Hydrocarbons Nitro

The nitro-hydrocarbons are neutral substances but when a nitro-group is introduced into a phenol or amine the acidic properties are greatly increased or the basicity decreased. The presence of a nitro-group also tends to make halogen atoms in the same molecule much more reactive. 

It will also reduce acid chlorides, acid anhydrides and aldehydes to primary alcohols, ketones to secondary alcohols, and amides to the corresponding amines R-CONHi -> R CHiNH. Nitro-hydrocarbons if aromatic are... 

Place about 1 g. of the nitro-hydrocarbon in a boiling-tube and add 5 ml. of cone. HCl and several pieces of granulated tin. Warm the mixture and shake continuously to break up the oily drops of the nitro-compound. When all the oil has disappeared (about 3 minutes heating) pour off the liquid from any undissolved tin into a 100 ml. conical flask. Cool and add cautiously 30% aqueous NaOH solution until the precipitate formed redissolves to give a dark-coloured solution. Cool the latter thoroughly and shake well with about 15 ml. of ether. Separate the ethereal layer in a separating-funnel, wash with water and evaporate the ether in a basin on a previously heated water-bath in a fume-cupboard atoay from all flames. The residue is either... 

In general, nitro-hydrocarbons are most readily identified by reduction to the corresponding amine (above), which is then identified as its benzoyl or other derivative (p. 374). (M.ps., pp. 550-551.)... 

K chlorate and aromatic hydrocarbons (such as naphthalene), and not more than 12% nitro-hydrocarbons (but no trinitro compds), the remainder consisting of paraffins, fatty oils, flour or other combustibles. It might also contain not more than 4% blasting gelatin. The prefixes Gesteins- and Wetter- were applied if the expls were intended for rock or coal mine use Ref Marshall, Diet (1920), 65... 

Plastit. A WWII plastic expl contg RDX 64, collodion cotton 3.5, and liq or semi-liq nitro-hydrocarbons 32.5% (Refs 1 2). Ref 3 states that it is a Swiss trade name for a plastic mil expl based on PETN, manufd by Schweiz, Sprengstoffe-Fabrik A-G Refs 1) All EnExpls(1946), 127 2)PATR 2510 (1946), Ger 134-R 3) Private communi-... 

The silica gel surface is extremely polar and, as a result, must often be deactivated with a polar solvent such as ethyl acetate, propanol or even methanol. The bulk solvent is usually an n-alkane such as n-heptane and the moderators (the name given to the deactivating agents) are usually added at concentrations ranging from 0.5 to 5% v/v. Silica gel is very effective for separating polarizable materials such as the aromatic hydrocarbons, nitro hydrocarbons (aliphatic and aromatic), aliphatic ethers, aromatic esters, etc. When separating polarizable substances as opposed to substances with permanent dipoles, mixtures of an aliphatic hydrocarbon with a chlorinated hydrocarbon such as chlorobutane or methylene dichloride are often used as the mobile... 

It has been recently described [55d) that aliphatic nitrile oxides can be formed in solution by treating an aliphatic a-nitro-hydrocarbon with phenylisocyanate in the presence of a catalytic amount of tri-ethylamine. Dehydration of the nitro compounds occurs with the con-committant formation of benzoylurea. From nitroethane, the reaction is formulated as follows ... 

Explosive Nitric Esters, Liquid. Spout wash water formed in the mfg of liquid expl nitric esters is created with a non expl aromatic nitro hydrocarbon e. g. 0-Nitro toluene (1), to extract the expl esters and render the wash water safe for disposal. Wash water from a Nitro glycerine (II) plant contg 0-35% II was treated at a rate of 25000 lbs/8 hrs with 1000 pounds of (I) which was continuous ly recycled so as to give a 2 1 wash water I vol ratio Ref W.G.Allan et al, Brit P7345 2 3 (1955)... 

The same replacement could be made in the low-freezing Nobel Arctic Carbonite, which contained NG 15.5, nitro-hydrocarbon 10.5, K nitrate 42.0, woodmeal 31.7 Ca... 

Red Star. A Brit sporting powder introduced in 1906 contg NC (insol) 52.2, NO (sol) 25.5, metallic nitrates 10.5, nitro-hydrocarbOns 7.0, vaseline 3.0 and moisture 1.8%... 

The nitro-hydrocarbons vary in their toxicological effects depending on whether the hydrocarbon is a pariffin or an aromatic. The pariffins are known for their irritant effects accompanied by nausea, and the effects on the central nervous system and liver becoming significant with acute exposures. The nitro-aromatics like nitrobezene, are much more hazardous. 

The reduction of aliphatic nitro-hydrocarbons in dilute alcoholic sulphuric-acid solution has been accomplished by Pierron.2 The /5-alkyl-hydroxylamines are obtained at platinum anodes and at a temperature of 15°-20° ... 

Rigid cartridges are produced by pressing a mixture made plastic either by means of a molten binding material (a nitro-hydrocarbon) or by a solution—collodion cotton in acetone for example. On cooling, or on evaporation of the solvent, the solid cartridge is obtained. 

When the column chemicals are thermally unstable and decompose exothermically, an excessive bottom temperature can cause a "runaway reaction and sometimes lead to an explosion. Some experiences with such explosions have been reported in distillation of peroxide, nitro, hydrocarbon oxide, and acetylenic compounds (16o, 96, 97, 209a, 275). 

Trinitrophenol, also known as picric acid, is composed of yellow crystals and is a nitro hydrocarbon derivative. It is shipped with not less than 10% water as a wetted explosive. There is a severe explosion risk when shocked or heated to 572°F, and it reacts with metals or metallic salts. In addition to being flammable and explosive, it is toxic by skin absorption. Picric acid has caused disposal problems in school and other chemistry laboratories where the moisture has evaporated from the container as the material ages. When the picric acid dries out, it becomes a high explosive closely related to TNT. Picric acid has been found in various amounts in school labs across the country. In a dry condition, picric acid is dangerous and should be handled by the bomb squad. The structure and molecular formula for picric acid are shown in Figure 6.3. 

Ammonium picrate is a nitro hydrocarbon derivative. It is composed of yellow crystals with not less than 10% water by mass. Ammonium picrate is highly explosive when dry and a flammable solid when wet, and is slightly soluble in water. The four-digit UN identification number for ammonium picrate with not less than 10% water is 1310. The primary uses are in pyrotechnics and explosives. The structure and molecular formula are shown in Figure 6.4. 

TLV of 1 ppm in air. The four-digit UN identification number is 1652. The NFPA 704 designation is health 3, flammability 2, and reactivity 1. Nitrobenzene is a nitro hydrocarbon derivative, but it is not very explosive. The primary uses are as a solvent, an ingredient of metal polishes and shoe polishes, and in the manufacture of aniline. The structure and molecular formula are shown Figure 8.29. 

The process which Straub employs to prepare hydrazo-compounds from nitro-hydrocarbons is yet to be mentioned. The chief feature of his experiments is that the original material and all intermediate products are retained in solution during the electrolysis by the selection of a suitable solvent, and the hydrazo-compounds are withdrawn from the action of the current by precipitation. 

Straub attains this end by subjecting the nitro-hydrocarbons to electrolytic reduction in a solvent made a conductor by the addition of potassium hydroxide, The quantity of the liquid used must be sufficient to keep in solution the azo- and azoxy-com-pounds corresponding to the nitro-hydrocarbon. 

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