DE2064918B2 - - Google Patents

Abstract

Indane derivs. as odorants. The cpds. are: where one of R1 and R2 is O and the other is H2; Y is H or with X forms epoxide; one of the dotted bonds completes a double bond unless the epoxide is present; if the double bond is conjugated with R2 when the latter is O, X is H (musk and wood odour) where R6 is alkyl or acyl (balsam odour) 3a, 7a, epoxy-hexaxydro-1,1,2,3,3-pentamethylindone (pine wood odour) where the dotted bonds represent not more than two double bonds opt. conjugated (strong amber and wood odour with pine note) where R3 is is carbonyl, OH, acyloxy, or alkyloxy (musk and fruity odour). Used in cosmetics and detergents.

Description

OH

10

wherein R is a carbonyl oxygen or a hydroxy or methoxy or acetoxy group and the 3a and 7a positions are unsubstituted.

2. 1,1,2,3,3-Pentamethylhexahydro-4 (5H) -indanone.

3. 1,1.2,3,3-Pentamethylhexahydro-5 (4 H) -indanone.

4.1 ^, S-pentamethylhexahydro ^ indanol.

5.!,! ^, S-pentamethylhexahydro-S-indanol.

6. Process for the production of saturated indanones according to claim 1 to 3, characterized in that that a pentamethylhexahydroindanol is used to prepare the corresponding ketone oxidized with an oxidizing agent containing hexavalent chromium.

7. Use of the saturated indane derivatives and according to Claims 1 to 5 as fragrances.

1.1,2,3,3-pentamethylhexahydro-5-indanol with the formula

the corresponding
Formulas

Indanyl methyl ether with the

The invention relates to saturated indane derivatives of the general formula

and the corresponding indanyl acetic acid esters with the formulas

40

where R is a carbonyl oxygen or a hydroxy or methoxy or acetoxy group and the 3a- and 7a-position is unsubstituted, as well as processes for their preparation and their use as fragrances.

These substances have a lingering, strong, woody amber aroma with a fruity and musky flavor Aroma notes.

The indanones contemplated here are 1,1,2,3,3 - pentamethylhexahydro - 4 (5H) - indanone with the formula

and

and l, l, 2,3,3-pentamethylhexahydro-5 (4H) -indanone of the formula

45

In the above formulas derived from the above formula, Rj is a methyl group and R ₂ represents the acetoxy group.

Alkylated indane compounds have already been described in German Auslegeschriften 1059 902 and 1045 399, it being stated that these have a pronounced musk odor. These known compounds, however, have an aromatic benzene nucleus within the Ind ^ Nge \, roughing stand, which is why the individual fragrance notes of indan derivatives can not be obtained according to the invention.

The alcohols according to the invention can be obtained directly from the corresponding pentamethylindane Sulphonation, alkali melting and hydrolysis to pentamethylindanol and subsequent hydrogenation to the Hexahydropentamethylindanol can be produced.

The alcohols can also be obtained directly from the pentamethylindane by treatment with an acyl halo

genid, such as acetyl chloride, in the presence of a Friedel-Crafts catalyst and by subsequent oxidation of the indane alkyl ketone with a peroxygen material, such as peracetic acid and the like, to the indanyl ester. The hydrolysis of these esters yields the indanol, which is then hydrogenated to the saturated indanol in the manner indicated below will. A tetrahydroindanol can also be produced by the Birch reduction of 5-indanol, as described in J. Am. Chem. Soc, 89, p. 1044, can be obtained. The tetrahydroindanols thus produced are then hydrogenated and oxidized to the ketone in the manner described below.

The ketones according to the invention can be prepared according to a number of synthetic routes. A the preferred way is the oxidation of a saturated or unsaturated l, l, 2,3,3-pentamethyl-4-indanol or -5-indanols under conditions which give the corresponding ketone. With this preferred one Path can be used any means that is able is to convert a secondary hydroxyl group to a carbonyl oxygen group. Examples such oxidizing agents are Jones reagent (a chromium trioxide-sulfuric acid mixture) and oxygen-metal systems.

The oxidation of the hydroxyl group is carried out with a hydrogenated indanol. In the event that the ketone is not saturated, the six-membered ring is subsequently hydrogenated with a catalyst under conditions which do not reduce the carbonyl group. Suitable catalysts for this reaction include metal catalysts such as Raney nickel or noble metals such as platinum and palladium, which are used at essentially superatmospheric pressures in the region of 50 to 125 atm. It is preferred to carry out the hydrogenation at from 150 to 25O ⁰ C and pressures of about 70.3 to 105 at.

