EP1373193A2

EP1373193A2 - 2,3,5,5-tetramethylhexanal derivatives

Info

Publication number: EP1373193A2
Application number: EP02727330A
Authority: EP
Inventors: Thomas Markert; Volker Porrmann
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2001-03-07
Filing date: 2002-02-26
Publication date: 2004-01-02
Also published as: JP4065407B2; JP2004527502A; US7060668B2; WO2002070466A3; US20040138092A1; DE10110858A1; WO2002070466A2

Abstract

The invention relates to compounds of the general formula (1), wherein R represents a group CH=N-OH or a group CN. The inventive compounds are characterized by interesting and original odor characteristics which diffuse extremely well and are suitable for use as fragrances, for example in cosmetic preparations, technical products or in alcoholic perfumery.

Description

"2,3,5,5-TetramethylhexanaI derivatives"

Field of the Invention

The present invention relates to 2,3,5,5-tetramethylhexanal derivatives and their use as fragrances.

State of the art

Many natural fragrances are available in completely inadequate amounts, measured by demand. For example, 5000 kg of rose petals are required to obtain 1 kg of rose oil. The consequences are a very limited world annual production and a high price. It is therefore clear that the fragrance industry has a constant need for new fragrances with interesting fragrance notes. On the one hand, the range of naturally available fragrances can be supplemented, on the other hand it is possible to make the necessary adjustments to changing fashionable tastes. It also makes it possible to meet the ever-increasing need for odor improvers for everyday products such as cosmetics and cleaning agents.

In addition, there is generally a constant need for synthetic fragrances that can be manufactured cheaply and with consistently high quality and that have original olfactory properties. In particular, they should have pleasant, near-natural and qualitatively novel odor profiles of sufficient intensity and should be able to influence the scent of cosmetic and consumer goods in an advantageous manner. In other words, there is a constant need Compounds that have characteristic new odor profiles combined with high adhesive strength, odor intensity and radiance.

2,3,5,5-tetramethylhexanal and its use as a fragrance is known from German Offenlegungsschrift DE-A-2723 623.

Description of the invention

It has been found that the compounds of the general formula (I) meet the above requirements excellently in every respect and can be used advantageously as fragrances with different nuanced odor notes with good adhesive strength.

The present invention initially relates to 2,3,5,5-tetramethylhexanal derivatives of the general structure (I)

(I)

where R is a radical -CH = N-OH or a radical -CN.

In a further embodiment, the invention relates to the use of compounds of the general structure (I) specified above as fragrances. The compounds (I) according to the invention, namely

• 2,3,5,5-tetramethylhexanal oxime and

• 2,3,5,5-tetramethyl-hexane-nitrile are characterized by an olfactory characteristic, dominated by currant and grapefruit notes. They have excellent stability in cosmetic and consumer perfume formulas.

The compounds (I) can be prepared by known synthetic methods of organic chemistry.

In perfume compositions, the compounds (I) enhance the harmony and charisma as well as the naturalness and also the adhesion, the dosage being matched to the desired fragrance note, taking into account the other constituents of the composition.

The fact that the compounds (I) have the above-mentioned fragrance notes was not predictable and is thus further confirmation of the general experience that the olfactory properties of known fragrances do not allow any conclusive conclusions to be drawn about the properties of structurally related compounds, because neither the mechanism of fragrance perception nor that The influence of the chemical structure on fragrance perception has been sufficiently researched and therefore it cannot normally be predicted whether a change in the structure of known fragrances will change the olfactory properties and whether these changes will be judged positively or negatively by the person skilled in the art.

Because of their odor profile, the compounds of the formula (I) are particularly suitable for modifying and enhancing known compositions. In particular, their extraordinary olfactory strength should be emphasized, which generally contributes to the refinement of the composition. The compounds of formula (I) can be combined with numerous known fragrance ingredients, for example other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts. The range of natural fragrances can include both volatile, medium and low volatile components. The range of synthetic fragrances can include representatives from practically all classes of substances.

Examples of suitable substances with which the compounds (I) can be combined are in particular:

(a) Natural products such as tree moss absolute, basil oil, agricultural oils such as bergotte oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil, cedarwood oil, sandalwood oil, East Indian oil, guaiac oil Cabreuva,

(b) alcohols such as farnesol, geraniol, citronellol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamon alcohol, sandalore [3-methyl-5- (2.2.3-trimethylcyclopent-3 -en- 1 -yl) pentan-2- ol], Sandela [3 -isocamphyl- (5) - cyclohexanol], muguetanol,

(c) aldehydes such as citral, HelionaF \, alpha-hexylcinnamaldehyde, hydroxycitronellal,

Lilial ^ - [p-tert-butyl-α-methyldihydrozimtaldehyde], methylnonylacetaldehyde,

(d) ketones such as allylionone, α-ionone, β-ionone, isoraldein, methylionone, nootkatone, calone, α-, ß- and γ-irone, Damascone,

