Chlorine reaction with dimethyl sulfide

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). 

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). 

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. 

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. 

A useful variant of the Darzens reaction has been reported for the preparation of fosfomycin from diethyl chloromethylphosphonate. Nucleophilic substitution of chlorine in diethyl chloromethylphosphonate with dimethyl sulfide gives the sulfonium salt, further converted into its stable ylide by the use of NaH in DMSO. The addition of the ylide to acetaldehyde produces diethyl 1,2-epoxypropylphosphonate, thus avoiding the problems associated with the stability of chloromethylphosphonate carbanions (Scheme 4.4). 

An alternative method for the formation of aldehydes or ketones makes use of the complexes formed from a methyl sulfide with chlorine or A-chlorosuccinimide (NCS), in what is called the Corey-Kim oxidation. With dimethyl sulfide the salt 28 is generated and reacts with the alcohol to give the alkoxysulfonium salts and hence, on treatment with a base, the carbonyl compound. This reaction has fovmd particular application in the oxidation of 1,2-diols in which one alcohol is tertiary, to give a-hydroxy-aldehydes or ketones without rupture of the carbon-carbon bond. For example, the aldehyde 32 is formed in good yield from the diol 31 using dimethyl sulfide and NCS followed by addition of triethylamine (6.29). This transformation is thought to depend on the preferential five-membered transition... 

Chromic acid and other Cr(VI)-containing compounds are toxic, so chemists have developed other reagents for oxidizing alcohols. Several are based on chlorodimethyl-sulfonium ion [(CH3)2SC1] as the oxidizing agent. Although chlorodimethylsulfonium ion can be prepared by the reaction of chlorine with dimethyl sulfide ... 

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). 

A powerful oxidizer. Explosive reaction with acetaldehyde, acetic acid + heat, acetic anhydride + heat, benzaldehyde, benzene, benzylthylaniUne, butyraldehyde, 1,3-dimethylhexahydropyrimidone, diethyl ether, ethylacetate, isopropylacetate, methyl dioxane, pelargonic acid, pentyl acetate, phosphoms + heat, propionaldehyde, and other organic materials or solvents. Forms a friction- and heat-sensitive explosive mixture with potassium hexacyanoferrate. Ignites on contact with alcohols, acetic anhydride + tetrahydronaphthalene, acetone, butanol, chromium(II) sulfide, cyclohexanol, dimethyl formamide, ethanol, ethylene glycol, methanol, 2-propanol, pyridine. Violent reaction with acetic anhydride + 3-methylphenol (above 75°C), acetylene, bromine pentafluoride, glycerol, hexamethylphosphoramide, peroxyformic acid, selenium, sodium amide. Incandescent reaction with alkali metals (e.g., sodium, potassium), ammonia, arsenic, butyric acid (above 100°C), chlorine trifluoride, hydrogen sulfide + heat, sodium + heat, and sulfur. Incompatible with N,N-dimethylformamide. 

Chlorination of Aromatic Compounds. NCS has also been used for the chlorination of pyrroles and indoles however, the reaction is less straightforward than when NBS and N-Iodosuccinimide are used. In the chlorination of 1-methylpyrrole, it has been demonstrated that basic conditions (NaHCOs, CHCI3) lead to the formation of 1-methyl-2-succinimidylpyrrole (eq 11). In the presence of catalytic amounts of perchloric acid, thiophenes and other electron-rich aromatic compounds have been chlorinated with NCS. (N-Chlorosuccinimide-Dimethyl Sulfide is used for the selective -substitution of phenols.)... 

The triazolo[l,5-a]pyridine-2-sulfonanilides (30) can be prepared by the general route as outlined in Scheme 2.4.5 [49, 50]. The intermediate 2-benzylthio-triazolo[l,5-a]pyridine (31) is prepared starting from an appropriately substituted 2-aminopyridine. The 2-aminopyridine is reacted with 0-mesitylenesulfonylhy-droxylamine to give the N-aminopyridinium mesitylate (32). Compound 32 is then reacted with thiocarbonyldiimidazole followed by benzyl chloride to give 31. Conversion of the benzyl sulfide, 31, into the corresponding sulfonyl chlorides (33) is accomplished with chlorine and water. The sulfonyl chlorides are converted into the desired sulfonanilide (30) by reaction with aniline in the presence of pyridine and a catalytic amount of dimethyl sulfoxide. 

Medvedeva et al. first investigated the substituted propynals 303 as aldehyde substrates involved MBH reactions. The initial attempt to conduct the MBH reaction in the presence of TiCU was unsuccessful because of oligomerization of the reaction mixture. However, promotion with TiCU and a catalytic amount of dimethyl sulfide in the chalcogeno-MBH reaction led to 2-[(Z, )-chloromethylidene]-3-hydroxy-1 -phenyl-5-organylpent-4-yn-1 -ones 304 by tandem a-hydroxyethynylation/p-chlorination of l-phenylprop-2-yn-l-one (Scheme 2.166). ... 

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