DE2064918A1 - Indane derivs as odorants - 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

Saturated Indane Derivatives The invention relates to saturated indane derivatives having the formula where R is a carbonyl oxygen or a hydroxy, acyloxy or alkyloxy group.

The substances have a persistent, strong, woody amber aroma with fruity and musky aromas.

The indanones contemplated herein are 1,1,2,3,3-pentamethylhexahydro-4 (5H) -indanone having the formula and 1,1,2,3,3-pentamethylhexahydro-5 (4H) -indanone of the formula The indanols and their derivatives contemplated herein include 1,1,2,3,3-pentamethylhexahydroindan-4-ol having the formula 1,1,2,3,3-pentamethylhexahydroindan-5-ol having the formula the corresponding indanyl-alkyl ethers with the formulas and and the corresponding indanyl esters with the formulas and a.

In the above formulas that differ from the above formula derive, R1 is a lower alkyl group, desirably one which is 1 to 5 carbon atoms, the methyl group being preferably a low one Represents alkyl group. R2 is a lower alkyl acyl group with 1 to 5 carbon atoms, with the acetyl group being preferred.

The alcohols can be obtained directly from the corresponding pentamethylindane by sulfonation, alkali melting and hydrolysis to pentamethylindanol and then Hydrogenation to the hexahydropentamethylindanol can be produced.

In the other case, the 3a, 7a-epoxypentamethylindane can with an aluminum trialkoxide treated to form the mono-unsaturated alcohol.

The alcohols can also be obtained directly from the pentamethylindane by treatment with an acyl halide such as acetyl chloride and the like 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 this ester gives the indanol, which is then added in the manner indicated below the saturated indanol is hydrogenated. A tetrahydroindanol can also be produced by the Birch reduction of 5-indanol as described in J. Am. Chem. Soc., 89, 1044 will be obtained. The tetrahydroindanols so produced are then hydrogenated and oxidized to the ketone in the manner described below.

The ketones of the invention can be synthesized in a number of ways getting produced. A preferred way is the oxidation of a saturated or unsaturated 4-indanol or 5-indanol under conditions which the corresponding Ketone yield. Any means can be used in this preferred approach is capable of converting a secondary hydroxyl group to a carbonyl oxygen group to-convert. Examples of such oxidizing agents are-Jones reagent (a mixture of chromium trioxide and sulfuric acid) and oxygen-metal systems.

The oxidation of the hydroxyl group is carried out on eni hydrogenated indanol carried out. In the event that the ketone doesn't becomes saturated, becomes the six-membered ring subsequently with a catalyst under such conditions hydrogenated, which do not reduce the carbonyl group. Suitable catalysts for this reaction include metal catalysts, such as Raney nickel or precious metals, such as platinum, palladium or the like, which at essentially super-atmospheric Pressures in the region of 50 to 125 at can be used. It is preferred that the To carry out hydrogenation at 150 to 2500C and pressures of about 70.3 to 105 at.

The oxidation takes place; by the secondary alcohol with oxidation systems based on hexavalent chromium compounds or oxygen-metal catalysts is treated. It is advisable to carry out the reaction in such a way that the alcohol is dissolved or dispersed in a reaction carrier, which serves to initiate the reaction in such a way that the alcohol is dissolved or dispersed in a reaction vehicle which serves to moderate the response and allow better control. Suitable carriers include oxygenated solvents such as acetone or lower Carboxylic acids such as acetic acid. Of course, it is preferred that a mutual Solubility of the indanyl alcohol and the oxidizing agent in the reaction carrier is present.

The crude reagent is prepared by using chromium trioxide or an alkali metal dichromate in aqueous sulfuric acid, e.g. 30 to 50% H2'S04, preferably 40 of an H2S04 ,, is dissolved. At least an equimolar amount of the Oxidizer is mixed with the indanol in the reaction vehicle to disintegrate Results to come.

It is preferred to use an excess of the oxidizing agent up to about 50 mol%, based on the weight of the indanol, to be used, with a molar excess from 25 to 40%, is preferred. The oxidation takes place at mild temperatures carried out in the region of 10 to 30 ° C. In a preferred embodiment the reaction is carried out at 15-2000.

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

After the reaction leading to the ketone has ended, the product can of the carrier and of unconverted starting materials or undesired by-products be separated according to the usual methods. These include washing that Distillation, crystallization, extraction, preparative chromatography and the like. It is preferred that the washed reaction product under one relatively high vacuum to fractionally distill, so that a pure product is obtained will. Product purities of 80% are readily available. Through a suitable Treatment can still lead to much higher purities.

