HMX Synthesis by using RFNA/P2O5 as a Novel Nitrolysis System

Article abstract of DOI:10.13005/ojc/340169

A novel and efficient approach for the synthesis of octahydro- 1, 3, 5, 7-tetranitro-1, 3, 5, 7- tetrazocine (HMX) was achieved through nitrolysis of 1, 3, 5, 7-tetracetyl-1, 3, 5, 7-tetraazacyclooctane (TAT) in the presence of red fuming nitric acid (RFNA) and P₂O₅. various parameters such as temperature, concentration of nitrating agent, time and mole ratio of RFNA/P₂O₅ has been investigated to develop the optimum conditions. The good yields, high purities, easy work-up and short reaction times are advantages of this method.

Full text of DOI:10.13005/ojc/340169

ISSN: 0970-020 X
CODEN: OJCHEG
018, Vol. 34, No.(1):
Pg. 576-579
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
2
www.orientjchem.org
(Brief Communication )
HMX Synthesis by using RFNA/P O as a Novel
2
5
Nitrolysis System
1
1
2
KHADIJEH DIDEHBAN , MOHAMMAD ALI ZAREI *, MORTEZA RADFAR
and YADOLLAH BAYAT2
1
Department of Chemistry, Payame Noor University, P.O. Box 19395-3697, Tehran, Iran.
2
Department of Chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3454, Tehran, Iran.
Corresponding author E-mai: ma.zarei51@yahoo.com
http://dx.doi.org/10.13005/ojc/340169
(Received: June 23, 2017; Accepted: October 01, 2017)
ABSTRACT
A novel and efficient approach for the synthesis of octahydro- 1,3,5,7-tetranitro-1,3,5,7-
tetrazocine (HMX) was achieved through nitrolysis of 1,3,5,7-tetracetyl-1,3,5,7-tetraazacyclooctane
(
TAT) in the presence of red fuming nitric acid (RFNA) and P O . various parameters such as
2 5
temperature, concentration of nitrating agent, time and mole ratio of RFNA/P O5 has been
2
investigated to develop the optimum conditions. The good yields, high purities, easy work-up and
short reaction times are advantages of this method.
Keyword: Octogen(Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), Synthesis,P O Nitrolysis.
2
5,
INTRODUCTION
have been reported in the literature, one of the first
methods developed by Bachmann in 1951 but
8
Nitrolysis is one of the key processes in
there are several undesirable features including
slow rate of production, poor yield, large amount of
hazardous wastes and great amount of by-products
such as RDX (hexahydro-1,3,5-trinitro-1,3,5-
triazine) and mixture of cyclic and linear nitramines.
synthetic chemistry and widely used in industry,
nitrolysis process mostly requires concentrated
amounts of nitric acid, great number of the energetic
materials such as HMX are produced by various
1
-5
nitrolysis processes . HMX (1,3,5,7-Tetranitro-
,3,5,7-tetraazacyclooctane), is one of the most
powerful high-melting explosives which is useful
1
In order to improve HMX production other
synthetic approaches involving TAT (1,3,5,7-
tetracetyl-1,3,5,7-tetrazacyclooctane), DADN(1,5-
diacetyl-3,7-dinitro-1,3,5,7-tetrazacyclooctane) or
6
,7
for military and non-military applications . In the
past decades various methods for HMX prepration
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4

