Table Of ContentCYCLOPARAFFINS VIII
THE PREPARATION OP TWO
1-ACYL-2-NITR0-2,3,3-TRIMETHYLCYCLOPROPANES
AND THEIR REACTION WITH ALKALIS
A Theaia
Submitted to the Graduate Faculty
of the
University of Minnesota
by
William Lawrence Kohlhase
In Partial Fulfillment of the Requirements,
for the Degree of
Doctor of Philosophy
April, 1952
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ACKNOWLEDGEMENT
The author v/ishes to express his appreciation
to Profes&or Lee Irvin Smith for the assistance and
guidance received throughout the research and in the
preparation of this manuscript*
Grateful thanks are due to the United States of
America for the aid reoeived under the provisions of
the Servicemen's Readjustment Act of 1944, Public
*
.
No. 346, 78th Congress.
The author is deeply indebted to hi3 wife,
Margaret, for the aid which she rendered in the
preparation of this thesis. Her companionship and
understanding throughout the period of the author's
graduate studies are most appreciated.
id'd
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TABLE OF CONTENTS
Page
Introduction. •• • 1
The Chemistry o f Cyclopropenes..................... 2
Background and Statement of the Problem........... 28
Discuasion of R e s u l t s ................................. 40
The Synthesis and Reactions of 1-Benzoyl-
2-nitro-2 ,3 ,3-trimethylcyclopropano......... 40
The Synthesis and Reactions of 1-Acetyl-
2-nitro-2 ,3,3-trime thylcyclopropane.......... 55
Theoretical Aspects of the Problem................. 62
Experimental.......... 70
)9,^-Dimethyiacrylic Acid........................ 71
^,^-Dimethyiacrylyl Chloride.................... 72
Iaopropylldoneace tophenone (XCIV).............. 72
^,p-Dimethyl-^-nifcrovalerophenone (XCIX)........ 75
y-Bromo-^,^— dime tiny 1-V-nitrovalerophenone (C).. 77
1-Benzoyl-B— ni tro— 2, 3 ,3-trimethylcyclo-
propane ( Cl). . - ....... 79
Action of Nitrogenous Bases on Cl.............. 82
Action of Sodium Methoxide upon 1-Benzoyl-
2-nitro-2,3,3 - trimethylcyclopropane (Cl).... 83
Formation o f 3,4-DImethyl-l-phenyl-2,5-
pontadienone (CXIII)......................... 83
Effect of Temperature on the Reaction
between C l and Sodium Methoxide...............91
Action of Potassium Hydroxide upon Cl........... 92
Ozonolyais o f 3,4—Dime thyl-l-phenyl-
2,5-penta.dienone (CXIII)......... 93
Action of Potassium Permanganate .upon 3,4-
Diraethyl— l-phenyl-2,5-pentadienone (CXIII).. 99
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Reaction between 3,4-Dimethyl-l-phenyl-
2,5-pontadienone (CXIII) and Maleic
Anhydride 103
4,4-Dimethyl-5-nitro-2-hexanone (CXXV)........ 104
Effect of Catalyata other than Diethylamine
upon the Reaction between Nitroethane
and Meaityl Oxide............................ 107
a) Sodium Methoxide..................... 107
b) Piperidine............................ 110
c) Triton B .............................. 112
d) Calcium Hydride....................... 113
5-Bromo-4,4-dimethyl-5-nltro-2-hexanone
(CXXVII)...................................... 115
1-Acetyl-2-nitro-2,3,3-trimethylcyclo
propane (CXXVIII)............................ 116
Preparation of l-Acetyl-2-nitro-2,3,3-tri-
methylcyclopropane (CXXVIII) from Meaityl
Oxide and Nitroethane without Isolating-
Intermedia tea................................ 119
2-Nitro-2,3,3-trimethyl-l-cyclopropane-
carbonylmothylpyridinium Iodide (CXXXIII).. 120
Reaction between Benzaldehyde and 1-Acetyl-
2-nitro-2,3,3-trimethylcyclopropane
(CXXVIII)............................... 122
2-Ni tro-2,3,3-trime thylcyclopropyl
m-Nitroa tyryl Ketone (CXXXI)................ 123
2-Nitro-2,3,3-trimethylcyclopropyl
Cinnamylidenemethyl Ketone (CXXXII)........ 124
Action of Sodium Methoxide upon 1-Acetyl-
2-nitro-2,3,3-trimethylcyclopropane (CXXVIII) 125
Action of Sodium Hydroxide upon 1-Acetyl-
2-nitro-2,3,3-trimethylcyclopropane
(CXXVIII)................................... 137
Calibration Curve for Melting-point Apparatus. 139
Data for Ultra-Violet Spectra................. 140
Graphs of Ultra-Violet Spectra................ 148
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Page
v
Graphs of Infra-Red Spectra.................... 155
Appendix A.......................................... 175
Experiments Directed toward the Synthesis of
Certain Cyclobutanes............................ 175
Introduction....................................... 175
Experimental..............................*........ 154
Propargylaldehyde Diethylacetal................ 184
Sodium Benzenesulfinate........................ 184
The Reaction between Propai’gylaldohyde
Diethylacetal and Benzenesulfinic Acid..... 185
Propargylaldehyde............................... 187
The Reaction between Propargylaldehyde and
Benzenesulfinic Acid..... . .................. 188
The Reaction between Sodium Benzenesulfinate
and Acrolein Dibromide...................... 194
The Reaction between Thiophenol and Acrolein
Dibrornide . Formation of Propargylaldehyde
Diphenylmercaptal (CLXX)....... 198
^-(Phenylmercapto)acrolein (CL)................ 200
Attempted Addition of Nitromethane to
|5~( Phenylmercapto )acroleln (CL)............. 202
Ultra-Violet Spectra............................ 205
Infra-Red Spectrum of the 2,4-Dinitrophenyl-
hydrazone of Propargylaldehyde.-.'............ '208
Appendix B ......................................... 209
The Reaction between LItromethane and
Acrolein..................................... 209
3-Isopropylacetylacetone and Some of
Its Derivatives.............................. 211
Bibliography....................................... 214
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INTRODUCTION
This thesis describes the preparation of two
nitrocyclopropyl ketones in which the only hydrogen
atom on the ring is attached to the carbon atom alpha
to the carbonyl group. Their behavior toward alkaline
reagents has been investigated and the results have
been correlated with earlier mechanisms proposed for
the reaction between alkali and nitrocyclopropyl
Jsetones. A complete review of the chemistry of cyclo
propane s is presented, since this type of compound
may be involved in the reaction of certain
nitrocyclopropyl ketones with alkali.
