WO1992021738A1

WO1992021738A1 - Use of isomeric 1,1,1-trialkyl-2-phenylethane derivatives as odoriferous substances, and fragrances containing these substances

Info

Publication number: WO1992021738A1
Application number: PCT/EP1992/001118
Authority: WO
Inventors: Klaus Bruns; Michael Dischmann; Thomas Markert; Heiner Westermann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1991-05-29
Filing date: 1992-05-20
Publication date: 1992-12-10
Also published as: DE59201157D1; EP0586442B1; JPH06507659A; EP0586442A1; DE4117669A1

Abstract

The invention concerns the use, as odoriferous substances, of isomeric 1,1,1-trialkyl-2-phenylethane derivatives of general formula (I), in which R1 to R3, independently of each other, are alkyl groups with 1 to 3 C-atoms and R4 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

"Use of isomeric III-trialkyl-2- ^p- henyl-ethane derivatives as fragrances, as well as fragrance constituents containing them"

The invention relates to the use of isomeric l, l, l-trialkyl-2-phenylethane derivatives as fragrances.

Many natural fragrances are available in completely inadequate amounts, measured according to need. For example, 5,000 kg of rose petals are required to obtain 1 k rose oil; the consequences are a very star 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 fragrances to complement the range of naturally available fragrances and make the necessary adjustments to changing modern tastes and the ever increasing need for odor improvers for products of daily use such as To be able to cover cosmetics and cleaning agents.

Acetic acid (1-phenyl-2,2,2-trichloroethyl) ester is a known, commercially available fragrance which has a mild, floral, rosy odor. However, halogenated compounds are increasingly viewed critically by the consumer, so that there is a need for suitable substitutes.

In addition, there is generally a constant need for synthetic odoriferous substances which can be produced cheaply and with a constant quality and have desired olfactory properties, ie pleasant, near-natural and qualitatively novel odor profiles of have sufficient intensity and are able to influence the scent of ko metic and consumer goods advantageous. Compounds were sought which should have characteristic new odor profiles b at the same time with high adhesive strength, odor intensity and radiance.

It has now been found that l, l, l-trialkyl-2-phenyl-ethane derivatives d of the general formula (I) meet this requirement in every respect and in an advantageous manner as fragrances with different nuanced floral, woody, spicy notes good adhesion can be used.

Rl

IR ² -C-CHPh-0-R ⁴ (I)

I R3

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 * to R3 independently of one another are alkyl groups with 1 to C atoms and the radical R ^{4 is} an alkyl or an acyl group with 1 to 5 carbon atoms or an alkoxycarbonyl or an alkoxyalkyl group with 2 to 5 carbon atoms mean as fragrances.

The C atom directly adjacent to the phenyl radical in the compounds of the general formula (I) represents a chiral center, so that these compounds can exist in different spatial forms. In the context of customary syntheses, the compounds according to the invention are obtained as a mixture of the corresponding isomers and are as such as a fragrance used. If desired, however, the enantiomeric compounds can be used alone as a fragrance.

The products to be used as fragrances according to the invention are produced by methods known per se in preparative organic chemistry. For example, Convert pivalinaldehyde by Grignard reaction with phenyl magnesium bromide to give 2,2-dimethyl-l-phenyl-propanol (II), which is e.g. by reaction with acetic anhydride in pyridine or dimethylaminopyridine to give the acetate (la), with dimethyl carbonate to the carbonate (Ib) or with ethyl vinyl ether in the presence of an acidic catalyst to give the acetal (Ic).

CH ₃

I H3C-C-CHPh-0H (II)

I CH ₃

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

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

The preparation of acetic acid (2,2-dimethyl-l-phenyl-propyl) ester (la) has already been described in the literature, see (a) DJCollins, HA Jacobs, Aust. J. Chem 1986 (39) 2095; (b) H. Sternerup, Acta Chem. Scand., Ser. B, 1974 (28) 969. However, in no case is there any information about any olfactory properties of the compound (la). CH ₃

I.

