17194 (13 mol %). Trituration with hexane removed 4,0.17 g (O.ooO86 mol, 100% recovery), leaving 6: white crystals; mp 147-150 "C; 0.77 g (0.0023 mol, 88%); mp 151-152 "C (hexane/benzene; EtOH); IR (Nujol) 1380 and 1180 (strong, SO3), 1345 and 1130 (strong, SOz) cm-'; 'H NMR (CDC13) 6 7.84 (d, J = 8 Hz, 2, o-S03Ar H), 7.5-7.3 (m, 7, m-S03Ar H,Ph), 4.66 (s, 2, SCH,O), of benzyl diazomethyl sulfone (5) [as a mixture with 0.17 g (0.00086 mol) of TsN3 (4); see above], and stirring was continued for 2 h. EgO (150 mL) was added and the solution was washed thoroughly with water, dried (MgSOI,), and evaporated, leaving 0.97 g of yellow crystals shown by 'H NMR to be composed of 6 (87 mol %) and 4.30 (s, 2, CHzPh), 2.47 (6, 3, CH& Anal. Calcd for C15H1605SZ: c, 52.93; H, 4.74; s, 18.84. Found: C, 52.91; H, 4.85; S, 18.78. Registry No . 1,4403-73-0; 2, 70-23-5; 3, 73178-38-8; 4, 941-55-9; (24) This recrystallized material is the monohydrate: 'H NMR (C-D3COCD3) 6 8.57 (s, 3, OH), 7.78 (d, J = 8 Hz,.2, o-SO3Ar H), 7.28 ( d , J = 8 Hz. 2. m-SOIAr H). 2.40 (s. 3. CHd. We did not find it necessarv to . . 1 use anhydrous TSOH (cf. ref 4). 5, 1588-80-3; 6, 73178-37-7; p-toluenesulfonic acid, 104-15-4.
CommunicationsUnexpected Behavior of an a-Tosyloxy Sulfone Compared with an a-Chloro Sulfone in Base-Induced Reactions Summary: Unexpeclzdly, a rate ratio for kms/kcl of 0.0011 was observed in 1,3 eliminations of (tosy1oxy)methyl benzyl sulfone and chloromethyl benzyl sulfone in t-BuOK/ t-BuOH (25 "C), while in MeONa/MeOH (25 "C) neither 1,3 elimination occurred; instead, the a-tosyloxy sulfone underwent facile S-0 cleavage to provide methyl ptoluenesulfonate and a-toluenesulfinic acid. Registry No. 2, 73178-37-7; 3, 5335-44-4; a-toluenesulfinic acid, 4403-73-0; styrene, 100-42-5; MeOTs, 80-48-8.