DE1811289A1 - Oxygenated decalin derivatives - Google Patents

Description

The present invention relates to new " oxygen-containing decalin derivatives, their use as odoriferous substances for the production of perfumes and perfumed Products and processes for the manufacture of the decalin derivatives mentioned.

The deealin derivatives according to the invention correspond to the formula

oa.

in which X represents oxygen or two monovalent radicals, of which one is hydrogen and the other is the group -0-CO-R, in which R is a straight or branched, saturated, aliphatic hydrocarbon radical with 1 to 6 carbon atoms or denotes a straight or branched, unsaturated, aliphatic hydrocarbon radical having 2 to 6 carbon atoms.

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R can be an alkyl radical, for example methyl, ethyl, n- and iso-propyl, n- and iso-butyl, n- and iso-amyl * n- and iso-hexyl or tert-butyl, or an alkenyl radical with one or two Double bonds, for example vinyl, propen- (1) -yl, allyl, iso-propen- (1) -yl, buten- (1) -yl, buten- (2) -yl, buten- (3) -yl. iso-butene- (l) -yl, iso-butene- (2) -yl, 3,3-dimethyl-allyl, iso-pentene (l) -yl, iso-penten- (2) -yl, iso- Hexen-ilJ-yl, iso-hexen- (2) -yl, iso-hexen- (3) -yl, butadien- (1,3) -yl, pentadien- (1,3) -yl, pentadiene- (2 , 4) -yl, iso-butadien- ( _{1,3) -yl f} isQ-pentadien- (1,3) -yl, hexadien- (2,4) -yl _i or isQ-hexadlene- (2; # ^ ) -yl »or an alkynyl radical, for example ethynyl * fropin- (1) -yl, propyn- (2) -yl. Butyn- (2) -yl, 3 * 3-dimethyl-propyn- '(1) -yl or 4-methyl-pentyn- (2) -yl represent.

The preceding list represents only a selection of residues. R can of course "others under the general definition denote falling remainders.

It has been found that the new decalin derivatives have particularly interesting and valuable odor properties and can therefore be used as odoriferous substances in the perfume industry. The new fragrances can be used in particular for the production of diluted or concentrated ^ perfumes and for perfuming products such as soaps, detergents and cleaning agents, cosmetic products, waxes and general products,

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- - 3 - ·. ■ ■ ■■■. ■.

which are normally perfumed for technical reasons be used.

The compound of formula I in which X is oxygen, that is, l, 7 ₁ 7-trimethyl-bieycloi4.4.0] Deean-one (3), occurs in two isomeric forms which can be represented by the formula shown below:

, H and

CH,

III ( trans )

Both isomers develop an intense, precious wood-like odor with an amber-like fragrance.

The esters of formula I wherein X is hydrogen plus the Group -O-CO-R represents, also develop intense noble wood-like Odors, however, have a higher adhesive strength than the ketones II and III.

The proportions in which the new decalin derivatives are used to achieve the desired odor effects vary within fairly wide limits and depend on the nature of the products that the new fragrances are added. For example, when making perfumes, quantities from $ 0.5 to $ 10 are used of the fragrances, based on the total weight of the perfume, achieved interesting results. When the new derivatives together

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used with other fragrances to perfume.products they can be added, for example, in amounts of $ 0.001 to $ 0.5, based on the weight of the product to be perfumed will. In other cases, for example in the production of Concentrates that are diluted with solvents or mixed with other fragrances before use or that are called so-called Serving perfume bases, the concentration of the decalin derivatives mentioned higher than 10 $, e.g. up to lg £ or even higher.

The quantity ranges listed above do not represent "absolute values," but are merely exemplary To understand information. Of course, other concentrations can be used depending on the particular olfactory effects that you want to achieve be used.

According to the invention, the esters of the formula

0-CO-R

'''■■■: ■■. ■ - ^'■■':;

(Formula I, X = H plus -OGOR), in which R has the meaning given above possesses, obtained by making a carbinol the formula

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with an acylating agent of the formula R-COX (VI) -, wherein R is the has the meaning given above and X denotes an easily cleavable leaving group, esterified.

