DE10114176A1 - New cyclohexene-acetaldehyde compounds for use as perfumes e.g. in lotions, shampoos, detergents, powders, aerosols and soaps - Google Patents

Abstract

Cylohex-1-en-1-yl-acetaldehydes with hydrogen and/or methyl groups at positions 3 and 5 and with hydrogen and/or 1-6C alkyl groups at position 4, with the proviso that at least one of these substituents is not hydrogen, are new. Cyclohexene-acetaldehydes of formula (I) are new. R1, R2, R5, R6 = H or methyl; and R3, R4 = H or 1-6C alkyl, with the proviso that the groups R1-R6 are not all H at the same time. Independent claims are included for: (a) perfume compositions containing compound(s) (I) in amounts of 1-70 wt%; (b) perfume compositions containing (I) together with compound(s) of formula (II), in which the exocyclic C=C double bond may be in the E or Z configuration, the total amount of (I) and (II) in the composition being 1-70 wt%.

Description

Field of the Invention

The present invention relates to cyclohexene acetaldehydes and their uses as fragrance substances.

State of the art

Many natural odoriferous substances are completely inadequate in relation to their needs Amount available. For example, 5000 kg are needed to obtain 1 kg of rose oil Rose petals necessary. The consequences are a very limited world year production as well as a high price. It is therefore clear that the fragrance industry ei has a constant need for new fragrances with interesting fragrance notes. one on the one hand, the range of naturally available fragrances can be supplemented, on the other hand, it makes it possible to make the necessary adjustments to changing to be able to make fashionable flavors. It also gets on this way possible the ever increasing need for odor improvers for Everyday products such as cosmetics and cleaning agents cover can.  

In addition, there is generally a constant need for synthetic fragrances that can be manufactured cheaply and with consistently high quality and the origi have olfactory properties. In particular, they should be pleasant, possible as close to nature and qualitatively new odor profiles of sufficient intensity own and be able to smell cosmetic and consumer goods beneficial to influence. In other words, there is a constant need Compounds that have characteristic new odor profiles with a high one Have adhesive strength, odor intensity and radiance.

EP-A-1 054 053 discloses the use of special substituted acetaldehydes as fragrances. The compounds disclosed in this published specification have the following structures (A) and (B):

The radical R in compound (A) has the meaning hydrogen or methyl.

Description of the invention

It has been found that the compounds of general formula (I) meet the above meet the requirements mentioned in every respect and in an advantageous manner Way as fragrances with different nuanced odor notes with good Adhesive strength can be used.  

The present invention initially relates to cyclohexenacetaldehydes of the general structure (I)

wherein the radicals R ¹ , R ² , R ⁵ and R ⁶ independently of one another are hydrogen or a methyl group and the radicals R ³ and R ^{4 are} independently hydrogen or an alkyl group having 1 to 6 carbon atoms, the proviso that not all radicals R ¹ to R ^{6 may} simultaneously be hydrogen.

In a further embodiment, the invention relates to the use of the Cyclohexenacetaldehydes of the general structure (I) specified above as Fragrances.

In one embodiment, such compounds (I) are used as fragrances in which at least one of the radicals R ¹ , R ² , R ⁵ and R ^{6 is} a methyl group. Before preferably in this embodiment, the radicals R ³ and R ^{4 are} each hydrogen. An example of such a compound is 2- (3,3,5-trimethyl-cyclohex-1-en-1-yl) acetaldehyde.

In one embodiment, such compounds (I) are used as fragrances in which at least one of the radicals R ³ and R ^{4 is} an alkyl group having 1 to 6 carbon atoms and the radicals R ¹ , R ² , R ⁵ and R ^{6 in} each case Mean hydrogen. Before this embodiment preferably applies that exactly one of the radicals R ³ or R ^{4 is} an alkyl group with 1 to 6 C atoms and the other radical is hydrogen.

Examples of such compounds are 2- (4-tert-butyl-cyclohex-1-en-1-yl) - acetaldehyde and 2- (4-tert-amyl-cyclohex-1-en-1-yl) acetaldehyde.

The compounds (I) can be prepared by known synthetic methods organic chemistry. It may be desirable to use such methods choose in which the compounds (I) according to the invention mixed with other Ren compounds arise (compare, for example, Examples 3, 7 and 8 of the lying registration); the compounds (I) can then, if necessary, by conventional means Cleaning methods from the mixture to the desired degree of purity enriched or completely isolated.

