DE2427465C3 - 4-alkyl-substituted acyl-polyalkylindanes, process for their production and their use as fragrances - Google Patents

Description

R ³ CO

H ₃ C CH,

in which R ^{1 is} a methyl, ethyl or isopropyl group, R? represents a hydrogen atom, a methyl group or an ethyl group and R ^{3 represents} a hydrogen atom, a methyl group or an ethyl group

2. Process for the preparation of the compounds according to claim 1, characterized in that a 4-alkyl-substituted polyalkylindan of the general formula

CH,

40

in which R ¹ and R ^{2 have} the meanings given in claim 1, acylated in a manner known per se.

3. Use of the 4-alkyl-substituted acyl-polyalkyl-indanes according to Claim 1 as fragrances.

55

The invention relates to those alkyl-substituted in the 4-position Acyl polyalkylindanes, compounds which, compared to the 5-alkyl-substituted acyl polyalkylindanes known as musk fragrances, have a strong, persistent develop the musk scent and a process for making these compounds.

The aim of the invention is to provide new acyl-polyalkylindanes which are alkyl-substituted in the 4-position, which can be used as synthetic musk fragrances and which have a superior musk fragrance unfold.

The invention thus relates to 4-alkylsubstitu-

H ₃ C CH ₃

in which R ^{1 is} a methyl, ethyl or isopropyl group,

R ^{2 represents} a hydrogen atom, a methyl group or a Ethyl group and R ^{3 is} a hydrogen atom, a Means methyl group or an ethyl group. The 4-alkyl-substituted acyl according to the invention

Polyalkylindanes can be produced easily and in good yields by using a 4-alkyl-substituted polyalkylindane of the general formula II

H ₃ C

in which R ¹ and R ^{2 have} the meanings given above, acylated in a manner known per se to introduce an acyl group having 1 to 3 carbon atoms. The 4-alkyl-substituted polyalkylindanes used as starting material for the preparation of the 4-alkyl-substituted acyl-polyalkylindanes according to the invention are likewise new compounds. These compounds can be prepared by alkylating an m-alkyl-substituted cumene or an m-alkyl-substituted -methylstyrene by methods known per se in the presence of a Friedel-Crafts catalyst (cf. Published Japanese Patent Application No. 9025/56).

Alkylating agents are e.g. B. olefins having 4 to 6 carbon atoms, secondary alcohols and / or tertiary alcohols.

Examples of m-alkyl-substituted cumoles or are m-alkyl-substituted a-methyl-styrenes

m-cymene, m-isopropenyl-toluene, m-ethyl-cumene, m-ethyl-a-methyl-styrene, m-diisopropylbenzene and m-isopropyl-a-methyl-styrene. Examples of suitable alkylating agents are 2-methyl-2-butene, 2-methyl-1-butene, 2-methyl-2-pentene, isobutylene, 2-methyl-1-butene, 2-methyl-1-pentene, tert-amyl alcohol, Dimethyl-n-propyl-carbinol, tert-butyl alcohol, Methyl isopropyl carbinol, ethyl isopropyl carbinol and methyl isobutyl carbinol. Of these Compounds are 2-methyl-2-butene, 2-methyl-1-butene, isobutylene, tert.-amyl alcohol, tert-butyl alcohol and methyl isopropyl carbinol are particularly suitable.

The above-mentioned condensation reaction for the preparation of the starting materials takes place in the presence of a Friedel-Crafts catalyst. Examples of catalysts of this type are protonic acids such as sulfuric acid, Lewis acids such as AlCl ₃ , AlBr ₃ , ZnCl ₂ , SnCU, BF ₁ or FeCl ₃ and solid acids such as silicon dioxide, aluminum oxide or cation exchange resins. Any acidic catalysts suitable for carrying out a Friedel-Crafts reaction can be used.

The condensation reaction can, if appropriate, be carried out in the presence of a solvent. It has been found that can be any used in the inventive method under the reaction-inert solvent, wherein, in particular ₅ paraffinic hydrocarbons, such as hexane or heptane are particularly preferred.

Regarding the reaction temperature, there were no particular restrictions, and generally temperatures of from -20 can be applied to +150 ⁰ C, and temperatures in the range of 0 to 20 ° C preferred.

The condensation can be carried out in the same way as conventional alkylation reactions will.