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THE CHEMISTRY OP CYCLOPROPENES
Only two hydrocarbons in this series are known,
cyclopropene itself and methylcyclopropene. Preundler
(1) was the first to claim the preparation of cyclo
propane; he thought it to be one of the constituents of
the gaseous by-products obtained in the preparation of
furan via the pyrolysis of alkaline earth furoates:
I U + C D + C 0*
q S'COOM
Although Preundler reported that the hydrocarbon gave no
test for an acetylene, Hurd and Pilgrim (2), who repeated
the work, found that the gaseous hydrocarbon was actually
a mixture containing about two-thirds of methylacetyleno•
The remainder could not be positively identified.
However, a comparison of the physical properties of the
dibromide and tetrabromide obtained from this non
ace tylenic portion with the values for the compounds
derived from the cyclopropone prepared by Schlatter (3)
shows that they must be derived from cyclopropene. In
any case, the yield of cyclopropene in the pyrolysis of
furoates is too low (0.2$) for preparative purposes.
The method of choice for preparing cyclopropene
involves the application to cyclopropylamine of the
Hofmann degradation of amines. This route, was first
reported by Demjanow and Dojarenko (4) who .claimed
j-f'
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3
yields of C3H4 hydrocarbons up to 6($. The pyrolysis of
trimethyl-cyclopropylammonium hydroxide (formed In the
usual manner) was carried out on platinized clay chips
at about 300°: ;
Methylacetylene amounted to about ten percent of the
hydrocarbons produced and was removed by washing the
mixture with ammoniacal cuprous chloride,
Schlatter (3) made a very detailed study of the
synthesis of cyclopropene; he used an eleven step process
in which glycerol was the starting material. He found
that the be3t yield of cyclopropene 4(45^) was obtained
by carrying out the pyrolysis of the quaternary hydroxide
at 320-330° on platinized asbestos.
Cyclopropene has a boiling-point of -36° at atmos
pheric pressure and cannot be stored without decomposition,
even at the temperature of Dry-ice. The addition of
bromine is a very vigorous reaction; the resulting
stable dibromide melts at 0°. Although the Russian
workers reported that the dibromide was readily converted
back to cyclopropene by action of zinc dust in hot Q0%
ethanol, Schlatter reported that cyclopropane was the
major product and that no cyclopropene could be found.
Demjanow and Dojarenko attempted to.prepare cyclopropene
glycol by action of cold dilute permanganate upon cyclo
propene, but the only products were those resulting from
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ring cleavagej formic acid was the only compound identified
8r 7
Zn ^
80 % EtOH
HCOOH + unidentified volatile
aldehydes
It ha3 been suggested that cyclopropene may be the
primary product of the electrolysis of salts of cl3-
cyclopropane-1,2-dicarboxylic acid, a reaction analogous
to the formation of ethylene from succinic acid:
CHx-COOH jj'Ht
CHz—CooH CHj.
C OOH
When Pichter and Spiogelberg (5) carried out the elec
trolysis, they obtained a hydrocarbon (C3II4) which they
concluded was allene; the identification wa3 made on the
basis of the melting-point of the tetrabromide• In
view of the known isomerization of cyclopropane to
propylene at room temperature in the presence of platinum
black, it was considered possible that the primary product
of the electrolysis was cyclopropene, which could then
isomerize at the platinum anode to the observed allene.
Methylcyclopropene, along with isobutylene, was
prepared by Merezhkovskii (6) from 1,2,3-tribromoiso-
butane via the following sequence 1
ifi
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?' 8r
CHt CH*
The presence of the methylcyclopropene In the mixture waa
indicated by the formation of butadiene by passage of the
products over hot alumina; more definite proof was ob-
tained by the production of acetoacetic acid upon oxidation
of the mixture with dilute aqueous permanganate.
One of the three products of the action of phos
phorous tribromide upon tetramethylbutlnediol is believed
to be l-bromo-2-[j2-(2-bromopropyl)] -3,3-dlmethylcyclo-
propene (7):
ch
No cyclopropenemonocarboxylic acids are known.
Two instances of the transient existence of such an acid
are recorded. The thermal evolution of carbon dioxide
from l,2-diphenylcyclopropene-3,3-dicarboxylic acid (I)
was observed by Darling and Spanagel (8) to give the
lactone II. This presumably involved a monocarboxyllc
acid intermediate.
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