Amines, reaction with nitric oxide

These are the most common diazeniumdiolates, formed by the reaction of secondary amines and polyamines with nitric oxide in basic media [214, 215]. They are stable solids, capable of regenerating two equivalents of nitric oxide along with the starting amine in neutral or acidic buffers. The half-life of NO generation varies from a few seconds to many hours, depending on the amine. The decomposition to NO is a spontaneous, first-order reaction at constant pH. 

Combustible when exposed to heat or flame. Can react with oxidizing materials. Explosive reaction with acetic acid + acetic anhydride + ammonium nitrate + nitric acid, 1-bromopenta borane(9) (above 90°C), iodoform (at 178°C), iodine (at 138°C). Reaction with nitric acid + acetic anhydride forms the military explosives RDX and HMX. Reacts violently with Na202. When heated to decomposition it emits toxic fumes of formaldehyde and NOx. See also AMINES. 

The mechanism of the reaction between nitric oxide and the amines is not known at present. In a reported 14) kinetic study low concentrations of NO were utilized. Reaction of NO with trace impurities in the solvent gave rise to a species whose spectrum was mistakenly assumed to be that of nitric oxide. The three-step scheme presented above is favored, with the first step probably being rate-controlling. 

Use Formation of diazotizing compounds by reaction with primary aromatic amines, source of nitric oxide. 

The conversion of a wide variety of P, S, and N organic compounds over H-mordenite and HZSM-5 catalysts has been described. The reaction of nitric oxide and chlorine near to equilibrium over H-mordenite was studied by use of a pressure-jump method. The preparation of aliphatic amines from the reaction of Ci—C3 alcohols and ethers with ammonia over HZSM-5, HZSM-11, and HZSM-21 has been described. The proportion of secondary and tertiary amines decreased as the size of alcohol or ether reactant increased. Chang and Silvestri showed that methanethiol is converted over HZSM-5 to hydrocarbons in a broadly similar way to methanol. However, a higher temperature (755 K) is required and even so 27.2 % total carbon remains unconverted as (CH3)2S. Propane is the major paraffin and the aromatics are largely C9. 

ACETIC ACID, 1,3-DIMETHYLBUTYL ESTER (108-84-9) CgHi Oj Forms explosive mixture with air (flash point 113°F/45°C). Violent reaction with strong oxidizers. Incompatible with sulfuric acid, nitric acid, caustics, aliphatic amines, isocyanates. Will swell rubber and can dissolve certain coatings. 

Combustible solid.Dust may form explosive mixture with air (flash point 334°F/168°C Fire Rating 1). Violent reaction with nitric acid forms explosive nitro materials in the presence of sulfuric acid. Dust and powder forms explosive mixture with air. Incompatible with strong acids, alkalis, aliphatic amines, alkanolamines, alkylene oxides, ammonia, epichlorohydrin, isocyanates, nitrates, nitromethane, sodium nitrite, strong oxidizers. On small fires, use dry chemical powder (such as Purple-K-Powder), Halon , alcohol-resistant foam, water spray, or CO2 extinguishers. Combustion produces phthalic anhydride and carbon oxides. 

---