Method for producing bicyclic 1,3-diketones

US6815563B2 · kind B2 · utility

Assignee

• BASF SE

Inventors

• Klaus Langemann · Worms, DE
• Ulf Misslitz · Neustadt, DE
• Ernst Baumann · Dudenhofen, DE
• Wolfgang von Deyn · Neustadt, DE
• Steffen Kudis · Mannheim, DE
• Thorsten Volk · Mannheim, DE
• Guido Mayer · Neheim, DE

Key dates

• Filing date: Jan 6, 2003
• Grant date: Nov 9, 2004
• Expiry date: Jan 6, 2023

Classification

• Technology area (CPC C): Chemistry; Metallurgy
• CPC primary: C07C2602/44
• WIPO field: Organic fine chemistry
• WIPO sector: Chemistry

Abstract

A process for preparing bicyclic 1,3-diketones of the formula I whereR1, R2, R3 and R4 are hydrogen, C1-C4-alkyl, C1-C4-alkoxy-carbonyl, halogen, cyano, nitro, C1-C4-alkylthio, C1-C4-alkylsulfenyl or C1-C4-alkylsulfonyl andZ is C1-C4-alkylene, O, S, N—R5 whereR5 is C1-C4-alkyl or C1-C4-alkylcarbonyl,which comprisesa) reacting a bicyclic olefin of the formula II with haloform in the presence of a base to give the ring-expanded product of the formula III  whereR1-R4 and Z are as defined above andX is halogen;b) hydrolyzing the allylic halogen of the compound of the formula III to the allyl alcohol of the formula IV c) oxidizing the allyl alcohol of the formula IV to the unsaturated ketone of the formula V d) reacting the ketone of the formula V with a nucleophilic ion Y− which stabilizes a negative charge to give the ketone of the formula VI e) hydrolyzing the ketone of the formula VI to the bicyclic 1,3-diketone of the formula I,novel intermediates and novel processes for preparing these intermediates are described.