The oxidation takes place “in that the secondary alcohol with oxidation systems a on the basis of hexavalent Chromium compounds or from oxygen-metal catalysts is treated. It is useful to make the reaction so that the alcohol in one Reaction mediator is dissolved or dispersed, which serves to moderate the reaction and a allow better control. Oxygen-containing solvents, such as acetone, or lower solvents are suitable Carboxylic acids such as acetic acid. Of course, it is preferred that the indanyl alcohol as well as the Oxidizing agents are soluble in the reaction mediator.

The Jones reagent is prepared by dissolving chromium trioxide or an alkali metal dichromate in aqueous sulfuric acid, for example 30 to 50% H ₂ SO ₄ , preferably 40% H ₂ SO ₄ . At least an equimolar amount of the oxidizing agent is mixed with the indanol in the solvent for best results. It is preferred to employ an excess of the oxidizing agent up to about 50 mole percent based on the weight of the indanol, with a molar excess of 25 to 40 percent being preferred. The oxidation is carried out at mild temperatures in the region of 10 to 30 ^° C. In a preferred embodiment, the reaction is carried out ^{at 15 to 20 ° C.}

The oxidation to form the ketones can also be carried out with the oxygen-metal-catalyst system described above be made. In this case, the oxygen can either be in pure form or in Mixture with an inert diluent, such as nitrogen, can be used. The catalyst is preferred a metal, like silver. Copper is also suitable.

After completion of the reaction leading to the ketone, the product from the solvent and of unconverted starting materials or undesired by-products using customary methods, such as washing, distillation, crystallization, extraction, preparative chromatography, are separated. It it is preferred to fractionate the washed reaction product under a relatively high vacuum distill so that a pure product is obtained. Product purities of 80% are readily available. With a suitable treatment one can still achieve much higher purities.

The compounds of the invention are suitable as fragrances. They can be used individually or in combination can be used to give a woody-musky, woody-amber or woody aroma to lend. As fragrances, they can be used as components of perfume mixtures.

The term "perfume mixture" includes a mixture of organic compounds, which for example, alcohols, aldehydes, ketones, esters, and often hydrocarbons, which so are mixed so that the combined smells of the individual components are pleasant or desirable Aroma.

In addition, the perfume blend can be a vehicle or carrier for the other ingredients contain. The vehicle can be a liquid such as alcohol, glycol or the like. The carrier can be a absorbent solid such as a gum or a component for encapsulating the mixture.

The proportion of the compounds according to the invention in perfume mixtures depends on many factors, z. B. on the other ingredients, their amounts and the desired effects. It has been shown that Perfume mixtures which contain as little as 2 percent by weight of the compounds according to the invention or their Mixtures containing, or even less, can be used to make soaps, cosmetics and to give other products a woody odor. The amount used can be up to 7% or extend more. In individual cases, the proportion depends on cost considerations, on the nature of the end product, the desired effect in the end product and the particular aroma sought.

The compounds according to the invention can also be used as fragrances for detergents and soaps, Room deodorants, perfumes, Roman waters, bath products such as bath oil, bath salts, hair products such as Varnishes, brilliants, pomades and shampoos, cosmetic preparations such as creams, deodorants, hand lotions, Solar powder, such as talc, powder powder, face powder, are used. When used as a fragrance of a perfumed item, as little as 0.011% of one or more of the new ketones are sufficient to generate one to give a fine, woody musk odor.

example 1
a) Production of pentamethylindanesulfonic acid

A 5-1 flask fitted with a stirrer, a condenser and a dropping funnel is added, 1500 g of concentrated sulfuric acid are added. To do this will be 500 g 1,1,2,3,3-pentamethylindane added dropwise

ben, the temperature being kept at 30 to 35 ° C. After the addition is complete, a further hour touched.

A 5-1 flask is fitted with a thermometer and a stirrer and placed in a dry ice-isopropanol bath. Add 1 liter of water to the flask. After cooling of the water to 1O ⁰ C the above reaction mixture is added dropwise to the water, the temperature being gebalten to 1O ⁰ C. After the reaction mixture has been added to the water, stirring is continued for 30 minutes. The contents of the flask are then filtered through a Buchner funnel in vacuo. The solids obtained are compressed to remove the water.