Since the m-alkyl - «- methylstyrene polymerize in certain cases in the presence of a catalyst or to Can cause side reactions, it is preferred to conduct the reaction in such a way that these compounds do not come into contact with the catalyst before the alkylation reaction occurs. Especially if a m-alkyl-cumene is used as the starting material it is preferred to conduct the reaction in such a way that the alkylating agent is added dropwise to one of the Catalyst, the m-alkyl-cumene and the solvent-containing solution are added. When an m-alkylcumene is used as a starting material, it is not absolutely necessary to add a solvent because the material itself can serve as a solvent. If the starting material is a m-alkyl-ot-methyl-styrene is used, it is preferred to use the m-alkyl-Λ-methyl-styrene add dropwise to a solution containing the catalyst, the alkylating agent and the Contains solvent.

According to the process according to the invention, the 4-alkyl-substituted polyalkylindan is the general Formula I then acylated in a manner known per se. For example, this is done by reacting a Compound of general formula II with an acylating agent containing 2 to 3 carbons in the presence a Friedel-Crafts catalyst in a solvent, whereby an acetyl group or a Propionyl group is introduced. These groups can be introduced in the 5- or 6-position, usually a mixture of an acylated compound whose acyl group is in the 5-position and an acylated compound whose Acyl group in the 6-position is obtained. Examples of inert solvents used in this reaction are aliphatic hydrocarbons such as pentane, hexane or heptane, halogenated hydrocarbons, such as chloroform, dichloromethane or dichloroethane, nitro hydrocarbons such as nitrobenzene or nitropropane, and carbon disulfide.

Examples of acylating agents are acetyl halides, acetic anhydride, propionyl halides and propionic anhydride. Acetyl chloride and propionyl chloride are particularly suitable. As Friedel-Crafts catalysts one can use those given above for the preparation of the compounds of general formula I. use.

The acylation reaction is preferably carried out at a temperature of -20 to +100 ⁰ C, more preferably ° at a temperature from 0 to 60 C.

The formyl group can also be introduced into the compounds of the general formula H in the customary manner. On an industrial scale, it is preferred to react a polyalkylindane of the general formula II with formaldehyde or paraformaldehyde and hydrochloric acid or zinc chloride at a temperature of, for example, 50 to 100 ^° C. and then to hydrolyze the chloromethylated product obtained with, for example, sodium hydroxide, potassium hydroxide or an organic amine. The formyl group can also be introduced with the aid of the Gattermann-Koch reaction, according to which the polyalkylindane of the general formula II is reacted with carbon monoxide, hydrogen chloride and aluminum chloride. The catalyst is then separated in a conventional manner from the compound of the general formula I obtained by introducing an acyl group into the polyalkylindane, after which the product is distilled to obtain the desired 4-alkyl-substituted acyl-polyalkylindane. The resulting 4-alkyl-substituted acyl-polyalkylindane is a mixture which consists predominantly of a polyalkylindane which is acyl-substituted in the 5-position and a polyalkylindane which is acyl-substituted in the 6-position. These compounds can be separated from one another or the mixture can be used as such as a musk fragrance.

The compounds of the general formula I according to the invention can either be used directly or according to an in cleaning carried out as desired with a perfume base, a perfume composition, a das Perfume or the fragrance-modifying material, a modified perfume composition or other in materials well known in the fragrance industry. When the new connections are in such perfume compositions are incorporated, they give them a soft note with long lasting effect. Furthermore, they can be in any desired form, e.g. B. in the form of the above Reaction product, in the form of the purified product or a mixed product into various Perfume products are incorporated. Examples of such perfume products are perfume, cologne Water, detergents, soaps, various skin and hair cosmetics, various bath products, various Medicinal cosmetics for the skin and for the hair, cosmetic powders, fragrances for interiors, deodorants and various masking agents.

The amount in which the compounds of the general formula I are used can be determined by the person skilled in the art depending on the type and use of the prepared product or the fragrance products can be varied. Amounts less than a few percent by weight are in the final fragrance product sufficient. Work is carried out on the intermediate products used to produce the final fragrance products the compounds of general formula I in low to high concentrations, for example can range from about 0.1 to 50 weight percent.

The following examples are intended to explain the invention further. The preparation examples 1 to 6 relate to Preparation of the starting compounds of general formula II and Examples 1 to 7 the preparation

of the products of the general formula I via the starting compounds of the general formula II.

