Sulfonic acids, reaction with chlorosulfonic acid

Polyketones can be sulfonated by reaction with chlorosulfonic acid the products are chemically reactive and are useful as strongly acidic esterification catalysts and ion-exchange resins. The sulfonation of ethylene-carbonyl copolymer was achieved by treatment of the substrate with chlorosulfonic acid in dichloroethane at 0 C. " ... 

Polyketones are sulfonated by reaction with chlorosulfonic acid (see Chapter 5, p 162) and sulfonated aromatic polyether-polyketones have been obtained by treatment with mixtures of sulfur trioxide and chlorosulfonic acid. The sulfonated polymers are compression mouldable at high temperatures. Poly(arylether ketone) fibres of good dyeability were produced by treating the fibres with chlorosulfonic acid, sulfuric acid or sulfur trioxide. ... 

The phthalocyanine dyes are prepared from chlorosulfonated phthalocyanine by condensation with the appropriate amine. Thus, phthalocyanine was tetrachloro-sulfonated by reaction with chlorosulfonic acid and the product condensed with 2-(2-methoxyethoxy) ethyl 4-aminobenzoate to yield the dye (A max = 672 nm) (Chapter 6, Section 1.2.7). 

In sulfonation reactions with chlorosulfonic acid, as well as with sulfuric acid and oleum, small amounts of sulfones are often formed as by-products. The sulfone is formed by the reaction of the sulfonic acid with unchanged starting material under the influence of the dehydrating action of the sulfonation reagent, according to the equation ... 

The reaction with chlorosulfonic acid affords the sulfonyl chloride rather than the sulfonic acid (Scheme 4.4). 

For sufficient surface area being retained after the functionality, PPN-6 (also known as PAF-1 [26]) with ultrahigh surface area and physicochemical stability was chosen as the starting material. The uniformly large pores would shuttle the reactants and improve the diffusion rates. In addition, the robust all-carbon scaffold of PPN-6 makes it an ideal candidate for attachment of polar functionalities on biphenyl species under harsh reaction condition. In detail, the sulfonate-grafted PAFs (PPN-6-SO3H) was synthesized by reaction with chlorosulfonic acid, and its lithium salt (PPN-b-SOsLi) was obtained by further neutralized with LiOH solution [69]. 

Under even more drastic conditions (150 °C, 4 hours), the same reaction mixture afforded the cyclic sulfone disulfonyl chloride 21 (45%). Attempted chlorosulfonations of a-chloro and a,a -dichlorodiphenylmethane by reaction with chlorosulfonic acid failed, possibly because die substitution of the a-hydrogens destroys the activating hyperconjugative effect on the phenyl rings. ... 

Iodonaphthalene by reaction with chlorosulfonic acid in carbon disulfide similarly afforded mainly the 4-sulfonic acid with a little of the sulfonyl chloride. ... 

With the 2-halonaphthalenes 79, the orientation of sulfonation depends on the nature of the halogen atom when it is chlorine or bromine, reaction with chlorosulfonic acid (one equivalent) in cold carbon disulfide gives a mixture of the 6- and 8-sulfonic acids (80, 81 X = Cl, Br) (Equation 24). 

Dibromofluorene 87, by reaction with chlorosulfonic acid (one equivalent) in chloroform, yields a mono-sulfonic acid, probably the 3-acid 88, although in this orientation the sulfonic acid group would be adjacent to the comparatively large bromine atom (Equation 27). ... 

The sulfonation of l-(2-hydroxyethyl)-2,4,6-trinitrobenzene 114 by reaction with chlorosulfonic acid followed by treatment with aqueous ammonia yields novel energetic sulfonate salts 115 (Equation 37). These salts can be used in conjunction with ammonium nitrate in explosive formulations. Studies of the relative reactivity of nitrobenzene and w-chloronitrobenzene towards chlorination in chlorosulfonic acid showed that the former compound was 4.77 times more reactive. 

A novel heparin-like material may be obtained by conversion of chitosan flake into the hydroxypropylchitosan, followed by reaction with chlorosulfonic acid and formamide to give the sulfonated derivative, which has good aqueous solubility. ... 

Poly(phenylene oxide) is stablized by a reaction with chlorosulfonic acid and poly(aryl ether) resins are sulfonated by a mixture of chlorosulfonic acid and a silyl halide followed by base-catalysed cleavage of the silyl group. Antistatic polyoxyphenylenes were obtained by surface sulfonation with a saturated solution of chlorosulfonic acid in n-hexane for 25-30 minutes. ... 

Sulfonated polyether ketones are obtained by reaction with chlorosulfonic acid and have potential as asymmetric membranes. Under suitable conditions, the polymer chain was not degraded, although chlorosulfonated derivatives were not isolated. ... 

Triisopropylbenzene 12, by reaction with chlorosulfonic acid at 20 °C, cyclized to the sulfonic acid ester 13 (Equation 4)."... 

