Process for the preparation of β-γ ene carbonyl...

Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters

Reexamination Certificate

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C568S400000, C568S398000

Reexamination Certificate

active

07932418

ABSTRACT:
The present invention relates to a preparation of β-γ ene carboxylic or ketone derivatives, which may also have particular requirement on the configuration of the carbon-carbon double bond. The method requires a thermal treatment of α-β unsaturated malonate or acetylacetonate derivatives in the presents of at least one carboxylic acid and at least one alkaline, alkaline-earth or lanthanide halide or carboxylates.

REFERENCES:
Corey, Journal of the American Chemical Society, The Mechanism of the Decarboxylation of alpha, beta—and beta, gamma—Unsaturated Malonic Acid Derivatives and the Course of Decarboxylative Condensation Reactions in Pyridine, 1952, 74, pp. 5807-5905.
Corey , Journal of the American Chemical Society, The Decarboxylation of alpha, beta—Unsaturated Malonic Acid Derivatives via beta, gamma—Unsaturated Intermediates. II. The effect of alpha Substituents Upon Product Composition and Rate,1953, 75, pp. 1163-1167.
International Search Report PCT/IB2007/050341 Dated Jun. 13, 2007.
R.V. Venkateswaran et al.Decarbalkoxylation of Alkylidene Cyano—Esters, 1979, pp. 553-558, Tetrahedron Letters, No. 6, Pergamon Press Ltd.
K.H. Schulte-Elte et al., XP-002393151,An Alternative Access to(±)—α—Irones and(±)—β—Irone via Acid-Mediated Cyclisation, 1992, pp. 759-765, Helvetica Chimica Acta, vol. 75.
A.P. Krapcho, XP-000999104,Synthetic Applications of Dealkoxycarbonylations of Malonate Esters, β-Keto Esters, α-Cyano Esters and Related Compounds in Dipolar Aprotic Media—Part 1, 1982, pp. 805-822, Georg Thieme Verlag, Stuttgart, NY.
A.P. Krapcho, XP-000999105,Synthetic Applications of Dealkoxycarbonylations of Malonate Esters, β-Keto Esters, α-Cyano Esters and Related Compounds in Dipolar Aprotic Media—Part 2, 1982, pp. 893-914, Georg Thieme Verlag, Stuttgart, NY.
A.P. Krapcho, XP-002393152,Synthetic Applications and Mechanism Studies of the Decarbalkoxylations of Geminal Diesters and Related Systems Effected in Me2SO by Water and/or by Water With Added Salts, 1978, pp. 138-147, J. Org. Chemistry, vol. 43, No. 1, American Chemical Society.
A.H. Dickins, XP008067320,The Chemistry of the Three-Carbon System, Part XX CycloPentylideneacetone and Cyclo-Pentylidenemethyl Ethyl Ketone, 1929, pp. 572-580, Journal of the Chemical Society, London.
V. Ragoussis et al.Palladium Catalyzed Reductive Decarboxylation of Allyl α-Alkenyl-β-Ketoesters. A New Synthesis of(E)-3-Alkenones, 2006, pp. 683-687, Tetrahedron Letters 47, Elsevier Ltd. (2005).
I.D. Entwistle,Use of 2-Nitrophenylpropionic Acid as a Protecting Group for Amino and Hydroxyl Functions to be Recovered by Hydrogen Transfer Reduction, 1979, pp. 555-558, Tetrahedron Letters No. 6, Pargamon Press Ltd.

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