Nitration hexamethylenetetramine

Hexamethylenetetramine Nitrates. The following nitrates were reported to have been prepd by various investigators ... 

Cyclonite was first prepared by Lenze [1], The method of manufacture by the nitration of hexamethylenetetramine nitrate with nitric acid is described in Henning s patent [2] of 1899. 

Both the 7-formyl compoimd and its 7-methyl analogue are readily methylated with methyl sulfate to give the 5-methyl derivatives." Similarly the 7-methyl compound has been acetylated to form the 5-acetyl-7-formyl compound. Although Vilsmeier formylation of the parent ring system was unsuccessful, the 7-formyl derivative was obtained using hexamethylenetetramine. Nitration and bromination both resulted in monosubstitution, and the products have been tentatively assigned as the... 

Acid—Base Chemistry. Acetic acid dissociates in water, pK = 4.76 at 25°C. It is a mild acid which can be used for analysis of bases too weak to detect in water (26). It readily neutralizes the ordinary hydroxides of the alkaU metals and the alkaline earths to form the corresponding acetates. When the cmde material pyroligneous acid is neutralized with limestone or magnesia the commercial acetate of lime or acetate of magnesia is obtained (7). Acetic acid accepts protons only from the strongest acids such as nitric acid and sulfuric acid. Other acids exhibit very powerful, superacid properties in acetic acid solutions and are thus useful catalysts for esterifications of olefins and alcohols (27). Nitrations conducted in acetic acid solvent are effected because of the formation of the nitronium ion, NO Hexamethylenetetramine [100-97-0] may be nitrated in acetic acid solvent to yield the explosive cycl o trim ethyl en etrin itram in e [121 -82-4] also known as cyclonit or RDX. 

Acetic anhydride and acetic acid increase the solubiUty of the two phases in each other, and they are employed for the commercial N-nitration of hexamethylenetetramine [100-97-0] (11) to form cyclotrimethylenetrinitramine [121-82-4] (RDX), (CH2)3(NN02)3. Renewed consideration has been given to replacing H2SO4 with an improved soHd catalyst to reduce the environmental problems of disposal or reconcentration of the waste acid and to increase production of desired nitrated isomers. For example, a catalyst with suitable pore size might increase the production of 4-MNT and reduce that of 3-MNT when toluene is nitrated. 

The nitration of hexamethylenetetramine, which contains the grouping CH2N—CH 2—... 

Tracer Studies on the Nitro lysis of Hexamine to RDX and HMX. The formation of RDX and/or HMX molecules from the nitration or nitrolysis of Hexamethylenetetramine (Hexamine) is a complex process and has been postulated to take place via two separate paths. One involves the selective cleavage of the Hexamine molecule to the appropriate cyclic nitramine (RDX, HMX or both) depending on the specific... 

It is made by the nitration of hexamine (hexamethylenetetramine), itself prepared from formaldehyde and ammonia. Hexamine was originally nitrated with a large excess of concentrated nitric acid at temperatures below 30°C and the product recovered by adding the reaction liquor to an excess of chilled water. Later the yield was improved by adding ammonium nitrate to the reaction as this reacts with the liberated formaldehyde. A much-used process converts the hexamine first to its dinitrate, which is then reacted with ammonium nitrate, nitric acid and acetic anhydride (the last reagent being re-formed from the product by use... 

Acetic acid, Acetic anhydride, Ammonium nitrate, Nitric acid See Nitric acid Acetic anhydride, Hexamethylenetetramine acetate... 

Cotton reacts with nitric acid to form a polymeric explosive material, nitrocellulose. Nitric acid reacts with hexamethylenetetramine, ammonium nitrate, and acetic anhydride to form cyclotrimethylenetrinitramine, a high explosive known as cyclonite, used to make plastic bombs ... 

It is reported that the compd is formed by the reaction of acetaldehyde-ammonia ammonia (Ref 1). This reaction yielded a max of 87% gum from which the separation of not more than 3% of Hexaethylidenetetramine was possible. Nitration attempt of the product was not considered practicable. The above reaction is analogous to the hexamethylenetetramine from which RDX is prepd by... 

Hexamethylenetetramine Explosives. Several explosive compositions containing hexamine in admixtures with oxidants or as chromium, copper nitrate, perchlorate, peroxide comps are known. Several hexamine/oxidant mixtures have been patented as explosive propellant compositions ... 

Methylamine occurs in herring brine 2 in crude methyl alcohol from wood distillation,3 and in the products obtained by the dry distillation of beet molasses residues.4 It has been prepared synthetically by the action of alkali on methyl cyanate or iso-cyanurate 5 by the action of ammonia on methyl iodide,6 methyl chloride,7 methyl nitrate,8 or dimethyl sulfate 9 by the action of methyl alcohol on ammonium chloride,10 on the addition compound between zinc chloride and ammonia,11 or on phos-pham 12 by the action of bromine and alkali on acetamide 13 by the action of sodamide on methyl iodide 14 by the reduction of chloropicrin,15 of hydrocyanic or of ferrocyanic acid,16 of hexamethylenetetramine,17 of nitromethane,18 or of methyl nitrite 19 by the action of formaldehyde on ammonium chloride.20... 

