Benzenesulfonyl chloride, 4-amino

A thiazole derivative that incorporates a fragment of the amphetamine molecule shows some CNS stimulant activity more specifically, the compound antagonizes the depression caused by overdoses of barbiturates and narcotics. Reaction of benzalde-hyde with sodium cyanide and benzenesulfonyl chloride gives the toluenesulfony1 ester of the cyanohydrin (141). Reaction of this with thiourea leads directly to aminophenazole (143) It is probable the reaction proceeds by displacement of the tosylate by the thiourea sulfur to give 142 addition of the amino group to the nitrile followed by tautomerization affords the observed product. ... 

Benzenesulfonyl chloride, 4-methyl- [p-Tol-uenesulfonyl chloride], 55, 57, 59 Benzenethiol [Phenol, thio-], 55, 122 Benzenethiol, copper(I) salt [Thiophenol, copper(I) salt], 55, 123 Benzenethiol, lithium salt [Thiophenol, lithium salt], 55, 1 22 Benzoic acid, 2-amino- [Anthramlic acid], p bromination of, 55, 23... 

The classic syntheses of the antibacterial sulfonamides involve reaction of the appropriate arylamine with an acid addition salt of p-amino-benzenesulfonyl chloride, or p-nitrobenzenesulfonyl chloride followed by reduction. Chemical interest largely resides in preparation of the corresponding arylamines. For the synthesis of sulfacytine (134), N-ethyl uracil (131) was converted to its thioamide (132) by reaction with phosphorous pentasulfide. The newly introduced sulfur is then displaced with ammonia in methanol to give 133. Standard reactions complete... 

Amino groups can also be derivatized using acyl chlorides that form amides. A number of suitable acyl chlorides including p-chloro-, p-methoxy-, p-nitroben-zoyl-, p-tolyl-, and p-nitro-benzenesulfonyl chloride have been successfully used for sensitive UV-Vis derivatization of nonabsorbing amine compounds (231). Among all those amide derivatives, p-methoxybenzamides appear more attractive because they exhibit high molar absorptivity at the convenient analytical wavelength of 254 nm. After derivatization in tetrahydrofuran-sodium hydroxide solu-... 

From the beginning of the 1960s, the progress in depsipeptide chemistry was connected with the utilization and further development of the mixed anhydride approach for the initial formation of the ester link between a suitably N-protected amino acid and the hydroxy acid ester. The reagent predominantly applied for the construction of the depsipeptide unit was benzenesulfonyl chloride in pyridine. This reagent, introduced by Shemyakin and co-workers in depsipeptide chemistry, was shown to be an efficient reagent for the formation of the ester bond between a protected amino acid and the hydroxy add component (Scheme 4).[21 22 ... 

Amino-pyridazines and -pyridazinones react with monomethyl- or N,N- dimethyl-form amide and other aliphatic amides in the presence of phosphorus trichloride, thionyl chloride, phosgene or benzenesulfonyl chloride to give mono- or di-alkylaminomethyl-eneamino derivatives. The same compounds can be prepared conveniently with N,N-dimethylformamide dimethyl acetal in high yield (Scheme 50). 

Tertiary amines do not react with nitrous acid, acetyl chloride, benzoyl chloride, benzenesulfonyl chloride, but react with alkyl halides to form quaternary ammonium halides, which are converted by silver hydroxide to quaternary ammonium hydroxides. Quaternary ammonium hydroxides upon heating yield (1) tertiary amine pins alcohol (or, for higher members, olefin plus water). Tertiary amines may also be formed (2) by alkylation of secondary amines, e.g., by dimethyl sulfate, (3) from amino acids by living organisms, e g, decomposition of fish in the case of trimethylamine. 

Into a solution of 15.9 grams of 3-amino-2-phenyl-pyrazole in 60 cc of anhydrous pyridine, 29 grams of p-carbethoxyamino-benzenesulfonyl chloride are introduced within about 25 minutes. When the reaction subsides, heating... 

Triethylamine (8) Ethanamine, N,N-diethyl- (9) (121-44-8) p-Toluensulfonyl chloride (8) Benzenesulfonyl chloride, 4-methyl- (9) (98-59-9) (lS,2S)-2-(N-Tosylamino)cyclohexanecarboxylic acid Cyclohexanecarboxylic acid, 2-[[(4-methylphenyl)sulfonyl]amino]-, (1S-trans)- (12) (110456-11-6)... 

The substituted benzenesulfonyl chloride (1 mole) is added portionwise to a mixture of the amino heterocycle (1-2-moles) and pyridine (500 ml) and heated for 1-2 h at 55-60°. For isolation of the product the mixture is poured into cold water, an excess of cold dilute hydrochloric acid, or dilute alcoholic hydrochloric acid. 

The methyl ester of DL-phenylalanine was recovered from its hydrochloride salt and was reduced with LiAlH4 to 3-phenyl-2-amino-l-hydroxypropane. Then 1.0 g such an alcohol (6.6 mmol) was dissolved in 20 mL cold pyridine containing 2.9 g benzenesulfonyl chloride (16.0 mmol) the solution was held at 5°C overnight. Ice was added (50 g) followed by cold 4 N HCl. The resulting solid was collected and crystallized from 95% ethanol to give 1.9 g 3-phenyl-2-benzenesulfonamido-l-(benzene-sulfonyloxy)propane, in a yield of 66%, m.p., 104.5-106.5°C. 

The universally applicable dioxazine pigment, especially Pigment Violet 23, which is distinguished by good color strength, is commercially important. It is produced by the reaction of 3-amino-N-ethylcarbazole and chloranil in o-dichloro-benzene at temperatures between 130 and 150 °C followed by oxidative ring closure to the dioxazine in the presence of benzenesulfonyl chloride. The 3-amino-N-ethylcarbazole required for the synthesis is produced from carbazole by N-alkyla-tion, e.g. with diethyl sulfate or ethyl chloride, and nitration followed by the reduction to the amine. 

The preparation of monoalkyl derivatives of diamines represents something of a synthetic problem. Procedure 13-3 involves acetylation of ethylenediamines under mild conditions to the monoacetyl ethyl-enediamine, protection of the second amino group by a Hinsberg reaction with benzenesulfonyl chloride, followed by N-alkylation of the acetamido group, and recovery of the iV-alkylethylenediamine by acid hydrolysis [15]. 

Benzenesulfonyl chloride added dropwise during 1 hr. at -10° to cyclohepta-none oxime and pyridine in dry ethylene chloride, stirred 1 hr. at -10 to 0°, 1-morpholino-l-cyclohexene added, warmed carefully wherupon exothermic Beckmann rearrangement occurs at ca. 20°, after 2 days treated with 50%-acetic acid, and stirred 4hrs. -> 2-(2-oxocyclohexylidene)-l-azacyclooctane (Y 79%) refluxed 5-10 hrs. in 2 iV NaOH until dissolved -> co-amino-7-oxotridecanoic acid (Y 80%). F. e. s. S. Hiinig et al., B. 700, 3039 (1967). 

In the synthetic scheme, 3-amino-9-ethylcarbazole 138 (2 mol) is condensed with chloranil 137 (1 mol) to form the intermediate 139. This intermediate is then converted into the dioxazine pigment 136 by oxidative cyclisation at around 180 °C in an aromatic solvent and in the presence of a catalyst such as aluminium(m) chloride or benzenesulfonyl... 

---