Sulfones isomers

In addition to 1,2-, 2,1-, and 1,4-aminonaphthols, sulfonated isomers of 1,7- and 2,6-isomers have also been diazotized, some of this work dating back to the early 1900s (Jacchia, 1902 Cain and Niccol, 1903 Kaufler and Karrer, 1907 Allan and Podstata, 1969). 

The interesting work of Martin and coworkers " on oxygen-substituted sul-furanes(VI) lO-S-4 and 12-S-6 species made available for the first time quasi mono-and bis-acetals of sulfones (1 and 2). Proton-catalyzed fragmentation of lb led to the sulfone isomer 3 the corresponding fragmentation of 2a gave, depending on reaction conditions, the isomeric sulfone 4 or a mixture of the sulfone isomers 4 and 5 . 

The 4-sulfonate isomers have found use in certain formulations. These materials are easily identified, since they have a single absorbance maximum in the wavelength region of interest that is centered at approximately 380 nm., and they have little or no absorbance at 436 nm (Figure 21). The absorbance spectra of two representative positive resist formulations are provided in Figures 22 and 23. These spectra were obtained by casting the resists on quartz substrates and then recording the absorbance... 

Finally, a few miscellaneous compounds which were identified in the Delaware River and which have not been previously reported as water contaminants will be discussed Chloro (trifluoromethyl) aniline and chloro (trifluoromethyl) nitrobenzene (no. 55 and 56) were identified in the water, they had maximum concentrations at river mile 78. Both compounds represent common sub-structures in various pesticide and dye molecules, and several of the companies located along the river have patents using these compounds (30-32j. It is possible that these compounds are actually present in the river water as such, but it is also possible that they are formed in the GC injection port by pyrolytic degradation of larger pesticide or dye molecules (see above). All three binaphthyl-sulfone isomers (no. 92) were identified in the river water near Philadelphia. Product literature for one of the companies in the area indicates production of condensed sulfonated polymers derived from naphthalene sulfonic acid and maleic anhydride. It seems likely that the binaphthylsulfones are formed as by-products during preparation of this commercial product. 

Lunar, L., S. Rubio, and D. Perez-Bendito. 2004. Differentiation and quantification of linear alkyl benzene-sulfonate isomers by liquid chromatography-ion-trap mass spectrometry./. Chromatogr. A 1031 17-25. 

The formation of undesired sulfonate isomers can often be corrected by variations in reaction temperature or time. These factors are discussed more fully in a subsequent section. The addition of inorganic catalysts, such as mercury, can also have an important directive influence on isomer formation in some cases. 

Preparation of the 2-sulfonate isomer is similar, except that no mercury is used and a higher temperature (146°C) is employed with 22 per cent oleum. In both processes, partial conversion minimizes yield loss from disulfonation and oxidation, but entails wasteful use of sulfonating agent since, for every pound of anthraquinone reacted, 2.1 lb oleum (equivalent as SO3) is used contrasted to 0.38 lb theoretical. When mercury is used, the anthraquinone is first mercurated, followed by displacement of the mercury by the sulfonate group. 

Chu S, Letcher RJ (2009) Linear and branched perfluorooctane sulfonate isomers in technical product and environmental samples by in-port derivatization-gas chromatography-mass spectrometry. Anal Chem 81 4256—4262... 

Sulfonic acid Isomer distribution data for the SO3 sulfonation are available for alkylbenzenes and their halogeno derivatives phenol and anisole, and their methyl, halogeno, and hydroxy and methoxy derivatives and naphthalene, and Its methyl, and hydroxy and methoxy derivatives. SO3 sulfonation Isomer distribution data are also available for a number of polycyclic aromatic hydrocarbons and 1,6-methano[10]annulenes, including some alkyl derivatives. ... 

N. Yu, W. Shi, B. Zhang, G. Su, J. Feng, X. Zhang, S. Wei and H. Yu, Occurrence of perfluoroalkyl acids including perfluorooctane sulfonate isomers in Huai River Basin and Taihu Lake in Jiangsu Province, China, Environ. Sci. Technol. 47, 710-717(2013). 

As in most electrophilic reactions, the abiUty to stabilize the positive charge generated by the initial addition strongly affects the relative rates. MX reacts faster than OX and PX because both methyl groups work in conjunction to stabilize the charge on the next-but-one carbon. Sulfonation was, at one time, used to separate MX from the other Cg aromatic isomers. MX reacts most rapidly to form the sulfonic acid which remains in the aqueous phase. The sulfonation reaction is reversible, and MX can be regenerated. 

Each isomer has its individual set of physical and chemical properties however, these properties are similar (Table 6). The fundamental chemical reactions for pentanes are sulfonation to form sulfonic acids, chlorination to form chlorides, nitration to form nitropentanes, oxidation to form various compounds, and cracking to form free radicals. Many of these reactions are used to produce intermediates for the manufacture of industrial chemicals. Generally the reactivity increases from a primary to a secondary to a tertiary hydrogen (37). Other properties available but not Hsted are given in equations for heat capacity and viscosity (34), and saturated Hquid density (36). 