The solids are mixed with 100 ml of a l% hydrochloric acid at 0 ⁰ C washed and pressed together, whereby 822.2 g of crude crystals. After drying overnight in a vacuum desiccator, the 773.9 g of crude solids are placed in 31% benzene and refluxed to remove additional water. The benzene mixture is cooled to 5O ⁰ C and filtered. The benzene is distilled off at a pressure of 50 mm Hg, whereby 1,1,2,3,3-pentamethylindane-sulfonic acid is obtained.

b) Production of pentamethylindanol

1 mole of the indanesulfonic acid thus produced is mixed thoroughly with 2 moles of sodium hydroxide. The mixture is heated to the melting temperature of 360 ^° C. and kept at this temperature for 2 hours. During the melting, the reaction mass is stirred mechanically.

When the heating is complete, the reaction mass is cooled and extracted with water. The product is then neutralized with dilute hydrochloric acid. The indanol formed is with benzene extracted. The benzene is driven off to give 1,1,2,3,3-pentamethylindanol.

c) Production of pentamethylhexahydroindanol

In a 200 ml steel autoclave, 70 g 1,1,2,3,3-pentamethylindan-5-ol, 5 g of a 5% rhodium catalyst on charcoal and 150 ml isopropyl alcohol are added. While the temperature in the autoclave is kept at 20 ^° C., hydrogen gas is fed in until a pressure of 72.1 atm is reached. While the hydrogen pressure is kept at about 72.1 at, the temperature of the reaction mass is ^{increased to 178 °} C. over a period of 3 hours (at this point the pressure increases to 105 at).

After 18 hours of hydrogenation at 105 at and 178 ° C, the crude reaction mass of the Freed solvent. The IR and NMR analysis shows that the reaction mass is 1,1,2,3,3-pentamethylindan-5-ol with the structure

- OH

contains.

Similar reactions are at a Raney nickel catalyst at 105 and 200 ⁰ C and at a palladium on carbon catalyst at 10.5 and carried out at 20O ⁰ C, giving essentially identical results.

An essentially identical reaction is carried out with 1,1,2,3,3-pentamethylindane-4-oil, whereby l, l, 2,3,3-hexahydroindan-4-ol with the formula

OH

is obtained.

A 500 ml reaction flask is charged with 50 g of the crude hexahydropentamethylindan-5-ol obtained by hydrogenating the indan-5-ol. A Jones reagent is prepared in which chromium trioxide is dissolved in 20% aqueous sulfuric acid. The flask contents is maintained at 15 to 2O ⁰ C, with 75 mm (0.33 mol) of Jones reagent were added. The contents of the reaction flask are then ^{stirred for 1} _1/2 hours over the 30 minutes required for the Jones reagent to be added.

The ketone is separated off by adding 25 cm ^{3 of} methanol and 50 cm ^{3 of} toluene. The organic layer is separated and the remaining aqueous layer is extracted with toluene. The toluene extract is added to the original extract and the organic material is washed neutral with water and then driven off and distilled.

The 33 g of the distilled material are mixed with 2 g of paraffinum liquidum and an antioxidant and distilled at a steam temperature of 96 to 120 ^° C. and a pressure of 1 to 2 mm Hg, whereby 23.5 g of pentamethylhexylhydro-5-indanone are obtained.

The purified material is a clear liquid with a boiling point of 96 to 99 ° C at 2.0 mm Hg The IR spectrum shows the following significant peaks: at 5.8 μ, at 7.1 μ and at 7.2 and 7.3 μ.

These peaks can be assigned to: a cyclohexanyl ketone, a methylene group adjacent to a carbonyl and a gem-dimethyl or methyl group. Raman spectroscopy shows no presence of carbon-carbon unsaturated bonds.

The ketone obtained in this way has an unmistakable woody amber odor with a musky smell A hit. This material is combined with a ketone called "Ketone BD-9", namely 3,5,5,7,7-pentamethyl-decahydro-2-naphthalenone compared. It is found that the indanone has a much better woody, amber-like character, while the Naphthalenone just has a simple woody aroma. The flavor characteristics are considered to be quite different rated.

The procedure described in Example 2 can be carried out with the corresponding pentamethylhexahydroindan-4-ol to obtain a flavor product similar to that obtained in Example 2 is.

Example 2

Preparation of 1,1,2,3,3-pentamethylhexahydroindan-4-ol

In a 5-1 stainless steel autoclave that comes with is provided with a hydrogen charge, the following substances are brought in:

180Og (8.14MoI) 1,1,2,3,3-pentamethylindane

(with a purity of 85%),
90 grams of Raney nickel.

Sufficient hydrogen is introduced into the autoclave to raise the pressure to 70.3 atm. The hydrogen feed is then continued at 3 ml / min. The autoclave is heated to a temperature in the range from 150 to 185 ^{° C. over a period of 8 hours.} During this time the pressure in the autoclave is kept at 105 atm.