The esterification can be carried out by known methods, for example using acylating agents VI in which X is a halogen, for example chlorine or bromine, or a tosyl group or a group R-COO-, in which R has the meaning given above. Zweckinässlgerweise using a Neutrali si erungsmittel capable of reducing the formed during the esterification (^ acid to bind, for example, an organic base such as triethylamine. Preferably used as the acylating agent is an anhydride in the presence of pyridine.

According to the invention, the esters of the formula IV are also obtained by adding 6,10-dimethyl-undecatriene- (1.5 * 9) with a mixture of a mineral acid and an organic acid of the formula R-COOH, in which R has the meaning given above owns, brings to implementation. Suitable mineral acids are, for example, sulfuric acid, phosphoric acid, perchloric acid and ti Hydrochloric acid.

According to the invention, the ketones II and III

obtained by oxidizing 1,7,7-trimethyl-bicyclo [ ⁱ l-.4.0] decanol- (3). The oxidation can be carried out by known methods, for example by means of silver carbonate in the presence of diatomaceous earth or by means of oxidation products of transition metals, for example chromium and copper [see, for example, Organic Chemistry ¹ by DJ Cram and GS Hammond, (1959), pp. 432-436, McGraw-Hill, New York],

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be performed. The oxidation can also be carried out by means of a Ketones in the presence of an aluminum alcoholate by method j of Oppenauer to be carried out. Suitable ketones are, for example, acetone, cyclohexanone, diethyl ketone and methyl ethyl ketone and methylhexyl ketone, while as alcoholates, for example Aluminum butoxide, aluminum isobutoxide or aluminum isopropoxide can be used. The oxidation is preferably carried out either with CrO or with methyl ethyl ketone in The presence of aluminum isopropylate carried out.

The oxidation product obtained by oxidation of the carbinois consists of a mixture of the cis and trans isomers of 1.7.7 ^l irimethyl-bieycloi4.4.0] decanone- (3). The solid cis-isomer is obtained in pure form by means of crystals of this mixture. The liquid trans isomer can be isolated from the mother liquors obtained in the fractional crystallization, for example by distillation or by preparative gas chromatography. The two isomers have similar odor properties, but the trans isomer has a somewhat more camphor-like odor note. The two isomers can optionally be used individually for perfumery purposes. For economic reasons, however, it is more expedient to use the mixture of the two isomeric ketones as a fragrance.

The carbinol of the formula V used to prepare the ketones II and III can be obtained, for example, by saponification the ester of the formula IV can be obtained. The saponification can by known methods, for example by means of alkalis, e.g.

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"■ 7"

KOH, NaOH, and LiOH, in the presence of aqueous alcohols, e.g. Methanol or amyl alcohol.

The 6,10-dimethyl- used to prepare the ester IV

undecatrien- (l, 5 »9) of the formula VII can by reacting a

■ ■. ■ I

Geranyl halide VIII, e.g. of chloride or bromide, with a Allyl halide IX, e.g. the chloride or broraide, among the usual Grignard reaction conditions can be obtained.

The preparation of the ketones II and III, the ester IV and the various intermediates is as follows Reaction scheme summarized in which X denotes halogen and R has the meaning already defined.

IX

'^ ^V S mineral acid

Mg

+ R-COOH

VIII

VII

Verseifu ng

Esterification 0-CO-R

OH

IV

oxidation

III

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ORIGINAL INSPECTED

- ft -

In the following working examples, temperatures are given in degrees Celsius.

Example. 1

By mixing the substances listed below, a fragrance composition of the 'Chypre' type was produced:

Components Parts by weight Undecanal, 10 # -ig ⁺ 10 Dodecanal, 10 # -Ig ⁺ 20th Synthetic rose oil 60 · Synthetic jasmine oil 120 Hydroxycitrone'llal 30th Isojasmone 5 • γ-methyl ionone 90 Styrax, 50 # 60 Cinnamyl alcohol 15th Bergamot 45 Celery oil, 10 # ⁺ 70 ^ Citral, 10 # ⁺ 30th Patchouli 100 Santa !, oriental 20th Vetyver bourbon 40 Cedryl acetate 15th Oakmoss, absolute, $ 50 40 Myrrh oil 20th Labdanum Cistus ^ absolute, 10 ^ - -ig ⁺ 20 Degreased natural civet 10 ^ -ig * 20th Ketone musk 60 Coumarin 30th Ethylvanillin 15th Jasmine, absolutely 10 Bulgarian rose oil '5

Total

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in diethyl phthalate

· ". ■ · ■ - 9 ■ -." ■

This mixture was 50 g of a mixture of eis- and trans-l, 7,7-trimethyl-bicyclo [4.4.0] decanone- (3) . (Weight ratio about i: l) added. One received on this Way a Rieehstoffkomposition, which had a pleasing amber-like and woody fragrance.

