Substitutions Chlorosulfonation

A series of fiber-reactive dyes have been made by the reaction of Sulforhodamine B with chlorosulfonic acid, an appropriately substituted diamine, and cyanutic chloride to yield dyes, eg, a Sulforhodamine B derivative (34), with good hghtfastness (42). 

The iso)tazole ring is rather resistant to sulfonation. However, on prolonged heating with chlorosulfonic acid, 5-methyl-, 3-methyl- and 3,5-diraethyl-isoxazoles are converted into a mixture of the sulfonic acid and the corresponding sulfonyl chloride. The sulfonic acid group enters the 4-position even when other positions are available for substitution. The sulfonation of the parent isoxazole occurs only under more drastic conditions (20% oleum) than that of alkyl isoxazoles isoxazole-4-sulfonic acid is obtained in 17% yield. In the case of 5-phenylisoxazole (64), only the phenyl nucleus is sulfonated to yield a mixture of m-and p-arenesulfonic acid chlorides (65) and (66) in a 2 1 ratio (63AHC(2)365). 

Imidazole, 2-amino-1 -methyl-4,5-diphenyl-tautomerism, 5, 368 Imidazole, 2-aroyl-mass spectra, 5, 360 synthesis, 5, 391, 402 UV spectra, 5, 356 Imidazole, 4-aroyl-synthesis, 5, 474 Imidazole, C-aroyl-UV spectra, 5, 356 Imidazole, aryl-nitration, 5, 396, 433 oxidation, 5, 433 Imidazole, 1-aryl-dipole moments, 5, 351 dearylation, 5, 449 ethylation, 5, 448 H NMR, 5, 353 hydroxymethylation, 5, 404 rearrangement, 5, 108 synthesis, 5, 390 thermal rearrangement, 5, 363 Imidazole, 2-aryl-chlorosulfonation, 5, 397 synthesis, 5, 475 Imidazole, 4-aryl-bromination, 5, 399 Imidazole, C-aryl-electrophilic substitution, 5, 432-433 nitration, 5, 433 Imidazole, N-aryl-reactions, 5, 448-449 structure, 5, 448-449 Imidazole, arylmercapto-... 

Sulfonation of the aromatic ring of l, 2, 2 -trifluorostyrene below 0 C does not give satisfactory yields with chlorosulfonic acid or a sulfur trioxide-dioxane complex Tar forms on heating In contrast, under similar conditions ipso substitution IS facile at the position of a trialkylsilyl or -stannyl group Thus, 4-trimethyl-silyl-T 2, 2 D-trifluorostyrene affords the corresponding trimethylsilyl sulfonate [20] (equation 9)... 

With weakly directing — I + M-substituents such as the halogens, the a-directing power of the ring sulfur dominates and substitution appears to occur exclusively in the 5-position. 2-Chloro-, 2-bromo-, and 2-iodo-thiophene are sulfonated both with chlorosulfonic aeid and in the 5-position. In the chlorination of chloro-... 

There are no reports of direct electrophilic substitution on system 3. The tria-zololpyridinone 188 is chlorosulfonated on the benzene ring (92GEP4020629)... 

Alkylated sulfonamide groups have proven useful additions to the phenothiazine nucleus. The same seems to hold true in the thioxanthene series. Chlorosulfonation of the benzoic acid, 38, followed by displacement with dimethylamine affords the sulfonamide, 39. This is then taken on to the substituted thioxanthone (41) by the sequence of steps shown above Grignard condensation followed by dehydration gives thiothixine (42). 

B) Preparation of 4-Amino-2-Chloro-5-(Methylsulfamyl)Benzenesulfonamide The 5-sub-stituted-2,4-dlsulfamyl anilines may be prepared by procedures described in the literature, for example, the general procedures in Monatsch. Chem. vol. 48, p 87 (1927), which involves the treatment of a m-substituted aniline with from 10 to 20 parts by weight of chlorosulfonic acid followed by the gradual addition of from about 90 to 170 parts by weight of sodium chloride. The resultant mixture is heated at approximately 150°C for about 2 hours after which the reaction mixture is poured into water and the resultant 5-substituted aniline-2,4-disulfonyl chloride is filtered and is then treated with concentrated ammonium hydroxide or suitable amine by standard procedures to obtain the corresponding disulfonamide. 

