Aminophenyl Disulfide

Submitted by Charles C. Price and Gardner W. Stacy. Checked by Cuff S. Hamilton and Theo Brown. 

In a S-1. round-bottomed flask equipped with a reflux condenser and a mechanical stirrer are placed 236 g. (1.5 moles) of / chloronitrobenzene, 960 g. (4 moles) of sodium sulfide nona-hydrate, and 2.5 1. of water. With rapid agitation, the reaction mixture is slowly heated to the reflux temperature (Note 1). Heating is continued over a period of 20 hours. 

The mixture is cooled to about 15 and filtered on a large Buchner funnel to remove insoluble material, chiefly -chloro-aniline. The filtrate is placed in a 5-1. three-necked flask, equipped with a dropping funnel, a mechanical stirrer, and a downward condenser it is concentrated by distillation over a flame to a volume of 1.5 1. (Note 2). The condenser is replaced by a thermometer, the stirrer is started, and the dropping funnel is charged with 230 ml. of 30% hydrogen peroxide. The temperature of the reaction mixture is maintained at 65-70° while the hydrogen peroxide is added dropwise over a period of about 2 hours (Note 3). 

The reaction mixture is cooled, and the crude / -aminophenyl disulfide, obtained as spherical lumps amounting to 125-150 g. and melting at 73°, is collected on a Buchner funnel. It is dissolved in 1 1. of hot ethanol, and the small amount of insoluble material is removed by filtration. To the hot solution is then 

The reaction mixture should not be heated too strongly as the temperature nears the boiling point, since the initial reaction is quite vigorous. 

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Aminophenyl disulfide Cystine, 2-Nitrophenyl disulfide Methyl disulfide, p-tolyl disulfide Benzyl disulfide Naphthothiophenes (NTH)... 

Dipyridyl disulfide and bis(2-aminophenyl) disulfide do not undergo hydroxysulfenylation using Pb(OAc)4 or in the absence of a metal salt, but each reacts satisfactorily in the presence of catalytic amounts of copper(II) acetate.2... 

SYNS BIS(o-Ai nNOPHENYL)DISULFIDE BIS(2-AMINOPHENYL)DISULFIDE 1,1 -BIS(2-AMlNOPHEKYL)DISULFIDE 0,0 -DIAMIN0... 

BIS(2-AMINOPHENYL)DISULFIDE see DXJ800 BIS(o-AMINOPHENYL)DISULFIDE see DXJ800 l,l -BIS(2-AMINOPHENYL)DISULFIDE see DXJ800 BIS(4-AMINOPHENYL)ETHER see OPMOOO BIS(p-AMINOPHENYL)ETHER see OPMOOO BIS(4-AMINOPHENYL)METHANE see MJQOOO BIS(p-AMINOPHENYL)METHANE see MJQOOO 2, 4-BIS(AMINOPHENYL)METHANE see MJP750 BIS(4-AMINOPHENYL) SULFIDE see TFIOOO BIS(p-AMINOPHENYL)SULFIDE see TFIOOO BIS(4-AMINOPHENYL) SULFONE see SOA500... 

The author s group tried to find the S MIE in the direct photolysis of is p-aminophenyl disulfide (ArS-SAr) in SDS micelles at room temperature [8]. 

The photolytic cleavage of alkyl aryl sulfoxides has been shown to occur via initial C—S bond homolysis, in accordance with the common mechanistic assumption. Secondary and tertiary alkyl groups show high chemoselectivity for alkyl C—S cleavage. Uniquely, alkene products have been isolated, formed by disproportionation of the initial alkyl radical, with the formation of benzaldehyde and racemization of primary alkyl compounds. An investigation into the photochemical conversion of N-propylsulfobenzoic imides into amides in various solvents revealed a solvent dependence of the observed mechanism. In ethanol, sulfur dioxide extension forms a biradical which abstracts a hydrogen atom from the solvent, whereas in aromatic solvents biradical formation by a single electron transfer is implicated. The photolysis and thermolysis of l,9-bis(alkylthio)dibenzothiophenes and /7-aminophenyl disulfide have been studied. 

C12H12N2S, Di-(p-aminophen.yl) sulfide 97 C12H12N2S2, Di (o-aminophenyl) disulfide. 97... 

The procedure outlined is essentially that of Lantz except for the use of hydrogen peroxide rather than air in the final oxidation. -Aminophenyl disulfide has also been prepared by heating a mixture of aniline, aniline hydrochloride, and sulfur, and by the reduction of -nitrophenyl disulfide with stannous chloride. ... 

In the preparation of di(p-aminophenyl) disulfide, sodium sulfide first displaces the activated halogen atom and then reduces the nitro group. The terminal step is... 

Benzothiazoles bearing a substituted phenyl group at C-2 can be prepared from the corresponding bis-(2-aminophenyl)disulfide (393). Treatment of (393) with an aroyl chloride affords the intermediate (394) which cyclizes to 2-arylbenzothiazoles (395) upon treatment with tin(II) chloride (Scheme 97) <93SC663>. 

A mixture of p-chloronitrobenzene, Na2S, and water slowly heated to boiling with rapid agitation, refluxed 20 hrs., cooled to ca. 15 , filtered, the filtrate concentrated, and treated dropwise at 65-70° with 30% H202 over a period of ca. 2 hrs. p-aminophenyl disulfide. Y 58-64%. (C. C. Price and Gr. W. Stacy, Org. Synth. 28, 14 (1948).)... 

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