The compounds of the invention are useful as flavorings. she can be used individually or in combination to create a woody, musky, to give a woody, aroma-like or woody aroma.

As odorants, they can be used as components of perfume mixtures can be used.

The term 'perfume mixture' as used herein. should be a mixture of organic compounds mean which, for example Alcohols, aldehydes, ketones, esters and often hydrocarbons which are mixed in such a way that the combined smells of the individual components are pleasant or give a desired flavor.

In perfume blends, the individual components wear their respective ones Odor properties contribute to the overall effect, but this represents the sum of the effects of the individual components. The individual compounds of the invention or their Mixtures can thus be used to improve the aroma properties of a perfume mixture to change, for example, by the olfactory note caused by another component the mixture is caused, increased or attenuated.

The proportion of the compounds according to the invention in perfume mixtures depends on many factors, e.g. on the other ingredients, their amounts and the desired effects. It has been shown that perfume blends that do so little such as 2% by weight of the compounds according to the invention or their mixtures contain or even less, can be used in soaps, cosmetics, and others To give products a woody smell.

The amount used can range up to 7% or more. in the The proportion of costs depends 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 either by themselves or in perfume mixtures as odor-forming components for detergents and soaps, Room decorations, perfumes, colognes, 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, sunscreens, powders such as talc, Dust powder1 face powder and the like can be used. When used as a The odor-forming component of a perfumed object is as low as 0.011 % of one or more of the new ketones made up for a subtle, woody, musky odor to rent.

In addition, the perfume admixture can be a vehicle or carrier for the other components. The vehicle can be a liquid such as alcohol, Be glycol or the like. The carrier can be an absorbent solid such as a gum or a component for encapsulating the mixture.

The invention is illustrated in the examples.

Example 1 a) Preparation of pentamethylindanesulfonic acid A 5 l flask, which is provided with a stirrer, a cooler and a dropping funnel, is with 1500 g concentrated sulfuric acid are added. For this purpose, 500 g of 1,1,2,3,3-pentamethylindane are added added dropwise, keeping the temperature at 30-350C. After he finished The addition is stirred for a further hour.

A 5 l flask is fitted with a thermometer and an RWhrer and placed in a dry ice isopropanol bath. ' Add 1 liter of water to the flask given. After cooling the water to 10 ° C, the above reaction mixture becomes added to the water in bulk, keeping the temperature at 10 ° C. After finished Adding the reaction mixture to the water is Stirred for another 30 minutes. The contents of the flask are then poured through a Buchner funnel filtered in vacuo. The solids obtained are used to remove the water compressed.

The solids are with, 100 ml of a'l% hydrochloric acid at OOC checked and compressed to give 822.2 g of crude crystals. To drying overnight in a vacuum desiccator removes the 773.9 g of crude solids brought into 3 l of benzene and refluxed to remove more water. The benzene mixture is cooled to 50 ° C. and filtered. The benzene is in one Pressure of 50 mm H distilled off, whereby 1,1,2,3,3 Pentamethy'lindan-sulfonic acid is obtained.

b) Preparation of Pentamethylindanol One mole of the thus prepared Indanesulfonic acid is mixed thoroughly with 2 moles of sodium hydroxide. The mixture is heated to the melting temperature of 36,000 and 2 hours at this temperature held. During the melting, the reaction mass is stirred mechanically.

After the end of the heating, the reaction mass is cooled and extracted with water. The product is then neutralized with internal hydrochloric acid. The indanol formed is extracted with benzene. The benzene is driven off, causing 1,1,2,3,3-pntamethylindanol is obtained.

c) Production of Pentamethylhexahydroindanol In a 200 ml steel autoclave 70 g of 1,1,2,3,3-pentamethylindan-5-ol, 5 g of a 5 point rhodium catalyst added to charcoal and 150 ml of isopropyl alcohol. While the temperature in the autoclave is kept at 200C, hydrogen gas is supplied until a pressure of 72.1 at achieved will. While the hydrogen pressure was held at about 72.1 at is, the temperature of the reaction mass over a period of 3 hours 178 0C increased (at this point the pressure increases to 105 at).

After an 18-hour hydrogenation at 105 at and 178 0C, the The raw reaction mass is freed from the solvent.

The IR and NMR analysis shows that the reaction mass has 1,1,2,3,3-pentamethylindan-5-ol with the structure contains.

Similar reactions are performed with a Raney nickel catalyst 105 at and 2000C and with a palladium on carbon catalyst at 10.5 at and at 2000C with essentially identical results will.