ZAREI et al., Orient. J. Chem., Vol. 34(1), 576-579 (2018)
577
9
DANNO (1,5-diacetyl-3-nitro-5-nitroso-1,3,5,7- According to Siele’s works DADN gave a
tetrazacyclooctane) have been proposed, the main better yield in compare to the Bachmann procedure
precursor for these alternative routes is DAPT (3,7- but this synthesis involves use of sulfuric acid and
diacetyl-1,3,5,7-tetraazabicyclo-[3.3.1]-nonane) polyphosphoric acid which are not required in the
which could be easily prepared from hexamine and Bachmann process.
acetic anhydride in good yield.
COCH3
N
NO
N
NO2
N
H COC N
N COCH3
H COC N
N COCH3
3
3
H COC N
N COCH3
3
N
N
N
COCH3
NO2
DANNO
NO
2
TAT
DADN
Fig. 1. main precursors for HMX synthesis
NO2
NO2
N
N
PPA
H COC N
3
N COCH3
O N N
2
N NO2
N
N
NO2
DADN
NO2
HMX
Fig. 2. synthesis of HMX from DADN
TAT is an extremely valuable precursor of
HMX which can be easily prepared by acetylation
of DAPT in presence of acetic anhydride and
EXPERIMENTAL
All starting chemicals were purchased
from commercial suppliers and without further
purification.The melting points are reported without
correction.
o
anhydrous sodium acetate at 110 C in high yield.
Nitrolysis of TAT to HMX involving the
reaction of TAT with a mixture of nitric acid and
o
phosphorus pentoxide at 75 C for 15 min crude
Instruments
HMX is obtained in 75-80% yield with impurities
such as SOLEX (1-acetyl-3,5,7-trinitro-1,3,5,7-
tetrazacyclooctane) which is the main by-product
of this process . In order to improve the yield and
purity of the product in the present work we changed
the condition of the synthesis and replaced the nitric
acid with RFNA, resulted pure product and more
than 95% yield. HMX with high purity plays an
important role in oil well drilling process and some
other important non-military industrial uses.
Melting points were determined on an
Electrothermal 9100 apparatus and were
uncorrected. FTIR spectra were obtained on a
1
Perkin-Elmer infrared spectrometer. H-NMR and
1
3
C-NMR spectra were run on Bruker DRX-300
1
AVANCE spectrometers at 300 MHz for H-NMR, 75
13
MHz for C-NMR. DMSO-d6 was used as solvent. The
purification of HMX was done using preparative HPLC
(column C18, 5μm and mobile phase,MeOH: H O).
2

5
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ZAREI et al., Orient. J. Chem., Vol. 34(1), 576-579 (2018)
General procedure for the Nitrolysis of TAT to
HMX
The reaction (Fig. 3) condition where
optimized by changing time, temperature and mole
ratio of RFNA/P O the results are summarized in
The procedure started by stirring RFNA
2
5,
o
(
30 ml) in 5 C and P O (12 g) added gradually to
2
5
Table. 1.
the reaction media while the temperature was fixed
o
at 5 C, after adding TAT to the solution temperature
According to the results, Low yields of
o
increased to 75 C and the mixture stirred for
HMX were obtain with lower amount of RFNA or
P O and lower ratio of RFNA/P O made an obvious
o
1
5 min. at 75 C. after that the reaction solution was
2
5
2
5
quenched in crushed ice (200 g) and pure HMX
precipitated and filtered, washed with water and
decline in the result of the reaction respectively 62%
and 55%, after finding the optimal molar ratio
influence of time and temperature were examined
which showed that reducing the time of the reaction
to less than 15 min. dropped the yield and
increasing the time didn’t improve the yield of
production.
o
dried to 0.99 g of HMX, yield 95%, m.p. 275 C
1
0
o
1
(
lit. mp 274-276 C), H NMR (DMSO-d , 300 MHz)
6
1
3
δ 6.2 (s, all protons); C NMR (DMSO-d , 75 MHz) δ
6
64 ; the purity was 100% identified on HPLC.
RESULTS AND DISCUSSION
In order to explain the mechanism of this
reaction and the high yield and purity, we can
consider the role of two sources of nitration agents
In this paper we used a novel system for
nitrolysis of TAT to HMX with the highest yield
compared to other works reported in literatures and
the highest purity.
+
(N O , NO ), first source of nitration agents is
2
5
2
O N
2
COCH3
N
N
NO2
N
H COC
RFNA/P O
3
2
5
N
N
O N
2
N
N
o
COCH3
75 C, 15 min
N
NO2
H COC
3
HMX
TAT
Fig. 3. synthesis of HMX from TAT
Table.1: Finding the optimized condition for HMX nitrolysis
o
Entry
RFNA
P O Temperature( C) Time(Min.)
Yield
m.p.
2
5
1
2
3
4
5
6
7
8
9
1
1
1
1
30
30
30
30
20
25
30
30
30
25
30
35
30
0
75
75
75
75
75
75
85
60
75
75
75
75
75
15
15
15
15
15
15
15
15
10
25
25
15
15
X
-
10
14
8
87
88
66
55
62
65
60
65
70
90
67
95
265
273
267
274
275
275
262
272
275
267
265
275
8
10
12
12
12
10
12
14
12
0
1
2
3

