Aliphatic explosives

As you now know, aliphatic organic compounds belong to the alkane, alkene, and alkyne classes of compounds. Aliphatic explosives fall into both the open-chain and cycloaliphatic groups. The major sources of oxidizer in most aliphatic explosives are from the nitrate ester group (—ONO2) and the nitramine group (—NH—NO2). The nitrate esters are usually made by direct nitration of an... 

The first and simplest group of open-chain aliphatic explosives is that which is derived from the paraffinic, or alkane, polyalcohols. The physical properties of some aliphatic explosives are given in Table 3.3. Figures 3.23 through 3.29 show the molecules for some of these explosives. 

Table 3.3 Physical Properties of Some Aliphatic Explosives...

All the preceding aliphatic explosives utilized the nitrate ester substituent as the oxidizer. The other most common oxidizer substituent in aliphatic explosives is nitramine, which is in the following pure explosives shown in Figures 3.30 through 3.35. 

For this group of liquid aliphatic explosive compounds, the TMD is found from ... 

These preceeding nine groups constitute the estimation of TMD for aliphatic explosives. The following four groups are for estimation of TMD of aromatic explosives. 

Table 7. Properties of Explosive Aliphatic Nitrate Esters...

The diazirines are of special interest because of their isomerism with the aliphatic diazo compounds. The diazirines show considerable differences in their properties from the aliphatic diazo compounds, except in their explosive nature. The compounds 3-methyl-3-ethyl-diazirine and 3,3-diethyldiazirine prepared by Paulsen detonated on shock and on heating. Small quantities of 3,3-pentamethylenediazirine (68) can be distilled at normal pressures (bp 109°C). On overheating, explosion followed. 3-n-Propyldiazirine exploded on attempts to distil it a little above room temperature. 3-Methyldiazirine is stable as a gas, but on attempting to condense ca. 100 mg for vapor pressure measurements, it detonated with complete destruction of the apparatus." Diazirine (67) decomposed at once when a sample which had been condensed in dry ice was taken out of the cold trap. Work with the lower molecular weight diazirines in condensed phases should therefore be avoided. 

Gilliland H.B. Hass, Synthesis of Certain Aliphatic Nitro Compounds" in ADL Synthesis and Testing of High Explosives , Report C-57625, Contr W-19-020-ORD-6436, 3 Jan 1949 (AD-222018), p i 05 21) N.D. Mason,... 

Dream reactions can be performed using chemical micro process engineering, e.g., via direct routes from hazardous elements [18]. The direct fluorination starting from elemental fluorine was performed both on aromatics and aliphatics, avoiding the circuitous Anthraquinone process. While the direct fluorination needs hours in a laboratory bubble column, it is completed within seconds or even milliseconds when using a miniature bubble column. Conversions with the volatile and explosive diazomethane, commonly used for methylation, have been conducted safely as well with micro-reactors in a continuous mode. 

With DMSO and aliphatic sulphoxides, dry perchloric acid also forms very unstable salts. If the acid concentration is 70% or more, when it comes into contact with DMSO, this gives rise to an immediate explosion. Aromatic sulphoxides give rise to far less dangerous interactions. 

Primary aliphatic or aromatic amines react with calcium (or sodium) hypochlorite to form A-mono- or di-chloroamines which are explosively unstable, but less so than nitrogen trichloride. 

Interaction, in presence of diluent below 0°C, with isopropylamine or isobuty-lamine caused separation of explosive liquids, and with aniline, phenylhydrazine and 1,2-diphenylhydrazine, explosive solids [1], In absence of diluents, contact with most aliphatic or non-aromatic heterocyclic amines often leads to uncontrolled oxidation and/or explosions [2], During oxidation of two steroidal dienes in dry pyridine at —35 to —40°C, on one occasion each of the reactions was accompanied by violent explosions [3],... 

Undiluted halogen compounds of the aliphatic series, such as ethyl bromide, chloroform, bromoform, and the like, should not be brought into contact with metallic sodium or potassium thus they must not be dried with these metals since very violent explosions may occur as a result of detonation (Staudinger). 

