DE1966337C3 - Dialkyl resorcinic acid esters - Google Patents

Description

their esters remain unconverted and have to be separated from the reaction mixture. The mixing the respondent, e.g. B. by violent Movement or turbulent mixing reduces and increases the contact time required hence the yield of the desired product.

If hypochlorous acid is used, the result is a two-phase, aqueous - non-aqueous one Reaction system, whereby the degree of contact between the two phases is an important, if not a controlling one Factor for determining the yield of the product. The degree of contact is determined by the Modified or regulated nature of movement or mixing.

It is desirable to carry out the reaction in an inert solvent for the dihydro-resorcylate because at the applied reaction temperatures, ie, about 20 to 30 ^u C, the Reakuonsteilnehmer Jn solid form. Suitable inert reaction solvents include non-reactive halogenated hydrocarbons such as chloroform and tetrachloroethane.

In general, the reaction is carried out at atmospheric pressure, although it can also be carried out under pressure. The reaction is usually carried out in the range of about 15 to 50C, in the range of about 20 to 30 ⁰ C. In general, the reaction is completed in about 1 to 10 hours because shorter periods of time adversely affect the yields, while longer periods of time provide no further advantages in the process.

The process is carried out so that the dihydroresorcinic acid or its ester in one inert organic solvent with chloroform dissolves or suspended, creating a two-phase Sludge of a solid and a saturated solution is formed. The oxidizing chlorine material, z. B. chlorine gas is introduced into the reaction system, e.g. B. by bubbling through the reaction mass initiated while vigorously stirring the reaction system to achieve intimate mixing. the Introduction of the oxidizing chlorine material will be discontinued when the chlorine is no longer absorbed becomes and the reaction mixture becomes clear. The organic solvent or vehicle then becomes removed from the reaction mass, the reactants are separated and the reaction product can be separated by any conventional technique such as distillation or selective extraction and be isolated.

The dialkylresorcinic acid esters of the invention provide suitable fragrances. In the case of perfume mixtures, d. H. in mixtures of compounds z. B. natural oils, synthetic oils, aldehydes, ketones, esters, lactones. Alcohols and often also hydrocarbons include, resorcic acid or its ester has its special odor characteristics at. The overall effect of the perfume blend can be more than the effect of each ingredient. Thus, the respective resorcinic acid or its ester can be used to improve the fragrance properties to change a perfume mixture, for example by increasing or dampening the odor-causing Proportion of another component of the mixture.

Perfume blends containing the resorcic acid esters of this invention or the new materials themselves may contain, in connection with carriers, vehicles, solvents, dispersants, emulsifiers, surfactants, aerosol propellants and fixatives can be used.

The amounts of the resorcic acid esters of this invention that are effective in perfume mixtures vary on various factors, including the other ingredients of the mixture, their amounts and the respective desired effects. It was found that perfume blends that only Contain 0.5% by weight of the compound of the invention

ίο, or even less, to be used for this can give such materials as lavender or "chypre" a basic oakmoss note, for use in soaps, cosmetics, lotions, handkerchief perfumes, and the like Products.

The invention is illustrated in the examples.

example 1
MethyM-isopropyl-o-methyl-resorcylate

A 2-1 flask with a stirrer, thermometer. Gas inlet and gas outlet pipe is provided, the following substances are introduced:

211g methyl - 3 - isopropyl - 6 - methyl - dihydroresorcylate,

1000 ml of chloroform.

Chlorine gas is passed through the reaction mixture at atmospheric pressure and room temperature until the chlorine no longer dissolves in the reaction mixture. The reaction mass is concentrated in a flash evaporator to give an oil which solidifies on standing. The solid material is dissolved in ether and the ethereal solution is washed with a saturated sodium bicarbonate solution until the aqueous washing liquids remain basic and the evolution of CO ₂ ceases. The ethereal solution is extracted with 10% sodium hydroxide at about 50 ^{° C.} The extracts are filtered in vacuo to remove traces of ether. The ether-free alkaline extract is acidified with concentrated hydrochloric acid at 5 ⁰ C until the pH of the second A rubber-like mass forms, which when left to stand

0 ^c C becomes solid. The solid is dissolved in methanol, decolorized with activated charcoal and recrystallized from a methanol-water mixture. The solid is dried to give a product of 36.2 g. The product is identified by NMR and mass spectroscopic analyzes as methyl 3-isopropyl-6-methyl resorcylate with a melting range of 125.6 to 135.8 ° C. The following mass spectroscopic data are available: 178, 192, 164, 224 and 226 (stem peak).