A substantially identical reaction is carried out with 1,1, 2,3,3-pentamethylindan-4-ol, giving 1,1, 2,3,3-hexahydroindan-4-ol with the formula is obtained.

A 500 ml reaction flask is filled with 50 g of the crude hexahydropentamethylindan-5-ol charged, which obtained by hydrogenation of the ind, an-5-ol obtained in Example 9 became.

A Jones reagent is made in which chromium trioxide in 20 points aqueous sulfuric acid is dissolved. The contents of the flask are kept at 15 to 200C, adding ts mm (0.35 moles) of the Jones reagent. The contents of the reaction flask is then 1/2 hour about 30 minutes required for the addition of the Jones reagent Minutes stirred.

The ketone is separated off by adding 25 cm3 of methanol and 50 cm3 of toluene are given. The organic layer is separated, and the remaining one aqueous layer is extracted with toluene. The toluene extract becomes the original one Given the 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 Primol.

Mineral oil and an antioxidant mixed and at a Distilled at a steam temperature of 96 to 1260C and a pressure of 1 to 2 mm Hg, whereby 23.5 g of pentamethylhexahydro-5-indanone are obtained.

The cleaned material is a clear liquid with a boiling point from 96 to 99 ° C at 2.0 mm Hg. The IR spectrum shows the following significant ones Peake: At 5.8 7u, at 7.1µ and at 7.2 and 7.3 µ. The peaks can be assigned to: one Oyclohexanylketon, one, to a carbonyl adjacent methylene group and one gem-methyl or methyl group. Raman spectroscopy shows no presence of Carbon-Carbon Unsaturation.

The ketone obtained in this way has an unmistakable woody amber odor with a musky touch. This material is labeled as "Ketone BD-9" designated ketone, namely 3,5,5,7,7-pentamethyl-decahydro-2-naphthalenone. The Indanoq is found to be a much better woody, amber-like one Has character, while the naphthalenone has just a simple woody aroma.

The aroma properties are considered to be quite different.

The method described in Example 2 can be followed accordingly Pentamethylhexahydroindan-4-ol, thereby obtaining a flavor product similar to that obtained in Example 2 is obtained.

Example 2 Preparation of 1,1,2,3,3-Pentamethylhexahydroindane-4-01 In a 5 liter stainless steel autoclave with a hydrogen charge is provided, the following substances are brought: 1800 g (8.14 mol) 1,1,2,3,3-pentamethylindane (with a purity of 85%) 90 g Raney nickel There is enough in the autoclave Hydrogen introduced that the pressure is increased to 70.3 at. The hydrogen charge is then continued at 3 ml / min. The autoclave is operated for a period of 8 Heated to a temperature in the range 150 to 18500 hours. During this The pressure in the autoclave is kept at 105 at * the end 1.641 g of crude product are removed from the autoclave, which after mixing with 10.0 Primol mineral oil can be distilled on a 30.5 cm Goodloe column. That Distillate is obtained in two fractions: Fraction I: Distilled at one temperature from 78 to 820C and a pressure of 4.0 mm Hg. It provides 401 g of 4,5,6,7-tetrahydro-1,1,2,3,3-pentamethylindane represent.

Fraction II: distilled at a temperature of 86 to 880C and a pressure of 3.5 to 3.8 mm Hg.

It represents 729 g of hexahydro-1,1,2,3,3-pentamethylindane.

A fraction I sample is further purified on a GIC column. The following structure is confirmed by the IR and PMR analysis: 195 g of the tetrahdorindane prepared above and 15 g of sodium acetate are placed in a 250 ml flask equipped with a thermometer, a stirrer, a reflux condenser and an ice bath. In the course of 4 hours at 250.degree. C. to 3000.degree. 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 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 with a Weight of 208 g remains. The crude epoxy product is after adding 4.0 g triethanolamine at 72 to 7400 and a pressure of 1.0 to 1.4 mm Hg on one 30.5 mm Goodlce column distilled.

In a 500 ml flask with a stirrer, a thermometer and a dropping funnel, 250 cm3 of toluene and 80 g of reflux condenser, given. The mixture is heated to reflux. There are 90 g of the one prepared above Epoxyhexahydrate was added dropwise over 1 1/4 hours with reflux.

The reaction mass is heated under a leakage flow for a further 10 hours, after which time it is on 250C aluminum trisopropoxide.

