J. Org. Chem. 1981, 46,5445-5447 When the irradiation was repeated in chloroform instead of dichloromethane, the reaction gave similar results to those reported above. Dark Reaction of Selenosulfonate 1 with Diazomethane. Selenosulfonate 1 (156 mg, 0.50 mmol) was dissolved in 2 mL of dichloromethane and excess ethereal diazomethane was added. The reaction mixture was allowed to stand for 17 h at room temperature in an apparatus completely wrapped in aluminum foil to exclude light. After removal of volatile material in vacuo, NMR analysis of the resulting oil indicated the presence of three components with signals at 6 5.52 (d, J = 10 Hz)and 5.18 (d, J = 10 Hz), 6 4.24 (8) and 3.44 (s), attributed to 4 (CH,), 3 (CH,), and 5 (OCH3),respectively, as well as the expected aromatic and aryl methyl resonances. The integrated intensities of these signals provided yields of 21%, 52%, and 27% for 3,4 and 5, respectively. A 110-mg portion of this mixture was separated by preparative TLC in 25% ethyl acetate-hexane to afford, in increasing order of R , 26 mg of the a-(phenylseleno) sulfone 3, identical (TLC, IR, ~ M R with ) an authentic sample (vide infra), 60 mg of a mixture of sulfinate esters 4 and 5, and 15 mg of diphenyl diselenide, identical (TLC, IR, NMR) with an authentic sample. The mixture of 4 and 5 could not be further separated. The presence of 5 was confirmed by comparing the mixture with an authentic sample (IR, NMR, GC-mass spectra); that of 4 was inferred from the NMR spectrum.g Finally, the mixture of 4 and 5 gave a mass spectrum showing m l e 326 and 324 at probe temperatures over 100 "C (M+of 4, %e and '%e, respectively) and mle 170 (M' of 5) at room temperature. (Phenylse1eno)methylp-Tolyl Sulfone (3). Methyl p-tolyl sulfone (170 mg, 1.00 mmol) and sodium hydride (30 mg, 1.25 "01) were refluxed 1h in 5 mL of toluene under nitrogen. The mixture waa then added to a solution of benzeneselenenyl chloride (239 mg, 1.25 mmol) in 5 mL of toluene. After being stirred for 30 min at room temperature, the solution was washed with water (2X), dried over anhydrous MgSO,, and evaporated to dryness under vacuum. The residue was separated by preparative TLC in 25% ethyl acetate-hexane to afford 91 mg (28%) of the title compound mp 74-81 OC; IR (filmof melted product) 1317,1303, 1145 cm-l; NMR 6 7.70 (d, J = 9 Hz, 2 H), 7.5-7.0 (complex, 7 H), 4.24 (8, 2 H), 2.40 (s,3 H); mass spectrum, mle 326 (M', %e), 324 (M+,'%e). Anal. Calcd for CI4HI4O2SSe:C, 51.69; H, 4.34; S, 9.86. Found: C, 51.79; H, 4.33; S, 10.14. Attempted Reaction of Sulfone 3 with Diazomethane. Sulfone 3, prepared in the preceding procedure, was dissolved in 1mL of dichloromethane. Excess ethereal diazomethane was added and the solution was irradiated as in the case of selenosulfonate 1. After 1 h, volatile material was removed in vacuo and the remaining residue consisted of unchanged 3 (melting point, NMR). Registry No. 1, 68819-94-3; 2, 79665-09-1; 3, 79665-10-4; 4, 79665-11-5; 5,672-78-6; methyl p-tolyl sulfone, 3185-99-7; benzeneselenyl chloride, 5707-04-0. (9) The AB quartet observed for the diastereotopic methylene protons in 4 closely resembles those in eimilar sulfinate esters such as benzyl p-toluenesulfiiate: Wilt, J. W.; Wagner, W. J. Chem. Id.(London) 1964, 1389.
Synthesis of Adamantane Derivatives. 56. Reaction of 1-Adamantyl Chloride with Trimethylsilyl Pseudohalide
5445
Chart I Me3SiR
1, R = C1
3,R=NC 4, R = NHCHO 7, R = SCN 8 , R = NCS 9, R = Br 12, R = NCO 13, R = NHCONH-t-Bu 14, R = N(Me)CN 16, R = N,
2, R = CN 5, R = CH=C=CH,
a
6, R = NCS 10, R = NCO 11, R = N=C=NMeb 15, R = N, 17, R = N=C
