EP0191365B1 - Araliphatic oximes, process for their production and perfume compositions containing such compounds - Google Patents

Description

worin R Wasserstoff, Methyl oder Äthyl ist.The invention relates to new fragrances. These are the compounds of the formula

wherein R is hydrogen, methyl or ethyl.

Formula 1 is intended to encompass the syn and anti forms of oxime I. The anti form is preferred.

The invention further relates to a process for the preparation of the compounds I.

worin R obige Bedeutung besitzt, mit Hydroxylamin bzw. einem seiner Salze umsetzt.This process is characterized in that a ketone of the formula

where R has the above meaning, reacted with hydroxylamine or one of its salts.

The reaction of the compound of formula II with hydroxylamine or a salt thereof can be carried out according to methods known per se, see e.g. B. Organikum, organic chemical basic internship, author collective; 7th edition; VEB German Publishing House of Sciences; Berlin 1967, 375, 555: The oxime is conveniently left as a salt, e.g. B. react as hydrochloride or sulfate in pyridine or sodium acetate-containing alcoholic solution or in aqueous alcoholic solution with the ketone II; the reaction temperature is preferably the reflux temperature of the reaction mixture.

The processing is expediently carried out according to methods known per se: distilling off most of the alcohol, adding an organic solvent, washing with water and finally removing the unreacted ketone.

The starting ketones 11 are known or can be prepared by methods known per se, e.g. B. by chain extension of the commercially available diisopropyl ketone, for example by means of arylalkyl halides.

The compounds I have special organoleptic properties which make them particularly suitable as fragrances.

The invention accordingly also relates to the use of the compounds I as fragrances.

The oximes according to the invention are distinguished by a special combination of perfume properties. They are either colorless or slightly colored, easily accessible, the individual approaches have a constant smell, are not irritating, stable and easy to use.

The compounds of formula I are reminiscent of notes of black currant, sage, grapes.

The olfactory notes are therefore completely different from those of the araliphatic oxime, 3-benzylpentan-2-, described in Swiss Patent Application No. 645/82 of February 3, 1982 (made available with European Patent Publication No. 85352 of August 10, 1983). on-oxims. That oxime smells of pepper nut, pyrazine and peas, so it lacks any fruity-berry note. This well-known oxime subsequently claimed no perfume interest. In particular, however, the odor strength in the case of the new oximes is surprisingly approximately 100 times greater than in the case of the known araliphatic oxime (compounds in 1% solution in isopropyl myristate applied to odor strips, measured immediately and / or after 24 hours). Because of this, the new compounds I can be used in a correspondingly more dilute solution.

• a) blumigen Kompositionen, in denen z. B. die Citrusnoten verstärkt zum Ausdruck kommen sollen (z. B. für Cologne-Typen u.ä., Extraits),
• b) des weiteren aber auch von fruchtigen Kompositionen, z. B. vom Typ Johannisbeere (Extrait-Typen), Kompositionen der femininen wie der männlichen Richtung), von
• c) Kompositionen mit grünen Noten, wo insbesondere ein erwünschter natürlicher Effekt erzielt wird, und schliesslich von
• d) Kompositionen, in denen generell der Charakter von natürlichen Ölen angestrebt wird, z. B. Flieder oder Lavendel.

Due to their natural smell and their retention time (long-term effect, especially with regard to freshness), they are particularly suitable for modifying known, e.g. B.

• a) floral compositions in which, for. B. the citrus notes should be increasingly expressed (e.g. for cologne types and the like, extraits),
• b) but also of fruity compositions, e.g. B. of the type currant (Extrait types), compositions of the feminine and the male direction), by
• c) compositions with green notes, where in particular a desired natural effect is achieved, and finally from
• d) compositions in which the character of natural oils is generally sought, e.g. B. lilac or lavender.

• Verbindung I: R=H_: starker und lang haftender Geruch, grün, natürlich, nach Salbei, nach schwarzen Johannisbeeren, aber blumiger;
• Verbindung I: R=CH₃: starker und sehr natürlicher Geruch nach Salbei, Weintrauben, Kelterhaus;
• Verbindung I: R=C₂H₅: starker und diffusiver Geruch, nach schwarzen Johannisbeeren.