Example 2

By mixing the substances listed below, a fragrance composition of flowery,. More 'Chypre' like Type made:

Components Parts by weight Decanal, 10 # -ig ⁺ 5, Undecenal, 10 # -ig ⁺ ■ 45 Dodecanal, $ 10 10 Synthetic lily of the valley 150 Synthetic rose oil 150 Synthetic jasmine oil 90 Synthetic carnation 60 Bergamot 90 Ylang 45 Tarragon, $ 10 ⁺ 30th

Oak moss, 'absolute, 50 # ⁺ 30 Labdanum Cistus, absolute, 10 # ⁺ 20

Benzoin tears, lQ # -ig ^{+ -} 10 Degreased natural civet,

10 ^ -ig ⁺ · 15

• y-methyl ionone "" 60

Patchouli 5

Santal, oriental 3Q

Coumarin 25

Ambrite musk 10

Ketone musk 50

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Orange blossom * absolute, lQ $ -ig 15

Jasmine, absolutely 10

Rose, absolutely 20

Undecalactone, lO ^ -ig *. 10 Vanillin,

Total 990

⁺ in diethyl phthalate

This mixture was 10 g of cis-l ^^ - trimethyl-bicyclo (4.4.0] decanone- (3) was added. In this way, a Fragrance composition with a pleasing amber-like and woody fragrance.

Example 3

a.) 6, 10-dimethyl -undecatriene- (1,5.9)

8 ^ g (3 * 5 mol) of defatted magnesium shavings were suspended in 100 ml of absolute ether. The magnesium was activated with an iodine crystal. Within 3 hours, first 300 g (1.75 mol) of geranyl chloride and then a solution of 268 g (3.5 mol) of allyl chloride in 800 ml of ether were added dropwise. The reaction mixture was heated to boiling for 4 hours, then cooled and poured into a solution of 200 g of NH ^ Cl in 1 liter of ice water. The solution was extracted with ether. After concentration, the extracts yielded 384 g of crude 6,10-dimethylundecatriene-il ^^ K ^{which was} further processed without prior purification.
b.) l, 7,7-trimethyl-bicyclof4.4.0 ] deoanol- (3)

The 384 g of triene obtained in accordance with paragraph a.) Were within about 1.1 / 2 hours at 50 dropwise a mixture of

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2.7 kg of 98% formic acid, 270 g of concentrated sulfuric acid and 1000 ml of dioxane were added. The reaction mixture was stirred at 60 ° for 3 hours, then cooled and then poured onto ice. After extraction with ether, the extracts were neutralized with 10 # aqueous sodium bicarbonate and washed neutral with water. The extract was dried and concentrated in the usual manner. The residue (430 g) was mixed with 140 g of potassium hydroxide, 140 ml of water and 1500 ml of methanol and stirred for 4 hours at reflux temperature. After removing the methanol under reduced pressure, the residue was extracted with ether. The extract was neutralized, washed and dried in the usual manner. By concentrating the extract and concentrating the residue (350 g) in vacuo, 1,7,7-trimethyl-bicyclo [4.4.0] decanol- (3) (boiling point 114-125 ° / 0.001 torr, melting point 53-54 °) received. c.) Oxidation of 1,7,7-trimethyl-bicyclof4.4.0] decanol - ('5)

A solution of 0.53 mol of CrO in 200 ml of water was added dropwise to a solution of 105 g (0.53 mol) of the carbinol prepared in accordance with paragraph b.) In 800 ml of glacial acetic acid over a period of about 2 hours at 40-45 °. The mixture was heated at 70 ° for 4 hours, then cooled and extracted with ether. The extract was treated and concentrated in the usual manner. One received 95 g of one! crude mixture of cis- and trans-l, 7-7-trimethyl-bicyclo [4.4.0] decanone- (3) i »weight ratio of about 1: 1. By recrystallizing the crude product twice in hexane, 46.5 g * of pure cis isomer with a melting point of 46 ° -47 ° were obtained. IR spectrum (liquid phase) ^:! 965, 1215, 1450, 1705, 2940 cm "¹; NMR spectrum (CCl ^): 0.86

