Organic chemistry of reduced species of sulfur dioxide
Date of Award
Doctor of Philosophy (PhD)
Donald C. Dittmer
Organic chemistry, Sulfer dioxide
Sodium hydroxymethanesulfinate (Rongalite) is a derivative of the unsymmetrical sulfoxylic acid (HSO$\sb2$-) and is used as a source of reduced species of sulfur dioxide. My work involved the development of a better solvent system than had previously been used with Rongalite, and employment of it in optimizing the yields and determining the mechanisms of the reactions of Rongalite with organic halides. Rongalite is reacted with organic halides as a slurry in a polar aprotic solvent, such as N,N-dimethylformamide (DMF) or 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (N,N-dimethylpropyleneurea, DMPU). The best method is the use of a slurry of Rongalite in DMF (or DMPU) with a phase transfer agent, tetrabutylammonium bromide.
Treatment of benzyl bromide, 4-cyanobenzyl bromide, and 1-bromodecane with Rongalite in DMF give symmetrical sulfones in good yields. Treatment of $\alpha$,$\alpha$$\sp\prime$-dichloro-o-xylene or $\alpha$,$\alpha$$\sp\prime$-dibromo-o-xylene with Rongalite in DMF gives 2,3-benzoxathiin-3-oxide and a polymeric o-xylylene. Use of a phase transfer agent, tetrabutylammonium bromide, in the DMF during the reaction of $\alpha$,$\alpha$$\sp\prime$-dihalo-o-xylene with Rongalite gives 2,3-benzoxathiin-3-oxide in good yields.
Treatment of allyl bromide with Rongalite in DMF gives bis-allyl sulfone and propene. Use of excess So$\sb2$ or a nucleophilic catalyst, sodium iodide, in this reaction generates good yields of bis-allyl sulfone.
Treatment of phenacyl chloride with Rongalite in DMF gives acetophenone in good yield. Treatment of phenacyl bromide with Rongalite in DMF gives a mixture of acetophenone and 1,4-diphenyl-1,4-butanedione. 1,4-Diphenyl-1,4-butanedione is generated when the same reaction is run in the presence of a drying agent, such as calcium hydride or anhydrous magnesium sulfate. Treatment of phenacyl bromide with Rongalite and excess SO$\sb2$ in DMF gives a mixture of acetophenone, 1,4-diphenyl-1,4-butanedione, and bisphenacyl sulfone.
Rongalite reacts with 4-nitrobenzyl bromide to generate different products, depending upon the reaction conditions. Treatment of 4-nitrobenzyl bromide with Rongalite and sodium or potassium bicarbonate in a DMF/H$\sb2$O solution gives 4,4$\sp\prime$-dinitrobibenzyl in good yield. Treatment of 4-nitrobenzyl bromide with Rongalite and sodium or potassium bicarbonate in DMF or a DMPU/H$\sb2$O solution gives bis(4-nitrobenzyl) sulfone in good yields.
Treatment of benzal bromide with Rongalite in DMF gives a mixture of trans-stilbene and 1,2-dibromo-1,2-diphenylethane. Treatment of the latter with Rongalite in DMF gives trans-stilbene in good yield. Treatment of hexabromobenzene with Rongalite in DMF gives a mixture of pentabromobenzene and isomeric tetrabromobenzenes.
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Hoey, Michael Dennis, "Organic chemistry of reduced species of sulfur dioxide" (1990). Chemistry - Dissertations. 123.