Explosives amines

Besides this thermally triggered decomposition of the initiator, radical formation can also be achieved with the help of a reaction with a solvent or odier compounds added on purpose. This so-called induced radical formation is worth mentioning because it may proceed like an explosion. Amines such as dimethylaniline are known to have this effect. 

CAUTION - The lower nitroalkanes form shock and/or temperature sensitive EXPLOSIVE compounds with amines and hydroxides. BE CAREFUL, DAMNIT You have been warned. 

Reactions with Organic Compounds. Tetrafluoroethylene and OF2 react spontaneously to form C2F and COF2. Ethylene and OF2 may react explosively, but under controlled conditions monofluoroethane and 1,2-difluoroethane can be recovered (33). Benzene is oxidized to quinone and hydroquinone by OF2. Methanol and ethanol are oxidized at room temperature (4). Organic amines are extensively degraded by OF2 at room temperature, but primary aHphatic amines in a fluorocarbon solvent at —42°C are smoothly oxidized to the corresponding nitroso compounds (34). 

Commercially, pure ozonides generally are not isolated or handled because of the explosive nature of lower molecular weight species. Ozonides can be hydrolyzed or reduced (eg, by Zn/CH COOH) to aldehydes and/or ketones. Hydrolysis of the cycHc bisperoxide (8) gives similar products. Catalytic (Pt/excess H2) or hydride (eg, LiAlH reduction of (7) provides alcohols. Oxidation (O2, H2O2, peracids) leads to ketones and/or carboxyUc acids. Ozonides also can be catalyticaHy converted to amines by NH and H2. Reaction with an alcohol and anhydrous HCl gives carboxyUc esters. 

The fate of the ion pair iatermediate depends on the stmcture of the amine and the reaction conditions. Certain tertiary amines, eg, dimethylaruline (DMA), react with specific diacyl peroxides such as diben2oyl peroxide (BPO) to generate free radicals at ca 20°C. Some reactions, eg, DMA—BPO, are explosive when neat reactants are mixed. Primary and secondary amines do not yield free radicals. 

To minimize the formation of fuhninating silver, these complexes should not be prepared from strongly basic suspensions of silver oxide. Highly explosive fuhninating silver, beheved to consist of either silver nitride or silver imide, may detonate spontaneously when silver oxide is heated with ammonia or when alkaline solutions of a silver—amine complex are stored. Addition of appropriate amounts of HCl to a solution of fuhninating silver renders it harmless. Stable silver complexes are also formed from many ahphatic and aromatic amines, eg, ethylamine, aniline, and pyridine. 

Amines and other bases cataly2e the exothermic decomposition of molten maleic anhydride [108-31-6] at temperatures above 150°C, accompanied by the rapid evolution of gaseous products (44,45). The rate of reaction reportedly increases with the basicity of the amine and higher initial temperatures. The reaction mixture can become explosive. 

By virtue of their unique combination of reactivity and basicity, the polyamines react with, or cataly2e the reaction of, many chemicals, sometimes rapidly and usually exothermically. Some reactions may produce derivatives that ate explosives (eg, ethylenedinitrarnine). The amines can cataly2e a mnaway reaction with other compounds (eg, maleic anhydride, ethylene oxide, acrolein, and acrylates), sometimes resulting in an explosion. 

Thermolysis of 4-methyl(4-phenyl)isoxazolin-5-one produced a-cyanophenylacetic acid <67JHC533). The pyrolysis of 3-methylisoxazoline-4,5-dione 4-oxime generated fulminic acid, which was trapped in a liquid N2 cooled condenser for further study. Pyrolysis of metal salts such as Ag or Na produced the corresponding highly explosive salts of fulminic acid 79AG503). Treatment of the oxime with amines generated bis-a,/3-oximinopropionamides (Scheme 65) <68AC(R)189). 

It is not advisable to store large quantities of picrates for long periods, particularly when they are dry due to their potential EXPLOSIVE nature. The free base should be recovered as soon as possible. The picrate is suspended in an excess of 2N aqueous NaOH and warmed a little. Because of the limited solubility of sodium picrate, excess hot water must be added. Alternatively, because of the greater solubility of lithium picrate, aqueous 10% lithium hydroxide solution can be used. The solution is cooled, the amine is extracted with a suitable solvent such as diethyl ether or toluene, washed with 5N NaOH until the alkaline solution remains colourless, then with water, and the extract is dried with anhydrous sodium carbonate. The solvent is distilled off and the amine is fractionally distilled (under reduced pressure if necessary) or recrystallised. 

Ethereal solutions of adipyl azide are quite safe, but the free azide is somewhat explosive and should not be isolated. If storage of an intermediate is desired, the azide should be converted to the urethane by the procedure given below. The urethane is quite stable to storage also, the procedure via the urethane gives improved yields in some amine syntheses. 

The cure reaction of structural acrylic adhesives can be started by any of a great number of redox reactions. One commonly used redox couple is the reaction of benzoyl peroxide (BPO) with tertiary aromatic amines. Pure BPO is hazardous when dry [39]. It is susceptible to explosion from shock, friction or heat, and has an autoignition temperature of 79°C. Water is a very effective stabilizer for BPO, and so the initiator is often available as a paste or a moist solid [40], The... 

Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials Avoid contamination with combustible materials, various inorganic and organic acids, alkalies, alcohols, amines, easily oxidizable materials such as ethers, or materials used as accelerators in polymerizations reactions Stability During Transport Extremely explosion-sensitive to shock, heat and friction. Self-reactive Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Not pertinent inhibitor of Polymerization Not pertinent. 

Tellurium nitride was first obtained by the reaction of TeBt4 with liquid ammonia more than 100 years ago. The empirical formula TeN was assigned to this yellow, highly insoluble and explosive substance. However, subsequent analytical data indicated the composition is Tc3N4 which, in contrast to 5.6a and 5.6b, would involve tetravalent tellurium. This conclusion is supported by the recent preparation and structural determination of Te6N8(TeCl4)4 from tellurium tetrachloride and tris(trimethylsilyl)amine (Eq. 5.5). The TceNs molecule (5.12), which is a dimer of Tc3N4, forms a rhombic dodecahedron in which the... 

From 5-chloro-l,2,3,4-thiatriazole and secondary amines Lieber et al. have prepared some 5-disubstituted-amino-l,2,3,4-thiatria-zoles. It seems possible that several other types of compounds could be prepared from 5-chlorothiatriazole, which, however, is very unstable (explosive). 

Important applications for titanium have been developed in processes involving acetic acid, malic acid, amines, urea, terephthalic acid, vinyl acetate, and ethylene dichloride. Some of these represent large scale use of the material in the form of pipework, heat exchangers, pumps, valves, and vessels of solid, loose lined, or explosion clad construction. In many of these the requirement for titanium is because of corrosion problems arising from the organic chemicals in the process, the use of seawater or polluted cooling waters, or from complex aggressive catalysts in the reaction. 

A better method for preparing primary amines is to use the azide synthesis, in which azjde ion, N3, is used for SN2 reaction with a primary or secondary alkyl halide to give an alkyl azide, RN3. Because alkyl azides are not nucleophilic, overalkylation can t occur. Subsequent reduction of the alkyl azide, either by catalytic hydrogenation over a palladium catalyst or by reaction with LiAlK4. then leads to the desired primary amine. Although the method works well, low-molecular-weight alkyl azides are explosive and must be handled carefully. 

This change in editorial leadership has resulted, perhaps inevitably, in a change in editorial policy which is reflected in the contents of Volume 8. There has been a marked de-emphasis on the inclusion of organic parent compounds followed by an exhaustive and voluminous cataloging of azide, azido, azo, diazido, diazonium, diazo, nitro, dinitro, polynitro, hitr amine, nitrate (esters and salts), dinitrate, poly nitrate, nitroso, polynitroso, chlorate, perchlorate, peroxide, picrate, etc, derivatives — regardless of whether any of these derivatives exhibit documented explosive or energetic properties. Only those materials having such properties have been included in this volume... 

Diazotizations should be carried out above room temperature only in cases where a relatively dilute aqueous system (< 1 m amine, < 1 m mineral acid) is used and the diazonium salt formed does not precipitate (Bersier et al., 1971). Diazotization in highly concentrated sulfuric acid may involve a high risk of explosive detonation if carried out at a higher temperature (see Sec. 2.2). 

Unfortunately, the hydroxyl amine intermediate is both explosive and... 

Aromatic nitro compounds include both important explosives and a number of agrochemicals. Concern with their fate has motivated extensive examination of their reduction to amines under a range of conditions. 

These are readily produced by nitration of aromatic compounds and are important explosives. The amines formed by reduction are able to undergo a nnmber of reactions, and have a wide range of application in the production of agrochemicals, dyestnffs, and pharmaceuticals. 

Nitrotoluenes including 2,4,6-trinitrotoluene (TNT) are important components of explosives and several nitroarenes including the antibacterial nitrofurans have established mntagenicity (Purohit and Basu 2000). Substantial effort has been directed to the degradation of nitroarenes, and to their reduction to amines. Although nitroarene reductases, noted in Chapter 3, Part 3, are distribnted in a range of biota, the products may not necessarily represent intermediates in the degradation... 

When hot, ammonia and compounds, which contain nitrogen-hydrogen bonds eg ammonium salts and cyanides react violently with chlorates and alkaline perchlorates. Diammonlum sulphate, ammonium chloride, hydroxyl-amine, hydrazine, sodamide, sodium cyanide and ammonium thiocyanate have been cited. So far as hydrazine is concerned, the danger comes from the formation of a complex with sodium or lithium perchlorate, which is explosive when ground. Many of these interactions are explosive but the factors which determine the seriousness of the accident are not known. 

A very similar explosive reaction was obtained with the same epoxide and with phenylamine, heterocyclic amines and N-substituted amines. In the Ie case, the reaction was described as not dangerous below 60 C and dangerous above 70 C. The large number of accidents that bring this epoxide and the amines mentioned into play were all caused by the fact that the reaction exothermicity was badly controlled. 

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