Synthesis of β-Keto Esters by Carbonylation of Halomethylketones

A. L. Lapidus; O. L. Eliseev; T. N. Bondarenko; O. E. Sizan; A. G. Ostapenko; I. P. Beletskaya

doi:10.1055/s-2002-20027

SHORTPAPER

Synthesis of β-Keto Esters by Carbonylation of Halomethylketones

A. L. Lapidus*^a, O. L. Eliseev^a, T. N. Bondarenko^a, O. E. Sizan^a, A. G. Ostapenko^a, I. P. Beletskaya^b
^a N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russian Federation
Fax: +7(95)1355303; e-Mail: oleg@ioc.ac.ru;
^b Department of Chemistry, Moscow State University, Moscow, Russian Federation
Fax: +7(95)9381844; e-Mail: beletska@org.chem.msu.su;

Abstract

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Abstract

A number of β-keto esters were synthesized by Pd-catalyzed carbonylation of halomethylketones in the presence of tributylamine in 68-86% yields. The reaction is completed in 2 hours at 110 °C and 10 bar CO pressure. Chloromethylketones are carbonylated selectively while 2-bromoacetophenone is partly reduced to acetophenone as a byproduct. The reaction can be carried out at atmospheric pressure though the rate stays low. The reaction mechanism is discussed.

Key words

halomethylketones - β-keto esters - carbonylation - palladium - catalysis

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References

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