DE842054C - - Google Patents

Description

The thermal cleavage of sterols has not yet produced any high molecular weight cleavage products especially as starting materials for the synthesis of sex hormones are important, in auc'h only delivered reasonably satisfactory yield. So was z. B. in the distillation of cholesterol chloride von M a u t h e r and S u i d a (monthly journals of chemistry, vol. 17 [1896], p. 829), in which a considerable residue was left, no smooth cleavage was obtained, and the known methods the oxidative breakdown of cholesterol (see Hop.pe-Seyler: Journal for physiological Chemie, Vol. 237 [1935], p. 66) only give extraordinary results low yields of valuable cleavage products.

It has now been found that the thermal cleavage of sterols> in the presence of heat transferring Catalysts at a suitable choice of temperature, surprisingly relatively high temperatures, is controllable. By coordinating the catalyst and Temperature on each other, extensive decomposition of the sterols is avoided, and there are high molecular weight cleavage products which can be used for hormone synthesis are obtained in good yield.

The cleavage proceeds particularly favorably if it is carried out in vacuo and in the shortest possible time where the starting product is passed over the catalyst in vapor form. at the cleavage of sterols can result in a neutral and an acidic component, where the the latter can contain carboxyl groups and phenolic hydroxyl groups; the separation these proportions can be determined by various methods,

ζ. BiVchiOmatpgraphisoh ,. take place. All components are important for hormone synthesis and can be obtained according to the method according to the invention as required. .... _v,. ,

Sterols · all 'in'3 abutment condition come a keto derivatives containing as cholesteryl before ^{the first} ^ tenon ^ ShÖlestaridn and others, for this ther -.- misfche cleavage; into consideration. . ■.; =

In particular, '

ίο oxidizing agents such as iron oxide, manganese, oxide, or others, find use.

B e i s.p i e 1 ι W>

2 g of cholestenone are in a vacuum in the course of ι hour in vapor form up to about ··; 6öo °.: Over; an iron sulfide (FeS) catalyst, which is advantageously used in lump form, passed, where the initial pressure of 0.5 mm increases in the course of the cleavage to about 4 mm. The viscous condensate obtained is broken down into its acidic and neutral components by shaking out its ethereal solution three times with η-sodium hydroxide solution and then washing it once with water. The ethereal solution then only contains the neutral components. The acidic .. * .-- ÄJ? T ^ il ^ .- iiv ⁱ iii} .--- Äi ¹ .acid with sulfuric acid and subsequent etherification are obtained from the alkaline solution, this acidic proportion is about 19%).

The neutral virus is then chromatographed decomposed in a manner known per se with aluminum oxide. Hexane, Carbon tetrachloride, benzene and methanol are used in the order given. The first Extracts preferably contain hydrocarbons,. the following fractions are predominantly composed from unchanged starting material, and

the other extracts then contain oxygen values Substances, ζ '. B. 'Ketones,' "'iri' which" double bonds may be present.

Using the same procedure, the acid content is 4.5% at a temperature of about 535 ° and 7.5% acid contents at a temperature of about : '585 ° received.

_: Κ. Be is ρ ie I 2

... · '"; 2. gSchholestenon are in a vacuum in the course of" ¹ hour in vapor form at about 580 ° over a; · '50 cm long layer of an iron oxide catalyst, the z. B. was produced by oxidation of iron filings in an air stream at 700 ⁰ , passed. In the course of the cleavage, the initial pressure rises from 0.5 trim to about 4 mm. The viscous, light brown colored condensate is a mixture of high molecular weight breakdown products of cholestenone, which is chromatographically broken down into its components.

Claims (3)

Patent claims: 1. Process for the thermal cleavage of sterols and their derivatives, thereby marked 'draws that. the cleavage is carried out in the presence of heat-transferring and / or oxidizing catalysts by heating to a high temperature: 'ii'üL ,: ■■. 2. The method according to claim 1, characterized in that that the cleavage is carried out in a vacuum in vapor form and in the shortest possible time will. 3. The method according to claim 1 and 2, characterized .. '; characterized that sterols, which are in the 3-position ... contain a keto group. © 5203 6.