2,4-Dihydroxy-3-methyl-benzaldehyde perfume compositions

Abstract

The effect of the characteristic odor note of Oak Moss in the combination of components in perfume compositions can be achieved by substituting 2,4-dihydroxy-3-methyl-benzaldehyde, produced in a one step synthesis from readily available material, for Oak Moss which is available only in limited quantities at high cost.

Description

This invention relates to 2,4-dihydroxy-3-methyl-benzaldehyde perfume compositions. In the art of perfumery, the extracts of lichens such as those marketed under the name of "Oak Moss" have become indispensable and are widely used as materials for perfumes. The natural extracts of Oak Moss, however, have limited availability and are very expensive. Applicants have discovered that when 2,4-dihydroxy-3-methyl-benzaldehyde is combined with other perfume components, it serves as a substitute for "Oak Moss" in the combination of components which determine the odor note of various perfume compositions. In addition, this chemical not only simulates with great fidelity the characteristic odor note of Oak Moss, it is much less expensive than natural oak Moss or its synthetic simulations, and can be prepared from readily available materials in a one step synthesis. The discovery of the unexpected odor note imparted by this chemical when combined with other perfume components becomes even more significant since its value in perfumery could not be predicted from the knowledge of a closely related chemical such as 2,6-dihydroxy4-methyl-benzaldehyde (ATRENOL) which, for all practical purposes, is odorless and therefore valueless in perfumery.

In accordance with this invention, at least 1% by weight of 2,4-dihydroxy-3-methyl-benzaldehyde is mixed with at least 1% by weight of one or more other perfume components. Desirably, the amount of 2,4-dihydroxy-3-methyl-benzaldehyde is 0.1 to 15% by weight; preferably 0.5 to 10% by weight; and most advantageously 1 to 9% by weight of the perfume composition.

The other perfume component or components comprise in their entirety at least 1% by weight and preferably at least 10% by weight of the total perfume composition.

The 2,4-dihydroxy-3-methyl-benzaldehyde perfume compositions of this invention may be used in soaps, creams, sachets and other cosmetic or household products.

The 2,4-dihydroxy-3-methyl-benzaldehyde having the following chemical structure: ##SPC1##

Was prepared by Elfeed Thomas Jones and Alexander Robertson [Journal of the Chemical Society, London, page 1691 (1932)] by the condensation of 2,6-dihydroxytoluene with zinc cyanide and excess hydrogen chloride. It may be produced by placing 496 g of 2-methyl-resorcinol, 712 g of n-methyl-formanilide and 300 ml of benzene in a 3-necked five liter flask fitted with an agitator, reflux condenser, dropping funnel and thermometer. After a homogeneous solution is obtained by agitation at room temperature, 808 g of phosphorus oxychloride are added over a period of 2 hours, maintaining the reaction temperature at 25.degree.-30.degree.C. After the addition is completed, agitation is continued for about 4 hours at 25.degree.-30.degree.C with occasional cooling. During the reaction, 600 ml of benzene are added to the reaction mixture.

The reaction mixture is cooled in an isopropanol-dry ice bath. 100 ml of ice water are added in one portion to the reaction mixture, followed by the addition with agitation of 2000 ml of a 50% aqueous sodium acetate solution over a period of 50 minutes (exothermic) allowing the reaction temperature to rise to a maximum of 65.degree.C. The reaction mixture is cooled to 20.degree.C and 1000 ml of a 50% aqueous acetate solution (precooled to 25.degree.C) are added under agitation in one portion. 800 ml of ethyl acetate (solvent) are added. The mixture is agitated for about 5 minutes and permitted to separate into an aqueous part and an organic layer, which is washed with 200 ml of water. The solvent (ethyl acetate) is removed by distillation under vacuum from a steam bath. The crude reaction product is cooled to 20.degree.C and the formed crystals are filtered on a Buchner funnel. The crystals are recrystallized from a solution of 1000 ml of water and 600 ml of methanol.

CROP I 310 g m.p. 158.degree.-160.degree.C (GLC: 100%)

To the mother liquor are added 300 ml of benzene and 100 ml of ether. The reaction mixture separates into two layers. The organic layer is washed three times with 200 ml portions of water and neutralized with a 10% aqueous solution of sodium bicarbonate. The solvent is removed by distillation from a steam bath under an ejector vacuum. The formed crystals are collected on a Buchner funnel and recrystallized from a solution of 200 ml of benzene and 100 ml of hexane.

CROP II 150 g m.p. 156.degree.-158.degree.C (GLC: 100%)

The combined Crops (I and II) are placed in a 3 liter 3-necked flask with an agitator and 1500 ml of water are added. The product is steam distilled for approximately 1 hour. The steam distillation is necessary to remove traces of contaminants which give an off-odor to the product. From 426 g of the product, 420 g of 2,4-dihydroxy-3-methyl-benzaldehyde having a melting point of 151.5.degree.-152.5.degree.C result after distillation.