In perfume compositions, the compounds (I) reinforce the harmony and the Charisma as well as the naturalness and also the adhesion, taking the dosage taking into account the other components of the composition on each desired fragrance is coordinated.

It was not before that the compounds (I) had the fragrance notes mentioned above and is further confirmation of the general experience that the olfactory properties of known odoriferous substances do not have a mandatory return allow conclusions to be drawn about the properties of structurally related connections because we the mechanism of fragrance perception still the influence of chemical Structure on fragrance perception are sufficiently researched and therefore nor Sometimes it cannot be predicted whether a changed structure will be known Fragrances lead to a change in the olfactory properties and whether these changes are judged positively or negatively by the expert.

The compounds of the formula (I) are particularly suitable owing to their olfactory profile especially for the modification and reinforcement of known compositions. here to be emphasized in particular their extraordinary smell strength, the whole generally contributes to the refinement of the composition.  

The compounds of formula (I) can be used with numerous known fragrances Ingredients, such as other natural, synthetic or other fragrances partial synthetic origin, essential oils and plant extracts combination Ren. The range of natural fragrances can be both light and include medium and low volatility components. The range of synthetic Fragrance substances 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 Ber gamotte oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, pat chouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil, cedarwood oil, San delholzöl, ostinisch, guajakholzöl, cabreuva,
• b) alcohols such as farnesol, geraniol, citronellol, linalool, nerol, phenylethylal alcohol, rhodinol, cinnamon alcohol, sandalore [3-methyl-5- (2.2.3- trimethylcyclopent-3-en-1-yl) pentan-2-ol], Sandela [3-isocamphyl- (5) - cyclohexanol], mugetanol
• c) aldehydes such as citral, helional ^R , alpha-hexylcinnamaldehyde, hydroxycitronellal, lilialR [p-tert-butyl-a-methyldihydrozimtaldehyde], methylnonylacetaldehyde, (d) ketones such as allylionone, α-ionone, β-ionone, isoraldein, methylionone Nootkaton, Calone,
• d) esters such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, Citronel lylacetate, decyl acetate, dimethylbenzylcarbinylacetate, ethyl acetoacetate, witch nyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, vetiveryl acetate, cyclo hexyl salicylate, isobornyl isobutyrate, evernyl
• e) Lactones such as gamma-undecalactone, 1-oxaspiro [4.4] nonan-2-one, cylopentade canolide, ethylene brassylate  
• f) ethers such as Herbavert, Ambroxan as well as various other components often used in perfumery such as Mo weft and sandalwood fragrances, indole, p-menthan-8-thiol-3-one, methyleugenol and methyl anthranilate.

In particular, the compounds (I) can be combined with compounds of the general structure (II)

wherein the radicals R ¹ to R ^{6 have} the meaning defined above for the compounds (I), are combined. It should be expressly stated that structure (II) is to be understood in such a way that the exocyclic C = C double bond can be E- or Z-configured.

Mixtures of compounds (I) and (II) are particularly attractive Odor profiles.

A preferred embodiment of the invention is set up accordingly the use of mixtures containing one or more of the compounds (I) and one or more of the compounds (II), as fragrances.

Also noteworthy is the way in which the compounds of structure (I) round off the scent notes of a wide range of well-known compositions and har monize without dominating in an uncomfortable way.  

The usable proportions of the compounds (I) according to the invention or their Ge mix - as such or in combination with one or more compounds (II) - in fragrance compositions range from about 1-70% by weight, based on the entire mix. 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 as well as in alcoholic perfumery (e.g. Eau de Cologne, Eau de Toilette, Extraits) can be used. There is also one Can be used to perfume technical products such as washing and cleaning products detergent, fabric softener and fabric treatment agent. To perfume this different products, these are the compositions in an olfactory effective amount, especially in a concentration of 0.05-2 wt .-% - be moved to the entire product - added. However, these values are not relevant restrictive limits, since the experienced perfumer also with even lower Concentrations still produce effects or new with even higher doses can build complexes.  

