DE2051319A1 - Substituted alkanes and alkanols and their esters - useful as perfumes - Google Patents

Abstract

Alkanes of formula : where R1 = a phenyl gp. (possibly Me or Et substd.) tetrahydronaphthyl or acenaphthyl; R2 = H, Ph or Me; R3 = H or Me; X1 and X2 = H, formyl or hydroxymethylene which can be esterified with 1-5C fatty acids; X1 and X2 cannot both = H; n = 0, 1 or 2. The cpds. are used as perfumes esp. the acetates, propionates or isobutyrates. They may be prepd. by hydroformylation of substd. alkanes followed by hydrogenation and possibly esterification.

Description

Substituted alkanals and substituted alkanols and their esters with fatty acids The invention relates to substituted alkanals of the formula in which R1 can have a phenyl radical of methyl groups or ethyl groups as a substituent, denotes a tetrohydronaphthyl radical or an azenaphthyl radical, R2 represents a hydrogen atom, a phenyl radical or methyl radical, R represents a hydrogen atom 3 or a methyl radical, X1 and X2 represent hydrogen atoms or formyl radicals with the restriction that X1 denotes a hydrogen atom if X2 stands for a formyl radical and X2 denotes a hydrogen atom if X1 stands for a formyl radical and n is 0, 1 or 2, as well as substituted alkanals of the formula I in which R1, R2 and R3 and n have the meaning given and X1 and X2 stand for hydrogen atoms or hydroxymethylene radicals with the restriction that X1 denotes a hydrogen atom if X2 stands for a hydroxymethylene radical and X2 denotes a hydrogen atom if X1 stands for a hydroxymethylene radical, as well as their esters with fatty acids with 1 to 5 carbon atoms.

The alkanals of the formula I are prepared, for example, by hydroformylation of substituted alkenes of the formula in which R1 can have a phenyl radical with methyl or ethyl groups as a substituent, a tetrahydronaphthyl radical or an azenaphthyl radical, R2 a hydrogen atom, 1 denotes a phenyl radical or a methyl group, R3 denotes a hydrogen atom or a methyl group and n stands for 0, 1 or 2, with carbon monoxide and hydrogen (volume ratio carbon monoxide: hydrogen such as 2: 1 to 1: 2) at temperatures from 0 80 to 160 C and pressures from 100 to 700 atm in the presence of carbonyl complexes of metals of group VIII of the Periodic Table, in particular those of the Cobalt, Rhodiums, Iridiums, Ruteniums and Iron. Preferred hydroformylation catalysts are rhodium carbonyl complexes.

The compounds of the formula II are in a manner known per se Implementation of, for example, alkyl aromatics with butadiene in the presence of alkali metals produced as catalysts (see German patent 557 514 or Journal of Organic Chemistry, Volume 32, 1967, page 3183, and Volume 30, 1965, page 82). In this way, by reacting toluene with butadiene, 1-phenylpentene-3 is obtained, by reacting ethylbenzene with butadiene 5-phenylhexene-2, by reacting Orthoxylene with butadiene 1-o-tolylpentene-3.

The compounds of the formula II are generally undiluted, with they serve as solvents themselves or together with suitable inert solvents such as hydrocarbons, for example benzene, toluene, xylene, cyclohexane, hexane, Heptane, petroleum ether or ethers, such as diethyl ether or tetrahydrofuran, in the hydroformylation reaction used.

In general, after the reaction has ended, the hydroformylation mixture is relaxed and cooled and, after separating the catalyst, the aldehydes of the formula I obtained by distillation. Since the boiling points are often very close to one another, if necessary, an aldehyde mixture is obtained.

By hydrogenating the aldehydes of the formula I in the presence of hydrogenation catalysts, for example nickel, cobalt, copper, chromium-containing catalysts such as Raney nickel, Raney cobalt, Copper chromite catalysts, at pressures of 1 ata up to 300 at and temperatures from +10 to + 1000C one obtains the corresponding alcohols of formula I.

