- Flavin/I2 catalyzed aerobic oxidative C–H sulfenylation of anilines
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A flavin/I2 catalyzed aerobic oxidative C–H sulfenylation of anilines with thiols under mild reaction conditions is presented for the first time. This metal-free reaction provides an atom-economic pathway to prepare various aryl sulfides with outstanding functional group compatibility. Moreover, it consumes molecular oxygen as the only terminal oxidant and produces environmentally-friendly H2O as the only byproduct.
- Jiang, Xinpeng,Shen, Zhifeng,Zheng, Cong,Fang, Liyun,Chen, Keda,Yu, Chuanming
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supporting information
(2020/07/24)
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- Silver ion mediated in situ synthesis of mixed diaryl sulfides from diaryl disulfides
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The AgNO3-mediated in situ scission of aromatic disulfides in the presence of electron-rich aromatic compounds results in the efficient synthesis of diaryl sulfides. Key features of this new methodology are high yields of aromatic and heteroaromatic sulfides, mild reaction conditions, simplicity, simple workup, and avoiding foul-smelling reactants like thiols. Georg Thieme Verlag Stuttgart · New York.
- Gogoi, Prasanta,Gogoi, Sandhya R.,Kalita, Mukul,Barman, Pranjit
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p. 873 - 877
(2013/05/21)
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- Imination of sulfur-containing compounds: XXXVI. A new method of synthesis and oxidative arylsulfonylimination of sulfenamides
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Sulfenylation of ammonia, amines, and arenesulfonamide sodium salts with N-(arylsulfenyl)-N,N′-bis(arylsulfonyl)sulfinimidamides afforded unsubstituted and N-substituted arenesulfenamides. Oxidation of the latter with N-chloro sulfonamide sodium salts gav
- Koval'
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p. 386 - 389
(2007/10/03)
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- A new sulfenylation reagent, 3-phenylsulfenyl-2-(N- cyanoimino)thiazolidine, and its optically active version
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We have developed a new sulfenylation reagent, 3-phenylsulfenyl-2-(N- cyanoimino)thiazolidine 3, that is readily available and stable upon storage. Compound 3 easily reacts with amines or thiols to give the corresponding sulfenamides or asymmetrical disulfides in excellent yields. It was also found that the α-sulfenylation reaction of carbonyl compounds with 3 proceeds smoothly. Furthermore, optically active 4-diphenylmethyl derivative 4 was synthesized as an asymmetric sulfenylation reagent, which realized 96% e.e. upon α-sulfenylation of a cyclic β-keto ester.
- Tanaka,Azuma,Fang,Uchida,Iwata,Ishida,In,Maezaki
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- Nitroarylamines via the Vicarious Nucleophilic Substitution of Hydrogen: Amination, Alkylamination, and Arylamination of Nitroarenes with Sulfenamides
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A new reaction of sulfenamides with electrophilic arenes under basic conditions is described. The σ adducts formed from nitroarenes and the anions of sulfenamides undergo elimination of thiol to produce the corresponding o- and/or p-nitroanilines. This reaction is analogous to the known alkylation and hydroxylation of nitroarenes via the vicarious nucleophilic substitution of hydrogen (VNS). The reaction gives access to a wide range of substituted nitroanilines, nitronaphthylamines, and aminoheterocycles. By means of the reaction with N-alkyl- and N-arylsulfenamides, it is possible to obtain N-alkylnitroanilines and nitrodiarylamines. By varying the structure of sulfenamide and the reaction conditions, particularly the nature and concentration of the base, it is possible to control the orientation of animation.
- Makosza, Mieczyslaw,Bialecki, Maciej
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p. 4878 - 4888
(2007/10/03)
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- N-hydroxypyridine-2(1H)-thione derivatives of carboxylic acids as activated esters. Part I. The synthesis of carboxamides
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The reaction between an acyl derivative of N-hydroxypyridine-2(1H)- thione (a Barton PTOC ester) and either an amine (primary or secondary), or the corresponding sulfenamide, led to the formation of a carboxamide in a clean transformation requiring minimal work-up and purification. The reaction with a sulfenamide is particularly useful since the only by-product, an unsymmetrical disulfide, is of both synthetic and biological value. In sterically demanding cases, Barton PTOC esters were more reactive towards benzenesulfenamides than to the corresponding free amines.
