DE2064918C3 - - 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

IO

wherein R is a carbonyl oxygen or a hydroxy or methoxy or acetoxy group and the 3a »and 7a positions are not substituted.

2. 1,1,2,3,3-pentamethylhexahydro-4 (5Hndanone.

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

4. ll ^ Ji-Pentamethylhexahydro- ^ indanol.
5.1.1,2,3.3-pentamethylhexahydro-5-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 according to Claims 1 to 5 as fragrances.

1,1,2,3,3-Pentaraethylhexahydro-5-indanol with the formula

OH

the corresponding indanyl-methyl-closer to the Formulas

OR,

and

OR,

The invention relates to saturated indane derivatives the general formula

and the corresponding indanyl acetic acid esters with the formulas

where R is a carbonyl oxygen or a hydroxy or methoxy or acetoxy group and the 3a- and 7a-position is not substituted. also to the process for their production 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

45 - OR ₂

40 and

OR ₁

Xa, "

one.

and 1.1.2.3,3-pentamethylhexahydro-5 (4 H (-indanone with the formula

F = O

In the above formulas derived from the above formula, R ₁ is a methyl group and R 2 is the acetoxy group.

Alkylated indane compounds are already in the German Auslegeschriften 1,059,902 and 1,045,399, it being stated that these have a pronounced musky odor. However, these known compounds have one aromatic benzene nucleus within the indangerous structure. why the individual fragrances of the Indane derivatives according to the invention cannot be obtained.

The alcohols according to the invention can be obtained directly from the corresponding pentamethylindane Sulfonation. Alkali melt and hydrolysis to pentamethylindanol and subsequent hydrogenation to the Hydroxahydropentamethylindanol can be produced.

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

"Mid, w" e acetyl chloride. jn the presence of a Friedel-Crafts catalyst and by subsequent oxidation of the indan-alkyl ketone with a peroxygen material such as peracetic acid, etc.., m the indanyl ester are produced. The hydrolysis of these I-th esters gives the indanol, which is then hydrogenated to the saturated indanol in the manner indicated below. A tetrabydroindanol can also be produced by the Birch reduction of the 5-indanol, as described in J. Am. Cheni. Soc., 89, p. 1044. The tetrahydroindanols so produced are then hydrogenated and oxidized to the ketone in the manner described below.

The ketones of the invention can be made by 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 Any means imitande of a secondary hydroxyl group to one can be used To convert carbonyl Saueruoffgruppe. Examples of such oxidizing agents are Jones reagent lein 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 that do not reduce the carbonyl group. Suitable catalysts for this reaction include metal catalysts such as Raney nickel or noble metals such as platinum, palladium, which are used in überalmo ^r substantially? Härischen pressures in the region of from 50 to 125 at. It is preferred to carry out the hydrogenation at 150 to 250 ° C. and pressures of about 70.3 to 105 atm.

The oxidation takes place by treating the secondary alcohol with oxidation systems based on hexavalent chromium compounds or with oxygen-metal catalysts. It is advisable to carry out the reaction in such a way that the alcohol is dissolved or dispersed in a reaction mediator. which serves to moderate the reaction and allow better control. Oxygen-containing solvents, such as acetone, or lower carboxylic acids, such as acetic acid, are suitable. Of course, it is preferred that the indanyl alcohol w ^; e also the oxidizing agent 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 . is resolved. At least an equimolar amount of the oxidizing agent is mixed with the indanol in the solvent. to get r, u 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. Si j uL constituents can be used as fragrances can be used by perfume blends.

The term "perfume blend" includes one Mixture of organic compounds, which for example alcohols, aldehydes, ketones. Ester and often includes hydrocarbons which are so mixed that the combined odors of the individual Components result in a pleasant or a desired 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. Soap. 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 pitch agents for detergents and soaps. Room deodorants. Perfumes, colognes. Bath products such as bath oil, bath salts, hair products such as Lacquers. Brilliantines. Pomades and shampoos, cosmetic preparations such as creams, deodorants. Hand lotions, Sun remedy. Powder, such as talc, powder powder. Face powder, serve. When used as a fragrance of a perfumed object, 0.011% is sufficient one or more of the new ketones. to give a fine, woody, musky odor.

example 1
a) Production of pentamethylindanesulfonic acid

A 5-liter flask with a stirrer, a cooler 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 L flask is fitted with a thermometer and a stirrer and placed in a dry ice-isopropanol bath. 1 liter of water is added to the flask. After cooling the water to 10 C , the above reaction mixture is added to the water dropwise while maintaining the temperature at 10 ¹¹ 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 1% 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 3 liters of benzene and refluxed to remove additional water. The benzene mixture is cooled to 50 ° 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

I mole of the indanesulfonic acid thus produced is mixed thoroughly with 2 moles of sodium hydroxide. ^ ₀ The mixture is heated to the melting temperature of 360 C and held at this temperature for 2 hours. The reaction mass is stirred mechanically during melting.

