains as a component.

The preparation of the compounds (Ia) is described in US Pat. Nos. 2,947,780 and 3,935,205. The method described in the first-mentioned US patent is based on the reaction of myrcenol with acrolein in a closed reactor at temperatures in the range of 150 ° C. The method described in the second US patent is based on the fact that 4- (4'-methyl-3'-pentenyl) -A3-cyclohexenecarboxaldehyde is converted to the adduct dimorpholinated on the aldehyde group and the adduct is hydrated, after which the two morpholino groups are split off.

The object of the invention is a process for the preparation of a mixture which contains the compound of the formula (Ia) as a component from an aldehyde group-containing starting material of the formula (2) given in claim 1, which consists of the p-isomer or a mixture of

There is 40 p and m isomer, without conversion of the aldehyde group. This object is achieved by a method with the features mentioned in claim 1.

Preferred acidic hydrating agents are mentioned in claims 2 and 3.

45 According to the invention, the starting material of the formula (2) can be hydrohalogenated with hydrogen bromide or hydrogen chloride by the process according to claim 4 and then hydrolyzed to the target product.

Furthermore, the starting material of the formula (2) can first be hydrohalogenated by the process according to claim 5, as in the process just mentioned according to claim 4, subsequently converted into the corresponding carboxylate and this can then be hydrolyzed to the target product.

55 The starting material of the formula (2) used in the process of claim 1 can be prepared according to the process of claim 6 by reacting myrcene with acrolein.

The reactions described are illustrated by the following 60 reaction scheme:

S

\ H (7)

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4th

(4) (R = lower alkyl)

(1) consists at least in part of the p-isomer, i.e. 4- (4'-methyl-4, -hydroxyamyl) -A3-cyclohexenecarboxaldehyde (Formula la); Mixtures of p- and m-isomer are also briefly referred to below as mixture (1) or lyral; the m isomer is 3- (4'-methyl-4'-hydroxyamyl) -A3-cyclo-hexenecarboxaldehyde;

(2) the p-isomer is 4- (4'-methyl-3'-pentenyl) -A3-cyclo-hexenecarboxaldehyde; Mixtures of p and m isomers are also referred to below as "myracaldehyde" and are preferred as the starting material of the formula (2); the m isomer is 3- (4'-methyl-3'-pentenyl) -A3-cyclohexenecarboxaldehyde;

(3) hydrohalogen derivative of (2) or of myracaldehyde;

(4) carbalkoxy derivative of (2) or of myracaldehyde;

(5) myrcenol;

(6) myrcene;

(7) Acrolein.

The reaction (6) + (7) to form the starting material of formula (2) can be achieved relatively quickly in good yields and under mild conditions when working in the presence of a catalytic amount of a Lewis acid catalyst, the zinc chloride , Tin chloride, zinc bromide, aluminum chloride, ethyl aluminum chloride or a mixture of two or more of these Lewis acids can be at a temperature in the range of about -20 to about 100 ° C and a pressure of about 1 to about 100 atm.

The molar ratio of acrolein: myrcene is from about 10: 1 to about 1:10, preferably about 1: 1.

The preferred temperature range is a function of the catalyst used. With zinc chloride or zinc bromide as a catalyst, the reaction temperature is in the range between 20 to 80 ° C, the most favorable temperature range being 40 to 50 ° C. Tin chloride, aluminum chloride and ethyl aluminum dichloride require a temperature in the range of -20 to 50 ° C, preferably 0 to 10 ° C.

One of the most prominent advantages of this process is that only moderate temperatures are required to obtain good yields and satisfactory reaction times. At the above moderate temperatures, the reaction times are from about 1 to 10 hours, with it being generally preferred to carry out the reaction within 7 to 9 hours. The amount of catalyst varies from about 0.2 to about 10% based on the reaction mass and depends on the temperature and the reaction time. A catalyst amount of 1 to 2%, based on the total weight of the reactants used, is preferred. The reaction can be carried out under 45 pressure, but since it does not require any special high-pressure techniques, as is the case with the known processes, it is preferably carried out at atmospheric pressure. It is also advantageous that no special regulations have to be observed when mixing the reactants. These can be added in any order or simultaneously. It was found,

that it is expedient to achieve the highest yields, first mixing the catalyst with myrcene and then adding the acrolein with good stirring. This addition 55 can take place, for example, by means of a metering pump in a period of 3 to about 6 hours, the reaction temperature being kept in the desired temperature range.

The reaction of starting material of the formula (2) or 60 of myracaldehyde and the acidic hydrating agent takes place at a temperature which can vary from 0 to 120 ° C. and depends on the catalyst system used. An example of the sulfonated copolymer of styrene and di-vinylbenzene (containing about 4% divinylbenzene) is the Dow Chemical Company product known under the trademark Dowex 50W-X4. An example of an activated alumina adsorbent is Filtrol 105 (trademark), which has the following properties:

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% By weight

100

nO

1

£ <L>

Ü

95

% By weight

78 0.

15

.-%

21st

Particle size analysis by roller (lo L / min. Air speed)

0-5 ji, wt% 8

0-20 n,% by weight 43

Tyler standard sieve by 100 stitches,

(0.147 mm clear mesh (

through 200 stitches,

(0.074 mm open mesh through 325 stitches,

(0.044 mm open mesh weight, g / cm3 free moisture, wt .-%

Free and combined moisture, (

(Loss at 926 ° C [1700 ° F])

Effective surface (BET method), SqM / gm. 300 acidity, phenolphthalein, mg • KOH / gm 4.8

Filter speed, cm3 / min. 38

Sealing against oil leakage,% by weight 35

An example of a silico-phosphoric acid polymerization catalyst is the product known as UOP-SPA-2 from Universal Oil Products Company of Des Piaines, Illinois.

The response time is primarily a function of four variables:

(1) reaction temperature;

(2) desired conversion;

(3) the hydrating agent used; and

(4) Concentration of the hydrating agent in the reaction mass.

In general, higher reaction temperatures result in shorter reaction times. However, reaction temperatures that are too high and / or reaction times that are too long in turn bring about a reduction in the conversion, specifically because of decomposition products. Higher concentrations of hydrating agents in the reaction mass shorten the reaction time for a given conversion of the desired reaction product. The response time can vary from 1 to 48 hours.

