Nitration aliphatic compounds

Oxidation followed by decomposition of the molecule may result in the formation of nitrated aliphatic compounds, as for example tetranitromethane and chloro-picrin in the nitrations of toluene or chlorobenzene respectively. 

It should be noted that aliphatic compounds (except the paraffins) are usually oxidised by concentrated nitric acid, whereas aromatic compounds (including the hydrocarbons) are usually nitrated by the concentrated acid (in the presence of sulphuric acid) and oxidised by the dilute acid. As an example of the latter, benzaldehyde, CjHsCHO, when treated with concentrated nitric acid gives ffi-nitrobenzaldehyde, N02CgH4CH0, but with dilute nitric acid gives benzoic acid, CgHgCOOH. 

Nitropyrene was the sole product formed from the gas-phase reaction of pyrene with OH radicals in a NOx atmosphere (Arey et al, 1986). Pyrene adsorbed on glass fiber filters reacted rapidly with N2O5 to form 1-nitropyrene. When pyrene was exposed to nitrogen dioxide, no reaction occurred. However, in the presence of nitric acid, nitrated compounds were produced (Yokley et al, 1985). Ozonation of water containing pyrene (10-200 pg/L) yielded short-chain aliphatic compounds as the major products (Corless et al, 1990). A monochlorinated pyrene was the major product formed during the chlorination of pyrene in aqueous solutions. At pH 4, the reported half-lives at chlorine concentrations of 0.6 and 10 mg/L were 8.8 and <0.2 h, respectively (Mori et al, 1991). 

Reaction CXIV. Action of Concentrated Nitric Acid on Aromatic Compounds. (B., 20, 333.)—Concentrated nitric acid up to 100% is required for nitrating many compounds which are not oxidised by this treatment. For this reason it is not used in the aliphatic series, nor with compounds containing an easily oxidisable side chain. The reaction is represented by the equation, ... 

Reactivity of organic compounds toward HO is estimated readily in most cases because of the large databases of values measured for reactions in water and air and the correlation equations relating rates of oxidation of aliphatic compounds in air and water, as well as the availability of Hammett SARs for reactions of aromatic compounds. In addition, 90% of HO rate constants in water and air are within 50% of 5 x 109 M 1 s Thus, the limiting indirect photoreaction rate constant for almost any compound in freshwater with more than 1 mg/L of NO3 will be 1.5 x 10 7 s 1 at 40°-50° latitude in summer, equivalent to a 50-day half life. In low-nitrate waters, the limiting half life will be extended correspondingly. 

The trichloromethyl group can be reduced to either the dichloro- or the monochloromethyl group by proper choice of the SSE 49 s With ammonium nitrate the dichloro compounds are formed in 64—94% yield, while with tetra-metliylammonium chloride as supporting electrolyte the monochloro derivatives are obtained in 63 to 95% yield. As trichloromethyl compounds are readily available by telomerization of olefins with CC14) this reduction opens a simple route to a, co-bifunctional aliphatic compounds. 

Konovalov [15] nitrated aliphatic hydrocarbons in sealed tubes at 120-130°C, using dilute nitric acid of concentration 6.5-19%. From normal hydrocarbons he obtained secondary nitro compounds in yields varying from 40% (2-nitro-hexane from hexane) to 49-50% (2-nitrooctane from octane). Aromatic hydrocarbons with an aliphatic substituted group when nitrated under the same conditions gave nitro derivatives with a nitro group in the side chain. For example, ethylbenzene, when nitrated with 12.5% nitric acid at 105-108°C, gives phenyl-nitroethane in 44% yield. The optimum yield is obtained with 13% acid. 

The aqueous layer is sepMated Mid the oil washed with water until alkali free when tested with phenolphthalein. The oil is steamed to remove un-nitrated toluene Mid aliphatic compounds. Distillation is continued until the oil coming over sinks in water. The distillate is collected and fractionated once or twice a yeM. It contains ca. 20% of nitrotoluenes. 

