A STUDY OF THE PREPARATION AND REACTIONS OF NITRAMIDE

128 Pages·04.6 MB·English

by  TILLSON, HENRY CHARLES

The Pennsylvania State College
The Graduate Sehool
/
Department of Chemistry
A STUDY
OP
THE PREPARATION
AND
REACTIONS OP NITRAMIDE
A Thesis
by
Henry Charles Tillson
Submitted in partial fulfillment
of the requirements
for the degree of
DOCTOR OP PHILOSOPHY
January 1951
Approved:
B V
' / ' • A
Departae
JAN 13 1951
Head, DepaHfflequ^T ChemlsEiy
INDEX
Page
INTRODUCTION.......................................... * 1
HISTORICAL........................ ............ 2
I. PREPARATION OP NITRAMIDE ..................... 2
A. Method of Thiele and Lachman 2
1. Preparation of Nitrourethane ......... 2
2. Preparation of Ammonium Nitrourethane.... 3
3. Preparation of Potassium Nitrocarbamate• • U
U, Preparation of Nitramide ...... U
B. Other Methods for the Preparation of
Nitramide ......... 7
C. Unsuccessful Attempts to Prepare Nitramide... 8
II. THE REACTIONS OF NITRAMIDE ....... 9
A. The Formation of Salts ........... 9
B. Reduction.............................. 10
C« Reaction with Diasomethane ..... 10
D. Reaction with Silver Cyanate ........ 11
E. Reaction with Aldehydes .............. 11
III. DECOMPOSITION OF NITRAMIDE ............. 1$
IV. STRUCTURE OF NITRAMIDE....................... 19
V* PROPERTIES OF NITRAMIDE.................. 20
DISCUSSION............ 23
I. NITRAMIDE ............................... 23
.'353459
Pag©
II. REACTIONS OF NITRAMIDE ................ . .... 26
Summary of Reactions ................... 30
III. ATTEMPTS TO FORM NITRAMIDE SALTS ............. 33
IV. OTHER ATTEMPTS TO PREPARE ALKYLIDENEDINITRAMINES. 3h
V. PROPERTIES OF NITRAMINE COMPOUNDS .............
EXPERIMENTAL........................................ Ul
I. PREPARATION OF NITRAMIDE ...... •.... WL
A. Preparation of Ammonium Nitrourethane..... 1*1
B. Preparation of Potassium Nitrocarbamate • •••• 51
C• Preparation of Nitramide...... $h
II. PROPERTIES OF NITRAMIDE ................... 60
A. Melting Point ........... 60
B» Stability ...... 60
C. Solubility.............. 61
D♦ Crystal Morphology .................. 61
E. Optical Properties .................. 62
F. Fusion Data ..... 62
III. REACTIONS OF NITRAMIDE WITH ALDEHYDES......... 6k
A. Formaldehyde ...................... 61*
B. Furfural...... ..................... . 6$
C. Acetaldehyde................... 66
D. Propionaldehyds ....................... 70
E. Butyraldehyde........ 71
F* Isobutyraldehyde ............ 72
G. Chloroace taldehyde ................ 71*
Pag©
IV. ATTEMPTED REACTIONS OF NITRAMIDE WITH AIDEHXDES . . . . 75
A. Glyoxal............................... 75
B. Benz aldehyde ......••••••••.....................75
C. Cinnamic Aldehyde ..... .................. . 76
Di Crotonaldehyde.............. 76
E. Heptaldehyde .............................. 77
V. ATTEMPTED SALT FORMATION WITH NITRAMIDE 78
A. Pyridine .................................. 78
B. Amnonia.......... 78
C. Methyl Amine .............. 79
D. Aniline ............... .................. . • 79
VI. RETiCTIONS OF NITRAMIDE WITH VARIOUS REAGENTS...... 81
A. Acetonitrile .............................. 81
B. Acrylonitrile .............................. 82
C. Ethylene Oxide ............................. 82
D« Acetyl Chloride .... 83
E. Acetic Anhydride ..... 83
VII. PROPERTIES OF THE PSC COMPOUNDS
(ALKYL IDENEDINITRAMINES) ............... 8U
A. PSC-1 (ethylidenedinitramine) ........... 81*
B. PSC-U (propylidenedinitramine) ....... 87
C. PSC-2 (butylidenedinitramine) ...... 90
D. PSG-6 (isobutylidenedinitramine) ..... 9U
E. PSG-$ (chloroethylidenedinitramine) ......... 99
Page
VIII. ALKYLIDENED1URETHANES .............». 100
A. Preparation of Ethylidenediure thane .... 100
B. Preparation of Butylidenediurethane ...*•••. 101
C. Attempts to Nitrate Alkylidenediurethanes .» 102
IX. MISCELLANEOUS REACTIONS ....................... 10k
A* Preparation of Nitrourethane .......... lOi;
B. attempted Condensation of Nitrourethane and
Butyraldehyde ....................... 10k
C. Preparation of Me thylnitramine ......... 10£
D.a ttempted Reaction of Me t hyInitramine ...... 106
E. Ultraviolet Absolution Spectra of
Metkylnitrajnine .................... 106
F* Preparation of Sodium
Methylenediisonitramine ........... • 107
G. Ultraviolet Absorption Spectra of Sodium
Ilethylenediisonitramine 108
SUMMARY.......................................... 110
APPENDIX....... .............................. Ill
BIBLIOGRAPHY............. ....................... . 120
ACKNOWLEDGEMENT