The cooled reaction mass is poured onto a mixture of 500 g of ice and 200 cm3 of a 15% sulfuric acid poured, stirred for 15 minutes and poured into a separated aqueous and an organic phase. The aqueous phase is with 200 cm3 Touol extracted and the toluene extract combined with the organic layer. The combined material is iit a saturated sodium bicarbonate solution and twice washed with 100 cm3 of water. The solvent is washed from the organic phase driven off, giving a crude product weighing 71 g will.

The crude product is on a 10.2 com Vigreux column at a Distilled at a steam temperature of 105 to 1070C 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 In a 200 ml stainless steel autoclave is 60 g of the tetrahydropentamethyl-4-indanol thus prepared, Added 5 g of a 5% rhodium catalyst on charcoal and 150 ml of isopropanol. The temperature of the autoclave is kept at 200C while hydrogen gas is introduced is that a pressure of 72.1 at is reached. The temperature is then to 18600 increases, whereupon the pressure rises to 105 at.

After long dehydration under the above conditions, the Discharged hydrogen and cooled the autoclave to room temperature. The solvent is stripped to give a crude product weighing 35 g will. The product is washed and distilled, giving 1,1,2,3,3-pentamethylhexahydroindan-4-01 is obtained.

Example 3 Preparation of 1,1,2,3,3-pentamethylhexahydro-4 (5H) -indanone In a 500 ml flask fitted with cooling devices, a stirrer, a thermometer, and a reflux tub is provided, 50 g of that prepared in Example 2 are Hexahydroindan-4-ols and 300 ml of acetone. Da8 Cemisch is stirred while 75 ml of Jones reagent are added. The reaction mixture is then 1 hour stirred and then mixed with 25 ml of ethanol and 50 ml of toluene.

The aqueous phase is removed. The organic phase is washed and neutralized with sodium bicarbonate.

The solvent is driven off and the organic remaining Material is distilled to give 1,1,2,3,3-pentamethylhexahydro-4- (5H) -indanone is obtained, which has a woody amber odor with a fruity noschus impact owns.

Example 4 Production of Soap Mixtures 100 g of soap chips (from a bilette soap made from talc and coconut oil) mixed with 1 g of the perfume blend given below until essentially one homogeneous mass was obtained. The soap has a characteristic woody-amber look , musky odor.

The perfume blend consists of the following ingredients: Ingredients Parts of vetiver oil 40 One of the indane compounds prepared according to Examples 1 to 3 60 sandalwood oil 100 geranium rose oil 200 musk extract (3%) 25 civet extract (3 %) 25 Benzyl-iso-eugenol 100 Coumarin 100 Heliotropin 50 Boie de Rose Oil 200 Benzoin Heart 100 1,000 Example 5 Preparation of a detergent mixture An oe total of 100 g of a detergent powder is mixed with 0.15 g of those given in Example 4 Perfume mixture mixed until a substantially homogeneous mass is obtained, which has a wood-amber-like or amber musk-like odor.

Example 6] Preparation of a cosmetic powder A cosmetic Powder is produced by mixing 100 g of powder with 0.25 g of one of the indan compounds is mixed according to one of Examples 1 to 3, This is done in a tugelmUhle. The cosmetic powders have a desirable woody, amber-like, woody appearance or woody musk-like odor, depending on the indanon used.

Example 7 Liquid Detergent Concentrated liquid detergents are used produced the 0.1%, 0.15 ko and 0.20% of the indane substances according to the examples 1 to 3 included by adding the appropriate amount of the indane compound to one as Ultra Chemical Company's P-87 liquid detergent and homogeneous be mixed with it. The detergent has one, depending on the indan used woody, holy-amber-like or woody-musky odor.

- P a t e n t a n s p r ü c h e -

Claims (8)

PATENT CLAIMS 1. Saturated Indan-DEriuvate with the general formula wherein R is a carbonyl oxygen or a hydroxy or lower alkoxy or acyloxy group. 2. 1,1,2,3,3-pentamethylhexahydro-4 (5H) -indanone. 3. 1,1,2,3,3-pentamethylhexahydro-5 (4H) -indanone. 4. 1,1,2,3,3-pentamethylhexahydro-4-indanol. 5. 1,1,2,3,3-pentamethylhexahydro-5-indanol. 6. A process for the production of saturated indanones, thereby g e k e n n 8 e i c h n e t that one can produce the corresponding ketone Pentamethylhexahydroindanol oxidized with a hexavalent chromium oxidizing agent. 7. A process for the production of saturated indanols, thereby g It is not noted that one can produce pentamethylhexahydroindanol Pentamethyl indanol hydrogenated. 8. Use of the saturated indane derivatives according to Claims 1 to 5, as components of perfume mixtures.