Benzenesulfenyl chloride

Another version of the double [2,3]-sigmatropic rearrangement, involving the sequence sulfenate - sulfoxide - sulfenate, has also been observed. For example, an effective one-pot epimerization procedure of 17a-vinyl-l 7/i-hydroxysteroids to the rather inaccessible 17-epimers has been achieved by the use of such a rearrangement (equation 35)137. Thus treatment of alcohol 76a with benzenesulfenyl chloride afforded the sulfoxide 77 as a single isomer and E-geometry of the olefinic double bond. Exposure of 77 to trimethyl phosphite in refluxing methanol produced a mixture of 76b and 76a in a 73 27 ratio. 

Principally, both unifold and twofold transformation types ensue in these cases. A unifold transformation occurs in the case of the rearrangement of cumyl benzenesulfmate, which arises from the conversion of cumyl hydroperoxide with benzenesulfenyl chloride (equation 2). Closely related sulfoxylate-sulfone rearrangements, which pass intermediate sulfmate steps similarly, are equally known . 

Benzene, cyclopropyl-, 44, 30 Benzene, 1-iodo-2,4-dinitso-, 40, 34 Benzene, iodoso-, 43, 60 Benzene, iodoso-, diacetate, 43, 62 o-Benzenedithiol, 49,64 Benzenehexoi, 42, 66 Benzenesulfenyl chloride, 2,4-DINITRO-, 44, 47... 

A variety of other activating systems have been employed for the promotion of sulfoxide-based glycosylation reactions, but none have been studied to the same extent as the triflic-anhydride-mediated reaction [86]. One of the most potent activators, benzenesulfenyl triflate, a by-product of the activation with triflic anhydride, has been shown to bring about rapid conversion of sulfoxides into glycosyl triflates [280]. Unfortunately, this reagent is unstable and has to be prepared in situ from silver triflate and benzenesulfenyl chloride. 

In addition to the sulfur-substituted enyne-allenes depicted in Schemes 20.18-20.20, the sulfoxide 141 was prepared by treatment of the enediynyl propargylic alcohol 108 with benzenesulfenyl chloride to induce a [2,3]-sigmatropic rearrangement (Scheme 20.29) [10]. The Myers-Saito cyclization of 141 occurs at 37 °C with a half-life of only 16 min. 

It is noteworthy that 108 reacts in AcOH with benzenesulfenyl chloride to give a 1 1 mixture of the sulfur analogues of 138 and 140, but when the reaction is carried out in the presence of LiClC>4 a complex mixture of at least five products was detected. From this comparison the authors suggest that areneselenenylation is much less affected by the solvent than arenesulfenylation, and if the reaction profiles for the two product-forming processes are assumed to be similar, the difference in product distributions can be interpreted in terms of a more efficient bridging ability of selenium than that of sulfur. In the addition of selenenyl derivatives, the solvent-dependent product distribution has also... 

Sodium nltromethylate Methane, n1tro-, lon(l-). sodium (8,9) (25854-38-0) Phenylsulfenyl choride Benzenesulfenyl chloride (8,9) (931-59-9) Nltromethane Methane, nitro- (8,9) (75-52-5)... 

The reaction proceeds smoothly and gives 326 in 43% yield. The stereochemistry of the addition is exo with respect to the norbomene moiety and in line with the usual cycloaddition behavior of quadricyclane [358]. The norbomene double bond in 326 is easily accessible by electrophiles, and, for example, the anti-addition of benzenesulfenyl chloride proceeds quantitatively at room temperature (Scheme 4.66). 

Benzene, (cHLORO-teri-BuTYL)-, 32, 90 2-chloro-1, 3-dinitro-, 32, 23 ETHYNYL-, 30, 72 HEXAMETHYL-, 35, 73 1,2,3-trimethyl-, 34, 56 Benzeneboronic ACID, 39, 4 Benzeneboronic anhydride 39, 3 Benzenediazonium chloride, 32, 84 Benzenesulfenyl chloride, 36, 101 Benzenesulfonyl chloride, 31, 83 9,10-o-Benzenoanthracene, 9,10-dihydro-, 39, 75 Benzhydrol, 33, 11 Benzhydryl chloride, 39, 74 Benzidine, 36, 21... 

Reaction with allene sulfoxides.1 Allenic sulfoxides are desulfurized by reaction with methyllithium. An example is the transformation shown in equation (I). The propynylcarbinol 1 is treated with benzenesulfenyl chloride to form the allene 2,... 

Tricyclenes. Benzenesulfenyl chloride reacts with 5-mcthylene-2-norbornene (1) to form the tricyclcnc derivative 2. This reaction was used to synthesize tricyclo-e a-santalol (3)1 and cyclosativene (4).2... 

N-Arylamidines act as 1,5-dinucleophiles towards sulfur dichloride, N-sulfinyltosylamide and bis(N-tosyl)sulfur diimide. The products are 1,2,4-benzothiadiazines (Scheme 14) (73ZOR2038, 68LA(715)223), and in the case of sulfur dichloride, chlorination of the aromatic ring also occurs. 1,2,4-Benzothiadiazines can also be prepared from N-arylamidines by reaction with sulfenyl chlorides or disulfides in the presence of NCS. Thus N-phenylben-zamidine and benzenesulfenyl chloride give the 1,2,4-benzothiadiazine (182) (78CC1049). 

Benzenesulfenyl Chloride or Phenylsulfochlbride. (Benzolsulfensaure-chlorid in Ger),CgHs.SCl. 

Cycloazasulfenylation (or sulfenocycloamination ) can be achieved by addition of benzenesulfenyl chloride to an alkene containing a remote nitrogen followed by treatment of the (3-chloro sulfide adduct... 

Toluenesulfenyl chloride has been prepared by the action of chlorine on a solution of -toluenethiol or />-tolyl disulfide in anhydrous carbon tetrachloride.2,3 Benzenesulfenyl chloride has also been obtained by the interaction of hydrogen chloride and N,N-diethylbenzenesulfenamide 4 and by reaction of benzenethiol with N-chlorosuccinimide.6 A comprehensive review dealing with sulfenyl halides and related compounds is available.6... 

Benzeneselenenyl halides, 34-37 Benzeneselenenyl iodide, 36 Benzeneseleninic anhydride, 37—39 Benzenesulfenyl chloride, 39-40 Benzenesulfonyl fluoride, 40 Benzenesulfonylnitrile oxide, 40-41 1 -Benzenesulfonyl-2-trimethylsilylethane, 41-42... 

LACTAMS Benzenesulfenyl chloride. Pentacarbonyl(methoxyalkyl)chromium carbenes. Triphenylphosphine-Diethyl diazodicarboxylate. 

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