Sulfones chlorination

The treatment methods for ruber wastewaters consist of various biological processes, and physico-chemical processes including coagulation, ozonation, activated carbon adsorption, aeration, sulfonation, chlorination, and aeration, and biological nutrient removal processes. The purpose of the treatment is to meet USEPA effluent limitations [4]. 

Even the comparatively unreactive phenoxazine and phenothiazine systems undergo halogenation and nitration with ease and it is normal to prepare monosubstituted derivatives by stepwise procedures rather than by direct electrophilic attack. Indeed, the nitration of phenoxazine is uncontrollable and even N-acylphenoxazines afford a mixture of di- and tetra-nitro products (03CB475). Similarly phenothiazine and nitric acid produce a complex mixture of nitrated sulfoxides and sulfones. Chlorine in DMSO at 40 °C reacts with phenothiazine to yield 3,7-dichlorophenothiazine, whereas cupric chloride gives the 1,7-isomer (76JPR353). Direct bromination of phenoxazine produces a mixture of 3-bromo- and 3,7-dibromo-phenoxazines, while thionyl chloride affords the 1,3,7,9-tetrachloro derivative (60ZOB1893). 

Most of the phenol used in the United States is made by the oxidation of cumene, yielding acetone as a byproduct. The first stqn in the reaction yields cumene hydroperoxide, which decomposes with dilute sulfuric acid to the primary products, plus acetophenone and phenyl dimethyl carbinol. Other processes include sulfonation, chlorination of benzene, and oxidation of benzene. The compound is purified by rectification. 

Sulfonation oxidation of hydrocarbon is similar to sulfonation-chlorination of hydrocarbon. Alkyl sulfonic acid can be synthesized under ultraviolet radiation by adopting saturated hydrocarbon, SO2, and O2 as raw materials. The reaction can be given by the following ... 

The word ionomer dates back to 1965, but materials of this type had been synthesized and investigated long before. Examples of early work include the investigation of Littman and Marvel in 1930, synthesis of an elastomer based on butadiene and acrylic acid in the early 1930 s, and the appearance in the 1950 s of du Font s Hypalon (sulfonated, chlorinated, and cross-linked polyethylene) [29]. 

Chemical treatments to modify surface groups (e.g. oxidation, sulfonation, chlorination, acetylation, quatemization)... 

When unsubstituted, C-5 reacts with electrophilic reagents. Thus phosphorus pentachloride chlorinates the ring (36, 235). A hydroxy group in the 2-position activates the ring towards this reaction. 4-Methylthiazole does not react with bromine in chloroform (201, 236), whereas under the same conditions the 2-hydroxy analog reacts (55. 237-239. 557). Activation of C-5 works also for sulfonation (201. 236), nitration (201. 236. 237), Friede 1-Crafts reactions (201, 236, 237, 240-242), and acylation (243). However, iodination fails (201. 236). and the Gatterman or Reimer-Tieman reactions yield only small amounts of 4-methyl-5-carboxy-A-4-thiazoline-2-one. Recent kinetic investigations show that 2-thiazolones are nitrated via a free base mechanism. A 2-oxo substituent increases the rate of nitration at the 5-position by a factor of 9 log... 

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). 

Substitution. Substitution products retain the same nuclear configuration as naphthalene. They are formed by the substitution of one or more hydrogen atoms with other functional groups. Substituted naphthalenes of commercial importance have been obtained by sulfonation, sulfonation and alkah fusion, alkylation, nitration and reduction, and chlorination. 

The cumene oxidation route is the lea ding commercial process of synthetic phenol production, accounting for more than 95% of phenol produced in the world. The remainder of synthetic phenol is produced by the toluene oxidation route via benzoic acid. Other processes including benzene via cyclohexane, benzene sulfonation, benzene chlorination, and benzene oxychl orin ation have also been used in the manufacture of phenol. A Hst of U.S. phenol production plants and their estimated capacities in 1994 are shown in Table 2, and worldwide plants and capacities are shown in Table 3. 

Very unstable modifications, like the reddish, chlorine-free a-copper phthalocyanine, can be stabilized with amides or salts of copper phthalocyanine sulfonic acids (59—63). Mixture with other metal phthalocyanines, eg, tin, vanadium, aluminum, or magnesium, also inhibits crystallization change and poor performance in binders and prints (flocculation) due to the hydrophobic character of unsubstituted phthalocyanines. 

PMB Sulfon ation Acylation Chloromethylation Ring chlorination... 

