DE4117669A1 - USE OF ISOMERIC 1,1,1-TRIALKYL-2-PHENYL-ETHANE DERIVATIVES AS A FRAGRANCE, AND THEIR COMPOSITIONS CONTAINING THESE - Google Patents

Abstract

The invention concerns the use, as odoriferous substances, of isomeric 1,1,1-trialkyl-2-phenylethane derivatives of general formula (I), in which R<1> to R<3>, independently of each other, are alkyl groups with 1 to 3 C-atoms and R<4> is hydrogen or an alkyl, acyl, alkoxycarbonyl or alkoxyalkyl group with a total of 2 to 5 C-atoms. These compounds, in particular the 2,2-dimethyl-1-phenylpropyl ester of acetic acid, have a complex rosy/woody character and high scent-emanation power, and can be mixed with each other or with other odoriferous substances in widely varying proportions, generally 1-70 % by wt. relative to the overall composition, to give new fragrances. These compositions can be used for perfuming cosmetic preparations and industrial products, as well as in alcohol fragances.

Description

The invention relates to the use of isomeric 1,1,1-trialkyl-2-phenyl ethane derivatives as fragrances.

Many natural fragrances are completely inadequate when measured by their needs amount available. For example, to gain 1 kg Rose oil 5000 kg rose petals necessary; the consequences are very strong 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 to the range of naturally available To add fragrance substances and make the necessary adjustments to changing mo make flavors and the ever increasing demand of odor improvers for everyday products such as cosmetics and cleaning agents.

Acetic acid (1-phenyl-2,2,2-trichloroethyl) ester is a known, com commercially available fragrance that has a mild floral-rosy smell Has. However, halogenated compounds are becoming increasingly popular viewed critically, so that there is a need for suitable substitutes.

In addition, there is generally a constant need for synthetic Fragrance substances that are cheap and of constant quality len and have desired olfactory properties, d. H. attached take odor profiles that are as close to nature as possible and qualitatively new  possess sufficient intensity and are able to smell kos to influence metallic and consumer goods advantageous. It was therefore searched for compounds that add characteristic new odor profiles high adhesive strength, smell intensity and radiance at the same time should point.

It has now been found that 1,1,1-trialkyl-2-phenyl-ethane derivatives of general formula (I) this requirement is excellent in every respect meet and advantageously as odoriferous substances with different nuanced floral, woody, spicy aromas with good adhesion Stability can be used.

The subject of the invention is therefore the use of isomeric 1,1,1- Trialkyl-2-phenylethane derivatives of the general formula (I), in which

• the radicals R ¹ to R ³ independently of one another are alkyl groups having 1 to 3 carbon atoms,
• - The radical R ^{4 is} an alkyl or acyl group with 1 to 5 carbon atoms or an alkoxycarbonyl or an alkoxyalkyl group with 2 to 5 carbon atoms, as fragrances.

The C atom directly adjacent to the phenyl radical in the compounds of general formula (I) represents a chiral center, so this Connections can exist in different spatial forms. In the context of Licher syntheses fall the compounds of the invention as mixtures of the corresponding isomers and as such are used as a fragrance  used. If desired, however, the enantiomerically pure ones can also be used Compounds used alone as a fragrance.

The preparation of the Pro to be used according to the invention as fragrances Products are made according to known methods of preparative organi chemistry. So z. B. Pivalinaldehyde by Grignard reaction with Convert phenyl magnesium bromide to 2,2-dimethyl-1-phenyl-propanol (II), that z. B. by reaction with acetic anhydride in pyridine or dimethyl aminopyridine to the acetate (Ia), with dimethyl carbonate to the carbonate (Ib) or with ethyl vinyl ether in the presence of an acidic catalyst to acetal (Ic) can be implemented.

Preference is given to using those compounds of the general formula (I) as fragrances in which the radicals R ¹ to R ^{3 are} methyl groups, in particular those in which the radical R ^{4 is also} an acyl radical having 1 to 3 carbon atoms means.

The use of acetic acid (2,2-dimethyl-1- phenyl-propyl) -ester (Ia) as a fragrance.

The preparation of acetic acid (2,2-dimethyl-1-phenyl-propyl) ester (Ia) has already been described in the literature, see (a) D. J. Collins, H. A. Jacobs, Aust. J. Chem 1986 (39) 2095; (b) H. Sternerup, Acta Chem. Scand., Ser. B, 1974 (28) 969. In no case, however, is there any information about any olfactory properties of the compound (Ia).  

In contrast, it is known that 4-tert-butylcyclohexyl acetate, which is used as a structure Tower features also contains a tert-butyl and an acetyl radical has olfactory properties that are described as woody, floral (K. Bauer et. al. "Common Fragrance and Flavor Materials", VCH publishing company, Weinheim 1990, p. 69).

Compound (Ia) in particular has remarkable odor properties that are in high demand in perfumery, namely rosy and woody with complex shades and great charisma. This particular Ge olfactory characteristics of the rose type are original and novel and soft on the olfactory characteristics of acetic acid known as (1-phenyl-2,2,2-trichloroethyl) ester significantly, which is particularly surprising is nice. In perfume compositions, the compound (Ia) reinforces the har monie and charisma as well as liability, the dosage being below Consideration of the other components of the composition on each desired fragrance can be matched.