In a stage of the synthesis, 4-(2-ethoxybenzamido)-l-methyl-3-propyl-pyrazole-5-carboxamide was chlorosulfonated by reaction with chlorosulfonic acid-thionyl chloride (18 hours) to yield 4-ethoxy-3-(5-aminocarbonyl-l-methyl-3-propylp5n-azol-4-yl) carbamoylbenzenesulfonyl chloride. In this reaction, sulfonation occurs preferentially para with respect to the more powerful electron-donating ethoxy group as would be anticipated (Chapter 6, Section 1.2.4). 

Chitosan was sulfonated by treatment with chlorosulfonic acid-formamide, in which the ratio of chitosan to formamide was 1 g 10 ml. Studies were made of the effects of the addition of chlorosulfonic acid, reaction temperature and time. The optimum conditions for the sulfonation were 4 ml of chlorosulfonic acid for 1 g of chitosan and a reaction temperature of 68 °C for 4 hours (see Chapter 5, Section 3.2). 

PPO and PPOBr were sulfonated by reacting with chlorosulfonic acid in chloroform [49]. The degree of sulfonation was determined by acid-base titration method. Under the reaction conditions only mono-aryl substitution of PPO and PPOBr occurred. The polymers were converted to the salt form by replacing the proton of the sulfonic acid group with Na-cation. Sulfonated PPO (SPPO) and sulfonated brominated PPO (SPPOBr), both in the Na-cation form (SPPONa and NaSPPOBr), were used for water removal studies. 

When two polymers interact or react with each other, they are likely to provide a compatible, even a miscible, blend. Epoxidized natural rubber (ENR) interacts with chloro-sulfonated polyethylene (Hypalon) and polyvinyl chloride (PVC) forming partially miscible and miscible blends, respectively, due to the reaction between chlorosulfonic acid group and chlorine with epoxy group of ENR. Chiu et al. have studied the blends of chlorinated polyethylene (CR) with ENR at blend ratios of 75 25, 50 50, and 25 75, as well as pure rubbers using sulfur (Sg), 2-mercapto-benzothiazole, and 2-benzothiazole disulfide as vulcanizing agents [32]. They have studied Mooney viscosity, scorch... 

The first step involved the reaction of PPO with chlorosulfonic acid according to a literature method (H). The sulfonated PPO was hygroscopic and unstable. We succeeded (12) in converting the sulfonate groups into stable sulfone groups by reacting them with aromatic compounds at elevated temperatures (120 0. The final dark solution was washed with dilute sodium bicarbonate, and the product precipitated in methanol, filtered and dried. 

Mulhaupt et al. synthesized novel soluble copoly-arylenes via a Ni(0)-catalyzed coupling reaction of aryl chlorides. Molar ratios of dichlorodiphenyl sulfone (a) to m-dichlorobenzene (y) were used to vary the amount of m-phenylene in the final copolymer. Then these copolymers were dissolved in chloroform and sulfonated with chlorosulfonic acid. The synthe-... 

The 3,7-disulfonyl chloride of dibenzothiophene 5,5-dioxide has been isolated from the reaction of biphenyl with chlorosulfonic acid. The reaction proceeds via the 2,4,4 -trisulfonyl chloride of biphenyl. This reaction has now been extended to give sulfonic acid derivatives of 3-phenyl- and 3-biphenylyldibenzothiophene 5,5-dioxide. Treatment of p-terphenyl with oleum or chlorosulfonic acid at 100° yields (141a) (46%), and similarly p-quaterphenyl yields 141b (47%). A later... 

Both types of wax are readily oxidized (24) and halogenated (116). The latter is an important commercial outlet, the products of which are used as extreme pressure additives for oil (112,113) and as intermediates in Friedel-Crafts condensations (119). Air oxidation leads to carboxylic acids, for which considerable use has been found both here and abroad. Sulfonates can be made by reaction of waxes with chlorosulfonic acid (37,104) or with sulfur dioxide and chlorine (46,99). 

The toluene-para-sulfonate group (OTs) is important as a leaving group if you want to carry out an S>j2 reaction on an alcohol (Chapter 17) and the acid chloride (tosyl chloride, TsCl) can be made from the acid in the usual way with PC15. It can also be made directly from toluene by sulfonation with chlorosulfonic acid CISO2OH. This reaction favours the ortho sulfonyl chloride which is isolated by distillation. 

The reaction of quinazolin-4(3i/)-one with chlorosulfonic acid gives the corresponding quin-azoline-6-sulfonyl chloride which can be characterized by conversion to 4-oxo-3,4-dihy-droquinazoline-6-sulfonamide (mp of hydrate 217-220°C). Sulfonation of 7-chloroquina-zolin-4(3 7)-one with fuming sulfuric acid in the presence of mercury(II) oxide affords a small amount of 7-chloro-4-oxo-3,4-dihydroquinazoline-6-sulfonic acid. ... 

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