Manufacturing example 1

A 500 ml flask equipped with a stirrer, dropping funnel, condenser and thermometer is charged with 100 g of sulfuric acid, 100 g of glacial acetic acid and 70.5 g of 2-methyl-2-butene. ^{At a reaction temperature} of 5 to 15 ° C., 132 g of m-isoprope- ι ο nyltoluene are added dropwise over the course of 2 hours. To terminate the reaction, stir the mixture for a further hour and then transfer it to a separating funnel. The catalyst is separated off and the mixture is washed slightly with water, neutralized with sodium hydroxide and washed twice with water. The vacuum distillation of the hydrocarbon phase obtained gives 45.7 g of a fraction with a boiling point of 70 ° C. to 99 ° C. / 2 mm Hg. By rectifying this fraction, 1,1,2,3,3,4-hexametylylindane is obtained as a fraction with a Boiling point from 102 ° C to 104 ° C / 4 mm Hg.

The structure of this compound is indicated by the mass spectrum, the infrared spectrum and the NMR spectrum identified. The physical characteristics are as follows:

Boiling point: 102 ° C to 104 ° C / 4 mm HG.
Infrared spectrum: Characteristic absorptions at 1380, 1364, 786 and 755 cm- ¹ .
Molecular weight determined by mass spectrometry: M ⁺ = 202.

The NMR analysis confirms the presence of 6 methyl groups.

Production Example 2 " ¹⁵

Feeding to the same flask as the, washed with lOOgm-cymene and 100 ml of 93% sulfuric acid used in Preparation Example 1 as catalyst, and bringing the flask contents to 30 ⁰ C. then added gradually over the course of 30 minutes dropwise

14.0 g of 2-methyl-2-butene are added. To end the reaction, the mixture is stirred for a further 3 hours and then transferred to a separatory funnel, after which the material is treated in the same way as described in Preparation Example 1. The unreacted cymene is separated and df by vacuum distillation: s reaction product is obtained 8.1 g of a fraction having a boiling point of 8O ⁰ C to 100 ° C / 3 mm Hg by rectification this fraction is obtained the desired product having a boiling point. from 102 ° C to 03 ° C / 4mmHg.

Production example 3

A 300 ml flask, which is equipped with a stirrer, a dropping funnel, a condenser and a thermometer, is charged with 20 ml of sulfuric acid as a catalyst, 100 ml of hexane and 22.1 g of tert-amyl alcohol, after which one is at a reaction temperature of 5 to 10 ⁰ C dropwise in the course of 30 minutes

32.1 g of m-isopropenyltoluene are added. To end the Reaction will continue the mixture for another hour; touched. Then you add water and transfer them Transfer reaction mixture to a separatory funnel. The water is separated and that contained in the oil acidic substance neutralized with sodium hydroxide. The reaction mixture is then left to stand and the alkaline layer. The material is then washed well with water and then drained the oil layer with calcium chloride. Then one draws off hexane under reduced pressure and distilled the remaining high-boiling substances under reduced pressure, 10.2 g of a fraction with a boiling point of 89 ° C to 105 ° C / 3 mm Hg. Rectifying this fraction gives 1,1,2,3,3,4-hexamethalindane.

Production example 4

The flask used in Preparation Example 3 is charged with 100 ml of hexane, 17.5 g of 2-methyl-2-butene and 2 ml of a boron trifluoride-ether complex serving as a catalyst and brings the material to a temperature of 0 ° C. Then add the Over 50 minutes, 33.0 g of m, p-isopropenyltolulene dropwise to. During this time, the reaction temperature is kept at 0 to 2 ° C. To terminate the Reaction, the mixture is stirred for a further 30 minutes and then treated in the same way as in Preparation Example 3 described way. The vacuum distillation of the reaction mixture gives 8.0 g of a fraction with a boiling point of 75 ° C to 128 ° C / 2mmHg. Gas chromatographic analysis of this fraction shows that it contains 18.5% of the desired product.

Production example 5

The flask described in Preparation Example 3 is filled with 20 ml of concentrated sulfuric acid as Catalyst, 100 ml of hexane and 22.1 g of methyl isopropylcarbinol are charged, after which 32.0 g of m.p-isopropenyltolu-

01 added dropwise over the course of 30 minutes. After the addition, the reaction is carried for a further hour and then treated through the reaction mixture as described in Preparation Example 3 in the same manner to yield 7.3 g of a fraction having a boiling point of 8O ⁰ C to 125 ⁰ C /

2 mm Hg. Gas chromatographic analysis of this fraction shows that it contains 1,1,2,3,3,4-hexamethylindane contains.