Hexamethylenetetramine, Citric acid. Hydrogen peroxide Nitric acid. Phosphorus pentoxide, Solex Nitric acid. Ammonium nitrate. Paraformaldehyde, Hexamine, Acetone, Acetic acid. Acetic anhydride Diethanolethylamine, Thionly chloride. Chloroform, Acetone, Sodium carbonate... 

Gorcia (Explosive). A Spanish blasting expl suitable for use in mines or quarries K perchlorate 65, Na nitrate 5, Mn dioxide 1.3, sucrose 26, urotnopine [hexamethylenetetramine, (CHjj)BN4] 1.4, icon filings 1.0 sulfur 1.3%... 

Compound Name Ammonium Hydroxide Hexamethylenetetramine Ammonium Acetate Ammonium Bifluoride Ammonium Sulfamate Ammonium Sulfamate Ammonium Benzoate Ammonium Bicarbonate Ammonium Dichromate Ammonium Bifluoride Ammonium Carbonate Ammonium Chloride Ammonium Citrate Ammonium Citrate Ammonium Pentaborate Ammonium Dichromate Nickel Ammonium Sulfate Ferric Ammonium Citrate Ferric Ammonium Oxalate Ferrous Ammonium Sulfate Ammonium Fluoride Ammonium Silicofluoride Ammonium Formate Ammonium Gluconate Ammonium Bicarbonate Ammonium Bifluoride Ammonium Sulfide Ammonium Hydroxide Ammonium Thiosulfate Ammonium Thiosulfate Ammonium Iodide Ferrous Ammonium Sulfate Ammonium Lactate Ammonium Lactate Ammonium Lauryl Sulfate Ammonium Molybdate Ammonium Chloride Nickel Ammonium Sulfate Ammonium Nitrate Ammonium Nitrate-Urea Solution Ammonium Oleate... 

This substance was isolated in the form of its barium salt by Hirst et al. [12] when investigating the nitration of hexamethylenetetramine to cyclonite. They found that hexamethylenetetramine, when dissolved in nitric acid at 40°C, yields the product (II) which is hydrolysed by barium hydroxide to form the barium salt of methylene-dinitramine. From this the free nitramine may be obtained ... 

The author did not cite the product as an explosive — he recommended its use in medicine — but in later patents [3] he proposed the use of cyclonite in the manufacture of smokeless propellant. In 1921 Herz [4] modified Henning s method by nitrating hexamethylenetetramine itself, not its nitrate. Hale [5] described in detail the preparation of cyclonite by nitrating hexamethylenetetramine, and reported its explosive properties. 

According to Somlo [16] the action of a 4% solution of NaOH at 60°C produces the total decomposition of cyclonite after 5 hr. Somlo also studied the decomposition of cyclonite by concentrated sodium hydroxide and found it to be complete within 2-4 hr at 60°C. Among the decomposition products he detected nitrates, nitrites, organic acids, ammonia, nitrogen, formaldehyde and hexamethylenetetramine. 

It is based on the fact that hexamethylenetetramine contains 6 methylene groups per 4 amino groups, i.e. the number of amino groups is lower then that required for obtaining two molecules of cyclonite. In order to supply the additional two amino groups the appropriate amount of ammonium nitrate is added to the nitrating nitric acid in accordance with the equation ... 

The first is the synthesis of hexamethylenetetramine in acetic anhydride from paraformaldehyde and ammonium nitrate ... 

The chemistry of the preparation of RDX is highly complex. When hexamethylenetetramine is reacted with nitric acid, hexamethylenetetramine dinitrate is formed which is then nitrated to form an intermediate Compound I as shown in Reaction 7.10. 

The SH-process involves continuous nitration of hexamethylenetetramine by concentrated nitric acid, with the production of nitrous gas. The RDX is filtered from the residual acid and stabilized by boiling in water under pressure and purified by recrystallization from acetone. 

In the K-process RDX is formed by reacting ammonium nitrate with a mixture of hexamethylenetetramine and nitric acid, and warmed as shown in Reaction 7.12. 

The by-product formaldehyde can be transformed into hexamethylenetetramine by reacting it with ammonium nitrate and thus increasing the yield. 

Lastly, the KA-process (Bachmann process) is based on the reaction between hexamethylenetetramine dinitrate and ammonium nitrate with a small amount of nitric acid in an acetic anhydride solution. The chemical reaction is presented in Reaction 7.15. 

Hexamethylenetetramine, acetic acid, acetic anhydride, ammonium nitrate and nitric acid are mixed together and held at 45°C for 15 min. Ammonium nitrate, nitric acid and acetic anhydride are then slowly added and left on a steam bath for 12 h. A precipitate forms containing 27% RDX and 73% HMX. This process is shown in Reaction 7.16 (overleaf). 

Weiss-Salz (White Selt). A compd, (H2C N.-S03K)3, produced in 1944 by the IG Farben-industrie at Hochst am Main, as an intermediate in the manuf of Hexogen. The compd was shipped to the Nobel plant at Hamburg, where it was nitrated. The production of white salt was stopped as soon as the method of direct nitration of hexamethylenetetramine to Hexogen was improved to make it more economical Refs 1) R.E. Richardson et al, CIOS Rept 25-18 (1945), 28-29 2) B.T. Fedoroff et al,... 

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