It has been found that the hydrating agent to be used in the process according to the invention is surprisingly extremely specific. Numerous hydrating agents or hydrating agent systems are unusable, for example:

64% sulfuric acid;

50% sulfuric acid;

30% sulfuric acid;

65% sulfuric acid-tetrahydrofuran mixture;

50% sulfuric acid-dimethylformamide mixture; and methanesulfonic acid.

The concentration of the hydrating agent in the reaction mass varies from about 3% (when these agents are used as a polymerization catalyst - such as silico-phosphoric acid) to about 50% when hydrating agents such as a p-toluenesulfonic acid-formic acid mixture or a p- Toluene sulfonic acid-acetic acid mixture can be used. Based on the reaction mass, preference is given to 3 to 10% by weight of polymerization catalyst (for example silico-phosphoric acid) or cation exchange resin (for example the Dowex 50W-X4 known under the trademark) or activated alumina adsorbent (for example the one under the trademark). well-known Filtrai grade 105). The hydrating agent, also based on the reaction mass, is preferably added in an amount of about 25 to 60% by weight, for example 65% aqueous sulfuric acid / acetic acid mixture or 50% aqueous sulfuric acid / tetrahydrofuran mixture, or 30% sulfuric acid-dimethylformamide

mixed, or p-toluenesulfonic acid-formic acid mixture,

or methanesulfonic acid-tetrahydrofuran mixture.

The ratio of protonic acid to second solvent, e.g. Sulfuric acid, methanesulfonic or p-toluenesulfonic acid: tetrahydrofuran, dimethylformamide or acetic acid, is preferably from about 1: 5 to about 5: 1 on a dry basis and weight: weight.

In summary, the advantages of the method according to the invention are as follows:

io 1) The reaction can be carried out in batches or continuously in standard kettles or standard vessels without pressure device;

2) The reaction can take place at moderate temperatures;

3) High throughput, high conversion and high yield are achieved;

4) The unpleasant smell and toxicity of certain Diels-Alder reagents, such as acrolein, do not occur, as is the case with known Diels-Alder reactions; and

5) Problems caused by the smell of morpholine or 20 other amines - which used to protect the carbox-

Aldehydes were used during the hydrogenation - and occur when removing such amines from the reaction mass, are completely switched off.

Suitable hydrolysis agents for the reaction (3) - »- (1) are bases, for example alcoholic solutions of alkali metal carbonates, bicarbonates and / or hydroxides or mixtures thereof. The conversion of the halogen group X of (3) into a carbalkoxy group (e.g. acetate) can be carried out using an alkali metal alkanoate 30 which has the formula

35

in which R is a lower alkyl and M is an alkali metal, such as sodium, and so the compound of formula (4) are obtained, which in turn can be hydrolyzed with a base, for example 40 aqueous alcoholic alkali metal hydroxide, under reflux to the target product.

The hydrohalogenation (2) -> (3) is e.g. using anhydrous hydrogen chloride or hydrogen bromide in an inert solvent such as glacial acetic acid 45. The reaction temperature is between 0 and 30 ° C, preferably 10 to 15 ° C. It is most convenient to work at atmospheric pressure, but higher pressures can also be used, which can shorten the reaction time. The range of weight ratios of myracaldehyde: hydrogen halide, HCl or HBr can vary from 10: 1 to 1: 1, the preferred weight ratio being about 5: 1. The range by weight of myracaldehyde: solvent is 1: 1 to 1:10, preferably 1: 5.

After the reaction has ended, the reaction mass is usually worked up by pouring it onto crushed ice and, for example, extracting the hydrochloromyracaldehyde (3) using an inert and volatile extraction solvent, such as diethyl ether. The extract is dried with an inert desiccant such as anhydrous magnesium sulfate and the solvent removed. The hydrochloromyracaldehyde is then preferably hydrolyzed or reacted with a carbalkoxylating agent to form the corresponding acylate or acetate of formula (4), which is then hydrolyzed.

The hydrolysis of the hydrochloromyracaldehyde or hydrobromacracaldehyde is preferably carried out in the presence of an aqueous base, such as an alkali metal carbonate,

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carbonate or hydroxide, carried out, for example sodium bicarbonate, potassium bicarbonate, sodium hydroxide, lithium hydroxide or potassium hydroxide. For example worked in an inert organic solvent, e.g. Isopropanol, at a temperature of between 50 and 120 ° C, preferably at the reflux temperature of the reaction mass (80 to 85 ° C in the case of a 50:50 water: isopropanol hydrolysis medium). The weight ratio of water: inert organic solvent can vary from 1: 5 to 5: 1, the preferred ratio being 1: 1. The weight ratio of base: water can vary from 1:25 to 1: 2, the preferred weight ratio being 1:10.

In order to replace the halogen group with an ester group, the hydrochloromyracaldehyde or the hydrobromacracaldehyde is reacted with the carbalkoxylating agent which, for. B. is an alkali metal salt of a lower alkanoic acid in an aqueous medium. For example, sodium acetate or potassium acetate in an inert solvent, such as toluene or xylene, are suitable, and the process is carried out at reflux temperatures. This reaction is preferably carried out in the presence of a phase converter, which can be one or more organic quaternary ammonium salts. Specific examples of such phase converters which can be used according to the invention are. Tricaprylmethylammonium chloride, cetyltrimethylammonium bromide and benzyltrimethylammonium hydroxide.

In general, the most preferred phase changers have the following basic formula:

R '. 4th

fi

N-I

R '

3rd

-R »2

wherein at least one of R'1; R'2, R'3 and R'4 are C6-Ci4-aryl, C6-C10-aralkyl, C6-C20-alkyl, C6-C14-alkaryl and C6-C20-alkenyl. The remaining R'2, R'3 and R'4 are methyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, l-methyl-2-propyl, 1 -Pentyl or 1-octyl groups. Z "is an anion, such as chloride, bromide or hydroxide.