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ORIGINAL INSPECTED

(OH, s), 0.96 (3H, s), 1.43 (8H, in), 1.95 (2H), 2.23 (2H, m), ppm

The mother liquors obtained during the crystallization were concentrated. The residue, consisting largely of the trans-isomer, was purified by preparative gas chromatography in a 'Carbowax 20M ¹ column of 2.5 ra at 150 ° with a helium flow of 40 ml per minute. The product obtained had the following NMR spectrum (CCl ₄ ): 0.87 (6H, s), 1.13 (3H, s), 1.5 (8H, m), 2.2 (4H, in) ppm (6).

Be i s ρ i e 1 4.

Production of 1,7,7-trimethyl-bicyclof4.4.0] decanone- (5)

A mixture of 19.6 g according to. Paragraph b.) Des

Example 1 prepared l, 7 _J .7-trimethyl-bicyclo [4 '4 "0] decanol (3), 72 g of methyl ethyl ketone, 50 ml of toluene" 10.5 g of aluminum isopropylate and 2 g of aluminum chloride was heated to boiling for 6 hours . After cooling, the reaction mixture was stirred together with 200 ml of 10 ^ sulfuric acid and then extracted with toluene.

became

The extract1 treated in the usual way and distilled. One received 8 * 2 g 1,77-trimethyl-bicycloi4,4 "Ojdecanon- (3) from bp. 85-90 ° / 0.001 Torr.

Example 5

Production of l, 7 »7-trimethyl-bicyclo [4.4.0idecanon- (3) a.) 6,10-dimethyl-undecatriene- (l, 5.9)

51 g (2.1 mol) of magnesium turnings were suspended in 1700 ml of ether and activated with an iodine crystal. A solution of 153 S (2.0 mol) of allyl chloride in 200 ml of ether was added dropwise

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added at such a rate that the reaction mixture was kept at reflux temperature during the dropping. The mixture was then refluxed for a further 2 hours and then a solution of 210 g (1.05 mol) of technical 82% geranyl chloride in 200 ml of ether was added dropwise at the reflux temperature. The reaction mixture was stirred for a further 2 hours at room temperature, then cooled to 10 and slowly acidified with 20% aqueous acetic acid. The mixture was extracted with ether, whereupon the extracts were neutralized with 10 # aqueous sodium hydroxide, washed with water and dried and concentrated in the usual way. 217 g of crude product were obtained in the form of a pale yellow liquid, the 6,10-dimethyl-undecatriene (1.5,9) content of which, according to analysis by gas chromatography, was about 80%. The raw product was further processed without prior purification,
b.) l, 7,7-trimethyl-bic.yclo [4.4.0idecanol- (3)

500 g of 6,10-dimethylundecatriene (l, 5> 9) produced according to paragraph a.) were at 30-35 ° in a mixture of 1 kg Acetic acid and 165 g of concentrated sulfuric acid were added dropwise. The reaction was strongly exothermic and lasted about 4 hours. That The reaction mixture was stirred for a further 3 hours at 40 °, whereupon 3 to 5 liters of ice water were added with vigorous stirring. The mixture was washed twice with petroleum ether (boiling range 80-100) extracted. The extracts were washed with 10% aqueous sodium hydroxide neutralized and washed with water. The remaining moisture was obtained by azeotropic distillation of the extract

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18.11283 ■

removed with the solvent.- Further concentration gave 562 g of crude product, which was refluxed for 4.1 / 2 hours together with 1124 g of amyl alcohol and -199 g (3 * 5 ^ mol) of potassium hydroxide The reaction mixture was stirred with 10 liters of water and then the alcoholic layer was separated off. By conventional treatment of the latter and distillation of the residue, 246 g of 7,7-trimethylbicyclo [4.4.0] decanol- (3) with a boiling point of 95-127 ° / were obtained. ö _i 025, ^L 0 _s 08 Torr.