1.641 g of crude product are removed from the autoclave, which after mixing with 10.0 paraffin liquidum can be distilled on a 30.5 cm fine fractionation column. The distillate comes in two Fractions receive:

Group I.

Distilled at a temperature of 78 to 82 ^° C. and a pressure of 4.0 mm Hg.It represents 401 g of 4,5,6,7-tetrahydro-1,1,2,3,3-pentamethylindane.

Group II

Distilled at a temperature of 86 to 88 ° C and a pressure of 3.5 to 3.8 mm Hg. It represents 729 g of hexahydro-l, l, 2,3,3-pentamethylindane.

A fraction I sample is further purified on a gas-liquid chromatography column. The following structure is confirmed by the IR and PMR analysis:

In a 250 ml flask equipped with a thermometer, a stirrer, a reflux condenser and an ice bath, 195 g of the tetrahydroindane prepared above and 15 g of sodium acetate are placed. In the course of 4 hours at 25 to 3O ⁰ C 124 of a 40% peracetic acid (0.65 mol) g of given. When the addition is complete, an equal volume of water is added to the reaction mass. The aqueous phase is separated off from the organic phase and 150 ml of toluene are added. The toluene extract is combined with the organic phase and washed with one volume of a 5% strength aqueous sodium hydroxide solution and then with one volume of water.

The solvent is driven off leaving a crude product weighing 208 g. The crude epoxy product is after adding 4.0 g of triethanolamine at 72 to 74 ° C and one Distilled pressure of 1.0 to 1.4 mm Hg on a 30.5 mm fine fractionation column.

^{250 cm 3 of} toluene and 80 g of aluminum triisopropoxide are placed in a 500 ml flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel. The mixture is heated to reflux. There are 90 g of the above prepared Epoxyhexahydroindans dropwise over a period of Y ^ hours under reflux added. The reaction mass is refluxed for a further 10 hours, after which it is cooled to 25 ° C.

The cooled reaction mass is poured onto a mixture of 500 g of ice and 200 cm ^{3 of} a 15% strength

ίο poured sulfuric acid, stirred for 15 minutes and separated into an aqueous and an organic phase. The aqueous phase is ^{extracted with 200 cm 3 of} toluene and the toluene extract is combined with the organic layer. The combined material is washed with a saturated sodium bicarbonate solution and twice with 100 cm ^{3 of} water. The solvent is driven off the washed organic phase to give a crude product weighing 71 g.

The crude product is distilled on a 10.2 cm Vigreux column at a steam temperature of 105 to 107 ⁰ C and a pressure of 2.1 to 2.3 mm Hg, whereby 4,5,6,7 - Tetrahydro - 1,1,2,3,3-pentamethyl-4-indanol is obtained. 60 g of the tetrahydropentamethyl-4-indanol thus prepared, 5 g of a 5% rhodium catalyst on carbon and 150 ml of isopropanol are placed in a 200 ml stainless steel autoclave. The temperature of the autoclave is kept at 20 ^° C. while hydrogen gas is introduced so that a pressure of 72.1 at is reached. The temperature is then increased to 18O ⁰ C, after which the pressure to 105 at einsteigt.

After 18 hours of hydrogenation under the above conditions, the hydrogen is released and the Autoclave cooled to room temperature. The solvent is driven off, creating a crude product weighing 35 g. The product is washed and distilled, whereby 1,1,2,3,3 - pentamethylhexahydroindane - 4 - oil obtained will.

Example 3

Production of 1,1,2,3,3-Pentamethy! Hexahydro - ^ H) indanone

In a 500 ml flask fitted with cooling devices, a stirrer, a thermometer, and a reflux condenser is provided, 50 g of the hexahydroindan-4-ol prepared in Example 2 and 300 ml of acetone given. The mixture is stirred while 75 ml of Jones reagent is added. The reaction mixture is then stirred for 1 hour and thereafter mixed with 25 ml of ethanol and 50 ml of toluene. The aqueous phase is removed. The organic phase will washed and neutralized with sodium bicarbonate. The solvent is driven off and what remains Organic material is distilled, giving 1,1,2,3,3-pentamethylhexahydro-4 (5H) -mdanone is obtained, which has a woody amber odor with a fruity musk impact.

309 583/438

Claims (1)

Patent claims: 1. Saturated indane derivatives of the general formula \ / R The indanols and their derivatives contemplated herein include 1,1,2,3,3-pentamethylhexahydro-4-indanol with the formula