The individual smell notes are the following:

• Compound I: R = H _: strong and long-lasting smell, green, natural, of sage, of black currants, but more floral;
• Compound I: R = CH ₃ : strong and very natural smell of sage, grapes, wine press;
• Compound I: R = C ₂ H ₅ : strong and diffusive smell, of black currants.

• - Naturprodukte, wie Angelikasamenöl, Baummoos-Absolue, Basilikumöl, Beifussöl, Bergamotteöl, Castoreum, acetyliertes Cedernholzöl (z. B. Vertofix® IFF bzw. Cedartone ®Givaudan), Corianderöl, Eichenmoos, Elemiöl, Galbanumöl, Geraniumöl, Jasmin Absolue und seine Substitute, Kamillenöl, Lavandinöl, Lavendelöl, Mandarinenöl, Mastix Absolue, Nelkenknospenöl, Neroliöl, Patchouliöl, Petitgrainöl Paraguay, Rosenöl, Rosmarinöl, Sandelholzöl, Styrax, Vetiveröl, Wermutöl, Ylang-Ylang-Öl, Ysopoel, Zibetöl, Zitronenöl.
• - Alkohole, wie Citronellol, Dimethylbenzylcarbinol, Dimetol ®Giv. (2,6-Dimethyl-2-heptanol), Geraniol, Linalool, Menthol, 3-Methyl-5- (2',2',3'-trimethyl-cyclopent-3'-en-1'-yl)-pentan-2-ol (Sandalore ®Givaudan), Nerol, Phenyläthylalkohol, Phenylpropylalkohol, natürliches Rhodinol, Terpineol, a-Terpineol, 2,2,8-Trimethyl-7-nonen-3-ol, Zimtalkohol.
• - Aldehyde, wie a-Amylzimtaldehyd, Citral, Cyclamenaldehyd, Decanal, 3,5-Dimethyl-cyclohex-3-en-car- boxaldehyd, n-Dodecanal, Heliotropin, a-Hexylzimtaldehyd, Hydroxycitronellal, Methylnonylacetaldehyd, p-tert. Butyl-a-methyl-dihydro-zimt-aldehyd (z. B. Lilial® Givaudan), n-Undecen-10-al.
• - Ketone, wie Acetylcedren, Allyljonon, p-Hydroxybenzylaceton, a-Jonon, 2,4,4,7-Tetramethyl-6,8-nonadien-3- on, p-Methylacetophenon, Methyljonon. 1,2,3,4-Tetrahydro-1,1-dimethyl-4-propionylnaphthalin.
• - Ester, wie Äthylacetoacetat, 3-Äthyl-1,1-dimethyl-cyclohex-3-en-2-carbonsäure-äthylester(Givescone ®-Givaudan), 3-Äthyl-1,1,4-trimethyl-cyclohexen-3-en-2-carbonsäureäthylester (Myrascone® Givaudan), Allylphenoxyacetat, Amylsalicylat, Benzylacetat, Benzylsalicylat, Bornylacetat, Cedrylacetat, Cinnamylformiat, cis-3-Hexenylacetat, cis-3-Hexenylbenzoat, Geranylacetat, Hexylsalicylat, Isobutylsalicylat, Linalylacetat, Linalylanthranilat, Methyldihydrojasmonat, 4-[4-Methyl-3-pentenyl]-cyclohex-3-en-1-yl-carbinylacetat (z. B. Myraldyla- cetat^e Givaudan), Oxyoctalinformiat Giv. (Δ¹-1,5,9,10-Tetramethyl-5-formoxy-octalin), Phenyläthylacetat, Styrallylacetat, Terpenylacetat, p-tert. Butylcyclohexylacetat.
• - Lactone, wie Cumarin, y-Decalacton, y-Dodecalacton, y-Nonalacton, y-Undecalacton.
• - verschiedene weitere, in der Parfümerie oft benützten Komponenten, wie Acetaldehyd-propylphenyl- äthylacetal, Cyclocitrylidenacetonitril, 1,1-Dimethyl-4-acetyl-6-tert. butylindan, Dodecahydro-3a,6-6-9a-tetramethyl(2,1-b)furan. Eugenol, Galaxolid IFF (7-Acetal-1,1,3,4,4,6-hexamethyltetralin), Indol, Isobutylchinolin, p-Menthan-8-thiol-3-on, Methyleugenol, Methyl-1-methyl-cyclododecyläther (z. B. Madrox® Givaudan), Moschus-Verbindungen (Ketonmoschus, 12-Oxahexadecanolid (z. B. Musk 174® Naarden), 8,12-Oxido-13,14,15,16-te- tranorlabdan (Fixateur 404⁰).

