Alcohols diphenyl sulfoxide

Oxidation of Alcohols. Diphenyl sulfoxide has been employed as an oxidant in conjunction with molybdenum (VI) and osmium (VIII) catalysts for the conversion of alcohols to carbonyl compounds. Diphenyl sulfoxide in combination with catalytic quantities of Mo02(acac)2 oxidizes alcohols to ketones or aldehydes. Higher yields are obtained with allylic or benzylic alcohols. Catal)dic OSO4 in association with Ph2SO can oxidize primary and secondary alcohols to aldehydes and ketones in the... 

Martin s sulfurane (1) enables quick and efficient elimination of secondary and tertiary alcohols 2 to yield alkenes 3 along with production of diphenyl sulfoxide (4) and alcohol 5.1,2 This highly reactive dehydrating reagent is effective at room temperature and below, and reactions are often complete in less than one hour. Primary alcohols rarely react to yield alkenes and instead are transformed into ethers. The title reagent is available from numerous commercial sources and can be prepared in large quantities according to several published procedures.3... 

Under conditions of direct photolysis, the dimer mechanism is not in effect for the deoxygenation of 9. The quanmm yield, lower than that reported for 200, is invariant over the concentration range of 0.6 to 30 mM in benzene or THF. Also, the quantum yield of deoxygenation of 9 is independent of added diphenyl sulfoxide up to about 50 equivalents and no diphenyl sulfide is observed. Finally, the deoxygenation is effected even at concentrations as low as <10 M in ether/isopentane/alcohol glass at 77K [100]. 

Precaution Dangerous fire hazard spontaneously flamm. in air vapor may flash back container explosion may occur under fire conditions explosive reaction with acetonitrile + diphenyl sulfoxide incompat. with strong acids, strong bases, strong oxidizing agents, alcohols, amines reacts violently with water hydrolyzed by water liberating acidic gas... 

C-Benzylation. The diphenyl sulfoxide and Tf20 combination, used in conjunction with benzyl alcohol, can be exploited as an efficient one-pot C-benzylating system for various sodium enolates (eq 1)P... 

Predominant formation of the C-benzylated product can be understood by considering the soft carbon nucleophile attacking the benzyl carbon of the oxosulfonium trilluoromethane sulfonate, with diphenyl sulfoxide acting as a soft leaving group. The reaction also proceeds smoothly with various other substituted benzyl alcohols with moderate to good yields. Sodium enolates derived from esters, a-cyano esters, a-aromatic and aliphatic ketones can also be benzylated with consistent high yields. 

C ( propyl) N phenylmtrone to N phenylmaleimide, 46, 96 semicarbazide hydrochloride to ami noacetone hydiochlonde, 46,1 tetraphenylcyclopentadienone to diphenyl acetylene, 46, 44 Alcohols, synthesis of equatorial, 47, 19 Aldehydes, aromatic, synthesis of, 47, 1 /3-chloro a,0 unsaturated, from ke tones and dimethylformamide-phosphorus oxy chloride, 46, 20 from alky 1 halides, 47, 97 from oxidation of alcohols with dimethyl sulfoxide, dicyclohexyl carbodumide, and pyndimum tnfluoroacetate, 47, 27 Alkylation, of 2 carbomethoxycyclo pentanone with benzyl chloride 45,7... 

Normal nucleophilic substitution occurred on treatment of 2-carbamoyl-3-chloropyrazine with alcoholic methylamine at 130° (423, 836) 2-chloro-3-(4 -morpholinocarbonyOpyrazine with morpholine at reflux in benzene (867) 2dimethyl sulfoxide at 65° (857) and cyclohexylamine in benzene at reflux (946) 3-chloro-2-methoxycarbonyl-5-phenylpyrazine with alcoholic methylamine at 140° (375) 2-carboxy-3-chloropyrazine with anhydrous ammonia at 100° for 5 hours (947) 2-carbamoyl-6-chloropyrazine with aqueous methylamine at reflux (940) 2-chloro-6-(4 -morpholinocarbonyl)pyrazine (and other amides) and 2-chloro-6-methoxycarbonylpyrazine with morpholine (and other amines) (870, 948, 949) and 2-chloro-6-methoxycarbonylpyrazine with liquid ammonia at 80° (870). 2-Chloro-3-methoxycarbonylpyrazine fused with guanidine carbonate gave 2-amino4-hydroxypteridine and its 7-methyl-, 7-phenyl, and 6,7-diphenyl analogues were prepared similarly (371,375). 

---