The alcohols of the formula I are usually by reacting with Fatty acids with 1 to 5 carbon atoms the corresponding fatty acid anhydrides or ketene, optionally in the presence of acidic catalysts and elevated temperature, for example 20 to 1500C, converted into the corresponding esters.

The aldehydes of the formula I and the alcohols of the formula I and their Esters with fatty acids with 1 to 5 carbon atoms, in particular their acetates, Propiates and isobutyrates are used as fragrances. You have a fresh, floral smell.

The invention is illustrated by the following examples.

The parts given in the following examples are parts by weight, they relate to parts of space like kilograms to liters.

Example 1 In a high-pressure vessel made of stainless steel of 800 volume parts Contents are 176 parts of 1-o-tolyl-pentene (3), 300 parts of benzene and 0.05 part of dimeric Cyclooctadienylrhodium chloride submitted and under a pressure of an equimolecular Mixture of carbon monoxide and hydrogen from 700 atm heated to 1000C for 5 hours. By pressing in the gas mixture of carbon monoxide and hydrogen during the Reaction, the pressure is continuously maintained at 700 atm. After finished Reaction, the reaction mixture is cooled and let down, and the solvent distilled off. The remaining residue is fractionally distilled. You get 177 parts of a mixture of 1-o-tolyl-3-formyl-pentene and 1-o-tolyl-4-formyl-pentane from the boiling point 93 to 970C at 0.25 mm Hg, which has a floral odor.

Example 2 In a high-pressure vessel made of stainless steel of 800 volume parts Contents are 235 parts of 1,1-diphenylpentene-3, 250 parts of benzene and 0.05 part of dimeric Cyclooctadienylrhodium chloride submitted and one under a pressure of 700 atm Equimolecular mixture of carbon monoxide and hydrogen for 6 hours at 1000C heated. After cooling and letting down the pressure, the reaction mixture is purified by distillation worked up. 235 parts of a mixture of 1,1-diphenyl -) - formylpentane are obtained and 1,1-diphenyl-4-formyl-pentane boiling point 148 to 16,000 at 0.1 mm Hg.

Example 3 In a high pressure vessel of 800 parts by volume are contents 252 parts of 1- (but-2-enyl) -1,2,3,4-tetrahydronaphthalene, 300 parts of benzene and 0.05 Parts of dimeric Cyclooctadienylrhodiumchlorid submitted and under a pressure of 700 atmospheres of an equimolecular mixture of carbon monoxide and hydrogen for 6 hours heated to 1000C. After cooling and letting down the pressure, the reaction mixture is through Worked up distillation. 266 parts of a mixture of 1-t2-formylbutyl-1-j1,2,3,4-tetrahydronaphthalene are obtained and 1-3-formylbutyl-1j-1,2,3,4-tetrahydronaphthalene with a b.p. 0.2 125 to 1340c.

Example 4 In a high pressure vessel of 800 parts by volume are contents 200 parts of 1,2-diphenylhexene-4, 300 parts of benzene and 0.05 part of dimeric cyclooctadiene rhodium chloride presented and under a pressure of 700 atü of an equimolecular mixture Carbon monoxide and hydrogen heated to 1000C for 6 hours. After the reaction has ended the reaction mixture is cooled and let down and then worked up by distillation. 149 parts of a mixture of 1,2-diphenyl-4-formyl-hexane and 1,2-diphenyl-5-formyl-hexane are obtained from boiling point 180 to 2230C at 0.4 mm Hg.

Example 5 In a high pressure vessel of 800 parts by volume are contents 19 parts of 4-acenaphthylbutene-2, 200 parts of benzene and 0.01 part of dimeric cyclooctadienylrhodium chloride presented and under a pressure of 700 atü of an equimolecular mixture Carbon monoxide and hydrogen heated to 1000C for 6 hours.