The hydrolysis of the carbalkoxylate obtained to form lyral is preferably carried out by heating the carbalkoxylate in aqueous alcoholic base, suitably aqueous methanolic sodium hydroxide solution, under reflux.

After the reaction has ended, a mixture of the formula (1) which contains the p-isomer of the formula (Ia) can be extracted with an inert, volatile extraction solvent, such as diethyl ether.

The extract is usually dried, stripped off from the solvent, preferably under reduced pressure, and the "raw" lyral obtained is fractionally distilled.

The mixture (1) obtainable according to the invention can be mixed with one or more perfume additives, e.g. Alcohols, other aldehydes, nitriles, esters, cyclic esters and natural essential oils can be mixed to create a pleasant and desired fragrance through combined and complementary fragrance notes of the individual components, in particular and preferably lilac, flowers, fern, floral fragrance and roses. Such perfume compositions usually contain (a) the main note or the "bouquet" or basis of the composition; (b) modifiers that round off and complement the main note; (c) fixatives that contain fragrances that give the perfume a special note during all stages of evaporation; and substances that delay evaporation; and (d) top notes conventionally derived from low-boiling, freshly scented substances.

s In the case of perfume compositions, it is the individual component that contributes to the special fragrance characteristics of the compositions. But the overall effect of the perfume composition is at least determined by the sum of the effects of each ingredient. Thus, the mixture (1) obtained according to the invention can be used to change, modify or enhance the aroma characteristics of a perfume composition, specifically by emphasizing or masking the odor reaction imparted by other components.

15 The effective amount of the mixture produced according to the invention in perfume compositions and perfumed articles and colognes depends on many factors, not least the other constituents, their proportions and intrinsic effects must be taken into account. 2o It has been found that the mixture (1) can be used in amounts of 0.01% or less (for example 0.005%), for example to give soaps, cosmetics or other products a sweet, aromatic fragrance reminiscent of lilac and lilies to lend or to enhance, improve or modify the fragrance 25. The amount added can be up to 70% of the fragrance component and depends on the cost, the nature of the end product, the desired effect and the particular fragrance sought.

30 The mixture (1) obtained according to the invention can be used alone or in perfume compositions or as a fragrance component in detergents and soaps, room sprays and deodorants, perfumes, colognes, toilet water, bath additives such as bath oils and bath salts, hair preparations (such as 35 hair lacquers, brilliants, pomades and shampoos) , cosmetic preparations (such as creams, deodorants, hand lotions and sunscreen creams) and in powders (such as talcum powder, dusting powder, face powder and the like). As a fragrance component, 1% of the mixture is sufficient to give a pleasant lilac-lily note, for example a preparation with a lily, flower, fern, bouquet and rose fragrance. In general, no more than 8% of the mixture (1), based on the end product, is required.

45 The perfume composition or fragrance component can contain a carrier for the mixture (1) produced according to the invention. This carrier can be liquid, for example a non-toxic alcohol or a non-toxic glycol or the like, or an absorbent solid such as a gum (e.g. gum arabic), or a capsule material (such as gelatin).

The invention is illustrated by the following examples.

The following substances were mixed together in a reaction flask equipped with a thermometer, magnetic stirrer and reflux-55 cooler:

Components

amount

60 myracaldehyde 100 g

Water 50 g

Cation exchange resin (sulfonated copolymer of styrene and divinylbenzene containing 4% divinylbenzal-65 monomer units, manufactured by Dow Chemical Company of Midland, Michigan; moisture content: 65.8%; sieve fineness: DIN 20-40; trademark: Dowex R 50W-X4 10 g

7

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Samples were taken and analyzed every 30 minutes or every hour in order to determine the percentage of the resulting mixture of p- and m-isomer of the formula (1). The analysis was carried out by gas-liquid chromatography (SE-30 column). The following table shows the time, temperature and percentage of the reaction product:

Components

amount

time

temperature

% Mixture of p- and

Hours

° C

m-isomer of formula (1)

10th

0

22

_

1

23

0

2nd

90

0

3rd

95

1.2

15

4th

95

1.8

5

100

2.8

6

100

2.8

7

100

2.8

8th

100

2.8

20th

9

100

2.8

10th

100

2.8

11

100

2.8

12th

100

2.8

22

21st

4.9

25th

* 24

24th

4.8

26

25th

4.6

29 '/ 2

64

5.4

IVA

103

9.1

31 Vi

100

3.7

30th

33%

100

2.0

35 Vi

100

0.1

36 Vi

100

complete decomposition

35

* At this point, 40 g of 90% formic acid was added to the reaction mass.

Example 2

185 g of a 33% strength aqueous sulfuric acid solution were placed in a 1 liter reaction flask equipped with a stirrer, thermometer, filling funnel and reflux condenser and the latter was heated to 40.degree. 220 g of myracaldehyde was added through the hopper over a period of 10 hours, the temperature being kept at 40.degree. This reaction mixture was kept at 43 ° C. for 14 hours and then determined by gas-liquid chromatography,

that 1.5% mixture of p and m isomer (1) had been formed. The reaction mixture was then held at a temperature in the range of 43 to 45 ° C for 14 hours, after which it was found that 2.8% of mixture (1) was formed. Another 8 hours at 24 ° C gave 4.0% mixture. At this point, a further 100 ml of tetrahydrofuran was added and this reaction mixture was heated at 74 to 75 ° C. under reflux for 12 hours. After this reaction time 13.9% mixture was found.

The reaction mass was then washed with water and then with saturated aqueous sodium carbonate solution. The solvent was removed in vacuo and the residue was found to be 14.8% mixture (1) by gas-liquid chromatography.

Example 3

The following substances were placed in a reaction flask equipped with a stirrer, thermometer, filling funnel and reflux condenser:

40

50

p-T oluenesulfonic acid

90% aqueous formic acid

38 g 180 g

The mixture was stirred until completely dissolved. After the reaction mass had cooled to 7 ° C, the addition of myracaldehyde began, in total 300 g over a period of 2 1/2 hours, the temperature being kept between 5 and 10 ° C. Subsequent gas-liquid chromatography showed the formation of approximately 10% mixture (1). The reaction mass was then heated to 24 ° C. and held at this temperature for 4 hours, after which a 20% mixture was determined. After the reaction mass had cooled to 9 ° C., 50 g of water were added and the mixture was stirred for 1 hour, the temperature being kept at 9 to 10 ° C. Then 30.7% mixture was found. Further stirring for 9 hours at 20 to 23 ° C showed no visible change in percent. The reaction mixture was then washed with water and saturated aqueous sodium carbonate solution and the solvent removed. 49.8% mixture (1) was found in the tube residue.