These olfactory properties were unpredictable and it was not expected that the compound (Ia) in a range by Known fragrances such as acetic acid (1-phenyl-2,2,2-trichloroethyl) ester is not covered, advantageously as a fragrance or as a component of Fragrance compositions can be used. This also confirms itself here the general experience that the olfactory properties be Known odoriferous substances no conclusive conclusions on the properties allow structurally related connections because neither the mechanism of the  Scent perception still the influence of the chemical structure on the scent perception are sufficiently researched, so not normally beforehand can be seen whether a changed structure of known fragrances for Change in olfactory properties leads and whether these changes be judged positively or negatively.

The compounds of formula (I) are suitable due to their odor profile especially for the modification and reinforcement of known composites onen. Its extraordinary smell should be emphasized in particular strength that generally contributes to the refinement of the composition.

The compounds of the formula (I) can be prepared using numerous known methods Fragrance ingredients, e.g. B. other fragrances natural, synthe table or partially synthetic origin, essential oils and plants Combine zen extracts. The range of natural fragrances can both light and medium and low volatile components and that of synthetic fragrances representatives from practically all Include substance classes. Examples are:

• (a) Natural products such as tree moss absolute, basil oil, agricultural oils such as berga moth oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, Pachouli oil, petitgrain oil, Paraguay, wormwood oil,
• (b) alcohols such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, Rhodinol, cinnamon alcohol, Sandalore [3-methyl-5- (2.2.3-trimethylcyclo pent-3-en-1-yl) pentan-2-ol], Sandela [3-isocamphyl- (5) -cyclohexanol],
• (c) aldehydes such as citral, Heliona ^R , α-hexylcinnamaldehyde, hydroxycitronelal, Lilial ^R [p-tert-butyl-αmethyldihydrozimtaldehyde], methylnonyl acetaldehyde,
• (d) ketones such as allyl ionone, α-ionone, β-ionone, methyl ionone.
• (e) esters such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, Citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzyl carbinyl acetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, Methyl dihydrojasmonate, vetiveryl acetate,  
• (f) Lactones such as γ-undecalactone, 1-oxaspiro [4.4] nonan-2-one as well as various other components often used in perfumery such as Ketone musk, indole, p-menthan-8-thiol-3-one, methyleugenol.

It is also remarkable how the connections of the Structure (I), especially (Ia), the olfactory notes of a wide range Round off well-known compositions and harmonize, but without being unpleasant dominant way.

The usable proportions of the compounds according to the invention or their Mixtures in fragrance compositions range from 1 to 70 weights percent, based on the total mixture. Mixtures of the invention Compounds (I) and compositions of this type can be used both for Perfuming cosmetic preparations such as lotions, creams, shampoos, be fen, ointments, powder, aerosols, toothpastes, mouthwashes, deodorants as also in alcoholic perfumery (e.g. Eau de Cologne, Eau de Toilet te, extraits) can be used. There is also an application for Perfuming technical products such as detergents and cleaning agents, soft dishwasher and textile treatment agent or tobacco. To perfume this Different products are these compositions in an olfactory risch effective amount, especially in a concentration of 0.05 to 2 Weight percent, based on the entire product, added. These values However, should not represent limit values, since the experienced perfumer too achieve effects with even lower concentrations or with still higher doses can build up new complexes.

The following examples are intended to explain the subject matter of the invention and are not to be interpreted as restrictive.

Examples 1. Preparation of precursor II

The compounds of the general formula I were prepared starting from 2,2-dimethyl-1-phenyl-propanol II, which was obtained as follows:
235.5 g (1.5 mol) of bromobenzene were added dropwise to 36.5 g (1.5 mol) of magnesium shavings in 300 ml of ether, the reaction mixture was diluted with a further 400 ml of ether and stirred under reflux for 30 minutes. After a solution of 103.3 g (1.2 mol) of pivalinaldehyde in 130 ml of ether was added dropwise, the mixture was stirred under reflux for a further 2 hours and hydrolyzed with ice / ammonium chloride solution.

For working up, the organic phase was washed with NaHSO ₄ and NaHCO ₃ solution and finally with water, dried over sodium sulfate and the solvent was removed in vacuo. This resulted in 196.5 g of crude product (99.7% of theory), which could be used without further purification.

2. Preparation of the compounds I according to the invention Example 1: Acetic acid (2,2-dimethyl-1-phenyl-propyl) ester (Ia)

103.9 g (0.63 mol) of alcohol II in 90 g (0.88 mol) of acetic anhydride treated with 0.6 g (4.9 mmol) of dimethylaminopyridine, 30 minutes at room temperature and then stirred at 100 ° C for 2 hours.

For working up, the mixture was diluted with 200 ml of ether and washed with 2N-HCl, 1N-NaHCO ₃ solution and water. After drying over sodium sulfate and distilling off the ether and excess acetic anhydride in vacuo, the residue was distilled at 0.1 mbar.