Production example 6

A 2 liter flask equipped with a stirrer, dropping funnel, condenser and thermometer is charged with 1000 g of 98% strength sulfuric acid and 100 g of glacial acetic acid. A mixture of 200 g of m-diisopropylbenzoI and 164 g of tert-amyl alcohol is added dropwise at a reaction temperature of 30 to 35 ° C. over the course of one hour. To end the reaction, the mixture is stirred for a further 2 hours. Thereafter, it is transferred to a separatory funnel and treated in the same manner as in Preparation Example 1. The reaction mixture is dried with sodium sulfate and unreacted m-diisopropylbenzene and other low-boiling substances are removed. Distillation at reduced pressure gives a fraction having a boiling point of 90 to 13O ⁰ C at 5 mm Hg.

This fraction is extracted with the aid of a high-temperature rotating belt precision fractionation apparatus purified, whereby 10 g of a colorless liquid with a boiling point of 105 to 110 ° C at 5 mm HG obtained will.

The structure of this compound is identified as that of 1,1,2,3,3-pentamethyl-4-isopropylindane with the aid of IR and NMR spectroscopy and the mass peak of M ^{+ = 230.}

example 1

A 300 ml four-necked flask is charged with a stirrer, a reflux condenser fitted with a calcium chloride tube, a dropping funnel and a thermometer is equipped with 8.5 g of aluminum chloride and 30 ml of carbon tetrachloride. A solution of is then added dropwise at a temperature of 20 to 25 ° C. over the course of 20 minutes 10.6 g of 1,1,2,3,3,4-hexamethylindane and 5.1 g of acetyl chloride in 30 ml of carbon tetrachloride were added. After the addition the mixture is stirred for an additional hour, then poured into ice water to decompose the catalyst and then wash with 100 ml of water. Then the reaction mixture is twice with 100 ml of a 5% aqueous sodium hydroxide solution to neutralize them. To remove the alkali, the Reaction product washed twice with 100 ml of water. Then the product is made with calcium chloride dried, after which the carbon tetrachloride is removed. Vacuum distillation of the product gives 7.8 g of a fraction with a boiling point of 145 ° C to 147 ° C / 1 mmHg, which corresponds to a yield of 61%.

Example 3

analysis

Calculated: C 83.55, H 9.90%;
found: C 83.3, H 10.1%.

In the mass spectrum, the compound peak M ^{+ is found} to be 244. In the infrared spectrum, a typical carbonyl absorption band can be observed at 1684 cm- '. From these values it can be seen that the product obtained by acetylating 1,1,2,3,3,4-hexamethylindane is acetylated 1,1,2,3,3,4-hexamethylindane.

Example 2

5.8 g of anhydrous aluminum chloride and 5 ml of carbon tetrachloride are introduced into the same apparatus from Example 1, and the mixture is cooled to 0 to 5 ° C. A mixture of 3.9 g 1,1,2,33,4-hexamethylindane and 2.7 g propionyl chloride is added dropwise with the aid of a dropping funnel over 30 minutes. The mixture is stirred for a further 2 hours to end the reaction. After the reaction has ended, the reaction mixture is transferred to a separatory funnel and treated in the same manner as indicated in Example 1. After drying over sodium sulfate, the solvent is removed. Distillation under reduced pressure gives 2.7 g of a fraction having a boiling point of 1 53-1 56 ° C at 1 mm Hg (yield 55%).

Analysis for CigthbO: Calculated: C 83.66, H 10.14%; found: C 83, SO, H 10.10%.

In the mass spectrum, the connection peak M ^{+ is found} to be 258. In the IR spectrum, a typical carbonyl ^{absorption band at 1695 cm-1} can be observed *.

Absent these values, it follows that the Compound is a propionylated in the nucleus 1,1,233,4-Hexamethylmdan.

1 g of the compound according to preparation example b

was acetylated in the same apparatus and under the same reaction conditions as in Example 1. the thus obtained compound was purified by distillation under reduced pressure, whereby 0.6 g of a colorless liquid with a boiling point of 149 to 154 ° C at 0.7 mm Hg in a yield of 50%

ίο was received.

Analysis for CmHjnO:

Calculated: C 83.77, H 10.36%:
found: C 83.97, H 10.30%.

The connection peak is found in the mass spectrum

M * with 272. In the IR spectrum, a typical carbonyl absorption band can be observed ^{at 1686 cm 1.} These values show that the product is acetylated 1,2,3,3-penta-methyl-4-isoproylindane.

