Sulfurization, of aromatic

Sulfurization of aromatic rings with thionyl chloride... 

Too little is known about the nature of these reactions, although possible overall reaction pathways, including dehydrogenation of tetrahydroaromatics, chlorination and sulfuration of aromatics and their conversion into SSCl derivatives, and the pentathiepin ring formation, were proposed. 

This usefulness of the correlation is twq-fpld first it provides information on the cetane indices that are not aViit le in the literature as in the cases of polynuclear aromatics and sulfur-containing aromatics, and second it helps provide an evaluation of the cetane index based on a few milligrams of sample, instead of the liter or so required for the motor method. 

Table 5.28 gives the modifications in physical/chemical characteristics resulting from deeper and deeper hydrotreatment (Martin et al., 1992). The sulfur contents could thus be reduced to first as low as a few hundred ppm, then to a few ppm. The level of aromatics in the selected example drops from 39% to 7% while the cetane number increases from 49 to 60. Note here that such a treatment, possible through experimental means, does not correspond to current industrial practice because of its high cost and its very high hydrogen consumption. 

During my Cleveland years, I also continued and extended my studies in nitration, which I started in the early 1950s in Hungary. Conventional nitration of aromatic compounds uses mixed acid (mixture of nitric acid and sulfuric acid). The water formed in the reaetion dilutes the acid, and spent aeid disposal is beeoming a serious environ-... 

To solve some of the environmental problems of mixed-acid nitration, we were able to replaee sulfuric acid with solid superacid catalysts. This allowed us to develop a novel, clean, azeotropic nitration of aromatics with nitric acid over solid perfluorinated sulfonic acid catalysts (Nafion-H). The water formed is continuously azeotroped off by an excess of aromatics, thus preventing dilution of acid. Because the disposal of spent acids of nitration represents a serious environmental problem, the use of solid aeid eatalysts is a significant improvement. 

The amount of sulfur in aromatic monomers can be determined by differential pulse polarography. Standard solutions are prepared for analysis by dissolving 1.000 mb of the purified monomer in 25.00 mb of an electrolytic solvent, adding a known amount of S, deaerating, and measuring the peak current. The following results were obtained for a set of calibration standards... 

Sulfonation of aromatic hydrocarbons with sulfuric acid is cataly2ed by hydrogen fluoride or, at lower temperatures, by boron trifluoride (144). The products obtained are more uniform and considerably less sulfuric acid is needed, probably because BF forms complexes with the water formed ia the reaction, and thus prevents dilution of the sulfuric acid. 

The significance of the total sulfur content of kerosene varies greatly with the type of oil and the use to which it is put. Sulfur content is of great importance when the kerosene to be burned produces sulfur oxides, which are of environmental concern. The color of kerosene is of Htde significance but a product darker than usual may have resulted from contamination or aging in fact, a color darker than specified may be considered by some users as unsatisfactory. Kerosene, because of its use as a burning oil, must be free of aromatic and unsaturated hydrocarbons the desirable constituents of kerosene are saturated hydrocarbons. 

One class of aromatic polyethers consists of polymers with only aromatic rings and ether linkages ia the backbone poly(phenylene oxide)s are examples and are the principal emphasis of this article. A second type contains a wide variety of other functional groups ia the backbone, ia addition to the aromatic units and ether linkages. Many of these polymers are covered ia other articles, based on the other fiinctionahty (see Polymers containing sulfur, POLYSULFONES). 

The aromatic sulfone polymers are a group of high performance plastics, many of which have relatively closely related stmctures and similar properties (see Polymers containing sulfur, polysulfones). Chemically, all are polyethersulfones, ie, they have both aryl ether (ArOAr) and aryl sulfone (ArS02Ar) linkages in the polymer backbone. The simplest polyethersulfone (5) consists of aromatic rings linked alternately by ether and sulfone groups. 