Sulphenone /5 (9-J(9-, /)-chlorophenyl phenyl sulfone (142), is a white soHd (mp 98°C). The technical material consists of ca 80% of this compound, with small amounts of 0- and y -isomers, bis(/)-chlorophenyl) sulfone, and diphenyl sulfone. Sulphenone is effective against all stages of mites. Its oral LD q to the rat is >2000 mg. 

Naphthalenesulfonic Acid. The sulfonation of naphthalene with excess 96 wt % sulfuric acid at < 80°C gives > 85 wt % 1-naphthalenesulfonic acid (a-acid) the balance is mainly the 2-isomer (P-acid). An older German commercial process is based on the reaction of naphthalene with 96 wt % sulfuric acid at 20—50°C (13). The product can be used unpurifted to make dyestuff intermediates by nitration or can be sulfonated further. The sodium salt of 1-naphthalenesulfonic acid is required, for example, for the conversion of 1-naphthalenol (1-naphthol) by caustic fusion. In this case, the excess sulfuric acid first is separated by the addition of lime and is filtered to remove the insoluble calcium sulfate the filtrate is treated with sodium carbonate to precipitate calcium carbonate and leave the sodium l-naphthalenesulfonate/7J(9-/4-J7 in solution. The dry salt then is recovered, typically, by spray-drying the solution. 

A naphthalene sulfonation product that is rich in the 2,6-isomer and low in sulfuric acid is formed by the reaction of naphthalene with excess sulfuric acid at 125°C and by passing the resultant solution through a continuous wiped-film evaporator at 245°C at 400 Pa (3 mm Hg) (26). The separation in high yield of 99% pure 2,6-naphthalenedisulfonate, as its anilinium salt from a cmde sulfonation product, has been claimed (27). A process has been patented for the separation of 2,6-naphthalenedisulfonic acid from its isomers by treatment with phenylenediarnine (28). 

The alpha-olefin sulfonates (AOS) have been found to possess good salt tolerance and chemical stabiUty at elevated temperatures. AOS surfactants exhibit good oil solubilization and low iaterfacial tension over a wide range of temperatures (219,231), whereas less salt tolerant alkylaromatic sulfonates exhibit excellent chemical stabiUty. The nature of the alkyl group, the aryl group, and the aromatic ring isomer distribution can be adjusted to improve surfactant performance under a given set of reservoir conditions (232,233). 

In the reaction of arulinium sulfate [542-16-5] with fuming sulfuric acid, the major products are m- and -aminoben2enesulfonic acid with less than 2% of the ortho isomer. With excess concentrated sulfuric acid (96.8—99.9%) at 60—100°C, the sulfate salt gives mainly the ortho and para isomers of the sulfonic acid (42). 

Sulfonic acids may be hydrolytically cleaved, using high temperatures and pressures, to drive the reaction to completion. As would be expected, each sulfonic acid has its own unique hydrolytic desulfonation temperature. Lower alkane sulfonic acids possess excellent hydrolytic stability, as compared to aromatic sulfonic acids which ate readily hydrolyzed. Flydrolytic desulfonation finds use in the separation of isomers of xylene sulfonic acids and other substituted mono-, di-, and polysulfonic acids. 

The ratio between the isomers obtained in coupling with 1,3- and 1,5-naphtholsulfonic acids depends on the reactivity of the diazo component. Energetic ones, such as the 2,4-dinitrobenzenediazonium compound, essentially couple only with l-naphthol-3-sulfonic acid [3771-14-0] in the para position, but 4-chloro-benzenediazonium salt (a weaker diazo) attacks the ortho position. Both isomers result when mononitrobenzenediazonium compounds are used. The tendency to couple para is greater in l-naphthol-5-sulfonic acid [117-59-9] C QHgO S (21). For the combination of... 

Diazophenols, ie, o-hydroxyaryldiazonium salts, couple to 1-naphthol in weaMy basic solution primarily in the para position, but as the hydroxyl ion concentration is increased, formation of the ortho isomer is favored and is frequentiy the sole product. Pyridine and pyridine derivatives, urea, and acetate, etc, used as buffers can also catalyze azo coupling reactions (28). l-amino-2-naphthol-4-sulfonic acid [116-63-2] (1,2,4-acid) and 1-naphthol yield the important Eriochrome Black A [3564-14-5] (18a, R = H) (Cl Mordant Black 3 Cl 14640) which is reportedly (20) a mixture of ortho and para isomers. 

The linear isomer is more valuable than the branched isomer (see Butyraldehyde). The product aldehydes ate hydrogenated to give so-called 0x0 alcohols long-chain products are converted iato sulfonates and used as detergents. 

The ring-chlorinated derivatives of toluene form a group of stable, industrially important compounds. Many chlorotoluene isomers can be prepared by direct chlorination. Other chlorotoluenes are prepared by indirect routes involving the replacement of amino, hydroxyl, chlorosulfonyl, and nitro groups by chlorine and the use of substituents, such as nitro, amino, and sulfonic acid, to orient substitution followed by their removal from the ring. 

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