Example 4

The following substances were placed in a 500 ml reaction flask equipped with a stirrer, thermometer, filling funnel and reflux condenser:

30 components

amount

Water myracaldehyde

Silico-phosphoric acid polymerization catalyst- UOP-SPA-2 (Universal Oil Prod. Corp. of Des Piaines, III.)

50 g 250 g 10 g

The reaction mixture was mixed at room temperature for 2 hours. No mixture (1) had formed during this time. The mixture was then heated to 50 ° C. and the reaction mixture was kept at this temperature for 2 hours, but no formation of the desired mixture was found. After the reaction mass had cooled, 50 g of formic acid were added, specifically at room temperature and stirred for 8 hours. The mixture was then heated to 70 ° C. and this temperature was held for 4 hours. After heating under reflux for 11 hours, gas-liquid chromatography gave 9% of the mixture (!) •

Example 5

The following substances were placed in a 500 ml reaction flask equipped with a stirrer, thermometer, filling funnel and reflux condenser:

55 components

amount

"Filtrol 105" (brand name) (activated alumina adsorbent from Filtrol Corporation, which has the following 60 properties: Particle size:

by rolling (101 / min. air speed) 0-5 n,% by weight 8

0-20 n,% by weight 43

65 through Tyler standard sieve

DIN 40% by weight 100

DIN 80% by weight 95

DIN 100% by weight 78

10 g

630597

8th

Components

amount

Bulk density g / cm3

Free moisture,% by weight Free and combined moisture,% by weight (loss at 926 ° C)

Open area (BET method) m2 / g acidity, phenolphthalein mg KOH / g

Filter speed. cm3 / min. Oil retention, wt% water myracaldehyde

0.67284 15

21st

300

4.8 38 35

50 g 250 g

The reaction mixture was stirred at room temperature for 21/2 hours, but then no formation of the mixture was found.

After stirring under reflux for 7 hours, gas-liquid chromatography gave 1% mixture (1). The addition of 100 ml of tetrahydrofuran and 3 hours of stirring at room temperature brought no visible change in the concentration of the mixture. The reaction mixture was then heated under reflux for 2 hours, then 50 g of formic acid was added and the mass was kept at room temperature for 12 hours, after which 1.5% mixture (1) was found. After heating under reflux for a further 4 hours, the content of mixture (1) rose to 1.9%. At this point, 100 g of acetic acid were added and the mass was stirred at room temperature for 11 hours. However, even this measure did not change the% content of the mixture. Only after another 71/7 hours of heating under reflux was a concentration of 4% of the total. desired product can be determined. The catalyst was then filtered and the reaction mixture washed until neutral. The analysis showed

18.0% solvent

76% myracaldehyde 4% mixture (1).

Example 6

The following substances were introduced into a 500 ml reaction flask equipped with a stirrer, thermometer and reflux condenser:

Components

amount

Myracaldehyde acetic acid sulfuric acid (64%)

100 g 100 g 50 g

Samples of the reaction mixture were taken at the specified time intervals. The following table shows the percentage of 4- (4'-methyl-4'-hydroxyamyl) -A 3-cyclohexenecarboxaldehyde determined by analysis:

Response time min.

15 75 195 300

Temperature ° C

78 40 33 33

% of the desired product (by area normalization)

33 58 69 73.7

Upon completion of the reaction, the mass contained (internal standard):

83% solvent 6.1% myracaldehyde 10.2% mixture (1).

Example 7

The following substances were introduced into a 500 ml reaction flask equipped with a stirrer, thermometer and reflux condenser:

Ingredients amount

Myracaldehyde 15 acetic acid p-toluenesulfonic acid

20th

25th

100g 100g 10g

The reaction mass was stirred at room temperature and samples were taken at different time intervals, different% contents of the desired mixture (1) being determined, as the following table shows:

Response time min.

% Mixture (1)

30 90 210 330

5.6 14.8 21 22.6

35

40

45

50

10 g of water were added to the reaction mass and the mixture was stirred for a further half hour. Thereafter, 18.9% mixture (1) was formed. After stirring for a further 4 hours at room temperature, 28% of the mixture in the reaction mass was determined (on a solvent-free basis). The gas-liquid chromatography showed the following raw% data: 91.6% solvent, 5.3% myracaldehyde

2.6% mixture (1) with a predominant proportion of (la). This mixture was distilled from the reaction mass and used in the following examples:

Example 8 A «Fougère» paraffin preparation

60

Parts by weight

Components

50

Cinnamon alcohol

40

Amborne musk

5

Vanillin

80

Coumarin

10th

Oak moss resinoid

125

Linalool

150

Linalyl acetate

50

Benzyl acetate

70

Phenylethanol

100

Bergamot oil

150

Lavender oil

50

Geranium oil (bourbon)

50

Sandalwood Oil E.I.

5

Eugenol

15

Isoeugenol

20th

Amyl salicylate

20th

Benzyl salicylate

20th

Product of Example 1

1010

9

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This product gives the "Fougère" perfume a very sweet, lilac-lily aromatic fragrance.

Example 9

A rose perfume was made from the following ingredients:

Parts by weight

Components

20th

Phenylethylphenylacetate

40

Phenylethyl salicylate

150

Geraniol

240

Phenylethanol

150

Citronellol

20th

Sandalwood Oil E.I.

75

Nonandiol diacetate-1,3

50

Geranyl acetate

20th

Geranylphenyl acetate

20th

Citronellyl formate

25th

Phenylethyl acetate

60

Phenylethyl propionate

20th

Phenylacetaldehyde 50% in

Diethyl phthalate

20th

Phenylacetaldehyde-l, 3-butylene-

glycolacetal

10th

Eugenol

10th

Methyl isoeugenol

50

alpha hexyl cinnamaldehyde

40

Product of Example 3

1030

This "rose" perfume had a sweet floral aroma, which was enhanced by the addition of the product from Example 3.