Examples example 1 Preparation of 1,1-diethoxy-3,3,5-trimethyl-cyclohexane

The present example demonstrates the preparation of 1,1-diethoxy-3,3,5- trimethyl-cyclohexane, a compound used as a precursor for the preparation of the Compounds according to the invention can be seen.

approach

• 1. 168.0 g (1.2 mol) 3,3,5-trimethylcyclohexanone
• 2. 207.0 g (1.4 mol) triethyl orthoformate
• 3. 0.26 g (1.9 mmol) of potassium hydrogen sulfate
• 4. 720 ml ethanol, methyl ethyl ketone (MEK)

apparatus

2 L three-neck flasks, stirrer, thermometer, nitrogen atmosphere.

execution

The components 1), 2), 3), and 4) are successively in the reak given flask and 24 hours at room temperature under a nitrogen atmosphere re stirred. The course of the reaction was checked by GC after 24 hours 86% product was formed. The reaction was started by adding 0.6 g of sodium Ummethanolat solution (30% in methanol) neutralized. On the rotary evaporator were excess ethanol and the ants formed in a water jet vacuum distilled off acidic acid ester. The raw diethyl ketal of 3,3,5-  Trimethylcyclohexanone had a purity of, determined by gas chromatography 94.6% and was used for further reaction without further purification.

Example 2 Preparation of 1,1-diethoxy-2- (1-ethoxy-3,3,5-trimethylcyclohexyl) ethane

The present example demonstrates the preparation of 1,1-diethoxy-2- (1- ethoxy-3,3,5-trimethylcyclohexyl) ethane, a compound that acts as a precursor for the Preparation of the compounds according to the invention can be seen.

approach

• 1. 246.6 g (1.1 mol) of 1,1-diethoxy-3,3,5-trimethylcyclohexane (manufactured according to Bei game 1)
• 2. 90 ml zinc chloride solution (10% in ethyl acetate)
• 3. 93.6 g (1.3 mol) of ethyl vinyl ether

apparatus

1 L stirrer with thermometer, reflux condenser and dropping funnel

execution

Components 1) and 2) were successively in the reaction weighed the flask and heated to 43 ° C while stirring. Component 3) was metered in continuously within 1 hour with stirring. The tempera rose the mixture to 53 ° C. The mixture was stirred at 48 ° C for 9 hours. It  however, no complete sales could be achieved. 6, 7% of the educt has did not respond.

workup

The batch was transferred to a separatory funnel and with water and washed sodium bicarbonate solution until neutral. The organic phase was dried over sodium sulfate and concentrated on a rotary evaporator.

306 g of crude product with a content of 52% were obtained. These were on distilled in a Vigreux column. In the main run, 146.8 g of 1,1-diethoxy-2- (1- ethoxy-3,3,5-trimethylcyclohexyl) -ethane obtained (boiling point 94-96 ° C / 0.02 mbar, purity determined by gas chromatography 98.7%).

analytics

The IR spectrum (film between NaCl) showed characteristic ethers bound at 1000, 1073, 1119 and 1187 cm ^-1 .

The ¹ H-NMR spectrum (in CDCl ₃ , 400 MHz) showed 2 methyl groups as singlets at 0.8 and 1.0 ppm, 1 methyl group as a doublet at 0.8 ppm and 3 methyl groups as triplets at 1.1 and 1.2 ppm. The 3 CH ₂ groups of the cyclohexane ring appeared as doublets of doublets at 0.7, 1.7 and 1.8 ppm. 3 CH ₂ groups from ethyl residues gave quadruplets at 3.3; 3.5 and 3.6 ppm. 4 individual protons were found at 0.9 (doublet), 1.4 (broadened doublet), 1.8 and 4.6 ppm (triplet, acetal proton).

odor characteristic

Slightly fruity in the smell, after 24 hours on the olfactory streak smell was no longer perceptible.  

Example 3

Preparation of 2- (3,3,5-trimethyl-cyclohex-1-en-1-yl) acetaldehyde in a mixture with 2- (3,3,5-trimethyl-cyclohex-1-yl) ethenal

approach

• 1. 146.8 g (0.63 mol) of 1,1-diethoxy-2- (1-ethoxy-3,3,5-trimethylcyclohexyl) ethane (manufactured according to example 2)
• 2. 95.6 g of formic acid
• 3. 25.8 g sodium formate
• 4. 41.4 g water

apparatus

0.5 L stirrer with thermometer, reflux condenser and dropping funnel ter.

execution

Components 2), 3) and 4) were introduced and with stirring brought to reflux temperature (112 ° C). The acetal prepared according to Example 2 component 1) was then continuously added dropwise over 1.5 hours. It fell the reflux temperature to 77 ° C. It was still 2 hours at this tempe rature stirred.  

