Clean Beckmann rearrangement of cyclohexanone oxime in caprolactam-based Brønsted acidic ionic liquids

The Beckmann rearrangement of cyclohexanone oxime to afford caprolactam in a novel caprolactam-based Bronsted acidic ionic liquid as catalyst and reaction medium proceeded with high conversion and selectivity at 100 °C. The occurrence of the Beckmann rearrangement of cyclohexanone oxime in such a Bronsted acidic IL was also confirmed with in situ FT-Raman observation. The key point is that the caprolactam product was one component of the ionic liquid, and a dynamic exchange between the resulting caprolactam product and the caprolactam from the ionic liquid is expected. Therefore, the strong chemical combination between the caprolactam product and the acidic ionic liquid was greatly decreased and the desired product in the solid was recovered through extraction with organic solvent after the reaction.

[1]  M. Poliakoff,et al.  Chemistry: A cleaner way to nylon? , 2005, Nature.

[2]  Robert Raja,et al.  Design of a green one-step catalytic production of e-caprolactam (precursor of nylon-6) , 2005 .

[3]  Juan Zhang,et al.  Investigation of physicochemical properties of lactam-based Brønsted acidic ionic liquids. , 2005, The journal of physical chemistry. B.

[4]  Juan Zhang,et al.  FTIR study on deactivation of sulfonyl chloride functionalized ionic materials as dual catalysts and media for Beckmann rearrangement of cyclohexanone oxime , 2005 .

[5]  Jaehoon Jung,et al.  Molecular dynamics study of the ionic conductivity of 1-n-butyl-3-methylimidazolium salts as ionic liquids , 2005 .

[6]  Juan Zhang,et al.  Pechmann Reaction in Non-Chloroaluminate Acidic Ionic Liquids under Solvent-Free Conditions , 2005 .

[7]  J. Nagy,et al.  Vapour-phase Beckmann rearrangement of cyclohexanone-oxime over Al-MCM-41 type mesostructured catalysts , 2004 .

[8]  T. Tatsumi,et al.  Liquid-phase Beckmann rearrangement of cyclohexanone oxime over mesoporous molecular sieve catalysts , 2004 .

[9]  M. Parrinello,et al.  Hydrogen bond driven chemical reactions: Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water. , 2004, Journal of the American Chemical Society.

[10]  Tatsuya Suzuki,et al.  Theoretical study on vapour phase Beckmann rearrangement of cyclohexanone oxime over a high silica MFI zeolite , 2003 .

[11]  K. Shanthi,et al.  Beckmann rearrangement over phosphotungstic acid/SiMCM-41 cyclohexanone oxime to ε-caprolactam , 2003 .

[12]  James H. Davis,et al.  From curiosities to commodities: ionic liquids begin the transition. , 2003, Chemical communications.

[13]  H. Olivier-Bourbigou,et al.  Determination of an acidic scale in room temperature ionic liquids. , 2003, Journal of the American Chemical Society.

[14]  M. Arai,et al.  Innovations in chemical reaction processes using supercritical water: an environmental application to the production of ε-caprolactam , 2003 .

[15]  P. Suarez,et al.  Ionic liquid (molten salt) phase organometallic catalysis. , 2002, Chemical reviews.

[16]  Hiroshi Sato,et al.  The development of new heterogeneous catalytic processes for the production of ε-caprolactam , 2001 .

[17]  W. Ou,et al.  Formation of ε-caprolactam via catalytic Beckmann rearrangement using P2O5 in ionic liquids , 2001 .

[18]  R. Sheldon Catalytic reactions in ionic liquids. , 2001, Chemical communications.

[19]  Jiajian Peng,et al.  Catalytic Beckmann rearrangement of ketoximes in ionic liquids , 2001 .

[20]  P. Wasserscheid,et al.  Ionic Liquids-New "Solutions" for Transition Metal Catalysis. , 2000, Angewandte Chemie.

[21]  J. Niederer,et al.  Active Sites of a [B]-ZSM-5 Zeolite Catalyst for the Beckmann Rearrangement of Cyclohexanone Oxime to Caprolactam , 2000 .

[22]  Osamu Sato,et al.  Acceleration of Synthetic Organic Reactions Using Supercritical Water: Noncatalytic Beckmann and Pinacol Rearrangements , 2000 .

[23]  S. J. Kim,et al.  Vapor phase Beckmann rearrangement of cyclohexanone oxime over a novel tantalum pillared-ilerite , 2000 .

[24]  W. Hölderich,et al.  Catalytically Active Sites for the Beckmann Rearrangement of Cyclohexanone Oxime to ε-Caprolactam , 1999 .

[25]  K. R. Seddon,et al.  The phase behaviour of 1-alkyl-3-methylimidazolium tetrafluoroborates; ionic liquids and ionic liquid crystals , 1999 .

[26]  Y. Ikushima,et al.  Noncatalytic Beckmann Rearrangement of Cyclohexanone-Oxime in Supercritical Water , 1998 .

[27]  W. Hölderich,et al.  SIMS/XPS study on the deactivation and reactivation of B-MFI catalysts used in the vapour-phase Beckmann rearrangement , 1998 .

[28]  M. Nguyen,et al.  A New Look at the Classical Beckmann Rearrangement: A Strong Case of Active Solvent Effect , 1997 .

[29]  T. Spiro,et al.  UV resonance Raman spectroscopy of cis—‐amides , 1995 .

[30]  Y. Izumi,et al.  VAPOR-PHASE BECKMANN REARRANGEMENT OF CYCLOHEXANONE OXIME OVER BORIA-HYDROXYAPATITE CATALYST , 1983 .