- Barton, Derek H. R.,Ferreira, J. Albert
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p. 9347 - 9366
(2007/10/03)
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- ON THE MECHANISM OF THE REACTION OF NITROSOBENZENES WITH BENZENETHIOL: THE INTERMEDIACY OF AMINOXYLS AND THEIR DEOXYGENATION
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The reaction of benzenethiol with several substituted nitrosobenzenes carried out inside the cavity of an EPR spectrometer evidences the formation of adducts through the detection of the corresponding thionitroxides.The macroscale reaction of benzenethiol with nitrosobenzene confirmed the formation of the adduct and clarified the nature of the intermediates.The formation of azoxybenzene, aniline and nitrobenzene shows that an electron-transfer process between nitrosobenzene and benzenethiol is in competition with nucleophylic addition of the latter to the former compound.The identification of S-phenylbenzenethiosulphinate as well as the isolation of compound 9, bearing a sulphinyl group on a benzene ring, implies the formation of a sulphinyl radical, which is considered to be responsible for the formation of the sulphinylamide.The formation of the sulpheneamide, the main reaction product, is attributed to the interaction of thiyl radicals with the intermediate thionitroxides.The crystal structure of S-methyl-S-phenyl-N-(o-sulphonylphenyl)benzenesulphilimine, the unexpected product of the methylation of compound 9, is also described.
- Alberti, Angelo,Benaglia, Massimo,Carloni, Patricia,Greci, Lucedio,Stipa, Pierluigi,et al.
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p. 555 - 562
(2007/10/02)
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- SULFENAMIDES AND SULFINAMIDES VIII. THE CHROMATOGRAPHY OF ARYL SULFENAMIDES
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Substituent effects with respect to position and extent of substitution in a series of N-aryl benzenesulfenamides (ArSNHAr') have been examined over several chromatographic systems.In normal phase TLC, although methyl substitution in either ring leads to
- Chan, Christopher,Cole, Edward R.,Southwell-Keely, Peter T.
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- N3-(ARYLTHIO-, ARALKYLTHIO- AND ALKYLTHIO)-5,5-DIMETHYLHYDANTOINS: SULFENYL GROUP TRANSFER REACTIONS AND THEIR PROPERTIES
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Sulfenyl-transfer reactions toward a variety of nucleophiles were successfully carried out using N3-sulfenyl-substituted 5,5-dimethylhydantoins (2a-c).During the course of the synthesis of 2 by the reaction of N1-bromo-5,5-dimethylhydantoin (1c) with disulfides, the sulfenyl groups were found to be at the position of N3 although the bromine was at N1 in the starting monobromohydantoin (1c).Some mechanistic speculations were considered for the formation of 2 from 1c.
- Takeda, Ken'ichi,Horiki, Kusuo
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p. 367 - 373
(2007/10/02)
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- SULFENAMIDES AND SULFINAMIDES III. CONJUGATIVE AFFINITY AND pKa VALUES OF ARYL SULFENAMIDES
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Relationships are discussed between the pKa values determined spectroscopically in aqueous media and the conjugative affinity of the sulfur atom in transmitting substituent effects in a series of aryl sulfenamides. - Key words: Sulfenamides; pKa values; c
- Bayfield, Raymond F.,Cole, Edward R.
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p. 237 - 242
(2007/10/02)
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- Alkyl- and Arylsulfenanilides by Cycloelimination of Propene from N-Aryl-S-isopropyl-sulfimides
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A series of N-aryl-S-isopropyl-S-alkyl- or aryl-sulfimides has been prepared and transformed into alkyl- or arylsulfenanilides, respectively, by thermal cycloelimination of propene. - Keywords: Sulfimides; Sulfenanilides; Thermolysis; Cycloelimination.
- Claus, Peter K.,Silbernagel, Waltraud,Franek, Walter,Rieder, Werner
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p. 841 - 850
(2007/10/02)
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- Acid-promoted Decomposition of Benzenesulphenanilides and N-Aryl Bis(benzenesulphen)amides
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The decomposition of 4'-substituted benzenesulphanilides (1a-d) in the presence of trifluoroacetic acid (0.6 equiv.) leads to N-arylbis(benzenesulphen)amides (6a-d) in variable yields, depending on the 4'-substituent, in addition to disulphide (4) and anilines (3a-d), whereas products arising from sulphenylation of the N-aryl ring result from 3'-methoxybenzenesulphenanilide (1g).The 4'-nitro- and 3'-nitro-benzenesulphenanilides (1e,f) react with a slight excess of trifluoroacetic acid to give only (4), the thiosulphonate (5), and aniline (3e,f).The findings are interpreted in terms of possible nucleophilic attack at the S-N bond of a protonated sulphenanilide by the nitrogen or the N-aryl ring of another sulphenanilide unit, according to the nature of the substituent and its position, with displacement of aniline (3).The reaction of (1a-d) with 1.5 equiv. of trifluoroacetic acid leads to complete disappearance of the initially formed amides (6a-d) with concomitant formation of phenazines (9) and/or p-quinone di-imines (8).Similar results are obtained by using boron trifluoride-diethyl ether.Di-imines (8) and phenazines (9) are explained on the basis of a mechanism initially involving nucleophilic attack by (1) and/or (6) and/or (3) at the ortho and para positions of an intermediate cation, possibly (18A) or (18B), and loss of the disulphide (4).
- Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
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p. 2261 - 2266
(2007/10/02)
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- N-Phehylsulphimide Formation and Rearrangement in the Thermal Reaction of Phenylnitrene with Sulphides
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Thermal reaction of phenyl azide (1) with thioanisole (2a), dimethyl sulphide (2b), and tetrahydrothiophen (2c) leads to the formation of 2-substituted anilines (3a-c) by Sommelet-Hauser rearrangement of the intermediate N-phenylsulphimides arising from phenylnitrene attack at the sulphur atom of (2a-c).Reaction with ethyl phenyl sulphide (2d) gives benzenesulphenanilide (8) and ethylene by cycloelimination of the resulting N-phenylsulphimide.Reaction with acyclic benzylic sulphides (2e-g) apparently leads only to the insertion products of phenylnitrene into benzylic C-H bond, presumably through Stevens rearrangement of the intermediate sulphimides, whereas Sommelet-Hauser rearrangement appears to compete favourably with Stevens rearrangement in the sulphimide resulting from reaction of phenylnitrene with the cyclic benzylic sulphide (2h).
- Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
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p. 771 - 776
(2007/10/02)
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- Benzenesulphenanilidyl Radicals. Part 2. Substituent and Solvent Effects on the Reactivity of 4'-Substituted Benzenesulphenanilidyl Radicals Produced by Oxidation with Lead Dioxide of the Corresponding Benzenesulphenanilides
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Oxidation of benzenesulphenanilide (1d) with lead dioxide in benzene affords the p-benzoquinone diimine (5d) together with minor amounts of N,N-bis(phenylthio)aniline (4d) and diphenyl disulphide (7a).The formation of the products is explained in terms of p-C-N coupling of the benzenesulphenanilidyl radicals (2d) and subsequent fragmentation of the resulting dimer.A similar trend is observed in the oxidation of 4'-chloro- and 4'-bromo-benzenesulphenanilides (1e) and (1f), whereas 4'-nitrobenzenesulphenanilide (1g) leads to the o-phenylenediamine (12g), arising from o-C-N coupling of the sulphenanilidyl radical (2g).The oxidation of the sulphenanilides (1e) and (1f) in acetonitrile produces the phenazines (3e) and (3f) and the disulphide (7a), whereas the anilide (1g) and 4'-cyanobenzenesulphenanilide (1h) give azobenzenes (11g) and (11h) and the disulphide (7a); these results are discussed in terms of a possible mechanism involving oxidation of the N-N dimers (14e-h) which are in rapid equilibrium with the corresponding sulphenanilidyl radicals (2e-h).Evidence is also presented that the oxidation of 2-nitrobenzenesulphenanilides leads to products ascribable to intermediate 2-nitrobenzenesulphenanilidyl radicals, in contrast with a previous claim.
- Balboni, Claudio,Benati, Luisa,Montevecchi, P. Carlo,Spagnolo, Piero
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p. 2111 - 2117
(2007/10/02)
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- In Search of New Sulfur Transfer Agents
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The chemistry of various sulfur-transfer agents is studied.The reaction of aromatic sulfenyl chloride 5 in the presence of imidazole and/or triethylamine gives the aryl disulfides 7 in 14-85 percent yield, whereas in the case of the corresponding benzylsulfenyl chlorides 9 in the presence of triethylamine and/or caprolactam, both disulfide 10 and benzyl chlorides 11 are formed in 0-81 precent and 10-72 precent yield, respectively. - The transfer reactions of 3-sulfenylated hydantoins 18 with amines are useful for the preparation of the unsymmetric sulfenamides 20 in 31 -61 percent yield.Analogous transfer reactions of compounds 23 and 24 with piperidine give N,N'-thiodipiperidine (3, X = CH2) in 71-80 percent.
- Sosnovsky, George,Krogh, James A.
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p. 121 - 136
(2007/10/02)
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