Example 4

2s 10 g of anhydrous zinc chloride are suspended and 12 g of paraformaldehyde in 140 g of 1,1,2,3,3,4-hexamethylindane, which is present in a flask with a Stirrer, a gas inlet, a thermometer and a tube fitted with a calcium chloride tube

ίο is equipped with a reflux condenser. The suspension is heated to 55.degree. C. with stirring and a vigorous stream of hydrogen chloride gas is introduced, taking care that the temperature is kept at 60.degree.
During the first hour, the chlorinated water

is substance gas absorbed quickly. After this reaction has expired completely, the gas is introduced for a further 2 hours. After cooling, they are separated the reaction mixture into layers with the aid of a separating funnel, of which the upper layer is covered with a aqueous, dilute sodium hydroxide solution washes until neutral and the material then with distilled under reduced pressure. Chloromethyl-l, l, 2,3,3,4-hexamethyl-indane is obtained with a boiling point of 130 ° C to 150 ° C / 2 mm Hg in the form of a colorless Liquid.

The chloromethylhexamethylindane obtained is converted into the formula-1, l, 2,3,3,4-hexamethylindane as follows.

In the course of 15 minutes, 50 g of des

so chloromethylhexa-methyl-indane in small portions to a warm mixture of 8 g of sodium hydroxide, 18 g of 2-nitropropane and 120 g of ethanol, which is present in a round flask equipped with a stirrer and a condenser. After the reaction has ended, the reaction mixture is brought more 15 minutes to simmer. The reaction mixture is then neutralized and, after cooling, the sodium chloride obtained as a by-product is filtered off with suction. The alcohol is then distilled off, the residue is diluted with water and extracted with benzene using a separatory funnel. The material is washed three times with 10% aqueous sodium hydroxide solution and finally with water until neutral. The solvent is then distilled off and the crude aldehyde was purified by vacuum distillation with 30 g of 1-formyl-J ^ 3.4 hexarneth; yl-indan nih receives a boiling point of 135 ° C to 138 ⁰ O33minHG

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Examples of perfume compositions

No. 1: Make the following preparation:

Components

Components

Weight lines

Undecylenealdehyde 10% 30

Methyl nonyl acetaldehyde 10% 10

/ f-phenylethyl alcohol 100

Stearyl acetate 20

Hydroxycitronellal 100

Methyl ion 150

Hexyl cinnamon aldehyde 60

Bergamot oil 50

Vetivenyl acetate 50

Coumarin 20

Ambergris 50

Jasmine oil · ■ 140

Rose oil 50

Ylang-Ylang Oil 100

Compound of general formula I 70

1000

Citronellol

Terpineol

Cedrol

Compound of the general formula I.

The above perfume composition has an excellent one Fragrance with a modern floral bouquet fragrance note, the fragrance being compared with a similar one Composition which, instead of the compound of general formula I, is an acetylated product of 1,1,2,3,3,5-hexamethyl-indane, a well-known compound, contains, lasts much longer.

No. 2: Prepare the following composition:

Components

Parts by weight

Geranium oil

Eugenol

Rosephenon

Coumarin

Benzyl acetate

/ 3-phenylethyl alcohol

Amyl salicylate

Linalyte acetate

Geraniol

50

20th

20th

20th

100

150

50

80

100

Weight parts

90

100

100

120

1000

The above perfume composition has a superior smell with a bouquet of flowers, wöbe the fragrance, compared with a similar preparation that replaces the compound of the general formula an acetylated product of 1,1,2,3,3,6-hexamethyl-yne dan, a known compound, lasts much longer.

No. 3: Prepare the following preparation.

Components

Weight parts

2s Eugenol IO

Undecylenealdehyde 10% 10

Methyl nonyl acetaldehyde 10

Bergamot Oil 100

Benzyl acetate 100

_, o-phenylethyl alcohol 50

y-methyl-ionone 150

Ionon 30

Hydroxycitronellal 80

Sandalwood Oil (Mysore) 50

Ylang-Ylang-Ö! 100

Amber 30

Vetiver-öi 30

Compound of the general formula I 200

1000

The above perfume preparation has a superior one Fragrance with a floral bouquet duimote, the smell compared with a similar preparation that instead of the compound of the general formula 1 1,1,2,3,3,5-hexamethylindane, a known compound, contains, lasts much longer.

Claims (1)

Patent claims: 1. 4-alkyl-substituted acyl-polyalkyl-indane der general formula η ² 71 ated acyl-polyalkylindanes of the general formula I. R ¹ H ₃ C CH,