After the reaction has ended, the reaction mixture is cooled and let down and worked up by distillation. 3.2 parts of a mixture of 2-formyl-4-acenaphthyl-1-butane are obtained and 3-formyl-4-facenaphthylj-1-butane with a boiling point of 180 to 0 201 ° C. at 0.2 mm Hg.

Example 6 In a high pressure vessel of 800 parts by volume are contents 100 parts of 1-phenylpentane-3, 300 parts of benzene and 0.05 part of dimeric cyclooctadienylrhodium chloride submitted and under 700 atmospheric pressure of an equimolecular mixture of carbon monoxide and hydrogen heated to 100 ° C for 6 hours. After the reaction has finished, this will be The reaction mixture is cooled and let down and worked up by distillation. Man receives 108 parts of a mixture of 1-phenyl -) - formylpentane and 1-phenyl-4-formylpentane from boiling point 92 to 1390C at 0.2 mm Hg.

Example 7 In a high pressure vessel of 800 parts by volume are contents 223 parts of 1-methyl-1-phenylpentene-3, 200 parts of benzene and 0.05 part of dimeric cyclooctadienylrhodium chloride presented and under a pressure of 700 atmospheres of an equimolecular Ge-0 mixture Carbon monoxide and hydrogen heated to 100 C for 6 hours. After the reaction has ended the reaction mixture is cooled and let down, and worked up by distillation.

256 parts of a mixture of 1-methyl-1-phenyl-3-formyl-pentane are obtained and 1-methyl-1-phenyl-4-formyl-pentane with a boiling point between 80 and 920C at 0.4 mm Hg.

Example 8 168 parts of a mixture of 1-o-tolyl -) - formylpentane and 1-o-Tdyl-4-formyl-pentane are used together with 5 parts and 30 parts of Raney nickel Filled methanol into an autoclave.

After purging with nitrogen, hydrogen is released up to a pressure of 50 at pressed on. Then it is heated to 800C and pressed for half an hour the pressure was adjusted to 50 atm again by hydrogen. Over the course of 12 hours are re-pressed 65 at.

The reaction product (177 parts) is obtained by fractionation in vacuo cleaned at 0.3 torr. 95 parts pass in the range from 0 0 102 to 104 ° C, 26 Parts between 104 and 108 0. The resulting mixture of 5-o-tolyl-2-methylpentanol- (1) and 4-o-tolyl-2-ethylbutanol- (1) has a pleasant floral odor.

Example 9 70 parts of a mixture of 5-o-tolyl-2-methylpentanol- (1) and 4-o-tolyl-2-ethylbutanol- (1) are added to 100 parts of acetic anhydride heated to reflux. The reaction has ended after one hour. The mixture will put in water and shaken out with soda solution. The organic phase is fractionated distilled. A mixture of 5-o-tolyl-2-methylpentyl (1) acetate and 4-o-Tolyl-2-ethylbutyl- (4) -acetate, which at a pressure of 5 Torr at 115 to 1180C distilled and has a floral odor.

Claims (1)

Claim Alkanes of the formula in which Rl represents a phenyl radical, which can have methyl or ethyl groups as substituents, a tetrahydronaphthyl radical or an acenaphthyl radical, R2 denotes a hydrogen atom, a phenyl radical or a methyl radical, R3 denotes a hydrogen atom or a methyl radical, X1 and X2 each represent a hydrogen atom or a formyl radical or a hydroxymethylene radical, which can be esterified with fatty acids having 1 to 5 carbon atoms, with the restriction that X1 denotes a hydrogen atom if X2 represents a formyl radical or a hydroxymethylene radical which can be esterified with fatty acids having 1 to 5 carbon atoms and X2 denotes a hydrogen atom if X1 denotes a formyl radical or a hydroxymethylene radical, which can be esterified with fatty acids having 1 to 5 carbon atoms, and n ° is 1 or 2.