DE1271100B - Process for the production of deuterochloroform - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

DESIGN SCREEN

Int. α .:

German class:

Number:
File number:
Registration date:
Display day:

C07c

BOIf
GOIj

12 ο -2/01

12c-l

42 h-20/01

September 28, 1964

June 27, 1968

Deuterochloroform is used as a proton-free solvent for organic chemical syntheses and for Spectroscopy of great importance. A broad-based application was previously the high price and its relatively uneconomical presentation.

Deuterated compounds usually cannot search for the corresponding hydrogen compounds known processes are produced. Low consumption of deuterium or deuterium oxide, high isotope content combined with high yields characterize the quality and economy of processes for the production of deuterated compounds.

A number of methods have been developed for the synthesis of deuterochloroform in recent years (For a summary see A. M u r r a y and D. L. Williams, Organic Synthesis with Isotopes, p. 1488 to 1490, Interscience Publishers, New York 1958), which, however, allows the connection to be made economically not allow. The yields of deuterochloroform based on deuterium oxide are either low, or the processes require a large excess of deuterium oxide after recovery Due to the auxiliaries used, its isotope content is so greatly reduced that it cannot be reused without enrichment.

Following the process of this invention becomes deuterochloroform obtained by reacting hexachloroacetone with deuterium oxide:

Method of manufacture
of deuterochloroform

CCl ₃ COCCl ₃ + D ₂ O

2CDCl ₃ + CO ₂

Reactions of hexachloroacetone with the formation of chloroform have already been described. she however, usually result in only 1 mole of chloroform.

We have now found that deuterochloroform can be prepared in the above formula, equation corresponding quantities by reacting hexachloroacetone with deuterium oxide in the presence of oxides or carbonates of the I. and II. Main group of the Periodic Table is reacted at 100 to 15O ⁰ C.

The yield of deuterochloroform is quantitative. The isotope content was determined using a Deuterium oxide of 99.7% determined by nuclear magnetic resonance spectroscopy to be over 99.5%.

Furthermore, we were able to find that when using alkali and alkaline earth carbonates these after Reaction are unchanged and can be used with advantage for further reactions.

The production of deuterochloroform can therefore be carried out continuously in a simple manner.

Applicant:

Carl Roth o. H. G.,

7500 Karlsruhe, Herrenstr. 26/28;

Dr. Hans Mueller from the Haegen,

7552 Durmersheim, Speyerer Str. 84

Named as inventor:

Dipl.-Chem. Dr. Hans Mueller from the Haegen,

7552 Durmersheim

To this end, hexachloroacetone and deuterium oxide are continuously added to the ^{catalyst mixture heated to 120 to 130 °} C. and the deuterochloroform formed is allowed to distill off. The reaction is quantitative according to the formula. The isotope content of the deuterochloroform obtained equals that of the deuterium oxide used.

The process according to the invention not only makes these important ones considerably cheaper deuterated compound achieved, but for the first time also a full utilization of the deuterium concentration; as a result, many new areas of application can still be opened up for deuterochloroform.

example 1

A mixture of 260 g of hexachloroacetone and 75 g of barium oxide is heated with 20 g deuterium oxide slowly to 15O ⁰ C. A mixture of deuterium oxide and deuterochloroform distills off from the reaction mixture. The lighter deuterium oxide is fed back into the reaction mixture by means of a phase separator. 220 g of pure deuterochloroform are obtained.

Example 2

Reaction according to Example 1 with the same amounts by weight of hexachloroacetone and deuterium oxide using 55 g of sodium carbonate as a catalyst. 223 g of deuterochloroform are obtained. The isotope purity for 99.7% D ₂ O is 99.5% (nuclear magnetic resonance spectroscopy).

Example3

260 g of hexachloroacetone and 20 g are added to the catalyst mass remaining in Example 2

809 567/591

Given deuterium oxide. The reaction mixture is heated up to 150 ⁰ C. 228 g of deuterochloroform are obtained. With 99.7% D ₂ O, the isotope content is 99.65%.

Example 4

To a mixture of sodium and calcium carbonate (1: 1) maintained at 120 to 130 ^° C., molar amounts of hexachloroacetone and deuterium oxide are added simultaneously and continuously. The rate of addition is adjusted so that the supply of starting materials in the reaction vessel, which has been reduced by the deuterochloroform formed, is continuously replenished. The reaction can be sustained uninterrupted. The yield of deuterochloroform is quantitative based on hexachloroacetone and deuterium oxide. The isotope purity is the same as that of the deuterium oxide used.

Claims (2)

Patent claims: 1. A process for the preparation of deuterochloroform, characterized in that hexachloroacetone with deuterium oxide in the presence of oxides or carbonates of the I. and II. Main group of the Periodic Table is reacted at 100 to 15O ⁰ C. 2. The method according to claim 1, characterized in that the reaction is carried out at 120 to 130 ° C carried out continuously.