After completion of the heating, the reaction _3S tion mass is cooled and extracted with water. The product is then neutralized with dilute hydrochloric acid. The indanol formed is extracted with benzene. The benzene is driven off to give 1,1,2,3,3 · pentamethylindanol.

c) Production of pentamethylhxahydroindanol

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 given. While the temperature in the autoclave is kept at 20 C, hydrogen gas is supplied, until a pressure of 72.1 at is reached. While maintaining the hydrogen pressure at about 72.1 atm, will the temperature of the reaction mass increased to 178 C over a period of 3 hours (in this case Point increases the pressure to 105 at).

After hydrogenation for 18 hours at 105 at and 178 ¹ C, the crude reaction mass is freed from the solvent. The IR and NMR analysis shows that the reaction mass 1,1.2.3.3-Pentamethylindan-5-ol with the structure

A substantially identical reaction is carried out with 1,1,2,3,3-pentumethylindan-4-ol, whereby 1,1,2,3,3-hexahydroindan-4-ol having the formula

ÜH

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 contents of the flask are maintained at 15-20 ° C. with the addition of 75 mm (0.33 mol) of Jones reagent. The contents of the reaction flask are then stirred ^for: / ₂ hours for the M) minutes required for the addition of the Jones reagent.

The ketone is by adding 25 cm 'of methanol and 50 cm- 'toluene separated. The organic layer is separated and the remaining aqueous Layer is extracted with toluene. The toluene extract is added to the original extract, and that Osj.anische material is washed neutral with water and then distributed and distilled.

The 33 g of the distilled material are mixed with 2 g of liquid paraffin and an antioxidant and distilled at a Dampf'.empcratur of 96 to 120 C and a pressure of 1 to 2 mm Hg, whereby 23.5 g of Pcntamethylhcxyhydro-5-indunon 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 _: /. 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 color A hit. This material is combined with a ketone called "Ketone BD-9", namely 3.5,5,7,7-pentamelhyl-decahydro-2-naphthalenone compared. It is found that the indanone is a much better woody, amber-like in character, while the naphthalenone has just a simple woody aroma.

The aroma properties are rated as quite different.

The procedure described in Example 2 can with dementsprechcnden Pentamethylhexahydroindan-4-ol is carried out, whereby an aroma product obtained we- ^4., The condition similar to that in Example 2

60! St.

contains.

Similar reactions are carried out with a Raney nickel catalyst at 105 at and 200 C and with a palladium on carbon catalyst 10.5 at and at 200 ° C., essentially identical results being obtained.

Example 2

Preparation of 1.1,2.3,3-pentamethylhexahydroindan-4-ol

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

1800 g (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 used over a period of time heated from 8 hours to a temperature in the range of 150 to 185 ° C. During this time the Pressure in the autoclave kept at 105 at.

1.641 g of crude product are removed from the autoclave, after mixing with 10.0 Paraffinum liquidum on a 30.5 cm fine fractionation column be distilled. The distillate is obtained in two fractions:

Group I.

Distilled at a temperature of 78 to 82 ° C and a pressure of 4.0 mm Hg. It represents 401 g 4,5,6,7-tetrahydro-l, l, 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 grams of hexahydro-1,1,2,3,3-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 fitted with a thermometer, a stirrer, a reflux condenser and an ice bath, 195 g of the above prepared Tetrahydroindane and 15 g of sodium acetate were added. Over 4 hours at 25 to 30 ° C 124 g of a 40% strength peracetic acid (0.65 mol) were added. When the addition is complete, an equal volume of water is added to the reaction mass. The watery one Phase is separated from the organic phase and mixed with 150 ml of toluene. The toluene extract is combined with the organic phase and with a volume of 5% aqueous sodium hydroxide solution and then washed with a 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 Pressure from 1.0 to 1.4 mm Hg on a 30.5 mm fine fractionation column distilled.

^{250 cm 3 of} toluene and 80 g of aluminum isopropoxide 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 Epoxyhexahydroindans prepared above was added dropwise under reflux over a period of ¹ l / »hours. The reaction mixture 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 placed on a 10.2 cm Vigreux column distilled at a steam temperature of 105 to 107 ° 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 thus prepared are placed in a 200 ml stainless steel autoclave Tetralv dropentamethyl-4-indanol, 5 g of a 5% Rhodium catalyst on charcoal and 150 ml of isopropanol added. The temperature of the autoclave is held at 20 ° C while introducing hydrogen gas that a pressure of 72.1 atm is reached. The temperature is then increased to 180 ° C., whereupon the pressure rises to 105 atm.

After hydrogenation for 18 hours under the above conditions the hydrogen is released and the autoclave is cooled to room temperature. The solvent is sold to give a crude product weighing 35 g. The Product is washed and distilled to give 1,1,2,3,3-pentamethylhexahydroindane-4-oil will.

Example 3

Preparation of 1,1,2,3,3-pentamethylhexahydro-4 (5th H) indanone

In a 500 ml flask equipped with cooling devices, a stirrer, a thermometer, and a reflux condenser is provided, 50 g of the in Example 2 produced hexahydroindan-4-ols 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 then: h 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 whereby 1.l, 2,3,3-pentamethylhexahydro ~ 4 (5H) -inda non, which has a woody amber odor with a fruity, musky touch sits.

409 635/3

Claims (1)

Patent claims: 1. Saturated indane derivatives of the general formula The indunols and their derivatives include 1.1,2.3,3-pentamethylhexuhydro-4-indanQl with the formula