Example 10

A «bouquet» parfim was made from the following ingredients:

Parts by weight

Components

20th

Amborne musk

40

Heliotropin

100

Benzyl acetate

80

4-tert-butylcyclohexyl acetate

130

alpha hexyl cinnamaldehyde

40

alpha amyl cinnamaldehyde

30th

Linalyl acetate

80

Terpineol

80

Geranyl acetate

80

Linalool

100

alpha-methyl ionone

25th

Methyl isoeugenol

15

Isoeugenol

40

Geraniol

60

Phenylethanol

20th

Styrallyl acetate

50

Vetiveryl acetate

5

10-Undecen-l-al

5

Product of Example 4

1000

The product from Example 4 gave the “bouquet” par for a sweet lilac-lily shade.

Example 11 Preparation of a Cosmetic Powder 100 g of talcum powder were intimately mixed with 0.25 g of the mixture obtained in Example 1 and containing m-isomers of (1) and predominantly p-isomer (Ia) in a ball mill. The powder had an excellent, sweet lilac-lily aroma.

Example 12 Perfumed Liquid Detergent Concentrated liquid detergents with a sweet lilac-lily scent were prepared which were 0.10%; 0.15% and 0.20% of the mixture (1) according to Example 6 with a predominant proportion of (la) contained. The seasoning additive was mixed homogeneously with the liquid detergent. All samples produced in this way had a sweet lilac-lily spice note, the intensity increasing with higher concentrations of the mixture mentioned.

Example 13

Production of colognes and handkerchief perfume

A mixture (1) prepared according to Example 2 with a predominant proportion of (la) was in a concentration of 2.5% in 85% aqueous ethanol in a colognes and in a concentration of 20% in 95% aqueous ethanol in a handkerchief perfume brought in. The mixture gave both the colognes and the handkerchief perfume a distinctive and certain sweet fleece-lily spice note.

Example 14 Preparation of a soap composition 100 g of soap chips were mixed with 1 g of the mixture (1) obtained according to Example 3 until a substantially homogeneous mass was formed. The perfumed soap composition had an excellent sweet lilac-lily aroma.

Example 15

Preparation of a detergent composition 100 g of detergent powder were mixed with 0.15 g of mixture (1) obtained according to Example 4 until a substantially homogeneous mass was formed. This composition had an excellent sweet lilac-lily aroma.

Example 16

Part A:

The following substances were introduced into a 250 ml reaction flask equipped with a stirrer and thermometer:

Ingredients amount

Sulfonated copolymer of styrene and divinylbenzene, containing 4% divinylbenzene monomer units;

Moisture content: 65.3%;

Sieving fineness: DIN 20-40,

Watermark Dowex® 50W-X4 100 g

Myracaldehyde 100 g

Acetic acid 100 g

The reaction mixture was stirred for 33 hours at room temperature. Samples were taken for the presence of Lyral, i.e. Mixture of formula (1), analyzed. The dates are as follows:

Sampling time:% Lyral in the

Hours of reaction mass

9 8

22 16

33 22.5

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

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10th

The reaction product was filtered, neutralized and fractionally distilled. The lyral went over at 141 to 153 ° C and 1.4 to 3.9 mm Hg. The distillate collected was then fractionated in a Goodloe column and a product was obtained, the boiling point of which was 125 to 126 ° C and 0.7 mm Hg.

Part B

The procedure of Part A was repeated, except for the temperature and the reaction time. It was worked at 60 to 62 ° C for 3112 hours. The following table shows the reaction times, the temperatures and the percentages of lyral.

Time temperature percent

45 min. 61 ° C 19.5%

2V2 hours 60 ° C 7.0%

3 V2 hours 61 ° C 3.5%

Part C.

A solution was made from the following ingredients:

Ingredients amount

Myracaldehyde 500 g

Acetic acid 1000 g deionized water 180 g

50 g of the copolymer (Dowex®) (preferably washed with 200 g of 10% sulfuric acid and rinsed with deionized water) were rinsed into a cooling column (20 mm) jacketed with cooling water using 80% acetic acid. The column was then rinsed with 500 g of 80% acetic acid. Then, due to gravity, the myracaldehyde / acetic acid / water solution flowed through the chromatography column, the temperature of which varied between 26 and 50 ° C over 6 hours. The following table shows the reaction time, temperature of the column and the percentage of lyral in the eluate and its total weight:

Time temperature ratio weight

Myracaldehyde: eluate

Lyral

30 min.

26 ° C

0

68 g

2 hours

36 ° C

0

72 g

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5 hours

27-49 ° C

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50 ° C

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90 g

Part D:

The process steps from Part C were repeated except for the temperature of the chromatography column, which was between 50 and 60 ° C. The following results were achieved:

Teit temperature ratio weight

Myracaldehyde: Eluate Lyral

P / 2 hours 57-60 ° C 20: 1 171g

3 hours 50 ° C 25: 1 125 g

4 hours 55 ° C 20: 1 98 g

Part E:

The following components were introduced into a reaction flask (250 ml) equipped with a stirrer and thermometer:

Ingredients amount

Myracaldehyde 25 g

Dowex® 50W-X4 50 g

Glacial acetic acid 50 g

The reaction mixture was stirred at room temperature for 48 hours with no lyral being formed. The mixture was then heated to 60 ° C. for 7 hours.

A 20 cm3 sample was taken and placed in a separatory funnel. 100 ml of water and 50 cm 3 of benzene were added to this sample, the resulting mixture was shaken vigorously and the water phase was separated from the resin / oil layer. The oil layer was washed with a sodium bicarbonate solution until neutral and dried over anhydrous magnesium sulfate. Then the benzene was evaporated and the oil layer was analyzed by preparative gas-liquid chromatography. The ratio of lyral: myracaldehyde was 43.5: 54.6.

