A New Route to 1,1-Disubstituted Cyclopropanes

✍ Scribed by Doz. Dr. J. Gosselck; Dipl.-Chem. G. Schmidt

• Publisher: John Wiley and Sons
• Year: 1968
• Tongue: English
• Weight: 211 KB
• Volume: 7
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.196804561

✦ Synopsis

polar additions or substitutions [71 induced us t o test the wider use of organotin deuterides for deuteration.

Using powerful catalysts such as Raney nickel, palladium, platinum [El, or anhydrous ZnClz (91, we obtained both Cdeuterated and C,U-bisdeuterated alcohols smoothly from organotin deuterides and aldehydes or ketones. To save deuteride we liberated the alcohol by deuterolysis (a) or hydrolysis (b), as required. However, a second equivalent of deuteride also effects this liberation, and is best used in the form of the more active compounds RZSnDZ which react in one step (c).

Working up is by fractional distillation. Yields are 70-95 %.

Alkyl chlorides, bromides, and iodides, aryl iodides, and acid chlorides can be deuterated even without a catalyst. Carbonyl, nitro, and nitrile groups, which are often attacked by the usual deuterating agents, are unchanged in this reaction. Acid chlorides afford [l-D]aldehydes[lol, and also the dideuterated esters. The ratio of the yields [I-Dlaldehyde: ester can be varied according to the experimental technique and the concentration of the reactants, as is recorded [7,111 for the analogous reaction with hydrides.