Reduction. Just as aromatic amine oxides are resistant to the foregoing decomposition reactions, they are more resistant than ahphatic amine oxides to reduction. Ahphatic amine oxides are readily reduced to tertiary amines by sulfurous acid at room temperature in contrast, few aromatic amine oxides can be reduced under these conditions. The ahphatic amine oxides can also be reduced by catalytic hydrogenation (27), with 2inc in acid, or with staimous chloride (28). For the aromatic amine oxides, catalytic hydrogenation with Raney nickel is a fairly general means of deoxygenation (29). Iron in acetic acid (30), phosphoms trichloride (31), and titanium trichloride (32) are also widely used systems for deoxygenation of aromatic amine oxides. 

Nitration. Direct nitration of aromatic amines with nitric acid is not a satisfactory method, because the amino group is susceptible to oxidation. The amino group can be protected by acetylation, and the acetylamino derivative is then used in the nitration step. Nitration of acetanilide in sulfuric acid yields the 4-nitro compound that is hydroly2ed to -rutroaruline [100-01-6]. 

Nitration of aromatic amines with urea nitrate in sulfuric acid is reported to yield the -nitro derivative exclusively (44). When the para position is blocked, the meta product is obtained in excellent yield. 

Electrolytic reductions generally caimot compete economically with chemical reductions of nitro compounds to amines, but they have been appHed in some specific reactions, such as the preparation of aminophenols (qv) from aromatic nitro compounds. For example, in the presence of sulfuric acid, cathodic reduction of aromatic nitro compounds with a free para-position leads to -aminophenol [123-30-8] hy rearrangement of the intermediate N-phenyl-hydroxylamine [100-65-2] (61). 

The largest use of NMP is in extraction of aromatics from lube oils. In this appHcation, it has been replacing phenol and, to some extent, furfural. Other petrochemical uses involve separation and recovery of aromatics from mixed feedstocks recovery and purification of acetylenes, olefins, and diolefins removal of sulfur compounds from natural and refinery gases and dehydration of natural gas. 

Sulfur dioxide acts as a dienophile ia the Diels-Alder reaction with many dienes (253,254) and this reaction is conducted on a commercial scale with butadiene. The initial adduct, sulfolene [77-79-2] is hydrogenated to a solvent, sulfolane [126-33-0] which is useful for selective extraction of aromatic hydrocarbons from... 

Nitrobenzotrichloride is also obtained in high yield with no significant hydrolysis when nitration with a mixture of nitric and sulfuric acids is carried out below 30°C (31). 2,4-Dihydroxybenzophenone [131 -56-6] is formed in 90% yield by the uncatalyzed reaction of benzotrichloride with resorcinol in hydroxyHc solvents (32) or in benzene containing methanol or ethanol (33). Benzophenone derivatives are formed from a variety of aromatic compounds by reaction with benzotrichloride in aqueous or alcohoHc hydrofluoric acid (34). 

Benzisothiazoles can be prepared by the reaction of aromatic chloro compounds with sulfur and ammonia. Thus, 2,6-dichlorobenzylidene chloride gives 4-chloro-l,2-benzisothiazole (72AHC(14)43), and 2-chlorobenzophenone gives 3-phenyl-l,2-benziso-thiazole (79GEP27 34866). 

Liquid/hquid reactions of industrial importance are fairly numerous. A hst of 26 classes of reactions with 61 references has been compiled by Doraiswamy and Sharma Heterogeneou.s Reactions, Wiley, 1984). They also indicate the kind of reactor normally used in each case. The reactions range from such prosaic examples as making soap with alkali, nitration of aromatics to make explosives, and alkylation of C4S with sulfuric acid to make improved gasoline, to some much less familiar operations. 

Impurities can sometimes be removed by conversion to derivatives under conditions where the major component does not react or reacts much more slowly. For example, normal (straight-chain) paraffins can be freed from unsaturated and branched-chain components by taking advantage of the greater reactivity of the latter with chlorosulfonic acid or bromine. Similarly, the preferential nitration of aromatic hydrocarbons can be used to remove e.g. benzene or toluene from cyclohexane by shaking for several hours with a mixture of concentrated nitric acid (25%), sulfuric acid (58%), and water (17%). 

---