Part F:

The following reaction participants were introduced into a 2 liter reaction flask equipped with a stirrer, thermometer and reflux condenser:

Ingredients amount

Myracaldehyde 196 g (1 mol)

Dowex® 50W-X4 583 g

Water 217 ml

The reaction mixture was heated to 60 ° C. and held at this temperature for 89 hours, with constant stirring. A 20 cm3 sample was then removed and 100 ml of water and 50 cm3 of benzene were added in a separating funnel. The mixture was shaken vigorously and the oil phase separated. After the oil phase had been dried over anhydrous magnesium sulfate, it was evaporated in a «Rinco» evaporator at 50 ° C. Gas liquid chromatography and IR analysis showed 29.4% lyral. The ratio of lyral: myracaldehyde was 32.5: 64.2.

Part G:

The following reaction participants were introduced into a 2 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and a nitrogen blanket:

Ingredients amount

Myracaldehyde 196 g

Dowex® 50W-X4 583 g water 67 ml

Glacial acetic acid 180 g (3 mol)

The reaction mixture was heated to 60 ° C. with stirring and kept at this temperature for 48 hours. A 20 cm3 was then removed and further treated in accordance with the process steps in Part F. Gas-liquid chromatography, IR and spectral analyzes showed 8.0% lyral. The ratio of myracaldehyde: lyral was 87.7: 8.0.

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Part H:

The following reaction participants were introduced into a 2 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and nitrogen blanket:

Ingredients amount

Myracaldehyde 196 g

Dowex® 50W-X4 620 g

Acetic acid 180 g (3 mol)

The reaction mixture was heated to 60 ° C. with stirring and kept at this temperature for 48 hours. The reaction mass was then treated further in accordance with the process steps in part F. Gas-liquid chromatography, IR and MS analyzes showed 25.3% lyral. The ratio of lyral: myracaldehyde was 24.8: 74.9.

Part One:

The following reaction participants were introduced into a 2 liter reaction flask equipped with a stirrer, thermometer and reflux condenser:

Ingredients amount

Myracaldehyde 98 g (0.5 mol)

Dowex® 50W-X4 620 g

Glacial acetic acid 240 g (4 mol)

The reaction mixture was heated to 60 ° C and held at this temperature for 24 hours. The reaction mass was then treated further in accordance with the process steps in part F. Gas-liquid chromatography, IR and MS analyzes showed 33.6% by-product with a ratio of lyral: myracaldehyde of 33.6: 57.2. 10 shows the gas-liquid chromatography profile of the reaction product after 24 hours.

Example 17

A clear, single-phase solution was prepared from 90 g myracaldehyde, 100 g acetic acid and 18 g deionized water. This solution was mixed with 20 g of the cation exchange resin from the Rohm and Haas Company, Philadelphia, known under the trademark "Amberlyst 15". This cation exchange resin is a copolymer of styrene and divinylbenzene, the monomer units of the divinylbenzene being the same as the monomer units of the styrene.

The reaction mixture was heated at temperatures of 25 to 80 ° C, with stirring. Samples were taken at various time intervals and examined for the content of lyral. The following table shows the reaction times, temperature and amount of lyral formed:

Time temperature Lyral

Percentage

2 Vi hours 25-65 ° C 3.2%

3 Vi hours 65-64 ° C 21%

4Vi hours 64-65 ° C 29.3%

5 hours 65-85 ° C 11.9% 5 V * hours 85-86 ° C 14.3%

(by internal standards)

and 36.9%

(by area normalization)

630 597

After adding 100 g of toluene, the reaction mixture was washed with water and saturated sodium carbonate solution. It was then evaporated and distilled to obtain a lyral with a boiling point of 133 to 135 ° C at 0.5 to 0.9 mm Hg.

Example 18

The following reactants were placed in a 500 ml reaction flask equipped with a stirrer, thermometer and reflux condenser:

Ingredients amount

Myracaldehyde 200 g

30% aqueous sulfuric acid 160 g

Dimethylformamide 50 g

The reaction mixture was heated from 25 ° C to the reflux temperature (117 ° C) and held under reflux for 5 hours. Then a further 100 g of dimethylformamide were added and samples were taken at different times, which were examined for gas-liquid chromatography for lyral.

The results are:

Time temperature Lyral

Percentage l'A hours 117 ° C 4.0%

3 '/ 4 hours 115 ° C 4.6%

5 hours 114 ° C 2.8%

Example 19

The following reactants were placed in a 250 ml reaction flask equipped with a stirrer, thermometer and reflux condenser:

Ingredients amount

Myracaldehyde 19.2 g (0.1 mol)

Imolar hydrochloric acid 100 ml (0.1 mol)

Isopropanol 100 ml

The reaction mixture was heated under reflux and with a stirrer for 4 hours.

Then 100 ml of water were added and the aqueous layer thus formed was extracted with three 50 ml portions of diethyl ether. The ether extracts were poured together and washed with three 50 ml portions of saturated sodium bicarbonate solution and then with three 50 ml portions of water. The ether extracts were washed with anhydrous magnesium sulfate, filtered and concentrated. Gas-liquid chromatography showed a ratio of 49% myracaldehyde to 47% lyral. The amount of lyre formed was confirmed by NMR and MS analyzes.

The lyral with a significant proportion of p-isomer (la) was then distilled from the reaction mixture and used in Examples 20 to 28 below.

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Example 20

A «Fougère» parfiim was made:

Parts by weight

Components

50

Cinnamon alcohol

40

Amborne musk

5

Vanillin

80

Coumarin

10th

Oak moss resinoid

125

Linalool

150

Linalyl acetate

50

Benzyl acetate

70

Phenylethanol

100

Bergamot oil

150

Lavender oil 45/47

50

Geranium oil (bourbon)

50

Sandalwood Oil E.I.

5

Eugenol

15

Isoeugenol

20th

Amyl salicylate

20th

Benzyl salicylate

20th

Product made after

Example 19

1010

This compound from Example 19 gave the perfume a very sweet, lilac-aromatic fragrance.

Example 21

A rose perfume was made from the following ingredients:

Parts by weight

Components

20th

Phenylethylphenylacetate

40

Phenylethyl salicylate

150

Geraniol

240

Phenylethanol

150

Citronellol

20th

Sandalwood Oil E.I.