H ₃ CC-CHPh-0- (C0) -CH ₃ (la)

I CH ₃

On the other hand, it is known that 4-tert-butylcyclohexyl acetate, which also contains a tert-butyl and an acetyl residue as structural features, has odor properties that are described as woody, flowery (K. Bauer et.al. "Co mon Fragrance and Flavor Materials "VCH publishing company, Weinheim 1990, p. 69).

The compound (la) in particular has remarkable olfactory properties that are very much in demand in perfumery, namely rosy-wood with complex shades and great charisma. This particular olfactory characteristic of the rose type is original and novel and softly differs from the olfactory characteristic of the acetic acid (l-phenyl-2,2,2-trichloroethyl) ester known as a fragrance, which is particularly surprising. In perfume compositions, the compound (la) enhances the harmony and charisma as well as the adhesion, whereby the dosage can be adjusted to the desired fragrance note taking into account the other components of the composition.

These olfactory properties were not predictable and it was not to be expected that the compound (la) would be advantageous in a range which is not covered by known fragrances such as acetic acid (l-phenyl-2,2,2-trichloroethyl) ester can be used as a fragrance or as a component of fragrance compositions. Thus, general experience is also confirmed here 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 the Fragrance perception, the influence of the chemical structure on the fragrance perception are sufficiently researched, so it cannot normally be predicted whether a change in the structure of known odoriferous substances will lead to a change in the olfactory properties and whether these changes will be assessed positively or negatively.

Because of their odor profile, the compounds of the formula (I) are particularly suitable for modifying and enhancing known compositions. It should be emphasized in particular their extraordinary smell strength, which contributes in general to the refinement of the composition.

The compounds of formula (I) can be used with numerous known fragrance ingredients, e.g. combine 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 and those of synthetic fragrances include representatives from practically all classes of substances. Examples are:

(a) Natural products such as tree absolute, basil oil, agricultural oils such as bergaot oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, patchouli 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-trimethylcyclopent-3-en-1-yl) pentan-2-ol ], Sandela [3-isocamphyl- (5) -cyclohexanol],

(c) aldehydes such as citral, helional, o-hexylcinnamaldehyde, hydroxycitronellal, lilial ^R [p-tert-butyl-α-methyldihydrocinnamaldehyde], methylnonyl acetaldehyde,

(d) Ketones such as allyl ionone, α-ionone, β-ionone, methyl ionone.

(e) esters such as allylphenoxyacetate, benzylsalicylate, cinnamylpropionate, citronellyl acetate, citronellylethoxylate, decyl acetate, dimethylbenzylcarbinylacetate, ethylacetoacetate, hexenylisobutyrate, linalyl acetate, methyldihydrojasmonate, vetivery1 acetate, (f) Lactones such as Undecalactone, l-0xaspiro [4.4] nonan-2-one and various other components often used in perfumery w

Ketone oschus, indole, p-menthan-8-thiol-3-one, methyleugenol.

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

The usable proportions of the compounds according to the invention or their mixtures in fragrance compositions range from 1 to 70 percent 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 for perfuming cosmetic preparations such as lotions, creams, shampoos, be fen, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and 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 washing and cleaning agents, fabric softeners and textile treatment agents or tobacco. For perfuming these various products, the compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.05 to percent by weight, based on the entire product. However, this value should not represent any limit values, since the experienced perfumer can also achieve effects with even lower concentrations or build new types of complexes with higher doses.

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 pivalaldehyde 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 NaHSÖ4 and NaHC0 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 invention

Example 1; Acetic acid (2,2-dimethyl-l-phenyl-propyl) ester (la)

0.6 g (4.9 mmol) of dimethylaminopyridine were added to 103.9 g (0.63 mol) of alcohol II in 90 g (0.88 ol) of acetic anhydride, 30 minutes at room temperature and then 2 hours at 100 ° C. touched. For working up, it was diluted with 200 ml of ether and washed with 2N-HC1, 1N-NaHC0 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 Odor: rosy, woody IR (film): 1742 cm " ¹ (Vc = o acetate) 740, 705 cm " ¹ (δς_H moπosubuiert Aromat) 1H-NMR (CDC): 0.92 ppm (S, 9H, (CH ₃ ) ₃ -C)

2.06 ppm (S, 3H, CH ₃ -C0)

5.46 ppm (S, lH, CH-0-COCH ₃ )

