Dimethyl sulfide-chlorine

Potassium permanganate. Dimethyl sulfide-Chlorine. Dimethyl sulfoxide. Dimethyl sulfoxide-Chlorine. Dimethylsulf-oxide Sulfur trioxide. Dipyridine chro-mium(VI) oxide. Iodine. Iodine-Potassium iodide. Iodine tris(trifluoroacetate). Iodosobenzene diacetate. Isoamyl nitrite. Lead tetraacetate. Manganese dioxide. Mercuric acetate. Mercuric oxide. Osmium tetroxide—Potassium chlorate. Ozone. Periodic acid. Pertrifluoroacetic acid. Potassium ferrate. Potassium ferricyanide. Potassium nitrosodisulfonate. Ruthenium tetroxide. Selenium dioxide. Silver carbonate. Silver carbonate-Celite. Silver nitrate. Silver oxide. Silver(II) oxide. Sodium hypochlorite. Sulfur trioxide. Thalli-um(III) nitrate. Thallium sulfate. Thalli-um(III) trifluoroacetate. Triphenyl phosphite ozonide. Triphenylphosphine dibromide. Trityl fluoroborate. 

Related Reagents. A/-Chlorosuccinimide-Dimethyl Sulfide Chromic Acid Dimethyl Sulfide-Chlorine Dimethyl Sulfoxide-Acetic Anhydride Dimethyl Sulfoxide-Dicyclo-hexylcarbodiimide Dimethyl Sulfoxide-Oxalyl Chloride Dimethyl Sulfoxide-Phosphorus Pentoxide Dimethyl Sulfoxide-Sulfur Trioxide/Pyridine Dimethyl Sulfoxide-Trifluoroacetic Anhydride Dimethyl Sulfoxide-Triphosgene Manganese Dioxide Pyridinium Chlorochromate Pyridinium Dichromate Ruthenium(rV) Oxide Silver(I) Carbonate on Celite 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3( 1 H)-ons. 

Stelson, A. W and J. H. Seinfeld, Chemical Mass Accounting of Uban Aerosol, Environ. Sci. Technol., 15, 671-679(1981). Stickel, R. E., J. M. Nicovich, S. Wang, Z. Zhao, and P. H. Wine, Kinetic and Mechanistic Study of the Reaction of Atomic Chlorine with Dimethyl Sulfide, J. Phys. Chem., 96, 9875-9883 (1992). Swartz, E J. Boniface, I. Tchertkov, O. V. Rattigan, D. V. Robinson, P. Davidovits, D. R. Worsnop, J. T. Jayne, and C. E. Kolb, Horizontal Bubble Train Apparatus for Heterogeneous Chemistry Studies Uptake of Gas-Phase Formaldehyde, Environ. Sci. Technol, 31, 2634-2641 (1997). 

Langer, S., B. T. McGovney, and B. J. Finlayson-Pitts, The Dimethyl Sulfide Reaction with Atomic Chlorine and Its Implications for the Budget of Methyl Chloride, Geophys. Res. Lett., 23, 1661-1664 (1996). 

Shekel, R. E., J. M. Nicovich, S. Wang, Z. Zhao, and P. H. Wine, Kinetic and Mechanistic Study of the Reaction of Atomic Chlorine with Dimethyl Sulfide, J. Phys. Chem., 96, 9875-9883 (1992). 

Corey and Kim described an oxidation,6a in which activated DMSO is not generated by activation of DMSO, but by oxidation of dimethyl sulfide. Although, they described only the use of chlorine and /V-chlorosuccinimidc as dimethyl sulfide oxidants, we propose that the name Corey-Kim oxidations be applied to alcohol oxidations, in which activated DMSO is generated by oxidation of dimethyl sulfide, regardless of the oxidant employed. 

Thus, Corey and Kim explained in 1972248 that reaction of dimethyl sulfide with chlorine yields chlorodimethylsulfonium chloride, which is precisely the same species described later249 as the activated DMSO species, generated during a Swern oxidation. 

