ether solution was dried over magnesium sulfate and the ether removed. A white crystalline residue remained which was diluted to 5.0 ml with CC14 and analyzed by ir for unreacted diaziridinone. Comparison of the infrared spectrum to a standard solution revealed that less than 4% of the diaziridinone had been destroyed; a band at 1665 cm-1 of very low intensity indicated the formation of the urea.A solution of sodium naphthalenide (2.1 mmol in 10.0 ml of THF) was treated with 0.297 g (0.99 mmol) of the diaziridinone under the same conditions as before affording 0.230 g of 1,3-bis-(1,1 -dimethyl-2-phenylethyl)urea, mp 180-182°, mmp 180-182°, and identical in infrared spectrum with an authentic sample.

The following sulfoxides were prepared by the oxidation of the corresponding sulfides with a nitric acid-acetic anhydride mixture: 5-hydroxy-2,3,4,5-tetrahydro-l-benzothiepm 1-oxide (2, 64% yield), 5-chloro-2,3,4,5-tetrahydro-l-benzothiepin 1-oxide (5, 43% yield), and 3,4-dihydro-l-benzothiepin-5(2fl>one 1-oxide (8, 45% yield).2,3-Dihydro-l-benzothiepin 1-oxide (II) was available by oxidation of the sulfide 10 with sodium metaperiodate or sulfuryl chloride ( -78°) followed by hydrolysis. The latter method has been shown to be a general procedure for the synthesis of sulfoxides in high yields. The intermediate in this synthesis appears to be a chlorine sulfide complex which at low temperature is best represented by the tetracovalent sulfur structure 14b.

The reaction of 2,3-dihydro-l-benzothiepin (7) and sulfuryl chloride at low temperatures gave approximately equal amounts of cis-(10) and irons-4,5-dichloro-2,3,4,5-tetrahydro-l-benzothiepin (11), characterized as their corresponding sulfones 12 and 13, respectively. Chromatography of cis-12 or reaction with KOH produced 5chloro-2,3-dihydro-l-benzothiepin ( 14). Elimination reactions and nmr spectra were used to assign stereochemistry. When 7 was treated with 1 or 2 equiv of '-chIorosuccÍnimide, 2-chloro-(8) or 2,2-dichloro-2,3-dihydro-lbenzothiepins (19) were formed and converted to their sulfones 18 and 20, respectively. An explanation for the different outcome of these two reactions is presented. The reaction of 8, 19, or 2,4-dichloro-2,3-dihydro-1-benzothiepin (24) with strong base gave 1-benzothiepin (9), 2-chloro-l-benzothiepin ( 27), and 4-chloro-l-benzothiepin (28). All of these compounds decomposed slowly at room temperature with extrusion of sulfur and formation of naphthalene. The 1-benzothiepins were oxidized to their corresponding sulfones 25, 31, and 32, which were also prepared by dihydrochlorination of the -chloro sulfones 18, 20, and 2,4-dichloro-2,3-dihydro-l-benzothiepin 1,1-dioxide (33). The thermal stability, mass spectra, and nmr spectra are discussed for both the 1-benzothiepins and their sulfones. The structure of these compounds appears to contain a puckered thiepin ring.

The alkaline hydrolysis of substituted phenyl benzenethiolsulfinates has been kinetically investigated.The rates were correlated with the second order kinetic equation, first order with respect to each of the hydroxide and the ester concentration . The second order rate constant for

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