A more comprehensive understanding of this invention is obtained by reference to the following examples of perfume compositions:CHYPRE PERFUME COMPOSITIONSEXAMPLE IParts by Weight______________________________________2.5 Oak Moss Extract (Evernia)2.5 2,4-Dihydroxy-3-Methyl Benzaldehyde22.5 Oil of Bergamot7.5 Oil Vetiver Bourbon5.0 Oil of Lavender7.0 Oil Sandalwood1.0 Oil Patchouli3.5 Oil of Cloves10.0 Extract of Jasmine8.0 Oil of Rose7.0 Isobutyl Salicylate5.0 Cinnamyl Alcohol10.0 Heliotropin5.0 Coumarin2.0 Oleoresin Tonka Beans1.5 Methyl Nonyl Acetaldehyde100.0______________________________________

EXAMPLE IIParts by Weight______________________________________29.6 Oil of Sandalwood15.0 Phenyl Ethyl Alcohol5.0 Oil of Cedarwood10.0 Oil Lavender30.0 Oil Patchouli3.0 Oil Vetiver2.0 Extract of Tonka Beans1.5 2,4-Dihydroxy-3-Methyl Benzaldehyde0.5 Oil Ylang Ylang0.3 Oil Sassafras0.2 Dimethyl Hydroquinone0.1 Oleoresin Labdanum1.0 Castoreum Extract (3% Solution)0.4 Vanillin0.7 Heliotropin0.7 Musk Ambrette100.0______________________________________ EXAMPLE IIIParts by Weight______________________________________17.6 Coumarin8.8 Oil Sandalwood8.8 2,4-Dihydroxy-3-Methyl Benzaldehyde8.8 Oil Patchouli5.9 Oil Vetiver35.4 Linalyl Acetate14.7 Phenylethyl Alcohol100.0______________________________________ EXAMPLE IVParts by Weight______________________________________32.8 Linalyl Acetate8.2 Coumarin4.9 Oleoresin Tonka Beans6.1 Oak Moss Extract (Evernia)4.1 2,4-Dihydroxy-3-Methyl Benzaldehyde4.9 Oil Patchouli24.6 Oil Cedarwood8.2 Oil Sandalwood4.1 Oil Vetiver Reunion2.1 Vanillin100.0______________________________________ EXAMPLE VParts by Weight______________________________________2.0 Oak Moss Extract (Evernia)15.0 2,4-Dihydroxy-3-Methyl Benzaldehyde13.0 Oil of Bergamot7.5 Oil Vetiver Bourbon5.0 Oil of Lavender7.0 Oil Sandalwood1.0 Oil Patchouli3.5 Oil of Cloves8.0 Extract of Jasmine4.0 Oil of Rose4.0 Phenyl Ethyl Alcohol7.0 Isobutyl Salicylate5.0 Cinnamyl Alcohol9.5 Heliotropin5.0 Coumarin2.0 Oleoresin Tonka Beans1.5 Methyl Nonyl Acetaldehyde100.0______________________________________ EXAMPLE VIParts byWeight______________________________________3.0 Oil of Sandalwood1.0 Oil of Rose0.5 Oil of Cedarwood1.0 Oil Lavender2.0 Oil Patchouli0.3 Oil Vetiver0.3 Extract of Tonka Beans0.1 2,4-Dihydroxy-3-Methyl Benzaldehyde5.0 10% Solution Oil Ylang Ylang in Benzyl Benzoate3.0 10% Solution Oil Sassafras in Benzyl Benzoate2.0 10% Solution Dimethyl Hydroqinone in Benzyl Benzoate1.0 10% Solution Oleoresin Labdanum in Benzyl Benzoate0.1 Castoreum Extract (3% Solution)0.4 10% Solution Vanillin in Benzyl Benzoate0.1 Heliotropin0.1 Musk Ambrette80.1 Benzyl Benzoate100.0______________________________________ FOUGERE PERFUME COMPOSITIONSEXAMPLE VIIParts by Weight______________________________________11.0 Oil Lavender5.0 Oil Patchouli8.0 Coumarin1.5 Heliotropin1.0 Musk Xylol0.5 Musk Ambrette2.5 Oil Geranium20.0 .alpha.-Terpineol7.5 Oil Cedarwood6.0 Oil Vetiver Reunion12.5 Phenylethyl Alcohol2.5 para-Methylacetophenone7.5 Linalyl Acetate5.0 Amyl Salicylate4.0 Oak Moss Extract (Evernia)4.5 2,4-Dihydroxy-3-Methyl Benzaldehyde1.0 Oleoresin Labdanum100.0______________________________________ EXAMPLE VIIIParts by Weight______________________________________4.0 2,4-Dihydroxy-3-Methyl Benzaldehyde3.2 Amyl Salicylate16.0 Coumarin4.0 Oleoresin Tonka Beans2.8 Phenylethyl Alcohol4.0 Heliotropin1.6 Vanillin13.6 Oil Vetiver Java4.8 Oil Patchouli24.0 Oil Lavender16.0 Linalyl Acetate6.0 Oil Neroli Bigarade100.0______________________________________

2,4-Dihydroxy-3-methyl benzaldehyde can replace partially or completely natural "Oak Moss" extract or any of the synthetic replacements of "Oak Moss". By adding any quantity of the chemical of this invention, the odor quality of natural "Oak Moss" may be achieved with great fidelity but with great reduction in cost.

Claims

1. A perfume composition comprising at least 1% by weight of 2,4-dihydroxy-3-methyl benzaldehyde and at least 1% by weight of one or more other perfume components.

2. A perfume composition of claim 1 in which the 2,4-dihydroxy-3-methyl benzaldehyde comprises 0.1 to 15% by weight of the perfume composition.

3. A perfume composition of claim 1 in which the 2,4-dihydroxy-3-methyl benzaldehyde comprises 0.5 to 10% by weight of the perfume composition.

4. A perfume composition of claim 1 in which the 2,4-dihydroxy-3-methyl benzaldehyde comprises 1 to 9% by weight of the perfume composition.