REACTIONS OF CESIUM WITH AROMATIC HYDROCARBONS A THESIS Presented to the Faculty ...

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REACTIONS OF CESIUM WITH AROMATIC HYDROCARBONS
A THESIS
Presented to
the Faculty of the Graduate Division
by
4)'17'
Thomas HP Longfield
In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy
in the School of Chemistry
Georgia Institute of Technology
November, 1973
REACTIONS OF CESIUM WITH AROMATIC HYDROCARBONS
Approved:
Dr. ErVng
Dr. unar±e6
Dr. E. ....
73
Date approved by Chairman: (cid:9)
li
ACKNOWLEDGMENTS
The author wishes to express his sincere appreciation to Dr.
Erling Grovenstein, Jr. for his suggestion of this problem and for his
advice, encouragement and assistance during the course of this work.
The author wishes to thank Dr. Charles L. Liotta and Dr. E. C. Ashby
for serving as members of his reading committee.
The graduate assistantship and the traineeships provided by the
Department of Chemistry which were supported by the National Science
Foundation and were held by the author during the course of this
research, are greatly appreciated. The help and encouragement obtained
from friends and fellow students (especially, Dr. John McKelvey, Dr.
Craig Smith, Ken French, A. B. Cottingham, Dr. G. Scott Owen, Dr.
Sammy Gabriel, and Dean Quest) has been invaluable and will always be
remembered. The author wishes to thank the staff (Don Lillie, Gerry
O'Brien, and George Turner) for their help.
Above all, the author is deeply indebted to his wife for her
patience, understanding, and encouragement and the many selfless
sacrifices she made throughout the period of graduate study.
ill
TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS (cid:9) ii
LIST OF ILLUSTRATIONS (cid:9) vi
LIST OF TABLES (cid:9) vii
SUMMARY (cid:9) xi
Chapter
I. INTRODUCTION (cid:9)
Factors Controlling Formation of Anion Radicals (cid:9) .(cid:127) (cid:127) 2
Reaction of Benzene with Alkali Metals (cid:9) 14
Reaction of Pyridine and Other Nitrogen Containing
Aromatic Compounds with Alkali Metals (cid:9) 19
Reaction of Biphenyl and Other Aromatic Hydrocarbons
with Alkali Metals (cid:9) 22
The Reaction of l,l,l-Triphenylalkanes with Ca-K-Na
Alloy (cid:9) 30
Reactions of Other Phenylalkanes (cid:9) and Fluorene
with Alkali Metals (cid:9) 31
Pyridinyl Radicals (cid:9) 40
Reactions of Olefins with Alkali Metals (cid:9) 42
Proposed Work (cid:9) 43
II. REAGENTS AND SOLVENTS (cid:9) 45
III. GENERAL PROCEDURE FOR REACTIONS AND INSTRUMENTAL
ANALYSIS OF PRODUCTS (cid:9) 54
General Procedure (cid:9) 54
Instrumental Analysis (cid:9)
55
IV. EXPERIMENTAL DETAILS (cid:9) 62
Reactions of Benzene and Cesium (cid:9) 62
Reaction of Benzene and Cesium in Tetrahydrofuran
at -20°C (cid:9) 62
Isolation and Identification of 1,1',4,0-
Tetrahydrobiphenyl (cid:9) 62
iv
TABLE OF CONTENTS (Continued)
Page
Chapter
IV. (Continued)
Study of the Temperature Dependence of the
Reaction of Cesium and Benzene in THF (cid:9) 68
The Use of H 0 D 0 CO I and (CH SO
2 ' 2 ' 2' 2' 3 )2
as Quenching Agents (cid:9) 68
Study of Hydrogen Evolution During Pyrolysis
of Benzene-Cesium Adduct (cid:9) 84
Reaction of Perdeuterobenzene (cid:9) 89
Reaction in THF at Room Temperature (cid:9) 93
Reaction with Excess Benzene (cid:9) 93
Reaction with Excess of Cesium (cid:9) 95
Reaction at Room Temperature with Solvent (cid:9) 96
Reaction of Benzene and Cs Alloy (cid:9) 106
Reaction at -70° (cid:9) (cid:127) (cid:127) (cid:127) 1o6
Reaction at Room Temperature (cid:9) 110
Reaction of Biphenyl and Cesium (cid:9) .111
Study in THF at Room Temperature (cid:9) 111
Study of Perdeuterobiphenyl in Tetrahydrofuran-d6 . (cid:9) 115
Preparation of 1,4-Dihydrobiphenyl (cid:9) 116
Reactions of Polyphenylalkanes with Cesium (cid:9) 116
Reaction of 1,1,1-Triphenylethane and Cs-K-Na Alloy . . (cid:9) 117
ESR Study of Products at -70° in THF (cid:9) 117
NMR Study of Products at -70° in THF (cid:9) 118
Reaction of Cesium Metal in Liquid Ammonia (cid:9) 118
The Temperature Dependence of This Reaction in THF (cid:9) 118
Reaction of 2,2-Diphenylpropane and Cs-K-Na Alloy in THF 123
Reaction at -70° (cid:9) 123
The Temperature Dependence of this Reaction . . . (cid:9) 126
Reaction of Diphenylmethane and Cs-K-Na Alloy in THF. (cid:9) 132
Reaction at -70° (cid:9) 132
The Effect of Warming This Reaction From -70° to -60° 137
Reaction of Tetraphenylmethane with Cesium in THF . . . 139
Reaction at -70° with Cs-K-Na Alloy (cid:9) 139
Reaction with Cesium at 36° (cid:9) 141
Reactions of cis-2-Heptene with Cesium Metal and Cs-K-Na (cid:9) 145
Alloy in THF (cid:9) 145
Reaction with Cesium Alloy (cid:9) 145
Reaction with Cesium Metal (cid:9) 146
TABLE OF CONTENTS (Continued)
Page
Chapter
V. DISCUSSION (cid:9) 151
.
