3-Thietanone 1,1-dioxides

The IR spectra of 0-alkyl, phenyl substituted thietanes have been assembled by Ohno et al. The absorption pattern derived from thietanone 1,1-dioxide has been illustrated. ... 

Treatment of diethyl ketals of 3-thietanone 1,1-dioxide with bases (NaOH, phenyllithium" ) results in the elimination of ethanol to give 3-ethoxythiete 1,1-dioxides, for example, 257. 3-Methoxy-2H-thiete 1,1-dioxide is obtained by elimination of methoxytrimethylsilane from the ketal of 2-trimethylsilyl-3-thietanone 1,1-dioxide. The cycloaddition of ketene yy.,4i7,494b.495a,s93,6oo. 49sa,60i sulfenes derived from... 

Treatment of 3-thietanone 1,1-dioxide with diazomethane, diazoethane, or ethyl diazoacetate gives 3-alkoxythiete 1,1-dioxides, for example, 263. ° A similar reaction occurs with 2-phenyl-3-thietanone 1,1-dioxide and diazomethane. Hydrogenation of the exocyclic double bond in 264 can be accomplished without... 

Thietanone 1,1-dioxides are intermediates in the synthesis of cyanine dyes used as photographic sensitizers. ... 

Thietanone 1,1-dioxides are unknown, although the tetraphenyl compound may be an intermediate in the oxidation of the 2-thietanone 308 with m-chloro-perbenzoic acid to the sulfinic-carboxylic acid anhydride 331. The methods discussed below apply to 3-thietanone 1,1-dioxides and derivatives. 

Thietanone 1,1-dioxide ketals and 3-aminothiete 1,1-dioxides are readily available by cycloaddition of sulfenes to ketene acetals and enamines, respectively (Section V.3.B.). Hydrolysis of these ketals " and the aminothiete sulfones (which are enamines) " " gives 3-thietanone 1,1-dioxides in fair to good yields, as exemplified by the hydrolysis of 133 and 402. Aqueous mineral acids or acidic ion-exchange resins catalyze the reaction. Cis-2-chloro-2,4,4-trimethyl-3-morpholinothietane 1,1-dioxide reacts with N sodium hydroxide to give 38% 2,2,4-trimethyl-3-thietanone 1,1-dioxide, but the trans isomer is recovered unchanged. 3-Methoxy- and 3-ethoxythiete 1,1-dioxide (enol ethers) are also hydrolyzed to 3-thietanone 1,1-dioxide. In several cases, the hydrolysis products are written as enols of the 3-thietanone sulfone. ... 

The 3-thietanone 1,1-dioxide structure proposed for the product of the reaction of azibenzil with sulfur dioxide has been shown by nmr spectroscopy to be incorrect.2,2,4,4-Tetramethyl-3-thietanethione 1,1-dioxide is obtained from the corresponding ketone (69% yield) by treatment with phosphorous penta-sulfide.5 ... 

The reaction of 3-thietanone 1,1-dioxide with methanol to give the hemiketal has been observed by nmr spectroscopy the equilibrium composition is 90% hemiketal-10% ketone.The 2,4-dinitrophenylhydrazone and the p-toluene-sulfonylhydrazone have been reported. 

Catalytic hydrogenation of 3-thietanone 1,1-dioxide failed, but the carbonyl group can be reduced to the alcohol in 56% yield by diborane in dioxane. Likewise, a thiocarbonyl group is reduced by sodium borohydride. ... 

Thermolysis of 3-thietanone 1,1-dioxide, 2,2-dimethyl-3-thietanone 1,1-dioxide, and 2-phenyl-3-thietanone 1,1-dioxide at 930-960°C results in extrusion of sulfur dioxide and carbon monoxide to give ethylene, isobutylene, and styrene. 

Photolysis of 3-thietanone involves both singlet and triplet excited states the initial products are sulfene and ketene, as determined by IR spectroscopy at liquid nitrogen temperatures in a pentane matrix.When the photolysis is done in methanol, isopropyl alcohol, or r-butyl alcohol, these intermediates are trapped as the acetate and methanesulfonate esters. In diphenylmethanol solvent, the bis-diphenylmethyl ether is formed by displacement of the alcohol on the sulfonate ester. Photolysis of tetramethyl-3-thietanone 1,1-dioxide gives dimethylketene. ... 

The a-methylene protons of 3-thietanone 1,1-dioxide are acidic (effervescence is observed in sodium bicarbonate solution). The base-catalyzed reaction of... 

---