(e) esters such as allylphenoxyacetate, benzylsalicylate, cinnamylpropionate, citronellyl acetate, decyl acetate, dimethylbenzylcarbinyl acetate, ethyl acetoacetate, hexyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, vetivery acetate, cyclyl hexyl isyl nyl isyl, nylylyl nyl isyl, hexyl isyl nyl isyl, nylylnyl isyl, nylylnyl isyl, nylylnyl isyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nylylnyl, nyl, (f) lactones such as gamma-undecalactone, l-oxaspiro [4.4] nonan-2-one, cyclopentadecanolide, ethylene brassylate, g) ethers such as herbavert, ambroxan, and various other components often used in perfumery such as musk and sandalwood Fragrance substances, indole, p-menthan-8-thiol-3-one, methyleugenol and methyl anthranilate.

Also noteworthy is the way in which the compounds of structure (I) _ round off and harmonize the olfactory notes of a wide range of known compositions, but without dominating in an unpleasant way.

2,3,5,5-tetramethyl-hexane-nitrile is characterized by excellent odor properties and good stability in alkaline media such as soap or detergents, detergents and cleaning agents. This stability is significantly better than that of 2,3,5,5-tetramethyl-hexanal.

The usable proportions of the compounds (I) according to the invention or their mixtures in fragrance compositions range from about 1-70% by weight, based on the mixture as a whole. Mixtures of the compounds (I) according to the invention and compositions of this type can be used both for perfuming cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and in alcoholic perfumery (e.g. Eau de Cologne, Eau de toilet, extraits) can be used. There is also an application for perfuming technical products such as detergents and cleaning agents, fabric softeners and textile treatment agents. To perfume these various products, the compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.01-2% by weight, based on the entire product. However, these values are not limiting limits, since the experienced perfumer can use even lower ones Concentrations can still have effects or build up new types of complexes with even higher doses.

B e i s p i e l e

Preparation of 2,3,5,5-tetramethylhexanal

2,3,5,5-Tetramethylhexanal is used as raw material in Examples 1 and 2 below. It was made as follows:

Approach:

1) 78 g (0.5065 mol) of 2-methylene-isononanal (manufactured according to FR 1508854)

2) 4 g 5% Pd / C hydrogenation catalyst (Degussa)

3) 100 ml of ethanol, technical

Equipment: 1 L box A 432 hydrogenation autoclave with steel insert and paddle stirrer.

Design: 1), 3) and 2) were successively weighed into the autoclave insert under inert gas (nitrogen) and inserted into the pressure vessel. After flushing with nitrogen, the reaction mixture was pressurized with 30 bar of hydrogen. An exothermic reaction took place, the temperature of the mixture rising from 17 to 40 ° C. After a reaction time of 2 hours, during which hydrogen was replenished to 50 bar at 100 ° C., the pressure remained constant at 50 bar for 5 hours. The mixture was then cooled, let down, the catalyst was filtered off and the reaction mixture was freed from solvent on a rotary evaporator. The sales control indicated a product concentration of 90.5% in addition to 2.4% educt. i

62 g of the crude product were used for distillation on a 15 cm Vigreux column. 41.5 g main run with a purity of 97% determined by gas chromatography were obtained at 30-31 ° C / 0.1 mbar. Yield: 52.5% of theory

Analysis: The IR spectrum (film between NaCl) showed characteristic vibrational bands at 1727 (CO) and 2701 cm ^"1 .

The 1H-NMR (400 MHz in CDC1 ₃ ) showed 2 signals for 3 methyl groups (singlet target molecule + isomer in the ratio 3: 1) at 0.9 ppm and 2 methyl groups at 0.9 ppm and 1.0 ppm (doublets ). As expected, the signals of the CH ₂ groups next to the two asymmetric carbon atoms were more strongly split with signal centers at 1.1 and 1.3 ppm (doublets from the doublet, the signal at 1.3 ppm is accompanied by a corresponding signal from the presumed secondary component ). The two methine protons (5 and 6 neighboring protons, respectively) appeared at 2.0 and 2.3 ppm (multiplets, the signal at 2.0 ppm was accompanied by the corresponding signal at 2.1 ppm, the suspected secondary component). The aldehyde proton was found as a weakly split doublet at 9.7 ppm (accompanied by a signal from the suspected secondary component). Based on the spectroscopic evaluation, it is assumed that the secondary component could be the 2,4,5,5-tetramethylhexanal.

Odor: Dry, aldehydic, minty, green in the smell and weakly ionic in the after smell (after 24 hours on the smell strip).

example 1

Preparation of 2,3,5,5-Tettamethyl-hexanal-oxime

Approach:

1) 33 g (0.2 mol) of hydroxylamine sulfate in 120 ml of water

2) 12.0 g (0.3 mol) sodium hydroxide in 24 ml water

3) 41.5 g (0.266 mol) 2,3,5,5-tetramethylhexanal (97%), prepared as described above

Apparatus: 1 L four-necked flask with stirrer and dropping funnel.