The Reactions of Benzene and Cesium (cid:9) 151
The Reaction at -70° in THF (cid:9) 151
The Reaction of Cesium with Benzene in THF at -20° . . . (cid:9) 156
The Reaction at Room Temperature (cid:9) 165
The Reaction of Cesium with Benzene in Excess Benzene
as Solvent at Room Temperature (cid:9) 178
The Reaction of Benzene with Cs-K-Na Alloy (cid:9) 180
The Reaction of Biphenyl and Cesium (cid:9) 183
The Reactions of Polyphenylalkanes with Cesium Alloy
or Cesium Metal (cid:9) 188
The Reaction of Diphenylmethane with Cesium Alloy (cid:127) (cid:127) . (cid:9) 188
The Reaction of 2,2-Diphenylpropane with Cs K-Na Alloy. (cid:9) 193
-
The Reaction of 1,1,1-Triphenylethane with Cs-K-Na
Alloy in THF (cid:9) 200
The Reaction of Tetraphenylmethane with Cs-K-Na Alloy
or Cesium Metal in THF (cid:9) 204
Summary of the Reactions of Aromatic Hydrocarbons with
Cesium (cid:9) 207
The Reactions of cis-2-Heptene with Cesium and Cs-K-Na
Alloy (cid:9) 209
VI. RECOMMENDATIONS (cid:9) 214
Appendices
A. MASS SPECTRA OF 1,1',4,4'-TETRAHYDROBIPHENYL AND THE
COMPOUND THOUGHT TO BE 3-PHINYLCYCLOHEXENE (cid:9) 217
B. DISCUSSION OF CALCULATION OF ANION RADICAL CONCENTRATIONS
DETERMINED BY ESR ANALYSIS (cid:9) 222
C. IR SPECTRA OF cis-9,9-DIMETHYL-4a,4b,2,7-TETRAHYDROFLUORENE
AND 1,1',4,4'-TETRAHYDROBIPHENYL (cid:9) 229
LITERATURE CITED (cid:9) 230
VITA (cid:9) 236
vi
LIST OF ILLUSTRATIONS
Figure (cid:9) Page
1. Apparatus Used for Pyrolysis of 1,1',4, 10-Tetrahydrobiphenyl . (cid:9) 67
2. Apparatus Used to Filter Benzene-Cesium Adduct (cid:9) 99
3. Assignment of nmr T-Values in 2,5-Dihydrodiphenylmethane . . (cid:9) .191
4. Assignment of nmr T-Vnlues in cis-9,9-Dimethyl-
4a,4b,2,7-Tetrahydrofluorene (cid:9) 197
vii
LIST OF TABTFS

Table (cid:9) Page
1. Equilibrium Constants for the Reaction:
Ether
+
Na + Biphenyl (cid:9) Na , Biphenyl ' (cid:9) 6
2. The Percentages of Solvent Separated Ion-Pairs in
8
9-Fluorenyl Salt Solutions at 25° (cid:9)
3. The Ionic Form of Naphthalide and Biphenylide Salts
in Ethereal Solvents 10
4. Relative Percentage Yield of Products Formed From the
26
Alkali Metal Reduction of Biphenyl (cid:9)
5. Columns for Gas Chromatographic Analysis of Reaction
58
Products (cid:9)
6. Typical Operating Conditions for Gas Chromatographic
Analysis (cid:9) 59
7. The Yields of Products Found at Various Reaction
Temperatures in Experiment 3-162 after Quenching with H O. . 70
2
8. Yields of I Quenches Found at Various Reaction Temper-
2
atures in Experiment 3-162 . . 73
9. Yield of Final Aqueous Quench in Experiment 3-162 74
10. Molecular Ions of Compounds of H2O and D 0 Quenches
2 75
in Experiment 3-162 (cid:9)
11. The Yield of Aromatized Carbonation Products in
Experiment 4-82 (cid:9) 80
12. The Yields of Products from the Dehydrogenation of the
82
Methylation Reaction (cid:9)
13. Relative Amounts of H HD and D in the Gas Liberated
2? 2 87
During the D20 Quench in Experiment 4-20 (cid:9)
14. The Quenching Methods Used in the Study of the Black
Precipitate Isolated from the Reaction of Benzene and
100
Cesium at Room Temperature in Experiment 3-112 (cid:9)
viii
LIST OF TABLES (Continued)
Table Page
