DE150827C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

e 150827 CLASS 12 o.

In patent specification 106512 is a method described to break down the ionone into its two components, α-ionone and β-ionone. The method is based on the fact that these ingredients when cooking with a weakly saturated alkali bisulfite solution can be converted into soluble hydrosulfone derivatives, and that the compounds of the α-ion and β-ion obtained in this way have differences in in terms of their ability to crystallize, dissociate and cleavage.

It has now been found that this method of separation also applies to the homologous Ionone, methylionon, dimethylionon, etc.

can expand.

Of those homologous ions which are made from citral and a homologous one Acetone are formed, which in addition to the carbonyl

- g ' ^ru PP ^{e contains} on the one hand a methyl group and on the other hand a methylene group, not only two but four isomers are possible. In the representation of the corresponding homologous pseudo-ionones, the aldehyde group of citral intervenes in both the methyl group and the methylene group, and each of the isomers that result is capable of forming two isomers, the α-ionone and the β-ionone corresponding homologous ionones .. When breaking down these homologous ionones, one has to deal with four different isomers, which differ in terms of different odor nuances and can therefore also be used in various commercial fields ... _; ,. _; These relationships occur z. B. with the to be obtained from citral and methyl ethyl ketone Methyljonon to days, which can be obtained by the process of patents 75062, 75120, 127424 and 133785.

The methyl ionone, which is obtained by the process of patents 75062 and 75120, consists of a mixture of the four theoretically possible isomers. By the method of the patent specifications 127424 and 133785 to be recovered a- and ß-methylionones, however, contain essentially two per isomers.

It has now been found that two of the methyl ionones present, and an α-methylionon and a β-methylionon harder under certain conditions to form those described in patent 106512 hydrosulfonic acid derivatives described are more capable than the other two. Man can therefore direct the reaction in such a way that the first two are already in the formation of the Hydrosulfonic acid derivatives are excluded if possible. As a starting material it is advantageous to choose those methylionones which, according to the procedure of the patents 127424 and 133785 were depicted and which were already rich in the ß-Methyljononen or the β-Methyljononen are. . '

Example:

100 parts of z. B. according to the patent document, 127424 by inversion with concentrated

Phosphoric acid represented α-methylionons two days with 400 parts of an approximately neutralized commercially available sodium bisulfite solution cooked. The undissolved parts are then separated from the bisulfite solution With ether, or in any other known manner, one drives one through the aqueous solution Steam flow to cleave the β · = compound formed and then decompose the solution by soda or caustic soda according to patent specification 106512.

The two components of the α-methyl ionon separated in this way, i.e. both that which remains undissolved after treatment with bisulfite, such as that caused by the decomposition of the Ci-methylionone obtained from hydrosulfonic acid compound are purified in the usual way by distillation in vacuo or in a stream of steam. Further cleaning can be done

by converting the ketones into condensation products with substituted ammonia (Semikarbazones, Hydrazonebenzenesulfoic acids, etc.) are carried out in a known manner cleaned and split again.

In this way the following two a-methylionones are obtained:

a-Methyljonon a, more easily soluble in bisulfite. Sp. 15 mm 137 to 142 ⁰ (uncorrected). Spec. Wt. About 0.927 at 20 ^0. Refraction η ο at 20 ° about I,; ooc |.

Semicarbazone des a-Methyljonon a F. 144 ⁰ .

a-Methyljonon b, sparingly soluble in bisulfite. Sp. 15 mm 135 to 140 ⁰ (uncorrected). Spec. Wt. About 0,931 at 20 ^0. Refraction π ο at 2O ° about 1.5003.

Semicarbazone des a-Methyljonon b F. 202 ⁰ .

In the same way as the a-methylionone can also that according to the patents mentioned ß-Methyljonon shown can be broken down into two isomers. So you get:

ß-Methyljonon a, more easily soluble in bisulfite. Sp. 15 mm 145 to 151 ° (uncorr.). Spec. Ge \ v. at 20 ⁰ about 0.935. Refraction n ^ at 20 ° about 1.5097.

Semicarbazon des, 8-Methyljonon a F. 138 to 139 ⁰ .

ß-Methyljonon b, sparingly soluble in bisulfite. Sp. 15 mm 135 to 140 ⁰ (uncorrected). Spec. Wt. At 20 ⁰ about 0.930. Refraction tore at 2O ° about 1.5073.

Semicarbazone des ß-Methyljonon b F. 175 to 176 ⁰ .

If the starting material used is those obtained by the process of patents 75120 and 75062, from all four. Methylionones consisting of isomers, a mixture of α-methylionone b and β-methylionone b remains undissolved in the process described above, and these can be separated by fractional crystallization of their condensation products with substituted ammonia. By cleaving the hydrosulfonic acid compound which has gone into solution by the process of patent specification 106512, the α -methylionon α and the β-methylionon a are also obtained here.

A further modification of the process described can be made in such a way that the pseudomethylionon is subjected to the action of a weakly acidic bisulfite solution and thus, like the methylionones, is split into two isomeric components, pseudomethylionon a (more easily soluble in bisulfite) and pseudomethylionon b (less soluble in bisulfite) , is disassembled. These two pseudomethyljonones show no noticeable differences when they are technically pure, but differ essentially from one another when they are inversed. It gives 80 ' namely pseudomethylionon α on inversion with phosphoric acid, formic acid, etc. (patent specification 127424) the α-methylionon a, on the other hand, on treatment with concentrated sulfuric acid, the ß-methylionon a. In the same way, either the a-methylionon b or the ß-methylionon b is obtained from the pseudomethylionon b.

According to the process of patents 75062 and 75120, on the other hand, a mixture of α -methylionone α and β-methylionone a is obtained from pseudomethylionone α , which are separated by repeated treatment with bisulfite solution (according to patent specification 106512).

Claims (2)

Patent Claims: 1. A process for the preparation of four isomeric methyl ionones, consisting in that the products obtainable from methyl ethyl ketone according to patents 75120, 75062, 127424 and 133758 treated with weakly acidic bisulfite solution and both the solution and the undissolved oil for themselves in the usual way on the a - and ß-isomers are processed. 2. Modification of the process protected by claim 1, characterized in that the pseudomethyljonon is broken down into isomers in place of the methylionon by treating with weakly acidic bisulfite solution, which are used individually for the preparation of two isomeric a- and 13-methylionons.