c.) Oxidation of 1,7 »7-Trlmethyl-bicyclof4.4.0Idecanol-

246 g of the carbinol produced in accordance with paragraph b.) were dissolved in 2.5 kg of pure acetone. 642 g of 'Jones' oxidizing agent (prepared according to J. Chem. Soc. 39, 1946) was added dropwise with cooling at such a rate, that the temperature of the reaction mixture remained between 23 ° and 25 °. The reaction mixture was during Left to stand for 2 hours and then together with 1.5 liters of water and 500 ml. Petroleura ether (boiling range 80-100 °) stirred. The mixture was left to stand overnight and then stripped twice with petroleum ether. By usual treatment

the combined extracts were obtained 220 g. raw ketone. Distillation of this crude product gave 107.6 g. of the mixture the cis and trans isomers of l, 7,7-trimethyl-bieyclo (4,4.0) -decanone- (3), 77-85 ° / 0.015-0.025 torr.

Example 6

Production of acetic acid-1,7,7 ~ trimethyl-bicyclo (4.4.0j decy1- (3) ~ ester

The crude ββ «8 2 9/1561 ■ obtained in accordance with paragraph-b ..) of Example 5

instead of being saponified, carbinyl acetate was fractionated. The pure ester was obtained in 87 # yield (boiling point 90-91 ° / 0.01 torr).

Analysis : Calculated for C ₁₅ H ₂₆ O ₃ : C 75.582 H 11.00? Found: C 75.77? H 11.09?

Nuclear Magnetic Resonance Spectrum (CCl ₁₁ ): Ο, 8θ (3H, s), 0.88 (3H, s), 1.00 (3H, s), 1.1-1.8 (12H, broad multiplet), 1 , 90 (3H, s), 4.80 (IH, broad band). ppm (fi).

Example 7

Production of acetic acid-1,737-trimethyl-bicyclof 4.4.θ) decyl- (3) -ester

22 g. 1,7> 7-trimethyl-bicyclo (4.4.0) decanol- (3) were together with 15 g. Acetic anhydride and 15 g. Pyridine during ' Heated at 90 ° for 2 hours. The reaction mixture was extracted with ether. By usual treatment of the extract 23 g of pure acetic acid l, 7,7-trimethyl-bicyclo (4.4.o) decyl (3) ester were obtained, Bp 90-91 ° / 0.01 torr.

Example 8

Instead of the acetic anhydride used according to Example 7 an equivalent amount of propionic anhydride, butyric anhydride or acrylic anhydride was used. Man obtained the corresponding esters of 1,7,7-trimethyl-bicyclo (4.4.o} decanols- (3) in comparable yields. The results are summarized in the table below ί

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Anhydride ester (bp)

Propionic anhydride 98-102 ° / 0.02 torr

Butyranhydride "113-117 ° / 0.05 torr

Acrylic anhydride 85-88 ° / 0.01 torr

Example 9 .

The reaction product of 6,10-trimethyl-undecatriene (1.5 »9)» formic acid obtained in accordance with paragraph b.) Of Example 3 and sulfuric acid was distilled in vacuo after the ether had been removed. The formic acid, 7,7-triraethyl-bicyclo (ii.i | .0) decyl (3) ester was obtained in this way of bp. 80-90 ° /, 0., Ol Torr.

Example 10

A fragrance composition of the following composition was produced:

Components Parts by weight Phenylethanol 155 Styrax, 50% * 215 Heliotropin 85 Citronellol 50 Vanillin 50 Ketone musk 40 Patchouli 25th Synthetic civet, lOjS-ig * 50 Benzyl acetate 280 Total q «50

* in diethyl phthalate

50 g of acetic acid - !, 7,7-trimethylbicyclo (i ». ¹ IvO) decyl (3) ester were added to this mixture. In this way, a perfume composition with a pleasant, natural, precious wood-like fragrance was obtained. . "··. · -. -

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Claims (1)

