Synthesis and Characterization of Amino Acid Ionic liquids and Low Symmetry Ionic liquids based

404 Pages·2015·7.95 MB·English

Synthesis and Characterization of Amino Acid Ionic liquids
and Low Symmetry Ionic liquids based on the
triaminocyclopropenium cation

Ruhamah Yunis

A Thesis Submitted in the Partial Fulfillment of the
Requirements for the Degree of Philosophy in Chemistry

Department of Chemistry
University of Canterbury

2015
Table of
Contents
Table of Contents

Table of Contents
1. Introduction……………………………………………………………………………….1
1.1 Ionic Liquids………………………………………………………………………………..1
1.1.1 Commonly used Cations and Anions
1.1.2 Properties
1.2 The Triaminocyclopropenium cation………………………………………………………4
1.2.1 Structure
1.2.2 Properties
1.2.3 Synthesis
1.2.4 Reactions
1.3 Amino Acid Ionic Liquids (AAILs)……………………………………………………..12
1.3.1 Amino Acid as the Cation or Anion without Modification
1.3.2 Metal CILs (MCILs)
1.3.3 Modification of Amino Acid Functional Groups
1.3.4 Ammonium
1.3.5 Phosphonium
1.3.6 Imidazolium
1.3.6.1 Without Modification of the Imidazolium cation
1.3.6.2 Imidazolium Rings Obtained from Amino Acids
1.3.6.3 Modification via Substitution at 1/3 position of imidazolium
I
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1.3.7 Imidazolinium
1.3.8 Thiazolium
1.3.9 Oxazoline
1.3.10 Pyridinium
1.3.11 Guanidinium
1.3.12 Cyclopropenium
1.3.13 Carbamates
1.4 Applications and Uses of AAILs…………………………………………………………43
1.4.1 Asymmetric Synthesis
1.4.1.1 Diels-Alder Reaction
1.4.1.2 Aldol Reaction
1.4.1.3 Michael Addition Reaction
1.4.1.4 Heck Reaction
1.4.1.5 Hydrogenation
1.4.1.6 A tandem Knoevenagel, Michael and ring transformation
1.4.1.7 Biginello Reaction
1.4.1.8 Cycloaddition of CO and expoxide
2
1.4.1.9 Dihydroxylation of Olefins
1.4.1.10 Synthesis of (S)-Hajos dione
1.4.2 Chromatography
1.4.3 Circularly-Polarized Luminescence (CPL) Spectroscopy
1.4.4 Chiral Discrimination Studies by NMR
II
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1.4.5 Fluorescence Spectroscopy
1.4.6 Biotechnology (Activating Agent)
1.4.7 Absorption of CO
2
References…………………………………………………………………………………………62
2 Experimental……………………………………………………………………………..71
2.1 Analytical Techniques……………………………………………………………………..72
2.1.1 NMR
2.1.2 Mass Spectrometry
2.1.3 Microanalysis
2.1.4 Water Content
2.1.5 Chloride Content
2.1.6 Viscosity
2.1.7 Conductivity
2.1.8 Thermal Gravimetric Analysis
2.1.9 Differential Scanning Calorimetry
2.1.10 Density
2.1.11 Polarimetry
2.1.12 Magnetic Susceptibility Balance
2.1.13 Miscibility and Solubility
2.2 Synthetic details…………………………………………………………………………..75
2.2.1 Pentachlorocycopropane
2.2.2 N-Ethylmethylamine
III
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2.2.3 N-Allylmethylamine
2.2.4 N-(2-Methoxyethyl)methylamine
2.2.5 Tris(dimethylamino)cyclopropenium chloride
2.2.6 Bis(dimethylamino)cyclopropenone
2.2.7 Bis(dimethylamino)methoxycyclopropenium methylsulphate
2.2.8 Bis(dimethylamino)cyclopropenone
2.2.9 Bis(diethylamino)methoxycyclopropenium tetrafluoroborate
2.2.10 Bis(diethylamino)methoxycyclopropenium trifluorosulfonate
2.2.11 Bis(diethylamino)ethoxycyclopropenium iodide
2.2.12 Bis(diethylamino)methoxycyclopropenium methylsulphate
2.3 Synthesis of Bis(dimethylamino)alkylaminocyclopropenium salts…………...…………80
2.3.1 Bis(dimethylamino)ethylaminocyclopropenium bis(trifluoromethanesulfonyl)amide
2.3.2 Bis(dimethylamino)allylaminocyclopropenium bis(trifluoromethanesulfonyl)amide
2.3.3 Bis(dimethylamino)propylaminocyclopropenium bis(trifluoromethanesulfonyl)amide
2.3.4 Bis(dimethylamino)-N-(methoxyethyl)aminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.3.5 Bis(dimethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide
2.3.6 Bis(dimethylamino)pentylaminocyclopropenium bis(trifluoromethanesulfonyl)amide
2.4 Synthesis of Bis(dimethylamino)dialkylaminocyclopropenium salts…….…………….83
2.4.1 Bis(dimethylamino)ethylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.2 Bis(dimethylamino)diethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
IV
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2.4.3 Bis(dimethylamino)allylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.4 Bis(dimethylamino)allylmethylaminocyclopropenium dicyanamide
2.4.5 Bis(dimethylamino)diallylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.6 Bis(dimethylamino)propylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.7 Bis(dimethylamino)propylmethylaminocyclopropenium dicyanamide
2.4.8 Bis(dimethylamino)dipropylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.9 Bis(dimethylamino)-N-(methoxyethyl)methylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.10 Bis(dimethylamino)-N-(methoxyethyl)methylaminocyclopropenium dicyanamide
2.4.11 Bis(dimethylamino)-N-(dimethoxyethyl)aminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.12 Bis(dimethylamino)butylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.13 Bis(dimethylamino)butylmethylaminocyclopropenium dicyamide
2.4.14 Bis(dimethylamino)dibutylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.15 Bis(dimethylamino)pentylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.4.16 Bis(dimethylamino)hexylmethylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
V
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2.4.17 Bis(dimethylamino)dihexylaminocyclopropenium
bis(trifluoromethanesulfonyl)amide
2.5 Synthesis of tris(alkylmethylamino)cyclopropenium
salts………………………………………………………..…………..………………...94
2.5.1 Tris(ethylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide
2.5.2 Tris(allylmethylamino)cyclopropenium dicyanamide
2.5.3 Tris(allylmethylamino)cyclopropenium bis(trifluoromethanesulfonyl)amide
2.5.4 Tris-(N-(methoxyethyl)methyl)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.5.5 Trisanilinocyclopropenium bis(trifluoromethanesulfonyl)amide
2.6 Synthesis of bis(diethylamino)cyclopropenium salt……………………………………97
2.6.1 1,2-Bis(diethylamino)-3-aminocyclopropenium methylsulphate,
[(Et N) C (NH )]MeSO , [E H ]MeSO
2 2 3 2 4 4 2 4
2.7 Syntheses of Bis(diethylamino)alkylaminocyclopropenium..............................................97