7.23 ppm (M, 5H, aromatic protons) MG (GC / MS): Cι ₃ Hχ8θ2 calc .: 206.29 found: 206 (isomers)

Example 2; Carbonic acid (2,2-diethyl-l-phenyl-propyl) -πιethyl-ester (Ib)

11.0 g (0.36 mol) of sodium hydride (80 ig in paraffin were suspended in 150 ml of dimethyl carbonate (DMC), over 0.5 hours with 55.0 g (0.33 mol) of 2,2-dimethyl-1- phenyl-propanol II in 150 ml of DMC and stirred under reflux for a further hour, the mixture was poured onto 500 g of ice, the aqueous phase was extracted with about 300 ml of ether, the combined organic phases were washed with water, dried over sodium sulfate and the solvents were removed in vacuo. After distillation at 0.1 mbar, 63.6 g remained as a colorless crystalline mass. Yield: 63.6 g (87% of theory) Boiling point (0.1 mbar): 48.5-49. 5 ° C odor: spicy-floral, typical carbonate note IR (film): 1750 cm " ¹ (V _C = o acetate)

748, 705 cm " ¹ (δς_H monosubstituted aromatic) ¹ H-NMR (CDC1?): 0.95 ppm (S, 9H, (CH ₃ ) ₃ -C)

3.71 ppm (S, 3H, CH ₃ -0-C0)

5.30 ppm (S, lH, CH-0-C0)

7.28 ppm (M, 5H, aromatic protons) MG (GC / MS): C ^ H ^ calc .: 222.28 found: 222 (isomers)

Example 3; 2,2-DiBjethyl-l-phenyl-propyl-l- (l-ethoxy-ethyl) ether (Ic)

41.0 g (0.25 mol) of 2,2-dimethyl-l-phenyl-propanol II and 250 mg of p-toluenesulfonic acid in 100 ml of ether were stirred with 18.7 for 1 hour g (0.26 mol) of ethyl vinyl ether were added. After stirring for a further 2.5 hours at room temperature, the mixture was worked up with 5% NaHC0 ₃ solution and washed with water, dried over sodium sulfate and the ether was removed in vacuo. Distillation of the residue at 0.15 mbar gave 53.2 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 (δc-H monosubstituted aromatic) ^ -NMR (CDCl-a): mixture of diastereomers

0.92 ppm (S, 9H, C (CH ₃ ) ₃ )

1.15 and 0.85 ppm (T, 3H, 0-CH2 ~ CH ₃ )

1.21 and 1.27 ppm (DAD-CH-CH ^)

3.21 and 3.54 ppm (M, 1H, 0-CH2-CH ₃ )

4.29 and 4.00 ppm (S, lH, C6H ₅ -CH-0)

4.44 and 4.56 ppm (Q, lH, 0-CH-0)

7.17 - 7.27 ppm (M, 5H, aromatic protons) G (GC / MS): Cι ₃ H ₁₈ 02 calc .: 236.36 found: 236 (isomers)

Koni ositionsbeis iel

1000

(a) DPG = dipropylene glycol

Claims

Patent claims

1. Use of isomeric l, l, l-trialkyl-2-phenyl-ethane derivatives of the al lg my formula (I), wherein

R

I R2-C-CHPh-0-R4 (I)

I R3

- The radicals R ¹ to R3 independently of one another alkyl groups with 1 to C 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 l, l, l-trialkyl-2-phenyl-ethane derivatives according to claim 1, in which the radicals R ¹ to R3 denote methyl groups, as fragrances.

3. Use of isomeric l, l, l-trialkyl-2-phenyl-ethane derivatives according to claim 2, wherein R ^{4 is} an acyl radical having 1 to 3 carbon atoms, al fragrances.

4. Use of isomeric l, l, l-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 a 2,2-dialkyl-l-phenyl-propane derivative of the formula I according to claim 1 bi 4 in an amount of 1 to 70 percent by weight, based on the overall composition.

6. Use of mixtures of l, l, l-trialkyl-2-phenyl-ethane derivatives of the formula I according to claim 1 to 4 together with known natural and synthetic fragrance components as fragrances in cosmetic preparations, technical products or alcoholic perfumery .