Claims 1. Compounds of the formula X in which X represents oxygen or two monovalent radicals, the other of which one is hydrogen and »the group -O-CO-R, where R is a saturated, straight or branched, aliphatic hydrocarbon radical with .1 to 6 carbon atoms or an unsaturated, straight or branched, aliphatic hydrocarbon radical with 2 to 6 Denotes carbon atoms. 2. Compounds of the formula II and III 3. cis-l, 7,7-trimethyl-bicyclo (4.4.0) decanone- (3). 4. trans-1,7,7-trimethyl-bicyclo (4.4.0) decanone- (3). 5 * compounds of the formula IV 0-CO-R 909829/156 Ί in which R denotes a saturated, straight or branched, aliphatic hydrocarbon radical having 1 to β carbon atoms or an unsaturated, "straight or branched, aliphatic hydrocarbon radical having 2 to β carbon atoms. 6, formic acid-ljTjT-trimethyl-bicyeiXo 4,4.0 ■ -decyl- (3) -ester. 7 "acetic acid l, 7 _s 7" trimethyl - bicyclo (4.4.o) decyl (3) ester., 8. Propionic acid l _> 7,7-trimethyl-bicyclo (4.4.o) -decylr (3) ester. 9. Butyric acid 1,7,7-triraethyl bicyclo (4.4.0) decyl (3) ester. 10. Acrylic acid-l, 7,7-trimethyl-bicyclo (4.4.0) -decyl- (3) -ester. 11. Use of compounds of the formula approx. in which X represents oxygen or two monovalent bests, the other one of which is hydrogen and I the group -O-CO-R, wherein R is a saturated, straight or branched, aliphatic Hydrocarbon radical with 1 to 6 carbon atoms or an unsaturated, straight or branched, aliphatic carbon hydrogen residues with 2 to 6 carbon atoms referred to as odoriferous substances or odor-modifying additives. 909829/15 & 1 12. Fragrance composition or perfumed Product characterized by a content of compounds of the formula. in which X represents oxygen or two monovalent radicals, the other of which one is hydrogen and ι the group -OCO-R, where R is a saturated, straight or branched, \ aliphatic hydrocarbon radical with 1 to 6 carbon atoms or an unsaturated, straight or branched, aliphatic ι ^ Hydrocarbons denotes a residue with 2 to 6 carbon atoms. 13. Process for the production of fragrance compositions, characterized by the use of Compounds of the formula in which X represents oxygen or two monovalent radicals, the other of which one is hydrogen and 1 is the group -0-CO-R, in which R is a saturated, straight or branched, aliphatic hydrocarbon radical having 1 to 6 carbon atoms or an unsaturated, straight or branched, aliphatic hydrocarbon radical having 2 to 6 carbon atoms referred to as fragrance components or odor-changing additives. 909829/1561 ORIGINAL INSPECTED 14. Process for the preparation of ketones of the formula II and III Ό characterized in that 1,7,7'-trimethyl »foieyelo (4" 4.0) decanol - (^) oxidized. $ 1. Process according to claim 14, characterized in that the cis isomer of _{1.7 9} 7 "-trimethyl-biöyGlo- (4.4.0) decanone- (3) is isolated by fractional crystallization of the oxidation product. 16. The method according to claim 14 and 15, characterized in that »that one obtains the trans isomer of l _§ 7s7 ™ ^ riraethylbicyolo (4.4.0} decanone- (3-5 from the mother liquors obtained during fractional crystallization» 17 »Process - for the yeast production of esters of the formula in which R denotes a saturated, straight or branched, aliphatic - hydrocarbon radical with 1 to β carbon atoms or 'an unsaturated * -' straight or branched, aliphatic hydrocarbon radical with 2 to 6 carbon atoms ₉ 'thereby that 1,7 »7-trimethyl biesreXo (4.4.0) deeanoi- <3) CV) with an aylating agent of R.
• Formula R-COX CVI) ₃ in which the meaning defined above and X ' denotes an easily cleavable leaving group »■ 9 09879/15 "esterified - is. 18. Process for the preparation of esters of the formula X ^ IV O-CO-R in which R is a saturated, straight or branched, aliphatic hydrocarbon radical having 1 to 6 carbon atoms or an unsaturated, straight or branched, aliphatic hydrocarbon radical having 2 to 6 carbon atoms referred to, characterized in that 6,10-dimethyl-undecatrien- (1.5 »9) with a Geraisch a mineral acid and an organic acid of the formula R-COOH, in which R has the meaning defined above, to react. 909829/1561 ORIGINAL INSPECTED