The compounds combine with numerous known fragrance ingredients of natural or synthetic origin, the range of natural raw materials comprising both light, medium and low volatile components, and that of synthetics can include representatives from practically all classes of substances, as follows from the following Compilation can be seen:

• - Natural products, such as angelica seed oil, tree moss absolute, basil oil, mugwort oil, bergamot oil, castoreum, acetylated cedarwood oil (e.g. Vertofix® IFF or Cedartone ®Givaudan), coriander oil, oak moss, elemi oil, galbanum oil, geranium oil, jasmine absolute and its substitutes , Chamomile oil, lavender oil, lavender oil, mandarin oil, mastic absolute, clove bud oil, neroli oil, patchouli oil, petitgrain oil paraguay, rose oil, rosemary oil, sandalwood oil, styrax, vetiver oil, wormwood oil, ylang-ylang oil, hyssopoel, lemon oil, civet oil.
• - Alcohols, such as citronellol, dimethylbenzylcarbinol, Dimetol ®Giv. (2,6-dimethyl-2-heptanol), geraniol, linalool, menthol, 3-methyl-5- (2 ', 2', 3'-trimethyl-cyclopent-3'-en-1'-yl) pentane -2-ol (Sandalore ®Givaudan), nerol, phenylethyl alcohol, phenylpropyl alcohol, natural rhodinol, terpineol, a-terpineol, 2,2,8-trimethyl-7-nonen-3-ol, cinnamon alcohol.
• - Aldehydes, such as a-amylcinnamaldehyde, citral, cyclamenaldehyde, decanal, 3,5-dimethyl-cyclohex-3-en-car-boxaldehyde, n-dodecanal, heliotropin, a-hexylcinnamaldehyde, hydroxycitronellal, methylnonylacetaldehyde, p-tert. Butyl-a-methyl-dihydro-cinnamon aldehyde (e.g. Lilial® Givaudan), n-undecen-10-al.
• - Ketones such as acetylcedrene, allyl ionone, p-hydroxybenzyl acetone, a-ionone, 2,4,4,7-tetramethyl-6,8-nonadien-3-one, p-methylacetophenone, methyl ionone. 1,2,3,4-tetrahydro-1,1-dimethyl-4-propionylnaphthalene.
• Esters, such as ethyl acetoacetate, ethyl 3-ethyl-1,1-dimethyl-cyclohex-3-en-2-carboxylate (Givescone®-Givaudan), 3-ethyl-1,1,4-trimethyl-cyclohexene-3- en-2-carboxylic acid ethyl ester (Myrascone® Givaudan), allylphenoxyacetate, amyl salicylate, benzyl acetate, benzyl salicylate, bornylacetate, cedrylacetate, cinnamyl formate, cis-3-hexenylacetate, cis-3-hexenylbenzoate, lanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylanyl acetate, lylyl acetate, lylyl acetate, - [4-methyl-3-pentenyl] -cyclohex-3-en-1-yl-carbinyl acetate (e.g. myraldyl acetate ^e Givaudan), oxyoctaline formate Giv. (Δ ¹ -1,5,9,10-tetramethyl-5-formoxy-octalin), phenyl ethyl acetate, styrallyl acetate, terpenyl acetate, p-tert. Butylcyclohexyl acetate.
• Lactones, such as coumarin, y-decalactone, y-dodecalactone, y-nonalactone, y-undecalactone.
• - Various other components often used in perfumery, such as acetaldehyde propylphenyl ethylacetal, cyclocitrylidene acetonitrile, 1,1-dimethyl-4-acetyl-6-tert. butylindane, dodecahydro-3a, 6-6-9a-tetramethyl (2,1-b) furan. Eugenol, galaxolide IFF (7-acetal-1,1,3,4,4,6-hexamethyltetralin), indole, isobutylquinoline, p-menthan-8-thiol-3-one, methyleugenol, methyl 1-methyl-cyclododecyl ether ( e.g. Madrox® Givaudan), musk compounds (ketone musk, 12-oxahexadecanolide (e.g. Musk 174® Naarden), 8,12-oxido-13,14,15,16-tetranorlabdan (fixator 404 ⁰ ).