In place of K-octyl iodide other derivatives such as w-octyl bromide, n-octyl />-toluenesulfonate, and w-octyl chlorosulfonate can be substituted the submitter reports that the yields of octanal in these cases are comparable. 

The copper-catalyzed additions of sulfonyl chlorides to conjugated dienes and trienes73 as well as to aryl-substituted cyclic olefins74 and substituted styrenes have been described75 for example, arenesulfonyl chlorides add to vinylarenes providing good to excellent yields75 of /J-chlorosulfones ... 

In the tris-pentafluorophenyl analog (TFPC), in contrast to other Co corroles, aromatic amines can substitute PPh3 to form six-coordinate trivalent bis(amine) complexes.788 Bis-chlorosulfon-ation of TFPC occurs regioselectively to give the 2,17-(pyrrole)-bis-chlorosulfonated derivative fully characterized as its triphenylphosphinecobalt(III) complex.789 The amphiphilic bis-sulfonic acid was also obtained. 

Very simple compounds such as alkyl-substituted tetrahydrofurans can be dehydrogenated by chlorosulfonic acid or by oleum, these reagents having some capacity for oxidation, and furylium ions are produced (Section III,B), but the technique has not been exploited synthetically.19 The presence of an easily eliminated group helps indeed, the terpenoid furan solidagenone might well be an artefact formed during isolation from an unstable hydrofuran... 

Monosulfonation and disulfonation were observed with 3,6-dinitro-9-acetylcarbazole 3,6-dinitrocarbazole gave the 1-substitution product. Chlorosulfonation of 3,6-dinitrocarbazole gave a mixture of mono- and di-chlorosulfonyldinitro derivatives. ... 

Schnur and co-workers " summarized typical reactions that can be performed on functional groups of substituted 2,4-oxazolidinediones without ring opening. These reactions include reduction with iron-acetic acid, chlorosulfonation, nucleophilic displacements of aromatic fluorides, and acid hydrolysis with HCl/formic acid. Nonetheless, there are examples of useful ring cleavage reactions involving 2,4-oxazolidinediones. 

Alkanes can be simultaneously chlorinated and chlorosulfonated. This commercially useful reaction has been applied to polyethylene (201—203). Aromatics can be chlorinated on the ring, and in the presence of a free-radical initiator alkylaromatic compounds can be chlorinated selectively in the side chain Ring chlorination can be selective. A patent shows chlorination of 2,5-di- to 2,4,5-trichlorophenoxyacetic acid free of the toxic tetrachlorodibenzodioxins (204). With alkenes, depending on conditions, the chlorination can be additive or substitutive. The addition of sulfuryl chloride can occur to form a 2-chloroalkanesulfonyl chloride (205). 

With aliphatic acids, even in the absence of pyridine, considerable chlorosulfonation occurs on irradiation 150 with short chain acids, e.g., propionic, isobutyric acids, the products isolated are the cyclic sulfo-carboxylic anhydrides (XLVI) in which the sulfo groups are in the 8-or 8- and y-positions. No products derived from substitution at a-posi-... 

Monosubstitution at a occurs in 255 with N-bromosuccinimide, N-chlorosuccinimide, and 25% nitric acid at 0° disubstitution (a a ) occurs with bromine or chlorine in acetic acid, thionyl chloride, chlorosulfonic acid, and 70% nitric acid and tetrasubstitution (a a bb ) is obtained with 90% nitric acid 254b behaves similarly. Tetra-cyanoethylene forms -complexes with 255 and 328,340 and the latter compound is slowly converted on standing to a C-substituted derivative with loss of HCN. 

Benzo[6]thiophene 1,1-dioxides have been made by cyclization procedures (Section 3.15.3.1.7). Homologs of acetophenone cyclize on treatment with chlorosulfonic acid to give 2-substituted 3-chlorobenzo[6]thiophene 1,1-dioxides (equation 86). Similarly 1,1-diaryl-1-propenes in concentrated sulfuric acid gave 2-methyl-3-arylbenzo[6]thiophene 1,1-dioxides (65JOC2840). Friedel-Crafts cyclization of l,l-diphenylethylene-2-sulfonyl chloride gave 3-phenylbenzo[6]thiophene 1,1-dioxide (equation 87) (59JA2000). Treatment of various biphenyl derivatives with fuming sulfuric acid forms the dibenzothiophene 5,5-dioxides (Section 3.15.3.1.7). 

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