Oxidation reactions with lead (IV) sulfonates and the preparation of potential antiradiation agents via thiirane 1,1-dioxides
Lead tetraacetate (LTA) in the presence of sulfonic acids was studied in the hope of producing a more potent oxidant than LTA (owing to displacement of the weaker acetic acid by strong sulfonic acids). LTA in the presence of CF/sub 3/SO/sub 3/H (greater than or equal to4 equiv.) will cleave benzopinacol to benzophenone. LTA in the presence of CH/sub 3/SO/sub 3/H will methanesulfonoxylate diethyl malonate, methyl acetoacetate, and ethyl cyanoacetate. In the presence of CH/sub 3/SO/sub 3/H, MeOH, and CHCl/sub 3/, LTA will convert dialkyl and diaryl disulfides to methyl sulfinate esters. In a variation with Pb/sub 3/O/sub 4/, CH/sub 3/SO/sub 3/H, and P/sub 2/O/sub 5/ in ChCl/sub 3/, diethyl malonate was converted to a methanesulfonoxymalonate ester and to the monochloro-and dichloromalonates. Pb/sub 3/O/sub 4/, CH/sub 3/SO/sub 3/H, and P/sub 2/O/sub 5/ in benzene gave phenyl methanoesulfonate. A camphor 1,10-episulfone was prepared by the reaction of D-(+)-10-camphorsulfonyl chloride with Et/sub 3/N and CH/sub 2/N/sub 2/. The episulfone was cleaved at the least-hindered carbon atom using p-thiocresolate to give the corresponding ..beta..-substituted ethanesulfinate salt. Also, thiirane 1,1-dioxide, prepared from SO/sub 2/ and CH/sub 2/N/sub 2/, was cleaved with sodium phenylmethanethiolate and p-thiocresolate, Li/sub 3/SPO/sub 3/, Na/sub 2/S/sub 2/O/sub 3/, and sodium p-toluenethiosulfate to give the corresponding ..beta..-substituted ethanesulfinates.
- Research Organization:
- Vanderbilt Univ., Nashville, TN (USA)
- OSTI ID:
- 6995630
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RADIOPROTECTIVE SUBSTANCES
CHEMICAL PREPARATION
SULFONATES
OXIDATION
ACETATES
LEAD COMPOUNDS
SULFONIC ACIDS
CARBOXYLIC ACID SALTS
CHEMICAL REACTIONS
DRUGS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
SYNTHESIS
400201* - Chemical & Physicochemical Properties