The reaction mixture was cooled, transferred to a separatory funnel and the aqueous phase separated. The organic phase was washed with 500 ml of ice water. The water phase was extracted 3 times with ether. The organic phases were combined and washed once with water, twice with sodium bicarbonate solution, twice with soda solution and once with water. The mixture was then dried over MgSO ₄ and concentrated on a rotary evaporator. 78.2 g of crude product were obtained, which showed two isomers in a purity, determined by gas chromatography, of 41.9% and 52.5%.

Distillation of the crude product on a 20 cm Vigreux column gave 61.4 g Main run (boiling point 60-65 ° C / 0.06 mbar) with a gas chromatograph agreed 98.3% purity of two isomers. The isomers were able to distill a ratio of 2: 1 or 1: 2 can be enriched.

analytics

The IR spectrum (film between NaCl) showed carbonyl vibration bands at 1673 and 1720 cm ^-1 and 2 bands at 2730 cm ^-1 .

The ¹ H-NMR spectrum (400 MHz, in CDCl ₃ ) was very complex and was interpreted as follows: 2 doublets at 5.8 and 5.9 ppm correspond to the olefinic proton of the alpha-beta unsaturated aldehyde (E and Z -Shapes in the ratio 1: 1). Coupled with the olefinic proton is the aldehydic proton, which gives 2 doublets at 9, 9 and 10.0 ppm. The characteristic signals for the 2 acetaldehyde derivatives gave two degenerate doublets from the doublet at 2.4 and 3.4 ppm for the CH ₂ group adjacent to the aldehyde group, the aldehyde proton appears as a broad singlet at 9.6 ppm.

odor characteristic

In the smell green, dry, dusty, iris and in the after smell after 24 hours on the smell strip: iris note  

Example 4 Isomerization of 2- (3,3,5-trimethyl-cyclohex-1-en-1-yl) acetaldehyde to 2- (3,3,5-trimethyl-cyclohex-1-yl) ethenal

The present example shows how a compound of the invention by definition by an (endocyclic) C = C- Double bond, can be isomerized to a substance in which the C = C double bond is arranged exocyclic. From this it can be seen that the compounds according to the invention also as intermediates for the preparation other connections are suitable.

approach

• 1. 40.0 g (0.23 mol) of 2- (3,3,5-trimethyl-cyclohex-1-en-1-yl) acetaldehyde in the Ge mixed with 2- (3,3,5-trimethyl-cyclohex-1-yl) ethenal (49.8% and 45.9%)
• 2. 104.7 g (1.75 mol) conc. Acetic acid (99%)
• 3. 0.5 g (0.11 mmol) bis (triphenylphosphine) palladium (II) chloride (15%)

apparatus

0.5 L stirrer, intensive cooler, Pt 100 thermocouple.

execution

Components 1) and 2) were successively introduced into the reaction flask weighed. The palladium complex 3) was then added with stirring. The mixture was heated to 94 ° C and ge for 4.5 hours at this temperature stir. The reaction control via GC showed a depletion of one compo nente over time and the enrichment of the other component. So left ben from 49.8% share of acetaldehyde component (with endocyclic double bond) after 5 hours reaction time still 9.5%. At the same time the rose Concentration of the ethenal component (with exocyclic double bond) of 45.9% to 79.9%.

workup

The acetic acid was largely distilled off and the residue neutralized with 10% sodium hydrogen carbonate solution. The organic phase was dried over sodium sulfate. 32.0 g of crude product with a gas color Graphically determined purities of 79.9% and 9.5% were used for distillation a rotating column.

Product fractions were obtained at boiling temperatures of 45-53 ° C / 0.06 mbar, the content of ethenal component was above 90%.

analytics

The IR spectrum (film between NaCl) showed carbonyl vibrational bands at 1673 and two bands at 2727 cm ^-1 . The carbonyl band at 1720 cm ^-1 (saturated aldehyde) lost over 50% of its intensity compared to Example 3.

