Hexamethylenetetramine oxidant

CfiH gNftOft, Hexamethylenetetramine oxide - hydrogen peroxide - water (1 1 1), 44B, 268... 

Azabicyclo[3.2.0]heptane-1-methyl chloride, 33B, Quinuclidinium tri-iodide iodine, 42B, 227 Hexamethylenetetramine oxide formic acid, 44B, 268 Hexamethylenetetramine oxide - thiourea (1 1), 44B, 269 -Diazapentacyclo[4.2.2.0 ]dec-7-ene, 42B,... 

Ammonia is used in the fibers and plastic industry as the source of nitrogen for the production of caprolactam, the monomer for nylon 6. Oxidation of propylene with ammonia gives acrylonitrile (qv), used for the manufacture of acryHc fibers, resins, and elastomers. Hexamethylenetetramine (HMTA), produced from ammonia and formaldehyde, is used in the manufacture of phenoHc thermosetting resins (see Phenolic resins). Toluene 2,4-cHisocyanate (TDI), employed in the production of polyurethane foam, indirectly consumes ammonia because nitric acid is a raw material in the TDI manufacturing process (see Amines Isocyanates). Urea, which is produced from ammonia, is used in the manufacture of urea—formaldehyde synthetic resins (see Amino resins). Melamine is produced by polymerization of dicyanodiamine and high pressure, high temperature pyrolysis of urea, both in the presence of ammonia (see Cyanamides). 

The early addition of Dimedon is reported234 to depress the formation of hexamethylenetetramine from formaldehyde in the presence of ammonia. O Dea282 found that the activated methylene center, sometimes formed in periodate oxidations of carbohydrates, reacts appreciably with the formaldehyde formed, thus giving low yields of apparent formaldehyde. He was able to depress this side reaction by the use of lowered temperatures and by the addition of benzaldehyde or of p-hydroxybenzaldehyde. The analyses for formaldehyde have often been more successful at a pH of 7.5 than at lower pH values.57, 68 59a 60 264... 

Formaldehyde, used in the production of phenolic and amino resins, is produced by the catalytic hot-air oxidation of methanol. In turn, hexamethylenetetramine is produced by the condensation of ammonia and 30% aqueous formaldehyde (formalin). 

Precipitation of Fe(OH)2 from FeCl2 solution with 2 M hexamethylenetetramine (urotropin) followed by oxidation for 3 h at 60 °C with a mixture of M NaN02 and HCI (Brauer, 1982). 

Hexamethylenetetramine Explosive. A powerful solid explosive was claimed to have been prepd by oxidizing hexamine with a solution of hydrogen peroxide, treating the resulting product with nitric acid and then, reoxidizing with H202 (Ref 1). After drying, this was mixed with AN, castor oil and turpentine (Ref 2)... 

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 ... 

It has been established that cyclotrimethylenetrinitrosoamine (II), a product of the nitrosation of hexamethylenetetramine, is oxidized with nitric acid (about 40%) to cyclonite (I). This confirms the structure of cyclonite. 

The oldest and simplest method of preparing cyclonite is based on the introduction of hexamethylenetetramine (hexamine) into an excess of concentrated nitric acid, s. g. 1.50-1.52, free of nitric oxides, at 25-30°C, thereafter pouring the whole into cold water. 

Another way to oxidize primary alkyl halides to aldehydes is by the use of hexamethylenetetramine followed by water. However, this reaction, called the Sommelet reaction. is limited to benzylic halides. The reaction is seldom useful when the R in RCH2CI is alkyl. The first part of the reaction is conversion to the amine ArCH2NH2 (0-44), which can be isolated. Reaction of the amine with excess hexamethylenetetramine gives the aldehyde. It is this last step that is the actual Sommelet reaction, though the entire process can be conducted without isolation of intermediates. Once the amine is formed, it is converted to an imine (ArCH2N=CH2) with formaldehyde liberated from the reagent. The key step then follows transfer of hydrogen from another mole of the arylamine to the imine ... 

The oxidation of a-hydroxy acids by benzyltrimethylammonium tribromide (BTMAB) to the corresponding carbonyl compounds shows a substantial solvent isotope effect, A (H20)/A (D20) = 3.57, but no KIE for a-deuteromandelic acid.133 The oxidation of glucose by hypobromous acid is first order in glucose and the acid.134 [l,l-2H2]Ethanol shows a substantial kinetic isotope effect when oxidized by hexamethylenetetramine-bromine (HABR) in acetic acid to aldehyde.135 Kinetics of the oxidation of aliphatic aldehydes by hexamethylenetetramine-bromine have been studied by the same group.136 Dioxoane dibromide oxidizes y-tocopherol to 5-bromomethyl-y-tocopherylquinone, which spontaneously cyclizes to 5-formyl-y-tocopherol.137... 

The oxidation of a-hydroxy acids by hexamethylenetetramine-bromine (HABR) is first order with respect to each of the hydroxy acids and HABR. The oxidation of o -deuteriomandelic acid exhibited a kinetic isotope effect of kn/ko = 5.91 at 298 K. The rates of oxidation of the substituted mandelic acids show excellent correlation with Brown s er+ values with negative reaction constants. A mechanism involving transfer of a hydride ion from the acid to the oxidant has been postulated.128... 

A ring-expanded analogue (74) is available if the hexamethylenetetramine is replaced by a mixture of ammonia and ethane-1,2-diamine (74MI1). This compound is resistant to methylation by methyl iodide on both nitrogen and phosphorus, but is oxidized on phosphorus by t-butyl hydroperoxide. 

Wyler patented an explosive composed of ammonium nitrate and hexamethylenetetramine, with or without nitrostarch, sodium nitrate, zinc oxide, hydrocarbon oil. 

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