Free radicals in the decomposition of organometallic compounds

94 Pages·05.163 MB·English

by  Woods, Lauren A.

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FREE RADICALS IN THE DECOMPOSITION OF
GROA NOMETA LL IC COMPOUNDS
Lauren A« Woods
A Thesis Submitted to the Graduate Faculty
for the Degree of
DOCTOR OF PHILOSOPHY
Major Subjects Organic Chemistry
Approved:
tajor Department
aDpewal !■n 11\ > dtoxLfkf aGraduate Co£4ege
Iowa State College
1943
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UMI Number: DP13062
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ACKNOWLEDGMENT
The author wishes to express his sincere re­
spect and appreciation to Dr. Henry Gilman for the
assistance and encouragement given during this
work.
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iii
TABLE OF CONTENTS
Page
INTRODUCTION. .................. 1
HISTORICAL .. . . . . . . . . . . . . . . . 3
Identification of Free Radicals. 5
Thermal Decomposition . . . . . . • • « • • • • . . 10
Group I . . . . • • • • • . . . • • . . . • • 10
Group II. . . . . . . . . . . . . . » • • • • IS
Group III ... . ......................... 21
Group I?.......... . 22
Group V. ................ . . 27
Group VI .. 28
Group VII. . . . . . . . . . . . . . . . . .. 30
Group VIII . ............ . . 31
Electrolytic Decomposition . . . . . . . . . . . • 35
Photochemical Decomposition • 38
Grganometalllc Radicals • 39
Redistribution Reaction • • • • . . . * • • « • • • 42
EXPERIMENTAL . . . . . . . . . . ............. ..... 46
Reaction of Dimethylmagnealum with Silver Bromide •• 46
Reaction of Dimethylmagneslum with Silver Iodide. •• 47
Reaction of Methyllithium with Methyl Iodide In
the Presence of a Catalytic Amount of
Gold Tribromlde • • . « • • • • • • . . • . • • 47
Reaction of Methylllthlum with Gold Tribromide . . . 48
Reaction of Zirconium Tetrachloride with
Methylmagneslum Iodide • • • • . . . . . . . . 49
Reaction of Zirconium Tetrachloride with
Dime thylmagne a ium . . . . . . . . . . . . . . . 49
Reaction of Methylmagneaium Chloride with
Tantalum Pentaehloride • . . . . . . . . . . . 50
Reaction of PhonyImagnesium Bromide with Brorao-
benzene in the Presence of Ferric Chloride* * * 50
Reaction of Phenylmagneslum Bromide with Bromo-
benzene in the Presence of Ferrous Chloride . . 51
Thermal Decomposition of Dimethylgold Bromide* * « * 51
Reaction of PhonyImagne a ium Bromide with Bromo-
benzene in the Presence of Nickelous Chloride • 52
Chromium Trichloride and Dimethylmagneaium . . . . . 53
Thermal Decomposition of Diphenylcadmium . . . . . . 53
Attempted Preparation of Dibenzylcadmlum • « • . . . 54
Attempted Preparation of Dlphenylantimony Chloride * 54
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Diphenylant Imony Chloride • • • • • • • • • • • « • 55
Dlphsn^lfintiisony Iodide 53
Attempted Preparation of Phenyl-£-tolylatibonic
Acid. . . . . . . . . . . . . . . . . . . . . . 56
Preparation of Tr 1 -£-chiorophenylantimony• • . . . . 57
Preparation of Tri-p-ehlorophenylantlmony
Dichloride. • • • • • . . . • • • . • • • • • • 5 8
Preparation of Tris(£-dimethylaminophenyl) ant lmony • 58
Attempted Preparation of Dlphenyl-c*-naphthyl-
antimony • • . . . . . . • • . . . . • • • • . 59
Attested Preparation of Diphenyl-ex'-naphthyl-
antimony from Dlphenylantimony Chloride in
Liquid Ammonia . • * • • • . . . . . . . . . . 60
Preparation of Diphenyl**oC-naphthylantimony from
Dlphenyl&ntimony Iodide in Liquid Ammonia • • 61
Preparation of Diphenyl-ert-naphthylantimony by the
Use of the Grignard Reagent • « • • • • • • • 62
Preparation of Diphenylmea11y1antImony • • • • • • • 63
Preparation of D iphenyl-£-c hi oroph© nylant imony. • • 64