The ¹ H-NMR spectrum (400 MHz, in CDCl ₃ ) showed 90% of the signals which were contained in the spectrum of the mixture (cf. Example 3) as a 45% component: 2 doublets at 5, 8 and 5, 9 ppm corresponds to the olefinic proton of the alpha-beta unsaturated aldehyde (ethenal component, E and Z forms in a ratio of 1: 1). Coupled with the olefinic proton is the aldehydic proton, which gives 2 doublets at 9, 9 and 10.0 ppm. The characteristic signals for the 2 acetaldehyde derivatives have disappeared, the aldehyde proton appeared as a broad singlet at 9.6 ppm with an integration of 10% compared to 90% for the aldehyde protons of the ethenal components.

odor characteristic

Clear from the smell of example 3 according to the invention distinguishable, fruity, earthy, dry, dusty, iris note and im After smell after 24 hours on the smell strip: Iris note.

Example 5 Preparation of 1,1-diethoxy-4-tert.butyl-cyclohexane

The present example demonstrates the preparation of 1,1-diethoxy-4- tert.butyl-cyclohexane, a compound used as a precursor for the preparation of Compounds according to the invention can be seen.

approach

• 1. 188.6 g (1.23 mol) of 4-tert-butylcyclohexanone
• 2. 218.6 g (1.47 mol) triethyl orthoformate
• 3. 0.24 g (1.8 mmol) potassium hydrogen sulfate
• 4. 740 ml ethanol, MEK

apparatus

2 L three-neck flasks, stirrer, thermometer, nitrogen atmosphere.

execution

Components 1), 2), 3) and 4) were in the reaction flask weighed in and 17 hours under nitrogen atmosphere and moisture exclusion stirred at room temperature.

The GC control showed 48.3% educt and 24.5% product and after 0.5 hours after 17 hours, 7.7% educt and 85.6% product. The batch was 1.8 g Sodium methoxide (30% in methanol) neutralized. After distilling off E thanol and ethyl formate remained 259.5 g of crude product with a Ge contains 8.1% educt and 91.9% diethyl ketal of 4-tert-butylcyclohexanone.

purification

246.6 g of crude product were distilled on a Vigreux column. 203.6 g main run were obtained at boiling temperatures of 54-56 ° C / 0.07 mbar. The purities of the fractions, determined by gas chromatography, were 97- 99.9%. (Two product peaks were observed in the GC, in most fractions NEN was the part caused by the splitting off of ethanol in the injector block Enol ether below 1%).

yield

71.8% of theory

analytics

The IR spectrum (film between NaCl) showed characteristic ethers bound at 1057, 1090 and 1117 cm ^-1 .

The ¹ H-NMR spectrum (400 MHz, in CDCl ₃ ) showed a singlet at 0.85 ppm (3 CH ₃ groups of the tert-butyl group), the two methyl groups of the ethyl radicals showed 2 triplets at 1.2 ppm, that overlap. The neighboring CH ₂ groups (4Hs) showed 2 quadruplets at 3, 4 and 3.5 ppm. The two CH ₂ groups, positions 2 and 6 of the cyclohexane ring, gave broadened doublets (2H each) at 1.6 and 2.05 ppm. The CH ₂ groups positions 3 and 5 of the cyclohexane ring appeared as doublets of triplets at 1, 2 and 1.3 ppm and the H at C-4 resulted in a triplet from the triplet at 1.0 ppm.

odor characteristic

In the smell green, fruity, rose oxide note, no aftertaste smell recognizable by the smell after 24 hours.

Example 6 Preparation of 1- (2,2-diethoxy-ethyl) -1-ethoxy-4-tert.butylcyclohexane

The present example demonstrates the preparation of 1- (2,2-diethoxy-ethyl) -1-ethoxy-4-tert.butylcyclohexane, a compound which is to be regarded as a precursor for the preparation of the compounds according to the invention

approach

• 1. 203.6 g (0.88 mol) of 1,1-diethoxy-4-tert-butylcyclohexane (prepared according to Example 5)
• 2. 72 ml of zinc chloride solution (10% in ethyl acetate)
• 3. 77.4 g (1.08 mol) of ethyl vinyl ether

apparatus

1L stirrer with thermometer, reflux condenser and dropping funnel

execution

Components 1) and 2) were successively in the reaction weighed the flask and heated to 48 ° C while stirring. Component 3) was metered in continuously within 1 hour with stirring. The temperature rose  the mixture to 62 ° C. The mixture was stirred at 48 ° C for 5 hours, a No increase in sales of over 65% was observed.

workup

The batch was transferred to a separatory funnel and with water and washed sodium bicarbonate solution until neutral. The organic phase was dried over sodium sulfate and concentrated on a rotary evaporator.