Syntheses of 5 energetic aliphatic azido compounds are described caution is necessary in handling these because of their impact-sensitivity [1], A later symposium on energetic materials, here meaning explosives and popellants, is reported [2], Individual compounds are ... 

Many of the reactions of A-chloro- and A-bromo-imides are extremely violent or explosive. Those observed include A-chlorosuccinimide with aliphatic alcohols or benzylamine or hydrazine hydrate A-bromosuccimmidc with aniline, diallyl sulfide, or hydrazine hydrate or 3-nitro-A-bromophthalimide with tetrahydrofur-furyl alcohol l,3-dichloro-5,5-dimethyl-2,4-imidazolidindione with xylene (violent explosion). Individually indexed compounds are ... 

The peroxyacids were until relatively recently the most powerful oxidants of all organic peroxides, and it is often unnecessary to isolate them from the mixture of carboxylic acid and hydrogen peroxide used to generate them. The pine lower aliphatic members are explosive (performic, particularly) at high, but not low concentrations, being sensitive to heat but not usually to shock. Dipicolinic acid or phosphates have been used to stabilise these solutions. The detonable limits of peroxyacid solutions can be plotted by extrapolation from known data. Aromatic peroxyacids are generally more stable, particularly if ring substituents are present [1],... 

Although aliphatic azides can be prepared under liquidrliquid phase-transfer catalytic conditions [3-5], they are best obtained directly by the reaction of a haloalkane with sodium azide in the absence of a solvent [e.g. 6, 7]. Iodides and bromides react more readily than chlorides cyclohexyl halides tend to produce cyclohexene as a by-product. Acetonitrile and dichloromethane are the most frequently used solvents, but it should be noted that prolonged contact (>2 weeks) of the azide ion with dichloromethane can produce highly explosive products [8, 9] dibromomethane produces the explosive bisazidomethane in 60% yield after 16 days [8]. 

Aliphatic azides (CAUTION A highly explosive azide may be formed when dichloromethane is used as the solvent)... 

In 1942, the Mallinckrodt Chemical Company adapted a diethylether extraction process to purify tons of uranium for the U.S. Manhattan Project [2] later, after an explosion, the process was switched to less volatile extractants. For simultaneous large-scale recovery of the plutonium in the spent fuel elements from the production reactors at Hanford, United States, methyl isobutyl ketone (MIBK) was originally chosen as extractant/solvent in the so-called Redox solvent extraction process. In the British Windscale plant, now Sellafield, another extractant/solvent, dibutylcarbitol (DBC or Butex), was preferred for reprocessing spent nuclear reactor fuels. These early extractants have now been replaced by tributylphosphate [TBP], diluted in an aliphatic hydrocarbon or mixture of such hydrocarbons, following the discovery of Warf [9] in 1945 that TBP separates tetravalent cerium from... 

Such xenobiotics as aliphatic hydrocarbons and derivatives, chlorinated ahphatic compounds (methyl, ethyl, methylene, and ethylene chlorides), aromatic hydrocarbons and derivatives (benzene, toluene, phthalate, ethylbenzene, xylenes, and phenol), polycyclic aromatic hydrocarbons, halogenated aromatic compounds (chlorophenols, polychlorinated biphenyls, dioxins and relatives, DDT and relatives), AZO dyes, compounds with nitrogroups (explosive-contaminated waste and herbicides), and organophosphate wastes can be treated effectively by aerobic microorganisms. 

A number of secondary high explosives containing both nitramine and nitrate ester functionality have been reported. Aliphatic examples include A-nitrodiethanolamine dinitrate (DINA) (110), prepared from the nitration of diethanolamine with nitric acid-acetic anhydride in the presence of zinc chloride,and A,A -dinitro-A,A -bis(2-hydroxyethyl)oxamide dinitrate (NENO) (111), prepared from the mixed acid nitration of A,lV -bis(2-hydroxyethyl) oxamide . 

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