Copper(II) Triflate as a Source of Triflic Acid: Effective, Green Catalysis of Hydroalkoxylation Reactions
書誌事項
- 公開日
- 2009-10
- 権利情報
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- http://onlinelibrary.wiley.com/termsAndConditions#vor
- DOI
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- 10.1002/adsc.200800750
- 公開者
- Wiley
この論文をさがす
説明
<jats:title>Abstract</jats:title><jats:p>The hydroalkoxylation of dicyclopentadiene (DCPD) and norbornene (NB) with 2‐hydroxyethyl methacrylate (HEMA) for the synthesis of industrially relevant monomers has been investigated with various metal‐based Lewis acids and strong Brønsted acids. In the absence of other additives, copper(II) triflate is the most efficient catalyst system. Kinetics, electron spin resonance (ESR), catalyst poisoning and cross experiments indicate that triflic acid (TfOH) is the true active catalyst in these reactions. This <jats:italic>in situ</jats:italic> generation of TfOH occurs <jats:italic>via</jats:italic> reduction of Cu(OTf)<jats:sub>2</jats:sub> by the olefin reagent (DCPD, NB). The copper ions present in the reaction mixture act as radical polymerization retardants, preventing polymerization of HEMA (which is observed with most other metal salts and strong Brønsted acids investigated), thus improving the selectivity and yield (up to 95%) for the desired products. These observations have led to the development of a highly effective green process, using bulk reagents (no solvent) and a cheap, metal‐free catalyst system, based on TfOH and a phenolic radical inhibitor (2,5‐di‐<jats:italic>tert</jats:italic>‐butylhydroxytoluene, BHT).</jats:p>
収録刊行物
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- Advanced Synthesis & Catalysis
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Advanced Synthesis & Catalysis 351 (14-15), 2496-2504, 2009-10
Wiley
