Sulfur compounds aromatic, references

A review published in 1993 compiled reports on bioconversion of Cl-sulfur compounds and included aromatic sulfur compounds as well but was more focused on volatile and low-MW organosulfur compounds [185], The reader is referred to this review for biodegradation of those sulfur molecules. 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

The positive identification of the sulfur compounds in crude oils is a difficult problem often complicated by the lack of reference compounds. This difficulty has been overcome by hydrodesulfurization (see Section VIII), which converts the sulfur compounds into known hydrocarbons. Treatment of a petroleum oil fraction with calcium hexammine converts the benzo[6]thiophenes present into aryl mercaptans, which are readily separable from accompanying aromatic hydrocarbons (e.g., naphthalene) and then identified by hydro-... 

Chlorinated and aromatic hydrocarbons, organic esters, aromatic hydroxy compounds, and certain ketones have an adverse effect on neoprene and consequently only Umited serviceability can be expected with them. Highly oxidizing acid and salt solutions also cause surface deterioration and loss of strength. Included in this category are nitric acid and concentrated sulfuric acid. Table 4.11 provides the compatibility of neoprene with selected corrodents. Reference 1 provides a more detailed listing. 

An excess of crotonaldehyde or aUphatic, ahcyhc, and aromatic hydrocarbons and their derivatives is used as a solvent to produce compounds of molecular weights of 1000—5000 (25—28). After removal of unreacted components and solvent, the adduct referred to as polyester is decomposed in acidic media or by pyrolysis (29—36). Proper operation of acidic decomposition can give high yields of pure /n j ,/n7 j -2,4-hexadienoic acid, whereas the pyrolysis gives a mixture of isomers that must be converted to the pure trans,trans form. The thermal decomposition is carried out in the presence of alkaU or amine catalysts. A simultaneous codistillation of the sorbic acid as it forms and the component used as the solvent can simplify the process scheme. The catalyst remains in the reaction batch. Suitable solvents and entraining agents include most inert Hquids that bod at 200—300°C, eg, aUphatic hydrocarbons. When the polyester is spHt thermally at 170—180°C and the sorbic acid is distilled direcdy with the solvent, production and purification can be combined in a single step. The solvent can be reused after removal of the sorbic acid (34). The isomeric mixture can be converted to the thermodynamically more stable trans,trans form in the presence of iodine, alkaU, or sulfuric or hydrochloric acid (37,38). 

Cyclic compounds in which one or more of the ring atoms is not carbon are termed heterocycles the noncarbon atoms are referred to as heteroatoms. We shall limit our discussions to compounds in which the heteroatoms are nitrogen, oxygen, or sulfur. For the purposes of studying and understanding their properties, heterocycles are conveniently grouped into two classes, i.e. non-aromatic and aromatic. 

The electron spin resonance (ESR) spectra of the radical ions of 230 indicate there are no large deviations from the free-electron g value that would have been expected had the 3d orbitals of the sulfur atom played an important part in influencing the spin density of the molecule. Consequently, structure 230 may not be the main contributor to the electronic structure of the compound. Such stability in this compound could be attributed to the inertness of the NSN group and the presence of the aromatic naphthalene ring. However, the H-NMR chemical shifts (8 = 4.45 ppm) suggest the compound is antiaromatic. The compound is therefore referred to as an ambiguous aromatic compound (78JA1235). 

The chain terminating additives are usually aromatic amines, phenols, or sulfides. Those that inhibit the catalytic effect of metallic ions such as Cu, Fe, Pb, Mn, and Co are generally organic sulfides, phosphites, or thiophosphates. Although oxidation or corrosion inhibitors are frequently referred to separately, many of the phosphorus and sulfur containing compounds are effective in both applications. The entire matter of oxidation is affected by many things, including the temperature of the lubricant and the material of construction of the equipment in which the lubricant is used. It is also materially affected by inherent resistance of the base oil to oxidation. 

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