75

Nonandiol diacetate-1,3

50

Geranyl acetate

20th

Geranylphenyl acetate

20th

Citronellyl formate

25th

Phenylethyl acetate

60

Phenylethyl propionate

20th

Phenylacetaldehyde 50% in

Diethyl phthalate

20th

Phenylacetaldehyde-l, 3-butylene-

glycolacetal

10th

Eugenol

10th

Methyl isoeugenol

50

alpha hexyl cinnamaldehyde

40

Product made after

Example 19

1030

The product of Example 19 enhanced the sweet floral aroma of the rose perfume.

Example 22

A «bouquet» perfume was made from the following ingredients:

Parts by weight of components

20 Amborne musk

40 heliotropin

100 benzyl acetate

80 4-tert-butylcyclohexyl acetate

130 alpha-hexyl cinnamaldehyde

40 alpha amyl cinnamaldehyde

30 linalyl acetate

80 terpineol

80 geranyl acetate

80 linalool

100 alpha methyl ionone

25 methyl isoeugenol

15 isoeugenol

40 geraniol

60 phenylethanol

20 styrallyl acetate

50 vetiveryl acetate

5 10-Undecen-l-al

5 Product manufactured according to

Example 19

1000

The addition of this product gave the “bouquet” par for a sweet lilac-lily shade.

Example 23 Preparation of a Cosmetic Powder 100 g of talcum powder were mixed with 0.25 g of the product from Example 19 in a ball mill. This powder had an excellent sweet lilac-lily aroma.

Example 24 Perfumed Liquid Detergent Concentrated liquid detergents with a sweet lilac-lily scent were prepared which were 0.10%; 0.15% and 0.20% of the product of Example 19, respectively. The additive was mixed homogeneously with the liquid base material. All of the samples produced in this way had a sweet lilac-lily flavor, the intensity increasing with increasing concentration.

Example 25

Preparation of a colognes and handkerchief perfume The product Example 19 was added to a colognes in a concentration of 2.5% in 85% aqueous ethanol and in a concentration of 20% (in 95% aqueous ethanol) to a handkerchief perfume. Both the colognes and the handkerchief perfume received a distinctive and certain sweet flowing spice of lily.

Example 26

The mixture (1) prepared according to Example 19 was made into a colognes in a concentration of 2.5% in 85% aqueous ethanol; and added to a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). Both preparations received a distinct and certain strong bouquet aroma with sweet lilac-lily notes.

Example 27

100 g of soap scraps were mixed with 1 g of the product from Example 19 to a substantially homogeneous mass. The scented soap had an excellent sweet lilac-lily aroma.

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Example 28

100 g detergent powder containing sodium benzene sulfonate was mixed with 0.15 g of the mixture prepared according to Example 19 until an essentially homogeneous mass was formed. This composition had an excellent sweet lilac-lily aroma.

Example 29

Production of Lyral by hydrochlorination of myracaldehyde and subsequent hydrolysis

(A) hydrochlorination

40 g of anhydrous hydrochloric acid were bubbled into a cooled (10 to 15 ° C.) solution of 200 g of myracaldehyde in 1000 g of glacial acetic acid over the course of an hour. The reaction mixture was stirred at 10-15 ° C for 15 hours and then poured over 2 kg of crushed ice. It was extracted with diethyl ether, the extracts washed with sodium carbonate solution and dried over anhydrous magnesium sulfate. After removing the diethyl ether in vacuo, 225 g of crude hydrohalogenated product (hydrochloromyracaldehyde) was obtained, which was hydrolyzed without further treatment.

(B) hydrolysis

The crude hydrohalogenated product (hydrochloromyracaldehyde) was stirred under reflux at 80 to 85 ° C for 10 hours in a mixture of 1000 g water, 1000 g isopropanol and 100 g sodium bicarbonate. Then the reaction mixture was diluted with 1000 g of water and extracted with diethyl ether. The diethyl ether extracts were dried over anhydrous magnesium sulfate and then the diethyl ether was removed in vacuo (0.5 atm.). An oil remained, which was distilled carefully, 54 g of lyral having a boiling point of 134 to 135 ° C. at 1 mm Hg being obtained. The yield was 25%, based on the starting material myracaldehyde.

Example 30

Production of Lyral by hydrochlorination of myracaldehyde and subsequent hydrolysis

(A) hydrochlorination

This is carried out as in Example 29.

(B) hydrolysis

The crude hydrohalogenated product was stirred under reflux at 80 to 85 ° C in a mixture of 1000 g of water, 1000 g of isopropanol and 90 g of potassium hydroxide for 10 hours. The reaction mass was then diluted with 1000 g of water, extracted with diethyl ether and the diethyl ether extracts were dried over anhydrous magnesium sulfate. After removing the diethyl ether in vacuo, an oil remained which was distilled carefully, 56 g of lyral passing over with a boiling point of 134 to 135 ° C. at 1 mm Hg. The yield of 26% is based on the myracaldehyde.

Example 31

(i) Preparation of myracaldehyde hydrochloride

A solution of 1000 g myracaldehyde in 2500 g toluene was cooled to -20 ° C. 200 g of anhydrous hydrogen chloride gas was bubbled into this solution over a period of 5 hours while maintaining the temperature at -10 to -20 ° C. The reaction mixture was left to stand at room temperature for 3 days. After removal of the toluene under reduced pressure, 1140 g of crude myracaldehyde hydrochloride remained.

(ii) Solvolysis of myracaldehyde hydrochloride

(a) A solution of 100 g myracaldehyde hydrochloride in a mixture of 100 g water and 500 g isopropanol

630597

was stirred for 2 hours at 80 ° C with 50 g of sodium acetate. After dilution with water, extraction with ether and removal of the solvent, 90 g of a product were obtained which contained 35% lyral.

(b) A solution of 100 g myracaldehyde hydrochloride in 250 g toluene was stirred under reflux for 3 hours with 50 g anhydrous sodium acetate and 1 g tricaprylmethyl-ammonium chloride (Aliquot 336R). After washing with water and evaporating the toluene, 95 g of a product was obtained which contained 50% lyral acetate. The hydrolysis of this acetate to form lyral was carried out by refluxing the crude product in aqueous methanolic sodium hydroxyl solution.