Use of mercuric catalysts has created a serious pollution problem thereby limiting the manufacture of such acids. Other catalysts such as palladium or mthenium have been proposed (17). Nitration of anthraquinone has been studied intensively in an effort to obtain 1-nitroanthraquinone [82-34-8] suitable for the manufacture of 1-aminoanthraquinone [82-45-1]. However, the nitration proceeds so rapidly that a mixture of mono- and dinitroanthraquinone is produced. It has not been possible, economically, to separate from this mixture 1-nitroanthraquinone in a yield and purity suitable for the manufacture of 1-aminoanthraquinone. Chlorination of anthraquinone cannot be used to manufacture 1-chloroanthraquinone [82-44-0] since polychlorinated products are formed readily. Consequentiy, 1-chloroanthraquinone is manufactured by reaction of anthraquinone-l-sulfonic acid [82-49-5] with sodium chlorate and hydrochloric acid (18). 

The aromatic nature of lignin contrasts with the aliphatic stmcture of the carbohydrates and permits the selective use of electrophilic substitution reactions, eg, chlorination, sulfonation, or nitration. A portion of the phenoUc hydroxyl units, which are estimated to comprise 30 wt % of softwood lignin, are unsubstituted. In alkaline systems the ionized hydroxyl group is highly susceptible to oxidative reactions. 

There has been considerable research on chlorine-resistant RO membranes (48—52). A poly(/n j -2,5 dimethyl)pipera2inthiofura2anainide used in the presence of low (3 mg/L) concentrations of chlorine resulted in a membrane life of three years (48). A copolyamide hoUow-fiber membrane for use in desalination has been developed that is resistant to 0.5 mg/L chlorine (49). Millipore Corporation has also developed a sulfonated polysulfone member that has desirable chlorine-resistance properties. 

In sulfamation, also termed A/-sulfonation, compounds of the general stmcture R2NSO2H are formed as well as their corresponding salts, acid hahdes, and esters. The reagents are sulfamic acid (amido—sulfuric acid), SO —pyridine complex, SO —tertiary amine complexes, ahphatic amine—SO. adducts, and chlorine isocyanate—SO complexes (3). 

Sulfochlorination of Paraffins. The sulfonation of paraffins using a mixture of sulfur dioxide and chlorine in the presence of light has been around since the 1930s and is known as the Reed reaction (123). This process is made possible by the use of free-radical chemistry and has had limited use in the United States. Other countries have had active research into process optimization (124,125). 

The cleavage products of several sulfonates are utilized on an industrial scale (Fig. 3). The fusion of aromatic sulfonates with sodium hydroxide [1310-73-2J and other caustic alkalies produces phenohc salts (see Alkylphenols Phenol). Chlorinated aromatics are produced by treatment of an aromatic sulfonate with hydrochloric acid and sodium chlorate [7775-09-9J. Nitriles (qv) (see Supplement) can be produced by reaction of a sulfonate with a cyanide salt. Arenesulfonates can be converted to amines with the use of ammonia. This transformation is also rather facile using mono- and dialkylamines. 

Fluorinated and Ghlorfluorinated Sulfonic Acids. The synthesis of chlorinated and fluorinated sulfonic acids has been extensively reviewed (91,92). The Hterature discusses the reaction of dialkyl sulfides and disulfides, sulfoxides and sulfones, alkanesulfonyl haHdes, alkanesulfonic acids and alkanethiols with oxygen, hydrogen chloride, hydrogen fluoride, and oxygen—chloride—hydrogen fluoride mixtures over metal haHde catalysts, such as... 

The organic chemistry of sulfuryl chloride involves its use in chlorination and sulfonation (172,175,196,197). As a chlorinating agent, sulfuryl chloride is often mote selective than elemental chlorine. The use of sulfuryl chloride as a chlorinating agent often allows mote convenient handling and measurement as well as better temperature control because of the lower heat of reaction as compared with chlorine. Sulfuryl chloride sometimes affords better selectivity than chlorine in chlorination of active methylene compounds (198—200) ... 

Miscellaneous. In ore flotation, sodium sulfite functions as a selective depressant. In textile processing, sodium sulfite is used as a bleach for wood (qv) and polyamide fibers and as an antichlor after the use of chlorine bleach. Synthetic appHcations of sodium sulfite include production of sodium thiosulfite by addition of sulfur and the introduction of sulfonate groups into dyestuffs and other organic products. Sodium sulfite is useful as a scavenger for formaldehyde in aminoplast—wood compositions, and as a buffer in chrome tanning of leather. 

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

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. 

Tetrachlorotoluene, C H Cl (mol wt 229.93) (1,2,3,5-tetrachloro-4-methylben2ene), is prepared from the Sandmeyer reaction on 3-arnino-2,4,6-trichlorotoluene. 2,3,4,5-Tetrachlorotoluene (l,2,3,4-tetrachloro-5-methylben2ene) is the principal isomer in the further chlorination of 2,4,5-trichlorotoluene. Exhaustive chlorination of -toluenesulfonyl chloride, followed by hydrolysis to remove the sulfonic acid group yields... 

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