The molecular ion is frequently not detectable in aliphatic alcohols, nitrites, nitrates, nitro compounds, nitriles and in highly branched compounds. 

Group III Solid, noncyclic, aliphatic compounds containing only nitro and (or) nitrate substituents ... 

Reduction of the double bond Polymerization Nitroacctylcncs Polynitro aliphatic compounds Nitration of hydrt>carbons Substitution of halogen Electrolytic methtnls Addition reaction Michael addition Diels-Aider addition Oxidative dimerization a. u>-Dinitroalkanes gcm-Dinitroalkanes I rinitromethane (nitroform) derivatives Properties of nitroform Manufacture of nitroform... 

The metal acetylacetonates have been successfully nitrated with several nitrating agents that have been used to nitrate reactive aromatic systems. Nitrating agents commonly used to nitrate aromatic and aliphatic compounds will destroy the metal chelate. 

Butyl diglycol [112-34-5] [2-(2-butoxyethoxy)ethanol, diethylene glycol monobutyl ether] is a clear, colorless, neutral liquid with a pleasantly mild odor. It is miscible with water and organic solvents, including aliphatic compounds. Butyl diglycol has a high solvency for cellulose nitrate, cellulose ethers, chlorinated rubber, poly(vinyl acetate), polyacrylates, and some oils, as well as for many synthetic resins, natural resins, and dyes. Polystyrene, poly(vinyl chloride), fats, and most oils are not dissolved. 

Aqueous solution of most aliphatic compounds can also dissolve hydrazine nitrate. The mixture aqueous solution of aliphatic amine and hydrazine nitrate... 

Thiosemicarbazones are of special interest, as they form insoluble compounds with monovalent metals such as silver, copper and mercury, which may be an aid to their separation from mixtures and to their quantitative determination. The colour of the nitrated phenylhydrazine derivatives can be characteristic of the type of carbonyl group. p-Nitrophenylhydrazones of aliphatic compounds are yellow or brown, those of aromatic compounds red. 2,4-Dinitrophenylhydrazones of saturated aliphatic aldehydes and ketones are yellow or orange, those of a, -unsaturated carbonyls are red, and those of simple aromatic compounds are yellow, orange or red. They are usually formed in excellent yields. 

Poly(vinyl alcohol)-Silver Nitrate Facilitated Transport Membranes for the Separation of Aromatic and Aliphatic Compounds... 

Aliphatic Nitrate Esters. Compounds in this class are prepared by 0-type nitration in which a nitro group is attached to an oxygen atom of the compound being nitrated. 

BM.as. per uso a cielo aperto is a reddish powder consisting of ammonium nitrate, cyclic aliphatic compounds, and metallic powders. 

Since aliphatic hydrocarbons (unlike aromatic hydrocarbons, p. 155) can be directly nitrated only under very special conditions, indirect methods are usually employed for the preparation of compounds such as nitroethane, CjHsNO. When ethyl iodide is heated with silver nitrite, two isomeric compounds are formed, and can be easily separated by fractional distillation. The first is the true ester, ethyl nitrite, C,HiONO, of b.p. 17° its identity is shown by the action of hot sodium hydroxide solution, which hydrolyses it, giving ethanol and... 

Unlike aliphatic hydrocarbons, aromatic hydrocarbons can be sul-phonated and nitrated they also form characteristic molecular compounds with picric acid, styphnic acid and 1 3 5-trinitrobenzene. Many of the reactions of aromatic hydrocarbons will be evident from the following discussion of crystalline derivatives suitable for their characterisation. 

Unloaded silica does not recover HPA from aqueous solution. The surface of silica gel modified with quarternary ammonium salts (QAS) gets anion-exchange properties. The aim of the work is the elaboration of solid-phase reagents on the base of ion associate of HPA with QAS immobilized onto silica surface for the determination of phosphoms and organic reductants. Heterocyclic (safranine and lucigenine) and aliphatic (trinonyloctadecyl ammonium iodide and tetradecyl ammonium nitrate) compounds have been examined as QAS. 

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