Sulphinyl halides

Sulphinyl Halides.—While the general route to sulphinyl halides starts with the sulphenyl halide, alternatives have been devised based on cleavage of a-trichlorosulphoxides with CI2 in aqueous media (the sulphoxides being formed by perchlorination of dialkyl sulphides ), and based upon sul-phenic acids. The nucleophilic character of the sulphur atom in a 

Kobayashi, H. Minato, Y. Miyaji, T. Yoshioka, K. Tanaka, and K. Honda, Bull. Chem. Soc. Japan, 1972, 45, 2817. 

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Thiol Disulphide Peroxy Sulphonyl/sulphinyl halide... 

Careful hydrolysis of alkyl or aryl sulphur trihalides, in particular trichlorides, yields either sulphinic acid or sulphinyl halide . The latter is obtained in good yields by reacting the trihalide with the stoichiometric amount of acetic acid (equation 19). 

Sulphinate Esters.—A wide variety of synthetic routes to sulphinate esters is represented in the recent literature. A one-step synthesis of alkyl t-alkane-sulphinates from a Grignard reagent and a sulphite has been explored. Among the reports of sulphinate syntheses from sulphinyl halides are three accounts of studies with unusual interest, viz. CF,SOF -> CF3S(0)0R, iV-t-butylsulphinyl-oxycarbamates from Bu SOCl and H0NR C(0)0R, and an asymmetric synthesis involving a sulphinyl chloride, an achiral alcohol, and an optically active tertiary amine. In the best experiment an optical purity of 45% was achieved in the asymmetric synthesis. ... 

Dialkyl cuprates may also be added to aryl vinyl sulphoxides and the resulting a-sulphinyl carbanions can be treated with various electrophiles such as aldehydes, ketones and alkyl halides (equation 350)643. 

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. 

The anions derived from a-sulphinyl carboxylic esters 358 can also be easily generated by NaH or Their reaction with alkyl halides gives monoalkylated products... 

Acylation of oc-sulphinyl carbanions. Synthesis of fS-oxosulphoxides. oi-Ketosulphoxides have found very broad application in organic synthesis (see, for example. Reference 532). For this reason, a great deal of examples of their syntheses appear in the chemical literature. The main approach to this class of functionalized sulphoxides involves the reaction of a-sulphinyl carbanions with carboxylic esters or acyl halides. 

Sulphinyl (thionyl) halides Sulphonyl (sulphuvyl) halides... 

Aryl sulphonyl chlorides may also be synthesized from the sulphinyl chloride, by oxidation with chlorine, in 80% yield573 (equation 146) or dimethyl sulphoxide574. Sulphinate esters may also be utilized as the precursor to sulphonyl halide via oxidative halogenation. For example, methyl methanesulphinate is converted to methanesulphonyl chloride in excellent yield at 0°C568. 

References to addition reactions of sulphenyl halides with alkenes and alkynes are given in the Sulphides section. An incidental bonus from a study of the addition of PhSCl to adamantylideneadamantane is the formation of the 4e-chloro-derivative and PhSSPh, via an intermediate thiiranium salt. Sulphenyl and selenenyl chlorides have been used for the dehydration of aldoximes to nitriles. Whereas sulphinyl chlorides yield sulphinate esters with alkoxytri-methylsilanes, no reaction occurs with sulphenyl chlorides. ... 

Suiphinyl and Seleninyl Halides.—Chlorinolysis of A -(alkylsulphinylmethyl)-phthalimides [PhtCH2S(0)R - RS(0)Cir and the formation of ff-chloro-alkane-sulphinyl chlorides from reactive methylene compounds with SOClj and pyridine illustrate new examples of known methods of preparation. The latter compounds have been shown to yield a-chloro-sulphines on reaction with a tertiary amine (MeCHClSOCl - MeCCl=S=0 MeCCl2SOCl). ... 

Miscellaneous reactions of cr-sulphonyl carbanions with electrophiles include processes involving arylsulphonylmethyl methyl ether anions, cr-sulphinyl sulphone anions, perfluorobutylsulphonylmethylmagnesium halides, nucleophilic substitution in aromatic nitro-compounds by cr-halogenosulphonyl... 

Allenic sulphoxides ArSOCH=C==CR R are available through the reaction of sulphenyl halides with propargyl alcohols HC CCR R OH. Friedel-Crafts reactions with toluene>p-sulphinyl chloride in the presence of AICI3, SnCh, or SbCl, give aryl p-tolyl sulphoxides, and an analogous product is obtained unexpectedly, using toluene-p-sulphonyl chloride with isoquinoline as substrate in the presence of excess NaH. ... 

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