Attempted Preparation of 1) 1 -oC-napht hyl
tolylantimony • • • • • • • • • • 65
Reaction of D iphe nylant imony Chloride with
Hydrazine Hydrate • • « • • • • • • • • • •• 66
Reduction of Triphenylantimony Dichloride with
Hydrazine Hydrate, • • • • • « • • • • * • « • 67
Reduction of Trl-p-tolylantimony bichloride to
R-Sb by Hydrazine Hydrate • • • , , . ....... 67
Reaction of jd-T ol yl a nt imony Dichloride with
Hydrazine Hydrate . . . . . . . . . . . . . . 68
Reaction of n-Butyl lithium with Tr iphenylant imony • 68
Reaction of Tri-j>-tolylant lmony with n-Butyl lithium 69
Reaction of Trl-p-chlorophenylantlmony with
n-Butylllthium . 70
Reaction of Diphenyl-04*naphthylantimony with
n-Butyllithium . . . . . . . . . 70
Reaction of Diph©nylmesitylantImony with
n~Butyllithium . . . . . . . . . . . . . . . . 71
ReactTon of D iphe nyl c hi or ophe nyl ant lmony with
n-Butylllthium . . . . . . . . . . . . . . . . 72
ReactTon of Tetrapbenylgermanium with
n-Butylllthium • • • • • • . » « • . . . . . • 72
ReactTon of tert.-Butyllithlum with Tetra-
phenylgermanium . . . . . . . . . . . . . . . 73
Reaction of TetraphenylallIcon with n-Butylllthium. 73
Reaction of Trlethylbismuth with Triphenylantimony, 73
Reaction of Tri-n-butylbIsmuth with
Triphenylarsenic • • • , . . . • . • • • . . • 74
DISCUSSION . . . . . . . . . . . . . . . . . . . . . . 75
SUMMARY ................. . . . . 85
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LIST OP TABLES
Page
Table Is Reaction of n-Butylllthium with Symmetric al
and Unsymmetrlcal Trlarylantimony Confounds. * 79
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INTRODUCTION
Some of the most urgent needs and desires In organo-
raetallic chemistry call for a wider application In industrial
and synthetic work* The utility of most of the known organo-
metallies has been explored rather extensively* Accordingly,
it appears to be advantageous to have recourse to organ©-
metallic derivatives which are relatively unknown at present*
This group includes compounds of a number of the more common­
ly available metals such as Iron* cobalt* nickel* copper and
others* From the point of view of cost* usable organometalllc
compounds of the more common metals would be the solution to
a number of industrial problems*
The use, particularly in synthesis, of an organometalllc
compound is often restricted to its participation as a reac­
tion intermediate* It Is unnecessary to Isolate the deriva­
tive as such* The Ideal example is the Grlgnard reagent
which can be prepared in a solvent and then used in the same
medium* More difficulties are encountered* however* with the
thermally tins table derivatives* Since the primary reaction*
as well as the secondary reactions which give by-products,
may operate through free radicals, the study of free radicals
in the decomposition of organometalllc compounds is of prime
importance.
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Free radicals are generally considered to be neutral
bodies which participate in reactions per se* These frag­
ments do not possess an electrical charge, but do contain an
impaired electron* As a result of the magnetically non-
compensated electron these bodies are paramagnetic* This fact
serves as a basis for one method of detection of free radicals•
This work considers free radicals to be operating in the
various coupling reactions which take place in the presence of
metallic salts* Thermally unstable organometalllc compounds
can be considered as intermediates * These compounds decompose
to give free radicals which undergo the usual characteristic
reactions*
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