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US 2006/0149095 A1Published application
Carbonylation of alpha-chloroketones to beta-keto esters using palladium carbene catalysts
OwnerJoseph Zoellerinventor
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Abstract
The present invention is a novel process for producing β-ketoesters 1 by contacting an α-chloroketone 2 with carbon monoxide and a hydroxyl-containing compound of formula R3OH in the presence of a base and a palladium carbene catalyst complex 3. The subject catalysts demonstrate superior rates and selectivity when compared to known (Ph3P)2PdCl2.
Claims13
A process for generating β-ketoesters of formula 1
- which comprises contacting an α-chloroketone of formula 2
- with carbon monoxide and R3OH in the presence of a base and a catalyst having formula 3
- wherein R1 and R2 are, independently, hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C1-C10 alkenyl, C1-C10 heteroalkyl, C1-C10 heteroalkenyl, or C4-C10 heteroaryl containing, in addition to the carbon content, up to three heteroatoms selected from O, S, or N, or R1 and R2 may be joined together with any of the foregoing groups to form a bridging group;
- R3 is C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C1-C10 alkenyl, C1-C10 heteroalkyl or C4-C10 heteroaryl containing, in addition to the carbon content, up to three heteroatoms selected from O, S or N;
- R4, R5 and R6 are, independently, C1-C20 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C1-C10 alkenyl, C1-C10 heteroalkyl, C1-C10 heteroalkenyl, or C4-C10 heteroaryl containing, in addition to the carbon content, up to three heteroatoms selected from O, S or N, or R4 and R5, and optionally R6, may be joined together with any of the foregoing groups to form a bridging group;
- Y is C1-C20 alkyl-N, C3-C10 cycloalkyl-N, C6-C20 aryl-N, heteroalkyl-N, heteroaryl-N, O, or S;
- wherein all substituents for R1-R6 may be substituted with C1-C20 alkoxy, C1-C20 aryloxy, C1-C20 carboxyl, C1-C20 amino, C1-C20 alkylamino, C1-C20 amido, or C1-C20 thioalkyl;
- and X is an anion.
5 more elements
A process for generating β-ketoesters of formula 1
- which comprises contacting an α-chloroketone of formula 2
- with carbon monoxide and R3OH in the presence of a base and a catalyst having formula 3
- wherein R1 is C6-C20 aryl, C3-C10 cycloalkyl or C1-C10 alkyl each of which may optionally be substituted with halogen, C1-C20 alkoxy, C1-C20 aryloxy, C1-C20 carboxyl, C1-C20 amino, C1-C20 alkylamino, C1-C20 amido, or C1-C20 thioalkyl;
- R2 is hydrogen;
- R3 is C1-C10 alkyl;
- R4 and R5 are collectively a bridging group;
- R6 is C1-C20 alkyl or C6-C20 aryl group;
- X is chloride, iodide or bromide;
- Y is N—R7 wherein R7 is C1-C20 alkyl or C6-C20 aryl and the contacting is performed at a pressure of about 0.1 to about 100 atmospheres absolute pressure (atm), and at a temperature of about 75° C. to about 175° C.
6 more elements
A palladium carbene carbonylation catalyst of formula 3
- wherein R4, R5 and R6 are, independently, C1-C20 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C1-C10 alkenyl, C1-C10 heteroalkyl, C1-C10 heteroalkenyl, or C4-C10 heteroaryl containing, in addition to the carbon content, up to three heteroatoms selected from O, S or N, or R4 and R5, and optionally R6, may be joined together with any of the foregoing groups to form a bridging group;
- Y is N—R7 wherein R7 is C1-C20 alkyl or C6-C20 aryl;
- and X is chloride, iodide or bromide.
Dependencies are inferred from the claim text.