Reaction of Lithium-Nitride With Aromatic Aldehydes.

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LSU Historical Dissertations and Theses Graduate School
1969
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Jules Michael Morris
Louisiana State University and Agricultural & Mechanical College
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RReeccoommmmeennddeedd CCiittaattiioonn
Morris, Jules Michael, "Reaction of Lithium-Nitride With Aromatic Aldehydes." (1969). LSU Historical
Dissertations and Theses. 1680.
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MORRIS, Jules Michael, 1937-
REACTION OF LITHIUM NITRIDE WITH
AROMATIC ALDEHYDES.
The Louisiana State University and Agricultural
and Mechanical College, Ph.D., 1969
Chemistry, organic
University Microfilms, Inc., Ann Arbor, Michigan
REACTION OF LITHIUM NITRIDE WITH AROMATIC ALDEHYDES
A Dissertation
Submitted to the Graduate Faculty of the
Louisiana State University and
Agricultural and Mechanical College
in partial fulfillment of the
requirements for the degree of
Doctor of Philosophy
in
The Department of Chemistry
* C'
Jules M.' Morris
B.S., Loyola University of the South, 1959
M.S., Louisiana State University, I962
August, I969
ACKNOWLEDGMENT
The author wishes to express his sincere appreciation for
the guidance given him by Dr. Paul E. Koenig, who planned and di­
rected this investigation, and to Dr. George R. Newkome for his
interest in the author as student and friend.
He also wishes to thank his wife, Judy, and his family for
the encouragement given and patience shown.
The financial assistance received from the Dr. Charles E.
Coates Memorial Fund of the LSU Foundation donated by George H.
Coates for the preparation of this Dissertation is gratefully ac­
knowledged .
ii
TABLE OF CONTENTS
PAGE
ACKNOWLEDGEMENT..................... ii
ABSTRACT . . . . . . . . x
INTRODUCTION................................. 1
HISTORICAL ..................................... 2
EXPERIMENTAL SECTION
Reaction of Benzaldehyde with Lithium Nitride . . . . . . 7
Preparation of Model Compounds of cis-N-(2-Benzamido-
1.2-Diphenylethenyl)Benzamide(l)
Trimer of Benzaldehyde......... 15
N-(l,2-Diphenylethenyl)Benzamide .................. 15
N-(2-Benzamido-l,2-Diphenylethyl)Benzamide ........ 14
cls-N-(2-Benzamidoethenyl)Benzamide ................ 14
trans-N-(2-Benzamidoethenyl)Benzamide .............. 15
Reactions of N-(2-Benzamido-l,2-Diphenylethenyl)
Benzamide
Acid Hydrolysis.................................... 15
Thermal Decomposition .............................. 16
With Benzoyl Chloride................. 18
With Sodium Benzoate and Benzoic Anhydride . . . . . 18
Ozonolysis in Formic Acid.......................... 19
Oxidation with Potassium Dichromate ............... 19
Oxidation x^ith Bromine ..................... 20
Attempted Base Hydrolysis............... 22
Preparation of Model Compounds of threo-N-(2-Hydroxy-
1.2-Diphenylethyl)Benzamide.
N,N'-Benzylidenebisbenzamide . . . . . . 22
threo-N-(2-Hydroxy-l,2-Diphenylethyl)Benzamide ... 22
Reactions of threo-N-(2-Hydroxy-1,2-Diphenylethyl)