The author sincerely thanks Dr. C, I. Noll for his guidance
and encouragement which were so generously offered throughout
this investigation.
Appreciation is due the Navy Department, Bureau of
Ordnance for the financial support of this investigation.
1
INTRODUCTION
Nitramide has played a part in the development of the
structures of the diazotates and in the development of the
Bronsted theory of acid and bases* However, due to its unstable
nature very little work has been done on its chemical reactions
other than decomposition studies*
The purpose of this work was to improve the method of
preparing nitramide, and to find out if nitramide entered into
any general reactions other than decomposition*
2
HISTORICAL
I. PREPARATION OF NITRAMIDE
The preparation of nitramide was first reported ty Thiele
and Laohman^® in I89U. The main steps in the procedure rtiay be
illustrated hy the following equations:
NHgCOOCgH^ — » N02NHC00C2H£ — * NHj^ (NOgNCOOCgH^)”"
NH^ (N02NC00C2% ) * W K+(NO2NC0OjV NH2N02
Variations of this procedure have been used by most 'workers sinee
that time* The changes have been mainly in improving the method,
rather than in devising fundamentally different procedures*
Because this method is the most important one, the development of
the variations will be described in considerable detail* The
reason for giving such a complete description of the method for
preparing nitramide is to help other interested workers to see
ways of improving the procedure, if possible. While the method
is satisfactory, it becomes cumbersome and tedious if large amounts
of amide are desired* Consideration will be given to all the
methods which have been found in literature*
A* Method of Thiele and Lachman
1* Preparation of Nitrourethane
1*9
Thiele and Lachman first prepared nitrourethane
by nitrating urethane with potassium nitrate and sulfuric acid*
3
The urethane was dissolved in concentrated sulfuric acid* After
the addition of the theoretical amount of potassium nitrate, the
reaction mixture was poured on ice* Host of the acid was
neutralized, and the solution was extracted with ether* On the
addition of ammonia gas to the ether solution, the ammonium salt1
of nitrourethane precipitated. It melted at 183°C* The ammonium
salt was decomposed with hydrochloric acid, and the solution was
extracted with ether* On evaporation of the ether extract, the
nitrourethane remained as a crystalline mass* On re crystalli­
zation from ligroin, it melted at 6U°C* No yield was reported*
While nitramide can be prepared from nitrourethane by alka­
line hydrolysis and decomposition of the potassium salt, it was
found^® unnecessary to isolate the nitrourethane since the
ammonium salt of nitrourethane could be used equally well*
2* Preparation of Ammonium Nitrourethane
Theile and Lachman in a later publication**0
described the preparation of nitramide in more detail. This
section and the two following are free translations of ap­
propriate sections of this paper**0.
To 500 cc. of well cooled concentrated, pure (traces of
nitrous acid loner the yield sharply) sulfuric acid there was
added with stirring 100 g. (1*12 moles) of pulverized urethane*
After the urethane was all dissolved, and the temperature was
h
below 0°C., 110 g* (1*21 moles) of ethyl nitrate was added* The
cooling was regulated so that the temperature dropped to -5°C.
within ten minutesj the lower the temperature the better* About
forty five minutes after this addition, the reaction mixture was
poured with stirring onto 1*5 to 2 kg* of ice* The aqueous so­
lution was extracted four times with 500 cc. portions of ether*
The dried ether solution was diluted to 3 or U liters, and the
ammonium salt was precipitated by adding a stream of dry ammonia
gas* The precipitated ammonium salt was filtered and air dried*
The yield was 90 to 100 g* (53 to 5950.
3* Preparation of Potassium Nitrocarbamate
A 25 g. (0.16 moles) a ample of ammonium nitro­
urethane was dissolved in 100 cc. of water cooled to 0°C. To this
solution was added 750 6o* of alcoholic potassium hydroxide (250 g*
potassium hydroxide per liter of solution) cooled to 0°C. j the
temperature rose to 7°G« The reaction mixture, placed in an ice
bath, was stirred to avoid local warming which caused the- evo­
lution of a gas* During this time the solution became filled with
fine white needles* After about an hour the precipitate was
rapidly filtered, washed well with alcohol, and dried in a desic­
cator* The yield was 20 to 25 g* (69 to 86£).
U* Preparation of Nitramide
Two preparations of nitramide were described*