Execution: 1) was placed in the flask and added dropwise with stirring in 10 minutes 2), the temperature rose from 17 to 25 ° C. While stirring and cooling with an ice bath, 3) was metered in in 35 minutes. The mixture then showed a light yellow color. The reaction mixture was heated to 80 ° C. and stirred at this temperature for 6 hours. After 6 hours the concentration of the product was 96%.

Working up: The mixture was cooled and extracted twice with 200 ml of ether each time, the ether phases were washed with water and sodium sulfate solution (pH 6.5) and dried overnight with sodium sulfate. The solvent was distilled off on a rotary evaporator and 46.4 g of crude product with a purity of 96% determined by gas chromatography was obtained as a residue. The crude product was distilled on a Kugelrohr still, 40 g of 97.2% product were obtained as the main run.

Yield: 87.9% of theory

Analysis: The IR spectrum (film between NaCl) showed characteristic vibrational band groups at 939, 1394, 1477 and 2959 cm ^"1 and a sack with a maximum at 3269 (OH) cm ^{" 1} .

The 1H-NMR (400 MHz in CDC1 ₃ ) showed signals for 3 methyl groups (1 singlet) at 0.9 ppm and for 2 methyl groups at 0.95 ppm and 1.05 ppm (doublets). The CH ₂ group gave doublets of geminal-coupled doublets at 1.0 and 1.3 ppm. At 1.7 and 2.3 ppm, two multiplets appeared for the two protons at C-2 and C-3. The multiplet at 2.3 ppm was accompanied by a correspondingly split H at 3.05 ppm (for the secondary component, presumably 2,4,5,5-tetramethylhexanal oxime). The olefinic H gave a signal for the minor component at 6.6 ppm and a signal (doublet from doublet) at 7.35 ppm. The OH proton appeared (unchanged) as a broad signal with a maximum at 7.8 ppm.

Odor characteristics: Floral, sweet, fruity, Chardonnay, white wine aroma, bitter, grapefruit, currant in the smell and bitter, grapefruit, cassis in the after smell (after 24 hours on the smell strip).

Example 2

Preparation of 2,3,5,5-tetramethylhexane nitrile

Approach:

1) 37.8 g (0.22 mol) of 2,3,5,5-tetramethylhexanal oxime (97.2%) prepared as described in Example 1

2) 54.4 g (0.5 mol) acetic anhydride

Equipment: 0.5 L four-necked flask with stirrer, PT 100 thermometer, 250 ml dropping funnel and reflux condenser.

Execution: 1) was placed in the reaction vessel and added dropwise in 40 minutes while stirring and cooling with an ice water bath 2). The temperature of the mixture rose from 22 ° C to 28 ° C. After all of 2) had been added, the mixture was heated to reflux at 140 ° C. and stirred at this temperature for 2.5 hours. The conversion after 2 hours was 93%.

Working up: The reaction mixture was diluted with 500 ml of cyclohexane, washed neutral with 2.5 L of water, dried over magnesium sulfate and concentrated on a rotary evaporator. 34.5 g of crude product were distilled on a 15 cm Vigreux column, 22.4 g of the main run went over at 28-30 ° C./0.05 mbar. The purity, determined by gas chromatography, was 98.8%. Yield: 86.4% of theory

Analysis: The IR spectrum (film between NaCl) showed characteristic vibrational band groups at 1367, 1470 and 2958 cm ^"1 and a band at 2239 (CN) cm ^{" 1} .

The 1H-NMR (400 MHz in CDC1 ₃ ) showed signals for 3 methyl groups (1 singlet) at 0.9 ppm and for 2 methyl groups at 1.1 ppm and 1.3 ppm (doublets). The CH ₂ group gave doublets of geminal-coupled doublets at 1.1; 1.3 and 1.4 ppm. At 1.7 and 2.6 ppm, two multiplets appeared for the two protons at C-2 and C-3. The multiplet at 2.6 ppm was accompanied by a correspondingly split H at 2.5 ppm (for the secondary component, probably 2,4,5,5-tetramethylhexanenitrile).

Odor characteristics: Aldehydic, fresh, fruity, Isononanal note, green, strong in the smell and is almost odorless in the after smell (after 24 hours on the smell strip).

Claims

claims

1. 2,3,5,5-tetramethylhexanal derivatives of the general structure (I)

(I)

where R is a radical -CH = N-OH or a radical -CN.

2. Use of 2,3,5,5-tetramethylhexanal derivatives of the general structure (I)

(I)

where R is a radical -CH = N-OH or a radical -CN, as fragrances.

3. fragrance compositions containing one or more compounds (I) according to claim 1, wherein the compounds (I) in the compositions in an amount of 1 to 70 wt .-% - based on the entire composition - contained.