236 g of crude product with a content of 62% (2 isomers in the ratio 2: 1) received. These were distilled on a Vigreux column. In the main run receive the 83.6 g of 1- (2,2-diethoxyethyl) -1-ethoxy-4 tert.butylcyclohexane (boiling point 93-94 ° C / 0.09 mbar, purity 97% determined by gas chromatography).

analytics

The IR spectrum (film between NaCl) showed characteristic ethers bound at 1000, 1028, 1070, 1120 and 1177 cm ^-1 .

The ¹ H-NMR spectrum (in CDCl ₃ , 280 MHz) showed a singlet (9H) at 0.8 ppm and 3 methyl groups as triplets at 1.2 ppm. The 3 CH ₂ groups of the ethyl residues gave 1 clean quadruplet at 3.3 ppm and 2 further split at 3.5 and 3.6 ppm. The CH ₂ groups appeared in the range between 1.5 and 2.0 ppm. The proton at C-4 of the cyclohexane ring was found at 0.9 (triplet, split), the proton at the acetal group gave a triplet at 4.7 ppm.

odor characteristic

There was only a weak smell and a smell after 24 hours the smell is no longer perceptible.  

Example 7 Preparation of 2- (4-tert-butyl-cyclohex-1-en-1-yl) acetaldehyde (60%, 2 isomers in a ratio of 5: 1) in a mixture with 2- (4-tert-butyl-cyclohexylidene) ethenal (38%)

approach

• 1. 83.6 g (0.27 mol) of 1,1-diethoxy-2- (1-ethoxy-4-tert-butylcyclohex-1-yl) ethane (manufactured according to Ex. 6)
• 2. 52.4 g formic acid
• 3. 13.9 g sodium formate
• 4. 22.5 g water

apparatus

0.5 L stirrer with thermometer, reflux condenser and dropping funnel ter

execution

Components 2), 3) and 4) were introduced and with stirring brought to reflux temperature (108 ° C). The acetal prepared according to Example 6 component 1) was then continuously added dropwise in 1.75 hours. there the reflux temperature dropped to 78 ° C. It was refluxed for 2 hours temperature stirred.

workup

The reaction mixture was cooled, transferred to a separatory funnel and the aqueous phase was separated off. The organic phase was washed with 500 ml of ice water. The water phases were extracted 3 times with ether. The organic phases were combined and washed once with water, twice with sodium hydrogen carbonate solution, twice with soda solution and once with water. The mixture was then dried over MgSO ₄ and concentrated on a rotary evaporator. 51.7 g of crude product were obtained, which contained three isomers in a gas chromatographically determined purity of 37.7%, 37.9% and 8.2%.

Distillation of the crude product on a 20 cm Vigreux column gave 37.7 g Main run (boiling point 83-87 ° C / 0.02 mbar) with a gas chromatograph agreed purity of 93.6% three isomers (ratio about 2: 1: 1).

yield

71% of theory

analytics

The IR spectrum (film between NaCl) showed characteristic CO vibrations at 1724 and 1674 cm ^-1 , as well as a band at 2717 cm ^-1 .

The ¹ H-NMR spectrum (400 MHz, in CDCl ₃ ) showed 2 singlets at 0.9 ppm (9 Hs, 3 methyl groups of the tert-butyl group). The signals for various CH ₂ groups in the range of 1.2 to 2.5 ppm could not be assigned. The CH ₂ group for the two acetaldehyde derivatives gave a broad singlet at 3.0 ppm. The ratio of the isomers could be read from the integration of the olefinic protons. The measured fraction showed a broad singlet at 5.6 ppm (approx. 65%) for the olefinic proton of the two cyclohexene derivatives, the olefinic proton of the ethenal derivative appeared as a doublet at 5.8 ppm (approx. 25%) and coupled with the neighboring aldehyde proton, which showed a doublet at 10.0 ppm. The alde hydproton of the cyclohexene derivatives gave a triplet signal at 9.6 ppm.

odor characteristic

Fresh, floral, lily of the valley in the smell, in the after smell green after 24 hours on the smell strip, muguetaldehyde note.  