(c) A mixture of 100 g myracaldehyde hydrochloride, 500 g isopropanol and 25 g sodium hydroxide was heated under reflux for 2 hours and then poured over crushed ice. After extraction with ether and removal of the ether, 85 g of a crude product was obtained, which contained 45% lyral.

Example 32

Production of lyral from myrcene (6) and acrolein using an aluminum chloride catalyst

A mixture of 0.5 g of aluminum chloride (0.0037 mol) and 10 cm 3 of toluene was placed in a 250 cm 3 flask equipped with a stirrer, condenser, thermometer, dropping funnel and drying tube. A mixture of 20 g (0.35 mol) of acrolein and 50 g (0.32 mol) of myrcene was added dropwise to the aluminum chloride-to-toluene mixture while the temperature of the reaction mass was kept at 0 ° C. over 11/2 hours has been. A dry ice isopropyl alcohol bath was used for this purpose. After the addition was complete, the reaction mass was stirred at a temperature of 0 to 20.degree. C. for 30 minutes. Then 30 cc of water and then 50 ccm of diethyl ether were added. The resulting organic layer was washed with two 50 cm3 portions of saturated sodium bicarbonate solution and then with two 50 cm3 portions of water. The organic layer thus washed was dried over anhydrous magnesium sulfate, filtered and concentrated.

The product obtained was fractionally distilled and Lyral with a boiling point of 133 to 135 ° C at 0.5 to 0.9 mm Hg was collected.

Example 33

Preparation of lyral from acrolein and myrcene (6) using an ethyl aluminum chloride catalyst

A mixture of 1.0 g (0.008 mol) of ethyl aluminum dichloride and 10 ccm of toluene was placed in a 250 cm3 flask equipped with a stirrer, condenser, thermometer, dropping funnel and drying tube. A mixture of 20 g (0.25 mol) acrolein and 50 g (0.32 mol) myrcene was added dropwise over 11/4 hours while maintaining the temperature at 0 ° C. A dry ice-iso-propyl alcohol bath was used here. After the addition was complete, the reaction mixture was stirred at a temperature of 0 to 20 ° C for 30 minutes. Then 30 cm3 of water and then 50 cm3 of diethyl ether were added. The organic layer formed was separated from the aqueous layer and washed with two 50 cm3 portions of saturated sodium bicarbonate solution and then with two 50 cm3 portions of water. The organic layer thus washed was dried over anhydrous magnesium sulfate, filtered and concentrated.

The product obtained was fractionally distilled and lyral with a boiling point of 133 to 135 ° C. at 0.5 to 0.9 mm Hg was collected.

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S

Claims (13)

630597 (1") 45 contains as a component, characterized in that starting material of the formula (2) 55 which consists of the p-isomer or a mixture of p- and m-isomer, with hydrogen chloride or hydrogen bromide to a hydrohalogenated product of the formula 60 65 2. The method according to claim 1, characterized in that one of the following is optionally used as the acidic hydrating agent: (a) a mixture of at least one protonic acid with at least one water-miscible organic solvent, (b) an ion exchange resin or a mixture of such resins, (c) an acidic polymerization catalyst or a mixture of such catalysts, or (d) an activated tone or a mixture of such tones. (2) H which consists of the p-isomer or a mixture of p- and m-20 isomers, with hydrogen chloride or hydrogen bromide to a hydrohalogenated product of the formula which consists of the p-isomer or a mixture of p- and m-isomers, by intimate mixing with an acidic hydrating agent without converting the aldehyde group. (2) \ 2nd PATENT CLAIMS 1. Process for the preparation of a mixture comprising the compound of the formula (1c) contains as a component, characterized in that starting material of the formula (1a) contains as a component, characterized in that io starting material of the formula 15 3rd 630 597 Conversion of the product with a carboalkoxylating agent to an ester product of the formula in which R is a lower alkyl radical, and hydrolyze the ester product to obtain the target product, performing all reaction steps without changing the aldehyde group. (3) in which X is chlorine or bromine and which consists at least partially of the p-isomer, the hydrohalogenated (3) H in which X is chlorine or bromine and which at least partially consists of the p-isomer, is reacted and then treated with a hydrolysis agent. 3. The method according to claim I, characterized in that the acidic hydrating agent used is: (i) mixtures of lower alkanoic acids with p-toluenesulfonic acid, (ii) mixtures of 30% aqueous sulfuric acid with tetrahydrofuran, (iii) mixtures of 30% sulfuric acid with dimethylformamide, (iv) mixtures of 50% sulfuric acid with tetrahydrofuran, (v) mixtures of 65% sulfuric acid with acetic acid, (vi) mixtures of methanesulfonic acid with tetrahydrofuran, (vii) sulfonated copolymers of styrene and divinylbenzene, (viii) mixtures of (a) sulfonated copolymers of styrene and divinylbenzene with (b) lower alkanoic acids, (ix) activated clays acting as absorbents, (x) silicophosphoric acid polymerization catalysts, or (xi) mixtures of aqueous hydrochloric acid and lower alkanol, and that the reaction is carried out at temperatures in the range from 0 to 120.degree. 4. A process for producing a mixture comprising the compound of the formula 25th 30th // O \ 5. A process for producing a mixture comprising the 35 compound of the formula 40 6. A process for producing a mixture comprising the compound of the formula HO contains as a component, characterized in that a compound of the formula is treated with acrolein to form material of the formula io which consists of the p-isomer or a mixture of p- and m-isomer, and in the presence of an acidic hydrating agent to the target product Formula (la) is implemented without converting the aldehyde group. 7. The mixture obtained by the process according to claim 1. 8. Mixture obtained by the process according to claim 4. 9. The mixture obtained by the process according to claim 5. 10. Mixture obtained by the process according to claim 6. 11. Use of a mixture prepared by the process according to Pa-25 tent Claim 1 as a fragrance. 12. Use of a mixture produced by the method according to claim 4 as a fragrance. 13. Use of a mixture prepared by the process according to Pa-30 claim 5 as a fragrance.