15. Relative Area Percent Yields of Products of H2O
Quench in Experiment 3-112 (cid:9) 101
16. Relative Area Percent Yields of the D 0 and Me0H
2
Quenches, Calculated from GC and GC-MS on an
OV 17 Column (VII) in Experiment 3-112 (cid:9) 103
17. Quenching Agents and Relative Area Percent Yields
of Products in Experiment 3-130 107
18. Calculations of Yields for the Reaction of Biphenyl
and Cesium in Experiment 4-16 , (cid:9) 112
19. Relative Amount of Biphenyl Remaining in 1 ml of
Aliquots of the Reaction Mixture at Various Times of
Reaction. Analysis on an SE 30 Column at 168° for
Experiment 4-66 (cid:9) 113
20. The Absolute Percent Yields of Final Products Found
in Experiment 4-66 by Analysis on a Carbowax 20 M
Column (I) at 170° (cid:9) 114
21. Heating Procedure and Sampling Schedule for the
Reaction Between 1,1,1-Triphenylethane and
Cs-K-Na Alloy (Experiment 2-96) (cid:9) 120
22. The Percent Yields of Products in the Reaction of
1,1,1 Triphenylethane with Cesium Alloy at Various
- (cid:9)
Temperatures 121
23. Schedule of Reactions Between 2,2-Diphenylpropane and
Cs-K-Na Alloy (cid:9) 128
24. Percent Yields of Products in the Reaction Between
2,2-Diphenylpropane and Cs-K-Na Alloy (Experiment 4-41)
as Determined by GC Analysis Using an SE 30 Column (III)
at 160° (cid:9) 129
25. GC-MS of Products in the Reaction Between 2,2-Diphenyl-
propane and Cs-K-Na Alloy (Experiment 4-41) as Determined
(cid:9)
by GC Analysis Using a Carbowax 20 M Column (I) at 178° . 130
ix
LIST OF TABLES (Continued)
(cid:9)
Table Page
26. Interpretation of the NMR Spectrum of Protonated
Products (Neat) in the Reaction Between Diphenyl-
(cid:9)
methane and Cs-K-Na Alloy (Experiment 4-51) 134
27. Interpretation of the NM?' Spectrum of Deuterated
Products (CDC1 ) in the Reaction Between Diphenyl-
methane and Cs-K-Na Alloy (Experiment 4-51) (cid:9) 135
28. NNB Spectrum of Sample 3, Experiment 4-54 (cid:9) 140
29. Analysis of the Reaction of Tetraphenylmethane and
Cesium Alloy at -70° (Experiment 4-27) Using a
Temperature Programmed OV 17 Column (V) (90° for
Four Minutes, then 10°/minute to 290°) (cid:9) 142
30. Gas Chromatography Results on a Temperature Programmed
Carbowax 20 M Column (I) (50° for 10 minutes, then 40°/
minute to 170° ) of Tetraphenylmethane and Cesium Alloy
(Experiment 4-27) (cid:9) 143
31. GC-MS Results in the Reaction of Tetraphenylmethane
and Cesium at 36° in Experiment 3-56 (cid:9) 144
32. Relative Area Percent Yields of Heptenes in Experiment
2-90 (cid:9) 148
33. Relative Area Percent Yields of Heptenes Found in
Experiment 2-104 (cid:9) 150
34. Results of the Reaction of Cesium Metal with Benzene
in. THF at -70° when Quenched with Water (cid:9) 153
35. Results of the Reaction of Cesium Metal with Benzene
in THF at -20° when Quenched with Water (cid:9) 158
36. Studies of Gas Evolution During the Reaction of Benzene
and Cesium in THF (cid:9) 166
37. Results of Aqueous Quench of the Product from the
Reaction of Cesium with Benzene at Room Temperature in
THF (cid:9) 169
38. Representative Yields of the Reactions of the Black
Precipitate Isolated from the Reaction of Benzene and
(cid:9)
Cesium at Room Temperature 179