Yield: 121.9 g (93.4% of theory)
Boiling point (0.1 mbar): 53-58 ° C
Smell: rosy, woody
IR (film): 1742 cm ^-1 (V _{C = O} acetate)
740, 705 cm ^-1 (δ _CH monosubstituted aromatic)
1 H-NMR (CDCl₃): 0.92 ppm (S, 9H, (CH₃) ₃-C)
2.06 ppm (S, 3H, CH₃-CO)
5.46 ppm (S, 1H, CH -O-COCH₃)
7.23 ppm (M, 5H, aromatic protons)
MG (GC / MS): C₁₃H₁₈O₂ calc .: 206.29 found: 206 (isomers)

Example 2: Carbonic acid (2,2-dimethyl-1-phenyl-propyl) methyl ester (Ib)

11.0 g (0.36 mol) of sodium hydride (80% in paraffin were dissolved in 150 ml Dimethyl carbonate (DMC) suspended over 55 hours with 55.0 g (0.33 mol) 2,2-dimethyl-1-phenyl-propanol II in 150 ml DMC and another 2 Stirred under reflux for hours. For working up, 500 g of ice were used pour, the aqueous phase extracted with about 300 ml of ether, which combined organic phases washed with water, dried over sodium sulfate and the solvents removed in vacuo. After distillation at 0.1 mbar remained 63.6 g as a colorless crystalline mass.

Yield: 63.6 g (87% of theory)
Boiling point (0.1 mbar): 48.5-49.5 ° C
Smell: spicy-floral, typical carbonate note
IR (film): 1750 cm ^-1 (v _{C = O} acetate)
748, 705 cm ^-1 (δ _CH monosubstituted aromatic)
1 H-NMR (CDCl₃): 0.95 ppm (S, 9H, (CH₃) ₃-C)
3.71 ppm (S, 3H, CH₃-O-CO)
5.30 ppm (S, 1H, CH-O-CO)
7.28 ppm (M, 5H, aromatic protons)
MG (GC / MS): C₁₃H₁₈O₂ calc .: 222.28 found: 222 (isomers)

Example 3: 2,2-Dimethyl-1-phenyl-propyl-1- (1-ethoxy-ethyl) ether (Ic)

41.0 g (0.25 mol) of 2,2-dimethyl-1-phenyl-propanol II and 250 mg of p-toluenesulfonic acid in 100 ml of ether were stirred with 18.7 g (0.26 mol ) Ethyl vinyl ether added. After stirring for a further 2.5 hours at room temperature, the mixture was worked up with 5% NaHCO ₃ solution and water, dried over sodium sulfate and the ether removed in vacuo. Distillation of the residue at 0.15 mbar gave 53.2 g of a colorless liquid.

Yield: 53.2 g (90% of theory)
Boiling point (0.1 mbar): 54 ° C
Odor: slightly woody
IR (film): 740, 705 cm ^-1 (δ _CH monosubstituted aromatic)
1 H-NMR (CDCl₃): mixture of diastereomers
0.92 ppm (S, 9H, C (CH₃) ₃)
1.15 and 0.85 ppm (T, 3H, O-CH₂- CH ₃)
1.21 and 1.27 ppm (D, 3H, O-CH- CH ₃)
3.21 and 3.54 ppm (M, 1H, O- CH ₃)
4.29 and 4.00 ppm (S, 1H, C₆H₅- CH -O)
4.44 and 4.56 ppm (Q, 1H, O-CH-O)
7.17-7.27 ppm (M, 5H, aromatic protons)
MG (GC / MS): C₁₃H₁₈O₂ calc .: 236.36 found: 236 (isomers)

Composition example

Odor characteristic: floral (rose)

Claims (6)

1. Use of isomeric 1,1,1-trialkyl-2-phenyl-ethane derivatives of the general formula (I), in which

• - The radicals R ¹ to R ³ independently of one another alkyl groups with 1 to 3 carbon atoms
• - The radical R ^{4 is} an alkyl or acyl group with 1 to 5 carbon atoms or an alkoxycarbonyl or an alkoxyalkyl group with 2 to 5 carbon atoms, as fragrances.

2. Use of isomeric 1,1,1-trialkyl-2-phenylethane derivatives according to claim 1, in which the radicals R ¹ to R ^{3 are} methyl groups, as fragrances. 3. Use of isomeric 1,1,1-trialkyl-2-phenyl-ethane derivatives according to claim 2, wherein R ^{4 is} an acyl radical having 1 to 3 carbon atoms, as fragrances. 4. Use of isomeric 1,1,1-trialkyl-2-phenyl-ethane derivatives according to claim 3, wherein R ^{4 is} an acetyl group, as fragrances. 5. Fragrance compositions, characterized by a content of one 2,2-dialkyl-1-phenyl-propane derivative of the formula I according to Claims 1 to 4  in an amount of 1 to 70 percent by weight based on the total Composition. 6. Use of mixtures of 1,1,1-trialkyl-2-phenylethane derivatives of formula I according to claims 1 to 4 together with known natural and synthetic fragrance components as fragrances in cosmetics preparations, technical products or alcoholic perfume merie.