Example 8

The synthesis sequence shown in Examples 5, 6 and 7 was repeated, being at the beginning of the sequence of 4-tert. Amylcyclohexanone was assumed.

The diethyl ketal was initially formed, to which ethyl vinyl ether was added, then the acetal cleavage / elimination was carried out.

Odor characteristic of the product obtained

A mixture of 2- (4-tert.amyl cyclohex-1-en-1-yl) acetaldehyde and 2- (4-tert.amylcyclohexyliden-1-yl) ethenal im Ratio 4: 1) smelled of citral, lilial and muguetaldehyde in the after smell smell after 24 hours on the smell strip the unchanged lily of the valley was found scent like in the smell again.

Example 9 Isomerization of 2- (4-tert-butyl-cyclohex-1-en-1-yl) acetaldehyde to 2- (4- tert.butyl-cyclohexylidene-1-yl) -ethenal

The present example shows how a compound of the invention by definition by an (endocyclic) C = C- Double bond, can be isomerized to a substance in which the C = C double bond is arranged exocyclic. From this it can be seen that the compounds according to the invention also as intermediates for the preparation other connections are suitable.  

Analogously to Example 4, 2- (4-tert-butyl-cyclohex-1-en-1-yl) acetaldehyde (60%) in a mixture with 2- (4-tert-butyl-cyclohexylidene) -ethenal (approx. 38%), manufactured according to Example 7, isomerized with a palladium complex as a catalyst. It was a product distribution of 12.3% of 2- (4-tert-butyl-cyclohex-1-en-1-yl) acetaldehyde 74.8% of 2- (4-tert-butyl-cyclohexyliden-1-yl) -ethenal obtained.

odor characteristic

The taste is dry, fresh, intense, very clean after May bell, in the smell, after 24 hours on the smell, an unchanged Muguetaldehyde odor characteristic.

Claims (8)

1. Cyclohexenacetaldehydes general structure (I)
wherein the radicals R ¹ , R ² , R ⁵ and R ⁶ independently of one another are hydrogen or a methyl group and the radicals R ³ and R ⁴ independently of one another What are hydrogen or an alkyl group having 1 to 6 C atoms, the proviso that not all of the radicals R ¹ to R ^{6 may} simultaneously be hydrogen. 2. 2- (3,3,5-trimethyl-cyclohex-1-en-1-yl) acetaldehyde. 3. 2- (4-tert-butyl-cyclohex-1-en-1-yl) acetaldehyde. 4. 2- (4-tert.amyl-cyclohex-1-en-1-yl) acetaldehyde. 5. Use of Cyclohexenacetaldehydes General Structure (I)
wherein the radicals R ¹ , R ² , R ⁵ and R ⁶ independently of one another are hydrogen or a methyl group and the radicals R ³ and R ⁴ independently of one another are hydrogen or an alkyl group having 1 to 6 carbon atoms, the proviso that not all of the radicals R ¹ to R ^{6 may} simultaneously be hydrogen, as odoriferous substances. 6. Use of mixtures containing one or more of the compounds (I) according to claim 1 and one or more of the compounds (II),
wherein the radicals R ¹ , R ² , R ⁵ and R ⁶ independently of one another are hydrogen or a methyl group and the radicals R ³ and R ⁴ independently of one another are hydrogen or an alkyl group having 1 to 6 carbon atoms, the proviso that not all of the radicals R ¹ to R ^{6 may} simultaneously be hydrogen, and with the further proviso that the exocyclic C = C double bond can be configured E- or Z- as fragrances. 7. Fragrance compositions containing one or more compounds gene (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 - ent are holding.   8. fragrance compositions containing one or more of the compounds (I) according to claim 1 and one or more of the compounds (II),
wherein the radicals R ¹ , R ² , R ⁵ and R ⁶ independently of one another are hydrogen or a methyl group and the radicals R ³ and R ⁴ independently of one another are hydrogen or an alkyl group having 1 to 6 carbon atoms, the proviso that not all of the radicals R ¹ to R ^{6 may} simultaneously be hydrogen, and with the further proviso that the exocyclic C = C double bond can be configured E- or Z-, the compounds (I) and (II) in total in the Compositions in an amount of 1 to 70 wt .-% - based on the entire composition - are included.