The compounds of the formula I can be used within wide limits, which can range, for example, from 0.01 (detergents) to 50% (alcoholic solutions) in compositions, without these values being intended to represent limit values, however, since the experienced perfumer can use even lower ones Concentrations can achieve effects or can build up new types of complexes with even higher doses. The preferred concentrations are between 0.05 and 10%. The compositions produced with I can be used for all types of perfumed consumer goods (Eaux de Cologne, Eaux de Toilette, extras, lotions, creams, shampoos, soaps, ointments, powders, deodorants, detergents, tobacco, etc.).

The compounds I can accordingly be used in the production of compositions and - as the above compilation shows - using a wide range of known fragrances. In the preparation of such compositions, the known fragrances listed above can be used in a manner known to the perfumer, such as B. from W.A. Poucher, Perfumes, Cosmetics and Soaps2, 7th edition, Chapman and Hall, London, 1974.

example 1

• Der Rückstand besteht nun aus dem rohen Oxim.
• IR Spektrum; typische Banden bei 3250 cm-¹ (breit),
• 1660 cm-¹ (mittelstark), 930 cm^-1 (stark)
• NMR; (60 MHz, CDCI₃) 8 = 9,7 (breit)
• Dieses rohe Oxim kann z. B. in Form einer 10 %-igen, oder sogar einer 1 %-igen Lösung in Isopropylmyristat in der Parfümerie Verwendung finden.

a) 100 g of hydroxylamine chlorohydrate are dissolved in one liter of ethanol and 100 g of pyridine in a round-bottomed flask equipped with a stirrer, thermometer and cooler. The mixture is stirred for a quarter of an hour at room temperature and 100 g of the ketone 11, R = H, ie 2,2,4-trimethyl-1-phenyl-3-pentanone, are added to the solution. The reaction mixture is kept at the reflux temperature for 2 hours. Most of the ethanol, namely about 3/4, is then distilled off. After cooling, pour on ice water and take up in ether. The ethereal solution is washed as follows: first with water. then for the elimination of the excess pyridine with 5% dilute hydrochloric acid, then again with water to the neutral point. After the ether has been evaporated off, 99 g of the crude oxime I (with R = H) are obtained, which still contain 77 g of unreacted ketone. This ketone (bp. 90 ° C / 1.5mmHg) is distilled off.

• The residue now consists of the crude oxime.
• IR spectrum; typical bands at 3250 cm- ¹ (wide),
• 1660 cm- ¹ (medium), 930 cm ^-1 (strong)
• NMR; (60 MHz, CDCI ₃ ) 8 = 9.7 (broad)
• This crude oxime can e.g. B. in the form of a 10%, or even a 1% solution in isopropyl myristate in perfumery use.

