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- Title
Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of the Bio-Sourced 10-Undecenenitrile: Selective and Productive Catalysts for Production of Polyamide-12 Precursor.
- Authors
Ternel, Jérémy; Couturier, Jean ‐ Luc; Dubois, Jean ‐ Luc; Carpentier, Jean ‐ François
- Abstract
The hydroformylation of 10-undecenenitrile ( 1) - a substrate readily prepared from renewable castor oil - in the presence of rhodium-phosphane catalysts systems is reported. The corresponding linear aldehyde ( 2) can be prepared in high yields and regioselectivities with a (dicarbonyl)rhodium acetoacetonate-biphephos [Rh(acac)(CO)2-biphephos] catalyst. The hydroformylation process is accompanied by isomerization of 1 into internal isomers of undecenenitrile ( 1 -int); yet, it is shown that the Rh-biphephos catalyst effectively isomerizes back 1 -int into 1, eventually allowing high conversions of 1/ 1 -int into 2. Recycling of the catalyst by vacuum distillation under a controlled atmosphere was demonstrated over 4-5 runs, leading to high productivities up to 230,000 mol ( 2)⋅mol (Rh)−1 and 5,750 mol ( 2)⋅mol (biphephos)−1. Attempted recycling of the catalyst using a thermomorphic multicomponent solvent (TMS) phase-separation procedure proved ineffective because the final product 2 and the Rh-biphephos catalyst were always found in the same polar phase. Auto-oxidation of the linear aldehyde 2 into the fatty 10-cyano-2-methyldecanoic acid ( 5) proceeds readily upon exposure to air at room temperature, opening a new effective entry toward polyamide-12.
- Subjects
HYDROFORMYLATION; RHODIUM catalyst selectivity; PHOSPHINE synthesis; ALDEHYDE reactivity; ISOMERIZATION; REGIOSELECTIVITY (Chemistry)
- Publication
Advanced Synthesis & Catalysis, 2013, Vol 355, Issue 16, p3191
- ISSN
1615-4150
- Publication type
Article
- DOI
10.1002/adsc.201300492