2.7.1 Bis(diethylamino)butylaminocyclopropenium methylsulfate
2.7.2 Bis(diethylamino)butylaminocyclopropenium bis(trifluoromethanesulfonyl)amide
2.7.3 Bis(diethylamino)butylaminocyclopropenium dicyanoamide
2.7.4 Bis(diethylamino)butylaminocyclopropenium tetrafluoroborate
2.8 Synthesis of bis(diethylamino)dialkylaminocyclopropenium salts…………..…………..99
2.8.1 Bis(diethylamino)dihexylaminocyclopropenium iodide
2.8.2 Bis(diethylamino)dihexylaminocyclopropenium iodide
2.8.3 Bis(diethylamino)dihexylaminocyclopropenium trifluoromethylsulfonate
2.9 Synthesis of Chiral Ionic Liquids from Amino Acids......................................................100
VI
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2.9.1 Bis(diethylamino)-S-(1-carboxyethylamino)cyclopropenium methylsulfate
2.9.2 Bis(diethylamino)- S-(1-carboxyethylamino)cyclopropenium TFSA
2.9.3 Bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium methylsulfate
2.9.4 Bis(diethylamino)-S-(2-carboxypyrrolidino)cyclopropenium TFSA
2.9.5 Bis(diethylamino)-S-(1-carboxy-2-methylpropylamino)cyclopropenium
methylsulfate
2.9.6 Bis(diethylamino)-S-(1-carboxy-2-methylpropylamino)cyclopropenium TFSA
2.9.7 Bis(diethylamino)-S-(1-carboxy-2-hyroxylpropylamino)cyclopropenium
methylsulfate
2.9.8 Bis(diethylamino)-S-(1-carboxy-2-hyroxylpropylamino))cyclopropenium TFSA
2.9.9 Bis(diethylamino)-S-(1-carboxy-4-guanidinobutylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.10 Bis(diethylamino)-S-(1,3-dicarboxy-ethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.11 Bis(diethylamino)-S-(1-carboxy-2-imidazolethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.12 Bis(diethylamino)-S-(1-carboxy-3-methylthioproylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.13 Bis(diethylamino)-S-(1-carboxy-3,3-dimethylethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.14 Bis(diethylamino)-S-(1-carboxy-2-methylbutylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.15 Bis(diethylamino)-S-(1-carboxy-2-(1H-indol-3-yl)ethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
VII
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2.9.16 Bis(diethylamino)-S-(1-carboxy-2-hydroxyphenylethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.17 Bis(diethylamino)-S-(1-carboxy-2-phenylethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.18 Bis(diethylamino)-S-(1-carboxy-2-hydroxyethylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.19 Bis(diethylamino)-S-(1-carboxy-3-carbamoylpropylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.20 Bis(diethylamino)-S-(1-carboxy-4-carbamoylbutylamino)cyclopropenium
bis(trifluoromethanesulfonyl)amide
2.9.21 Tetrakis(diethylamino)-bis(bis(diethylamino)cyclopropenium)-S-(1-carboxy-5-
aminopentylamine)cyclopropenium bis(trifluoromethanesulfonyl)amide
2.10 Synthesis of Tris(diethylamino)cyclopropenium salts………………………………….113
2.10.1 Tris(diethylamino)cyclopropenium p-toluenesulfonate
2.10.2 Tris(diethylamino)cyclopropenium trifluoromethanesulfonate
2.10.3 Tris(diethylamino)cyclopropenium iodide
2.10.4 Tris(diethylamino)cyclopropenium pentafluorophenoxide
2.10.5 Tris(diethylamino)cyclopropenium tetrachloroferrate(III)
2.10.6 Tris(diethylamino)cyclopropenium trichlorostannate(II)
2.10.7 Tris(diethylamino)cyclopropenium tetrachlorozincate(II)
2.10.8 Tris(diethylamino)cyclopropenium tetrachlorocuprate(II)
2.11 Synthesis of Tris(dibutylamino)cyclopropenium salts………………………………..116
2.11.1 Tris(dibutylamino)cyclopropenium tetracyanoborate
2.11.2 Tris(dibutylamino)cyclopropenium tris(pentafluoroethyl)trifluorophosphate
VIII