Example 2

Methyl S-ethyl-o-methyl resorcylate

The procedure according to Example 1 is carried out, whereby methyl 3-ethyl-6-methyl-resorcylat is obtained by the methyl - 3 - isopropyl - 6 - methyl - dihydro - resorcylate used in Example 1 by methyl - 3 - ethyl - 6 - methyl - dihydro - resorcylate is replaced. The product has a fruity and caramel-like top note. Its base note is "mousse" -like. Its mass spectroscopic data are: peaks at 163, 178, 210 (stem peak).

Example 3 Methyl S-n-propyl-o-methyl resorcylate

The procedure according to example '. is carried out to produce methyl O-n-propyl-o-methyl resorcylate, by using the example '. used methyl-3-isopropyl-6-methyl-dihydro-resorcylate Methyl - 3 - η - propyl - 6 - methyl - dihydro - resorcylate is replaced. The product obtained has a smelting area from 133.2 to 135.6 ° C and a basic one »Mousse« odor-forming note.

Example 4 Methyl 3-isobutyl-6-methyl resorcylate

The procedure of Example 1 is carried out to methyl 3-isobutyl-6-methyl-resorcylate obtained by the methyl 3 - isopropyl - 6 - methyl - dihydro - resorcylate used in Example 1 Replaced methyl-S-butyl-o-methyl-dihydro-resorcylate will. The product obtained has a basic "mousse" odor-forming character and Melting range from 127.4 to 128.6 ° C.

Example 5 Methyl 3-n-butyl-6-methyl resorcylate

The method according to Example 1 is carried out to methyl 3-n-butyl-6-methyl resorcylate obtained by the methyl 3 - isopropyl - 6 - methyl - dihydro - resorcylate used in Example 1 Methyl - 3 - η - butyl - 6 - methyl - dihydro - resorcylate is replaced. The product obtained has a »Mousse« odor-forming note.

Example 6 Perfume mixture The following mixture is prepared:

The above perfume mixture is an important part of the "Chypre" essence. The methyl-3-ethyl-6-methyl-resorcylai is used as a substitute for oak moss. This perfume is incorporated into a tissue perfume with a content of 0.1 % by weight. The methyl 3-ethyl-o-methylresorcylate gives this fragrance a natural and distinctive oakmoss note.

Example 7 Perfume mixture The following mixture is produced:

component G 50 Benzyl acetate 100 Rosewood 150 cedar 100 2o linalyl acetate 80 a-ionone 20th Ethyl cinnamate 50 Amyl cinnamic aldehyde 50 25 iso-eugenol 100 Coumarin 50 Methyl-S-isopropyl-o-methyl-resorcylate 50 Musk xylene 100 , _n Styrax resin

Component g

Jasmine liquid, A 15

Rose liquid 5

Orris solution 6

Sandal oil 6

Bergamot 120

Patschull oil 6

Musk ketone, 1/5 in B. B. 60

Vetivert oil 5

Methyl 3-ethyl-6-methyl-resorcylate 200 (tincture 1/5)

Coumarin 2

Vanillin

Heliotropin 2

Synthetic roses 25

Rose, Otto, Bulgarian 10

Pigment oil 5

Olibanum resinoid 10

Bitter orange oil 4

Muskrat Oil 2

Musk tincture, 3% 250

Alcohol 4000

4734.5 The above perfume mixture is an important part of the "chypre" essence. Methyl 3-isopropyl-6-methyl resorcylate is used as a substitute for oak moss. This perfume is turned into a soap perfume incorporated with a content of 0.1%. The methyl - 3 - isopropyl - 6 - methyl resorcylate confers this scent a natural and distinctive oak moss nole.

Example 8

Perfume mixture The following mixture is produced:

component
_ -

Benzyl acetate

Rosewood

cedar
Linalyl acetate

a-ionone

Ethyl cinnamate

Amyl cinnamic aldehyde
Iso-eugenol

Coumarin

50

100

150

100

80

20th

50

50

100

Methyl S-n-butyl-o-methyl resorcylate 200 Musk xylene 50

Styrax resin 100

The above perfume blend is an important part of the "chypre" essence. Methyl 3-n-butyl-6-methyl resorcylate is used as a substitute for oak moss. This perfume is turned into a soap perfume incorporated with a content of 0.1%. The methyl - 3 - η - butyl - 6 - methyl resorcylate confers this scent a natural and distinctive oak moss note.

Claims (1)

(| p COOCH ₃ HO OH wherein R is ethyl, n-propyl, isopropyl, η-butyl or Is isobutyl. 20th