Sulphenyl chloride

TABLE 13. Synthesis of ally sulphoxides from sulphenyl chlorides, RSC1, and allyl alcohols R Alcohol Sulphoxide Yield (%) Ref. 

TABLE 14. Allenic sulphoxides from propargylic alcohols and sulphenyl chlorides, RSC1... 

Reaction of equimolar amounts of the thiocarbamate (91) with (chlorocarbonyl)sulphenyl chloride gave l,2,4-dithiazoline-5-one (92) and the 1,2,4-thiadiazole (93) the relative amounts of (92) and (93) being very dependent on the solvent used in the reaction. The mechanism of formation of both (92) and (93) was discussed <96JOC6639>. 

Rearrangement of acetylenic sulphenates to the allenic sulphoxides 151 was discovered when the synthesis of propargylic ester of trichloromethanesulphenic acid 152 was attempted (equation 86). This reaction is of general scope and gives very good yields of allenic sulphoxides (Table 14) from structurally diverse cohols and various sulphenyl chlorides Reaction of alkynols 153 with benzenesulphenyl chloride in the presence... 

Sulphenyl chlorides, e.g. C13CSC1, can also be used as sources of thiyl radicals, but here the addition is initiated by Cl- and the R S will thus become attached to the other carbon atom of the double bond ... 

On reacting 3,3-disubstituted-l,2-alkadienephonic dialkyl esters with methyl-sulphenyl chloride, 1,2-oxaphosphole derivatives and 1,2-adducts were isolated [108], In the case of dialkyl esters of 3-methyl-1,2-butadienephosphonic acid, the formation of dialkyl esters of 1,3-butadienylphosphonic acid was also detected (Scheme 45). 

It has been established that alkadienephosphonates bearing bridge-substituent at C3 atom of the alenephosphonate system on reaction with alkyl(aryl)sulphenyl chlorides lead to the formation of spyrocompounds [111]. 

The 1,2-alkadienephosphine oxides react smoothly with dialkoxyphosphonyl-sulphenyl-chlorides affording 2,5-dihydro-l,2-oxaphosphonium salts 145 and 146 (Scheme 59) [117]. 

Similar to the reaction pathway discussed above, 181 reacts with dialkoxyphos-phonyl-sulphenyl chlorides affording 184 (Scheme 74) [117],... 

The iodo-phosphine (50) decomposes at temperatures above —50 °C to give the phosphorane (51).42 Phosphorus trichloride is oxidized by the sulphenyl chloride (52).48 Aryl- and alkyl-dichlorophosphines have been converted into the phosphor-... 

To date, however, only few reactions between phosphine and a non-metal halide, in which a chemical bond is formed between phosphorus and a non-metal by HCl condensation, are known. To these, apart from the above-mentioned reactions, belongs also the reaction with CF3SCI which, depending upon the chosen proportions of the reactants, in a sealed tube at -95 °C leads to the formation of (CF3S)2PH or (CF3S)3P Both compounds are not very stable thermally and decompose at 40-50 °C. Tris(trifluoromethylthio)-phosphine forms an unstable adduct with chlorine, which decomposes at 0 °C to give a mixture of PCI3, bis(trifluoromethyl)-disulphide and trifluoromethyl-sulphenyl chloride. 

A number of a,/J-unsaUiraled acyl silanes have been prepared from silyl enol ethers of acyl silanes (Scheme 41)129. Addition of phenyl sulphenyl chloride to the silyl enol ether with subsequent elimination of chlorotrimethylsilane gives the a-(phenylthio)acyl silane. Oxidation to the sulphoxide followed by in situ elimination of benzenesulphenic... 

A further example of this general type of reaction is provided by the synthesis of cyclooctene sulphide (6).4 Here an alkene is converted into an adduct with succinimide-A-sulphenyl chloride (reaction formulated in full in Expt 8.3), which is reduced with lithium aluminium hydride at — 78 °C to form the product. 

Succinimide-iV-sulphenyl chloride. Chlorine gas (CAUTION) is passed for 8 hours through a stirred solution of the foregoing compound (53.7 g) in chloroform (250 ml) warmed to 50 °C. Nitrogen gas is passed through the mixture to remove excess chlorine, followed by evaporation in vacuo to give succinimide-N-sulphenyl chloride (65.1 g, 93.3%) as yellow crystals, m.p. 65-67 °C. 

Hydrocarbon B.P. °C (/mmHg) dY> nfT Adducts with 2,4-dinitrophenyl sulphenyl chloride Mercurides... 

Chlorinolysis is another reaction mode observed in some sulphides, in which sulphur retains its oxidation state. For example, phenyl trityl sulphide and benzyl trityl sulphide were converted into trityl chloride and sulphenyl chlorides [26]. Thiirane and thietane reacted similarly with 3-(dichloroiodo)pyridine to afford chlorinated disulphides [25] ... 

Electrophilic addition of sulphenyl halides to alkenes occurs, by all the evidence, via cyclic thiiranium ions (Mueller, 1969) and a comparison of the rates of addition to the double and triple bond would be quite interesting. Unfortunately, direct kinetic data for strictly comparable and typical cases are not available. Phenylacetylene has been reported (Kharasch and Yannios, 1964) to react 102 times slower than styrene (in acetic acid at 25°) with 2,4-dinitrobenzenesulphenyl chloride. On the other hand, Thaler (1969), by means of competitive experiments carried out in dilute paraffin solutions at — 70°, estimated that methane-sulphenyl chloride adds to mono- (and di-)alkylacetylenes 50-100 times more slowly than to the corresponding alkenes (cis) (but only ca. twice slower than to trans dialkylethylenes). The paucity of information does not allow generalizations and further work in this area seems desirable also with respect to the much larger rate differences observed in those bromine additions to triple and double bonds which also occur via bridged species. 

Addition of sulphenyl chlorides to allene gives anti-Markownikoff adducts, as shown in equation (17) (Jacobs and Johnson, 1960 Mueller... 

Steps (a) and (b) of Scheme 6 constitute the Arens mechanism. Therefore, equation (244) was simply a case of attack on Cl in which the ion-molecule (PhC=C CISC,-H,-p) was the key intermediate. Attack of acetylide on the sulphur of the sulphenyl chloride leads to the product given in equation (244). Support for this step is the well-known reaction of sulphenyl chloride with carbanions to yield sulphides . The disulphides which sometimes turn up in the haloalkyne-thiolale processes (see Table 6) are easily explained by the sulphenyl halide reacting with the thiolates. 

R R P(S)SC1, have been synthesized as a unique probe for the study of nucleophilic displacement reactions at a dicoordinate sulphur atom. The key intermediate in their preparation was the amide (188 R = L-menthyl) the diastereoisomers of which were readily separated in their ensuing reaction with Me SiCl each afforded the corresponding sulphenyl chloride each of the latter... 

Sulphenyl chloride A molecule of the general formula RSC1. 

Five-membered cyclic phosphorotrithioates (12) are reported to be formed from 2-chloro-l,3,2-dithiaphospholans and sulphenyl chlorides in acetic acid or acetic anhydride. ... 

New reactions of various phosphazenes with a wide range of electrophilic species continue to be reported. These include those of alkoxy-derivatives with dialkyl sulphates, e.g. to give (56), or with sulphenyl chlorides, e.g. the reaction that produces (57) (see Scheme 4). With pyridine, compound (56) can be converted into two isomeric products (58) and (59). 

The sulphenyl chloride (52) reacts with strongly activated aromatic rings to give 5 -aryl phosphorothioate esters the selenium analogue behaves similarly. ... 

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