ZAREI et al., Orient. J. Chem., Vol. 34(1), 576-579 (2018)
579
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1
P O and nitric acid which produce by-product of the first reaction. This concentrated
2
5
phosphoric acid as a by-product.The second source amounts of nitration agents could turn all of the acetyl
12
o
of producing nitration agents, is N O (in RFNA) at groups onTAT to nitrogen dioxide at 75 C and completes
2
4
presence of the phosphoric acid which is the the reaction to the highest yield and purity.
O N
COCH3
2
HNO + P O
5
3
2
N
N
NO2
H COC
3
N
N
N
N
N O + H PO
O N
2
COCH3
2
4
3
4
N
N
NO2
H COC
3
TAT
HMX
Fig. 4. Two different source of the reagents for TAT nitrolysis
CONCLUSION
reported in literatures which is more than 95% of
HMX per mole of TAT and pure HMX which means
In conclusion, the RFNA/P O mixture is a no by-products such as RDX and SOLEX. short
2
5
powerful and efficient reagent in the ambient time reaction time, excellent yield and purity, easy
and temperature for nitrolysis of TAT to the valuable work-up are among the advantages of this
HMX, therefore this procedure has the highest yield procedure.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
Hua, Q.; Zhiewn, Y.; Chunxu, L. Ultrason. 8.
Sonochem., 2008, 15(4), 326.
Bayat,Y.; Mostafavi, M. M.B.Kor.Chem.Soc., 9.
Bachmann, W.E.;Sheehan, J.C.J.Am.Chem.
Soc., 1949, 71, 1842.
Siele, V. I.; Warman, M.; Leccacorvi, J.;
Hutchinson, R. W.; Motto, R.; Gilbert, E.
Prop.Explos. Pyro., 1981, 6, 67.
Ampleman, G.; Marois, A.; Thiboutot, S.;
Hawari, J.;Greer, C.W.;Godbout, J.;Sunahara,
G. I.; Shen, C. F.; Guiot, S. R. J. Labelled
Compd. Radiopharm., 1999, 42, 1251.
Millar, R. W.; Colclough, M. E.; Golding, P.;
Honey, P. J.; Paul, N. C.; Sanderson, A. J.
Philos.T. Roy. Soc. A., 1992, 339.
2
012, 33, 3552.
Yi, W. B.; Cai, C. Prop. Exp. Pyro., 2009, 34,
61.
1
10.
11.
Zhi, H.Z.;Luo, J.;Feng, G.A.;Lv, C.X.Chinese.
Chem. Lett., 2009, 20, 379.
Lukasavage, W. J.; Behrmann, L. A.; Voreck,
W. E. WO Patent 20000733285., 2000.
Greenfield, M.; Guo, Y. Q.; Bernstein, E. R.
Chem. Phys. Lett., 2006, 430, 277.
Siele, V. I.; Gilbert, E. E. US Patent 3939148., 12.
976.
Olah, G. A.; Malhotra, R.; Narang, S. C.
“Nitration: methods and mechanisms”., 1989.
1