Date of Award

Summer 2003

Document Type

Thesis

Degree Name

Master of Science in Applied Chemistry - (M.S.)

Department

Chemistry and Environmental Science

First Advisor

Sanjay V. Malhotra

Second Advisor

Joseph W. Bozzelli

Third Advisor

Tamara M. Gund

Abstract

Two new chiral ionic liquids of oxazolinium cations derived from a-pinene: 9,9-Dimethyl-4-propenyl-5-propyl-3 -oxa-5-azonia-tricyclo [6.1.1.0 2,6] dec-4-ene tetrafluoro borate ([ChIPOZ] [BF4]) and 9,9-Dimethyl-4-propenyl-5-propyl-3-oxa-5-azonia-tricyclo [6.1.1.0 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.

Included in

Chemistry Commons

Share

COinS