Benzamide
With Excess Benzoyl Chloride . . . . . . . 25
Base Hydrolysis.................................... 25
iii
PAGE
Reaction of p-Tolualdehyde with Lithium Nitride...... 24
Reaction of N-(2 Toluamido-l,2-bis-_£-
Tolylethenyl)Toluamide(lIl)........................ . . 29
Preparation of Miscellaneous Compounds
£-Tolualdehyde......................... 50
meso-1,2-Diphenylethylenediamine ...................... 52
threo-1,2-Diphenyl-2-Aminoethanol.................. 55
ery thro -1.2-Dipheny 1-2-Aminoethanol................ 55
Dibenzamide....................... 54
2,4,5-Triphenylimidazole .............................. 54
2,4,5.-Triphenyloxazole............................. 55
Hydrobenzamide ......................................... 55
Benzoin oxime ......................................... 56
Miscellaneous Reactions
Reaction of Benzaldehyde with Gaseous Ammonia . . . . 56
Acid Hydrolysis of N-(l,2-Diphenylethenyl)Benzamide. . 57
Acid Hydrolysis of Benzamide....................... 57
Attempted Pyrolysis of 2,4,5-Triphenylimidazole. . . . 57
Attempted Pyrolysis of 2,4,5-Triphenyloxazole . . . . 58
Pyrolysis of Hydrobenzamide .......................... 58
RESULTS AND DISCUSSION
Reaction of Aromatic Aldehydes with Lithium Nitride. . . . 59
Ester Formation........................................ 40
Alcohol and Acid Formation............................. kk
Benzoin Condensation of Aromatic Aldehydes ............... 45
threo-N-(2-Hydroxy-l,2-Diphenylethyl)Benzamide
Formation................... 4o
Mass Spectrum...................................... 48
NMR Spectrum ..................................... 49
Properties and Structure of Amides I and III.......... 52
Formation of Amides I and III and Triarylimidazoles
IV and V ................................................ 55
Hydrolysis of Amides I and III............... 56
iv
PAGE
Cyclization of Amides I and III.......................... 59
Ozonolysis of Amide I in Formic Acid.................... 6l
Oxidation of Amide I with Potassium Dichromate
in Glacial Acetic Acid............................ 01-
Oxidation of Amide I with Bromine in
Glacial Acetic A c i d .................................... 65
Mass Spectra of Ethenyl-bis-Amides...................... . 66
CONCLUSIONS . . . . . ... 70
APPENDIX A
Thin Layer Chromatography, Method and Conditions ........ Jl
Gas Chromatography, Method and Conditions. . . . . . . . . 75
Infrared Method for the Determination of Composition
of threo -N- (2--Hydroxy-1,2-diphenylethy 1)benzamide
Benzyl Benzoate Mixtures . . . . . ...................... j6
Infrared Method for the Determination of Composition
of Benzamide-Benzil Mixtures ............................ 77
Molecular Weight Determination in Camphor .............. 80
APPENDIX B
Infrared Spectra ........................................ 82
APPENDIX C
Mass Spectral Data...................................... 90
APPENDIX D
Nuclear Magnetic Resonance Spectra . . . . . . .......... 99
APPENDIX E
Reaction of Lithium Nitride with o'-Chlorotoluene.......... 102
Reaction of Lithium Nitride with Pyridine. . ............ 102
BIBLIOGRAPHY..................... 10^
VITA .......... 109
v
LIST OF TABLES
TABLE PACE
1 Reaction of Benzaldehyde (IJ18 mol.) with Lithium
Nitride (0.278 mol.). Reaction yields........... . 12
2 Reaction Products from £-Tolualdehyde (0.001-5 mol.)
and Lithium Nitride (0.028 mol.). ... ................ 27
5 Column Chromatography of jp-Tolualdehyde and
Lithium Nitride Reaction Mixture. . . . . . ............ 28
k Selection of a Suitable Solvent (for tic) . . . . . . . 'Jl
5 Rf Values for Compounds Derived from Benzaldehyde
In Mixed Solvent Systems ..................... 72
6 Rf Values for Compounds Derived from £-Tolualdehyde.
In Mixed Solvent Systems . . . . . . . .......... .. 73
7 TLC of Benzaldehyde Reaction Mixture.................. 77
8 TLC of _£-Tolualdehyde Reaction Mixture................ 77
9 GLC Response Factors and Rf Values.................... "jG
10 Ratio of Absorbance at 3390 cm-1 : 1000 cm 1
For Mixtures of Benzamide in Benzil................... 77
11 Ratio of Absorbance at I63O cm-1 : 1720 cm'1
for mixtures of N-(2-Hydroxy-l,2-Diphenylethyl)
Benzamide in Benzyl Benzoate .......................... 77
12 Molecular Weight Determinations in Camphor . . . . . . 81
vi
LIST OF FIGURES
FIGURE PAGE
............
1 Apparatus for Pyrolysis Studies
2 Infrared Spectrum of cis-N-(2-Benzamido-
.............
l,2-Diphenylethenyl)Benzamide . . 82
3 Infrared Spectrum of cis-N-(2-Toluamido-l,2-
Bis-£-Tolylethenyl)Toluamide.......................
4 Infrared Spectrum of N-(2-Benzamido-l,2-
. .
Diphenylethyl)Benzamide ........................... 8U
5 Infrared Spectrum of cis-N-(2-Benzamidoethenyl)-
Benzamide .......................................... . . 85
6 Infrared Spectrum of trans-N-(2-Benzamidoethenyl)-
..........................
Benzamide
7 Infrared Spectrum of threo-N-(2-Hydroxy-l,2-
Diphenylethyl)Benzamide (isolated from reac-
8 Infrared Spectrum of threo-N-(2-Hydroxy-1,2-
.......... . . .
Diphenyl ethyl) Benzamide 88
9 Infrared Spectrum of N-(2-Benzoyloxy-l,2-
.................
Diphenylethyl)Benzamide
10 Mass Spectrum of cis-N-(2-Benzamido-l,2-
................
Diphenylethenyl)Benzamide
11 Mass Spectrum of cis-N-(2-Toluamido-l,2-
.............
Bis-j>-Tolylethenyl)Toluamide
12 Mass Spectrum of trans-N-(2-Benzamidoethenyl)-
..........................
Benzamide
13 Mass Spectrum of cis-N-(2-Benzamidoethenyl)-
..........................
Benzamide
2k Mass Spectrum of threo-N-(2-Hydroxy-1,2-
.............
Diphenylethyl) Benzamide
15 Mass Spectrum of threo-l,2-Diphenyl-2-
. . . .
Aminoethanol (from hydrolysis of Amide Ii).
vii
FIGURE PAGE
16 Mass Spectrum of thrco-1,2-Diphenyl-
2-Aminoethanol................... .................. 97
17 Mass Spectrum of crythro-1,2-Diphenyl-
2-Aminocthanol . . . „ .............................. 97
18 Mass Spectrum of meso-1,2-Diphenylethylenediamine ... 98
19 NMR Spectrum of _threo-N-(2-Hydroxy-1,2-
Diphenylethyl)Benzamide . . . . . . . . . . . ........ 99
20 NMR Spectrum of threo-1,2-Diphenyl-2-
Aminoethanol........................ 100
21 NMR Spectrum of threo-1,2-Diphenyl-2-
Aminoethanol (from Hydrolysis of
Amine II) .............................. 101
viii