Synthesis and application of novel chiral ionic liquids derived from alpha-pinene
Department of Chemistry and Environmental Science
Master of Science
Malhotra, Sanjay V.
Bozzelli, Joseph W.
Gund, Tamara M.
Chiral ionic liquids
Two new chiral ionic liquids of oxazolinium cations derived from a-pinene: 9,9-Dimethyl-4-propenyl-5-propyl-3 -oxa-5-azonia-tricyclo [184.108.40.206 2,6] dec-4-ene tetrafluoro borate ([ChIPOZ] [BF4]) and 9,9-Dimethyl-4-propenyl-5-propyl-3-oxa-5-azonia-tricyclo [220.127.116.11 2,6] dec-4-ene hexafluoro phosphate ([ChIPOZ][PF6]). Both these chiral ionic liquids have been applied in enantiomeric copper-catalyzed 1,4-addition reactions with diethyl zinc. The enantiomeric excess for product using [ChIPOZ][BF4] is above 70% and for [ChIPOZ][PF6] is above 30%. Chiral ionic liquids worked as phase transfer catalysts In this reaction.
α-Pinene was used as the "chiral pool" in the synthesis of amino alcohol through a two-step reaction, followed by conversion to an oxazoline. Reaction of oxazoline with alkyl bromide gave 9,9-Dimethyl-4-propenyl-5-propyl-3-oxa-5-azonia-tricyclo [6.1. 1.02,6] dec-4-ene bromide ([ChIPOZ][Br]). This organic bromide was used as the starting material for synthesis of chiral ionic liquid. Three additional novel compounds were obtained during the synthesis: But-2-enoic acid (2-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] hept-3-yl)-amide (Amide), 2,9,9-Trimethyl -4-propenyl -3-oxa -5-aza -tricyclo [6.1.1 .02,6] dec-4-ene (Oxazoline) and 9,9-Dimethyl-4-propenyl-5-propyl-3-oxa-5-azoniatricyclo [6.1.1.02,6] dec-4-ene bromide ([ChIPOZI [Br]).
Products formation in each step of synthesis was confirmed by FT-IR, NMR and Mass Spectrometry analysis.
njit-etd2003-103 (80 pages ~ 2,660 KB pdf)
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Created June 22, 2004