As operation with gaseous chlorine is dangerous and inconvenient, Corey Kim oxidations are normally performed by oxidation of dimethyl sulfide with /V-chIorosuccinimide rather than with chlorine. This results in the formation of a different kind of active DMSO species, in which a sulfur-nitrogen bond is present. 

Among other electrophilic reagents ctq>able of twinging about the Pummerer rearrangement are halides of organic and inorganic acids. As these halides transform sulfoxides into a-chlorosulfides they complement the sulfide chlorination route to these compounds. Thionyl chloride reacts readily with sulfoxides and 3-keto sulfoxides methyl phenyl sulfoxide furnishes chloromethyl phenyl sulfide (equation 37). Benzoyl chloride and acetyl chloride behave similarly. d yanuric chloii is transformed into cyanuric acid by dimethyl sulfoxide, which in turn is transformed into methyl chloromethyl sulfide (equation 3g).54,S5... 

Interestingly, this intermediate is identical to that fonned in the reaction of dimethyl sulfide with chlorine, a mixture well known to be useful in the oxidation of alcohols to carbonyl compounds. ... 

Dimethyl sulfoxide and chlorine form highly reactive intermediates which are of some limited use as oxidants for alcohols. These intermediates are related to those derived from the reaction of the halogens with dimethyl sulfide and probably have a structure such as (27). When formed at -4S C they allow the oxidation of primary and secondary alcdiols to aldehydes and ketones when used in a two-fold excess. For very simple alcdiols the reaction proceeds in yields of greater than 90%, but there are considerable drawbacks if some types of additional functionality are present in the molecule, e.g. alkenes react very rapidly to form vicinal dichlorides. 

Dimethyl snlfoxide-Oxalyl chloride, 8, 200. Swern and co-workers have suggested that the acutal oxidizing agent from DMSO and oxalyl chloride is 1, formed by almost instantaneous loss of CO2 and CO. This is also the reagent obtained by Corey and Kim from dimethyl sulfide and chlorine. (4, 191). 

Chlorodimethylsulfonium chloride (generated from chlorine and dimethyl sulfide) can be used in the same way for preparation of a-chloro ketones. 

OxUatiou of primary and secondary alcohals to carbonyl compounds. Corey and Kim report that the complex of N-chlorosuccinimide and dimethyl sulfide is somewhat superior to the complex of dimethyl sulfide and chlorine (this volume) for oxidation of primary and secondary alcohols the formation of hydrogen chloride is avoided and yields are generally higher. The procedure is illustrated for the oxidation of 4-r-butyl-cyclohexanol (2) to 4-r-butylcyclohexanonc (4). The complex (1) is prepared by addition of dimethyl sulfide (4.1 mmole) to a stirred solution of NCS (3.0 mmole) in toluene at 0° under argon. The mixture is cooled to -25° and a solution of 4-r-butylcyclo-hexanol (2.0 mmole, mixture of cis and trans) in toluene is added dropwise. The stirring is continued for 2 hr. at — 25° and then triethylamine (3.0 mmole) in toluene is added dropwise. The ketone (4) is obtained in almost quantitative yield. As in oxidation with the complex of dimethyl sulfide and chlorine, an intermediate sulfoxonium complex (3) is involved. 

Oxidation of primary and secondary alcohols to carbonyl compounds, Treatment of dimethyl sulfide in carbon tetrachloride at 0° with 1 eq. of chlorine in the same solvent results in rapid formation of the partially insoluble complex (I). This complex has been used by Corey and Kim for oxidation of primary and secondary alcohols. In a typical... 

Dimethyl sulfide and chlorine or, better still, dimethyl sulfide and N-chlorosuccinimide, form a system capable of the selective dehydrogenation of alcohols to aldehydes or ketones. The intermediates, such as (013)28 C1 Cr, react with bases according to the scheme in equation 25 [720],... 

Dimethyl sulfide and chlorine or A-chlorosuccinimide (NCS) oxidize primary alcohols to aldehydes in high yields under very mild conditions. 

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