Aromatic hydrocarbons nitro derivatives

Polycyclic organic matter, derived from the total exhaust emission, is an extremely complex mixture. It includes a large number of compounds such as polynuclear aromatic hydrocarbons (PAH), derivations of PAH such as nitro-PAH and amino-PAH, oxygenated PAH such as phenols and quinones, and heterocyclic aromatic compounds containing sulfur and oxygen. In order to assist in the identification of classes of toxic compounds it is possible to fractionate the exhaust emissions into vapor and... 

Nitro-substituted polycyclic aromatic hydrocarbons (nitro-PAHs) are formed during the combustion of fossil fuels at high temperatures with a vast supply of combustion air. In this reaction, conversion of nitrite (NO2) to nitric acid is an important intermediate step. Another source of nitro-PAHs is the photochemical radical-mediated conversions of parent PAHs to nitro-derivatives. Combustion at high temperatures with a vast supply of combustion air may lead to the formation of 1-nitropyrene (1-NP), whereas photochemical conversion of pyrene gives rise to 2- and 4-nitropyrene [24,25]. 

Solvents can be classified into three categories according to their polarity namely, polar protic, dipolar aprotic and non-polar. Most of the common solvents fall under one of following chemical classes Aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, phenols, ethers, aldehydes, ketones, carboxylic acids, esters, halogen-substituted hydrocarbons, amines, nitriles, nitro-derivatives, amides and sulfur-containing solvents (Marcus, 1998). In certain cases a mixture of two or more solvents would perform better than a single solvent. 

Gibson, T. L., Nitro Derivatives of Polynuclear Aromatic Hydrocarbons in Airborne and Source Particulate Matter, Atmos. Environ., 16, 2037-2040(1982). 

K. -W. Naujack, U. Mohr, and H. Ernst, Contribution of Polycyclic Aromatic Hydrocarbons and Nitro-Derivatives to the Carcinogenic Impact of Diesel Engine Exhaust Condensate Evaluated by Implantation into the Lungs of Rats, Cancer Lett., 37, 173-180 0 987). 

Jager, J., Detection and Characterization of Nitro Derivatives of Some Polycyclic Aromatic Hydrocarbons by Fluorescence Quenching after Thin-Layer Chromatography Application to Air Pollution Analysis, J. Chromatogr., 152, 575-578 (1978). 

Nielsen, T., Isolation of Polycyclic Aromatic Hydrocarbons and Nitro-Derivatives in Complex Mixtures by Liquid Chromatography, Anal. Chem, 55, 286-290 (1983). 

CA 53, 17513 (1959). Materials useful as rocket fuels, semisolid or gelled fuels for bursting and tail-ejection-type bombs, and incendiary fuels for flame throwers and hand grenades are described. They are made by mixing 0.1-25% by wt of satd, unsatd, or aromatic nitrohydrocarbons or their mixts, such as nitro- or dinitromethane, -ethane, -propane, or -butane with divinylated ketoses or diaryl deoxyketitols prepd by reaction of C3 g ketose sugars with C6 M aromatic hydrocarbons. The latter include CfiH, toluene, naphthalene, anthracene and their alkylated derivs... 

Fiedler, H., and W. Miicke, Nitro derivatives of polycyclic aromatic hydrocarbons . In The Handbook of Environmental Chemistry, Vol. 3, Part G, O. Hutzinger, Ed., Springer, Berlin, 1991, pp. 97-137. 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

Many compounds have been tested as ignition quality improvers—additives which shorten the ignition delay to a desirable duration. An extensive review in 1944 (6, 43) listed 303 references, 92 dealing with alkyl nitrates and nitrites 61 with aldehydes, ketones, esters, and ethers 49 with peroxides 42 with aromatic nitro compounds 29, with metal derivatives 28 with oxidation and oxidation products 22 with polysulfides 16 with aromatic hydrocarbons nine with nitration and four with oximes and nitroso compounds. In 1950, tests at the U. S. Naval Engineering Experiment Station (48) showed that a concentration of 1.5% of certain peroxides, alkyl nitrates, nitroaikanes, and nitrocarbamates increased cetane number 20 or more units. 

Many polycyclic aromatic amines and aldehydes are commercially available, but their supply is very limited. Preparation of these starting materials is necessary for studying the (3-lactam formation reaction [93]. Nitro compounds are the precursors for the amines. An important task was to prepare polycyclic aromatic nitro compounds, particularly those of chrysene, phenanthrene, pyrene, and dibenzofluorene in good yield. Nitration of these hydrocarbons with concentrated nitric acid in sulfuric acid is a widely used reaction for this purpose. Our research culminated in facile synthesis of polyaromatic nitro derivative 9 starting from polyaromatic hydrocarbons (PAHs) 8 through the use of bismuth nitrate impregnated with clay (Scheme 1) ([94, 95] for some examples of bismuth nitrate-catalyzed reactions... 

The preparation of phenols by the hydrolysis of diazonium salts with hot aqueous acid, and by a recent milder procedure suitable for diazonium salts having additional acid-sensitive groups, is discussed in Section 6.7.1, p. 922, and illustrated in Expt 6.69. Although these methods enable an aromatic hydrocarbon system to be converted in good yield into a phenol via the corresponding nitro and amino derivatives, the shorter route involving the alkaline fusion of the sulphonic acid discussed above may often be preferred. 

Aromatic nitro compounds that contain a side chain (e.g. nitro derivatives of alkylbenzenes) may be oxidised to the corresponding acids either by alkaline potassium permanganate (Aromatic hydrocarbons, Section 9.6.3, p. 1238) or, preferably, with a sodium dichromate-sulphuric acid mixture in which medium the nitro compound is more soluble. 

Nitro-polycyclic aromatic hydrocarbons, referred to as nitro-aromatic compounds hereafter, constitute one of the most troubling classes of environmental pollutants. They are derivatives of polycyclic aromatic hydrocarbons (PAHs) that contain two or more fused aromatic rings made of carbon and hydrogen atoms and at least one nitro group (Fig. 10.1). Concern about these compounds arises partly from their ubiquity nitro-aromatic compounds are released to the environment directly from a variety of incomplete combustion processes [1] and are also formed in situ by atmospheric reactions of PAHs [2]. Nitro-aromatic compounds have been found in grilled food in diesel, gasoline, and wood-smoke emissions and are commonly found in atmospheric particulate matter, natural waters, and sediment [3-8],... 

K.K. Colvert, P.P. Fu, Xanthine oxidase-catalyzed DNA binding of dihydrodiol derivatives of nitro-polycyclic aromatic hydrocarbons. Biochem. Bioph. Res. Co. 141, 245-250 (1986)... 

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. 

It has been shown that aromatic hydrocarbons can be nitrated by pemitrous acid even at very low acid concentrations (e.g. 2%) at room temperature. The hydroxylation of the hydrocarbon takes place simultaneously in many cases. A characteristic feature of the reaction is that the nitro group mostly takes the meta position with respect to the substituent already present. If a nitro and a hydroxyl group are introduced simultaneously the hydroxyl group nearly always takes the ortho or para position with respect to the substituent already present. Diphenyl derivatives are also formed. 

At high temperatures 2,4,6-trinitro-m-xylene is readily dissolved by acetic acid and by aniline. 2,4,6-Trinitro-m-xylene forms eutectics with aromatic hydrocarbons and their nitro derivatives. Some of the available data are tabulated (Table 90). 

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