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LD3907
*£L Leshin, Richard, l92l|.-
The reaction betr;ecn aliphatic nitro
compounds and isocyanates.
50p. tables.
Thesis (Ph.D.) - N.Y.U., Graduate
School, 1952. C93098
Bibliography :p.Ij.5-Jj.6.
1.Aliphatic compounds. 2.nitro
compounds. 3.Isocyanates. I|.-Dis3erta-
tions, Academic - K.Y.U. - 1952.
Shell Usi
Xerox University Microfilms, Ann Arbor, Michigan 48106
THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED.
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LIBRARY OF
UW7 YT-r.r. TNTVTITTY
THE REACTION BETWEEN
ALIPHATIC NITRO COMPOUNDS AND ISOCYANATES
Richard Leshin
A dissertation in the
Department of Chemistry
submitted to the faculty of the
Graduate School of Arts and Science of New York University
in partial fulfillment of the requirements
for the degree of
Doctor of Philosophy
Kovomhor 30| 1951
( I ^ S'?*
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This thesis is dedicated
to my wife and my parents.
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Aeknowle dgement
The author is deeply indebted to
Professor Robert N. Boyd for his
invaluable counsel and guidance
throughout the course of this
■work.
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TABLE OF CONTENTS
Subject Page
INTRODUCTION AND SCOPE .......................... 1
THE KNOWN CONDENSATIONS INVOLVING- THE
LABILITY OF THE ct-HYDROGEN ATOMS OF PRIMARY
AND SECONDARY ALIPHATIC NITRO COMPOUNDS ......... 2
The Aldol Condensation ..................... 2
The Michael Condensation....................3
THE DEVELOPMENT OF THE REACTION BETWEEN
ALIPHATIC NITRO COMPOUNDS AND ISOCYANATES .... 6
History .................................. 6
The Present Investigation.................12
EXPERIMENTAL............................; ... 15
Preparation of the Starting Material .... 15
Attempted Condensations .................21
Preparation of New Compounds...............29
TABLE I - NxSubstituted c(-Nitroacetamides .... 40
TABLE II - N-Substituted d-Carbethoxy-
ofc-Nitroacetamides.........................41
SUMMARY........................................42
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TABLE OF CONTENTS (Cont’d)
Subject Page
ACKNOWLEDGEMENTS...............................44
BIBLIOGRAPHY...................................45
APPENDIX.......................................47
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- 1 -
INTRODUCTION AND SCOPS
The chemistry of the aliphatic nitro compounds
had its start in 1872, when Meyer and Stuber (25)
prepared nitropentane by the action of silver nitrite
on amyl iodide. When it was discovered in 1895 that
primary and secondary nitroparaffins would react with
aldehydes in a typical aldol condensation (15)» new
impetus was given to the development of reactions
involving the activity of the labile <tf-hydrogen atoms
in RCH2NO2 and R2CHNO2.
In spite of the difficulty of preparing the
nitroparaffins in quantity, much of the fundamental
work in the field of aliphatic nitro chemistry was
done in the first quarter of this century. In 1934,
the vapor-phase nitration process was patented (13)*
This process made use of natural gas and petroleum,
and cheap nitric acid or nitrogen dioxide derived
from the oxidation of synthetic ammonia. It was ini
tiated commercially in 1940 (10), whereupon the nitro
paraff ins became available, cheaply and in quantity,
and thus opened up what was a veritable new field of
organic chemistry.
With the dual purpose of extending the range of
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- 2 -
condensations of nitro compounds, and of producing
ofc-nitrocarboxylic acid derivatives, a study of the
various known condensations of aliphatic nitro com
pounds was made. The results of this study indic
ated that the reaction between isocyanates and ali
phatic nitro compounds should afford an answer to
both purposes. Accordingly, a series of experi
ments were undertaken to investigate the possibil
ities of this reaction.
THE KNOWN CONDENSATIONS INVOLVING THE LABILITY OF
THE flt-HYDF.OGEN ATOMS OF PRIMARY AND SECONDARY ALI
PHATIC NITRO COMPOUNDS.
The Aldol Condensation
The reaction between nitroparaff ins and alde
hydes was discovered by L. Henry (15)• It is a
base-catalyzed reaction, the general equation for
which may be written as:-
R* H
RR*CKN02+ R"CHO toss > R-0--J-R"
N02 OH
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- 3
■When R’ = H,
H-9-OH
R-9-NO2
H-C-OH
For nitromethane, where R and R* = H, a third mole
cule of formaldehyde will condense to give:-
H H-C-OH
CH3N02+ 3HCH0 baae-» HO-C1 Ct -N0o2
H H-C-OH
t
H
Nitromethane and formaldehyde condense most
readily, the rate with other nltroalkanes and alde
hydes decreasing as the respective members of the
series increase in size. A rate study of this re
action has recently been made at this University by
Pader (29).
The Michael Condensation
The Michael Condensation is the base-catalyzed
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