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Bibliographic Information
Preparation of 1,3,5-trinitro-1,3,5-triazacyclohexane. Dimun, Milan; Truchlik, Stefan;
Kabatova, Viera; Zeman, Svatopluk. (Czech.). Czech. (1987), 3 pp. CODEN: CZXXA9
CS 235559 B1 19870215 Patent written in Slovak. Application: CS 83-4167 19830609.
CAN 109:190456 AN 1988:590456 CAPLUS (Copyright 2002 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
CS 235559 B1 19850515 CS 1983-4167 19830609
Abstract
The yield of the title compd. (I), produced by nitrolysis of hexamethylenetetramine (II),
and the safety of the process, increased significantly in the presence of urea nitrate (III).
Thus, treating 710 parts 96.1% HNO3 at 15-17 with 100 parts II contg. 0.7-1% III,
stirring the mixt. 20 min at 18-19, pouring it into 3000 parts H2O at 55-60, and filtering
the sepd. product gave 74.2-74.8% I, vs. 70.2% obtained in the absence of III.
Bibliographic Information
Process for RDX manufacture. Zeman, Svatopluk; Dimun, Milan; Truchlik, Stefan;
Kabatova, Viera. (Czech.). Czech. (1987), 3 pp. CODEN: CZXXA9 CS 235560 B1
19870215 Patent written in Slovak. Application: CS 83-4168 19830609. CAN 108:78258
AN 1988:78258 CAPLUS (Copyright 2002 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
CS 235560 B1 19850515 CS 1983-4168 19830609
Abstract
Nitrolysis of hexamethylenetetramine (I) in the presence of 0.7-1% dicyan diamide (II)
gives RDX in 72.5-72.8% yield and increased purity. A mixt. of I and II was added with
stirring to a .apprx.7-fold excess of 96.1% HNO3 at 9-17, kept 25 min, poured into
water at 55-60, stirred, filtered, and dried for 3 h at 90.

Bibliographic Information
A study on condensation of ammonium nitrate in the process of hexamine nitrolysis. Yao,
Qizheng; Zhang, Yujian. Dep. Chem. Eng., East China Inst. Technol., Nanjing, Peop.
Rep. China. Proc. Int. Pyrotech. Semin. (1991), 17th(Vol. 1), 244-8. CODEN: PPYSD7
ISSN: 0270-1898. Journal written in English. CAN 116:177204 AN 1992:177204
CAPLUS (Copyright 2002 ACS)
Abstract
In the manuf.of RDX by nitrolysis-nitration of hexamine, results reported by G. F.
Wright (Can J. Res., 1949, 27B, 520-594), that a 2nd mole of RDX forms by
condensation of NH4NO3 with HCHO (from nitrolysis fragments), are unconvincing,
in view of the ability of ammonium salts to condense with nitramines and HCHO
under similar conditions. Instead, it is proposed that NH4NO3 takes part in condensation
reactions via its dehydrated intermediate (or analog), nitroamide, which then reacts with
HCHO and methylenenitramine to form RDX. A possible mechanism for the formation
of nitroamide involves reaction of NH4NO3 with N oxides (specifically, NO, N2O3, or
NO2), formed under nitration conditions in the presence of a dehydrating agent
Bibliographic Information
Study on the nitrolysis of hexamethylenetetramine by NMR-spectrometry. IV. A novel
mechanism of the formation of RDX from HA. Fang, Zhijie; Wang, Shaofang; Li,
Fuping. Inst. Chemical Eng., Nanjing Univ. Sci. Technology, Jiangsu, Peop. Rep. China.
Int. Annu. Conf. ICT (1996), 27th(Energetic Materials), 89.1-89.7. CODEN: IACIEQ
Journal written in English. CAN 125:172518 AN 1996:514567 CAPLUS (Copyright
2002 ACS)
Abstract
The mechanisms of the nitrolysis of hexamethylenetetramine (hexamine or HA) with
nitric acid and with the mist. of nitric acid and ammonium nitrate to form 1,3,5-trinitro1,3,5-triazacyclhexane (hexogen or RDX) were studied by NMR tracing. It was found
that HA immediately disappeared, while RDX was formed gradually, which indicates the
formation of some intermediates in the HA nitrolysis to give RDX. The chem. shift of the
peaks in the 1H and 13C NMR tracing spectra disagreed with the possible cyclicstructure intermediates proposed by G. F. Wright (1969) and co-workers . Comparison
of the 13C NMR spectra showed that the nitrolysis fragments in K process can be used to
form RDX. Based on the results, structures of intermediates were proposed. All the
evidences mentioned above suggested a novel mechanism of the formation of RDX form
HA, i.e., the nitrolysis of HA first gives some open-chain methylenenitramine
intermediates, and the condensation of the latter gives RDX under certain conditions.

Bibliographic Information
Study on the nitrolysis of hexamethylenetetramine by NMR spectrometry. Part 2. Some
new evidence of the intermediate of HOCH2NHNO2 as a possible precursor to RDX.
Fang, Zhi Jie; Chen, Li; Wang, Shao Fang; Chen, Ju; Li, Fu Ping. Institute Chemical
Engineering, University Science Technology, Nanjing, Peop. Rep. China. Propellants,
Explos., Pyrotech. (1997), 22(2), 78-80. CODEN: PEPYD5 ISSN: 0721-3115. Journal
written in English. CAN 127:83507 AN 1997:332267 CAPLUS (Copyright 2002 ACS)
Abstract
The RDX yield from nitrolysis of hexamethylenetetramine (HA) together with
methylenedinitramine (MDNA) in 90% HNO3 was greater than 100%. MDNA decompd.
completely in 90% HNO3, forming O(CH2ONO2)2, whereas in HNO3-NH4NO3
system, the decompd. fragments of MDNA condensed to form RDX. Based on a
comparison of the exptl. results to the 1H-NMR spectra obtained by following the
decompn. reaction of MDNA with HNO3, the intermediate, HOCH2NHNO2, was
postulated as one of the possible precursors to RDX both in Hale and in K process.

Bibliographic Information
Unusual behavior of 1-acetoxy-2,4,6-trinitro-2,4,6-triaza-8-nitroxyoctane in the presence
of sulfuric acid. Gafarov, A. N.; Punegova, L. N.; Marchenko, G. A.; Novikov, S. S.
USSR. Zh. Org. Khim. (1980), 16(8), 1774-5. CODEN: ZORKAE ISSN: 0514-7492.
Journal written in Russian. CAN 94:65633 AN 1981:65633 CAPLUS (Copyright 2002
ACS)
Abstract
Treatment of the title compd. with 88% H2SO4 at 0 for 30 min gave 73%
trinitrotriazacyclohexane I; increasing the temp. to 5 increased the yield of I to 86%.