• IR Spektrum; typische Banden bei 3250 cm-¹ (breit).
• 1650 cm-¹ (schwach), 935 cm-¹ (stark)
• NMR; (60 MHz, CDCI₃) 8 = 9,2 (breit)

b) If the 2,4,4-trimethyl-5-phenyl-3-hexanone is used as the starting material in the above process, the 2,4,4-trimethyl-5-phenyl-3-hexanone oxime is obtained;

• IR spectrum; typical bands at 3250 cm- ¹ (wide).
• 1650 cm- ¹ (weak), 935 cm- ¹ (strong)
• NMR; (60 MHz, CDCI ₃ ) 8 = 9.2 (broad)

• IR Spektrum; typische Banden bei 3300 cm-¹ (breit),
• 1650 cm^-1 (schwach), 940 cm^-1 (stark).
• Das 2,4,4-Trimethyl-5-phenyl-3-heptanon ist durch Alkylierung von Diisopropylketon mit 1-Chlor-1-phenyl- propan erhältlich; Sdp. 78 - 79° C/0,2 mmHg.
• IR Spektrum: typische Banden bei 1705 cm-¹ (stark).

c) If the 2,4,4-trimethyl-5-phenyl-3-heptanone is used as the starting material in the above process, the 2,4,4-trimethyl-5-phenyl-3-heptanone oxime is obtained;

• IR spectrum; typical bands at 3300 cm- ¹ (wide),
• 1650 cm ^-1 (weak), 940 cm ^-1 (strong).
• The 2,4,4-trimethyl-5-phenyl-3-heptanone can be obtained by alkylating diisopropyl ketone with 1-chloro-1-phenyl-propane; Bp 78-79 ° C / 0.2 mmHg.
• IR spectrum: typical bands at 1705 cm- ¹ (strong).

Example 2 A. Cologne composition

Durch die Zugabe von 50 Gewichtsteilen einer 10 %-igen Lösung der bevorzugten Verbindung I (R = H) wirkt die entstehende Cologne-Base viel natürlicher. Die etwas camphrige Note des Bornylacetats, die man vorher wahrnahm, wird durch die Zugabe des Oximes zugedeckt. Gleichzeitig wird die Sandelnote von Sandalore noch hervorgehoben. Die neue Base wirkt zudem difussiver. Der mit der Zugabe des Oximes erzielte Effekt entspricht dem Effekt, der durch Zugabe eines Naturproduktes erzielt würde.

By adding 50 parts by weight of a 10% solution of the preferred compound I (R = H), the resulting Cologne base has a much more natural effect. The somewhat campy note of bornylacetate, which was noticed before, is covered by the addition of the oxime. At the same time, Sandalore's sandal note is emphasized. The new base also looks more diffusive. The effect achieved by adding the oxime corresponds to the effect that would be achieved by adding a natural product.

B. If 50 parts by weight of a 1% solution of compound 1 (R = CH ₃ ) in isopropyl myristate is added to the Cologne composition of Example 2 A, the resulting base looks fresher and greener. The camphoric note is covered and the petitgrain oil is emphasized, which gives the natural character of the resulting composition extraordinary.

C. Spicy base

The addition of 50 parts by weight of a 10% solution of 2.2.4-trimethyl-1-phenyl-3-pentanone oxime in isopropyl myristate brings the above base more freshness and more life. The phenolic, somewhat medicinal smell disappears in favor of a minty, fresh, light note. The spicy note becomes sharper, drier, tart, with a nuance of black currants. The base is particularly suitable for men's perfumes.

Claims (7)

1. Compounds of the general formula

wherein R is hydrogen, methyl or ethyl.

2. 2,2,4-Trimethyl-1-phenyl-3-pentanone oxime.

3. An odorant composition, characterized by a content of a compound of the formula

wherein R is hydrogen, methyl or ethyl.

4. An odorant composition, characterized by a content of 2,2,4-trimethyl-1-phenyl-3-pentanone oxime.

5. A process for the manufacture of the compounds of the formula

wherein R is hydrogen, methyl or ethyl, characterized by reacting a compound of the formula

wherein R has the above significance, with hydroxylamine or one of its salts.

6. The use of compounds of the formula

wherein R is hydrogen, methyl or ethyl, as odorants.

7. The use of 2,2,4-trimethyl-1-phenyl-3-pentanone oxime as an odorant.