Vol. 33, No. 8, August 1968
2-METHYLENETHIETE 1, D DIOXIDES 3027
9.10 (-SO2-); T::? 8.11-8.92 (multiplet, 12 H, -CH2- of piperidino groups), 7.25-8.08 [multiplet, 8 H, (-CH2-)2N- of piperidino groups], 6.56 (broad triplet, J = 6.0 Ha, H, >CHNgo%) of a colorless solid, mp 95-97'. Recrystallization from ether-petroleum ether (bp 60-8O0) afforded pure 2-methyl-4-phenylthietane 1,ldioxide (3): mp 107-109";: : :A 7.62, 8.47, and 8.80 (-SOz-); T : $ ' * 8.48 (broad doublet, J = 7.0 Ha, 3 H, methyl group), 7.25-7.75 (multiplet, 2 H, ring methylene protons), 5.55-5.95 (multiplet, 1 H, nonbenzylic a-sulfonyl proton), 4.68 (multiplet, 1 H, benzylic a-sulfonyl proton), and 2.60 (singlet, 5 H, phenyl group). (9) R. Hoffmann and R. B. Woodward, J . Amer. Chem. Sac., 87, 2046 (1965). (10) W. E.Truce and V. V. Badiger, J . OW. Chem., 49, 3277 (1964). (11) Melting points were determined with a Thomas-Hoover melting point apparatus and are corrected. Infrared spectra were recorded with a Perkin-Elmer Infracord Model 137 spectrometer fitted with sodium chloride prisms. Ultraviolet spectra were determined with a Cary 14 recording spectrometer. Nuclear magnetic resonance spectra were obtained with a Varian A-60 spectrometer purchased with funds made available through the National Science Foundation. The mass spectrum was measured with an AEI MS-9 mass spectrometer at an ionizing energy of 70 eV. The microanalyses were performed by the Scandinavian Microanalytical Laboratory, Herlev. Denmark.
3030 PAQUETTE AND ROSEN Anal. Calcd for CloH~202S:C, 61.19; H, 6.16; S, 16.34. Found: C, 61.18; H, 6.17; S, 16.22. Reaction of 2-Methylene-4-phenyl-2H-thiete1,l-Dioxide (1) with Dimethylamine.-Into a cold (-20') solution of 0.30 g (1.6 mmol) of 1 in 20 ml ether was distilled excess dimethylamine and the resulting brown mixture was left overnight at 0'. Evaporation of the solution and trituration of the residual brown oil with ether afforded on cooling 0.20 g (45.5%) of 2-dimethylaminomethyl-3-dimetliylamino-4-phenylthietane 1,l-dioxide (4), mp 76-78'. Recrystallization from ether gave pure 4 (unassigned isomer): mp 84-85'; : : :A 7.50, 8.55, and 8.67 p (-SO2-); TE::l3 7.83 and 7.60 (two singlets, 6 H each, dimethylamino groups), 6.90 (doublet, J = 6.0 Ha, 2 H, -CH,NM&), 6.43 (doublet, J = 10.0 Hz, 1 H, >CHNMe2), 5.55-5.95 (multiplet, 1H , nonbenaylic a-sulfonyl proton), 4.82 (doublet, J = 10.0 Ha, 1 H, benzylic proton), and 2.52 (singlet, 5 H, phenyl group). Anat. Calcd for C14Hz~Nz02S: C, 59.54; H, 7.85; N, 9.92. Found: C, 59.63; H, 7.85; N, 9.57. 3,4-Dihydro-l,4,4'-triphenylspiro[ 1,4-epoxynaphthalene-2( lH),Z'[ZH-]thiete] l',l'-Dioxide (6).-A solution of 0.7 g (2.6mmol) of 1,3-diphenylisobenzofuran (5)12 and 0.5 g (2.6 mmol) of 1 in 10 ml of benzene was refluxed for 16 hr under an atmosphere of nitrogen. The resulting brown solution was concentrated to an oil which was chromatographed on neutral alumina. Elution of the column with ether-petroleum ether (1:2) afforded 1.15 g (79.2%)of colorless adduct, mp 210-212' dec. An analytical sample of 6 was obtained from benzene-petroleum ether:ACHC" mp 207-209', with prior formation of yellow color a t 165'. CD'Cll mar 7.67 and 8.69 p (-SO*-);" : :A 262 mp (e 27,900); sTMs6.67 and 7.17 (AB quartet, J = 13.0 Ha, 2 H, methylene protons), 3.38 (singlet, 1 H, styrene proton), 2.20-3.15 (complex pattern with singlet a t 2.68, 17 H, fused aromatic ring protons and phenyl groups), and 1.88 (complex pattern, 2 H , fused aromatic ring protons). Anal. Calcd for ( ; 3 & 2 0 3 S : C, 77.89; H, 4.80; S, 6.93. Found: C, 78.21; H, 4.92; S,6.74. 3,4-Dihydro-l,3,4,4'-tetraphenylspiro [ 1,4-epoxynaphthalene2(1H),2'[2H-]thiete] l',l'-Dioxide (8).-A solution of 1.05 g (3.8 mmol) of 1,3-diphenylisobenzofuran(5) and 1.0 g (3.7 mmol) of 7 in 15 ml of toluene was refluxed for one day under an atmosphere of nitrogen. The toluene was removed in vacuo and the yellow residue was chromatographed on neutral alumina. Elution of the column with ether-petroleum ether (1:3) gave 0.4 g (20.0%)of yellow adduct, mp 211-213' dec. Recrystallization of this material from benzene-petroleum ether gave colorless crystals of 8: mp 216O, with prior formation of yellow color a t 190'; ?: A: 7.66 and 8.69 p (-Sot-); ' : :A 263 mp (e 12,970) and end absorption; ~2': 5.40 (multiplet, 1 H, benzylic proton), (12) M . S. Newman, J . Org. Chem., 56, 2630 (1961).
The Journal of Organic Chemistry 3.94 (broad singlet, 1 H, styrene proton), 2.28-3.18 (complex pattern with singlet superimposed a t 2.92, 22 H, fused aromatic ring protons and phenyl groups), and 1.68-1.91 (complex pattern, 2 H, fused aromatic ring protons). Anal. Calcd for CaeHzeO& C, 80.27; H, 4.87; S, 5.95. Found:-C, 80.20; H, 4.95; S, 5.94. Further elution of the column with ether-petroleum ether (1 :1) and ether gave 1.5 g of an oily solid. Recrystallization of this material from benzene-petroleum ether afforded 0.45 g of a .mixture of 8, dibenzoyl ethylene, and 7, mp 162-165'. Treatment of 6 with Hydrogen Bromide.-A stirred mixture of 0.65 g (1.4 mmol) of 6 and 10 ml of glacial acetic acid containing 0.5 ml of acetic anhydride was treated with gaseous hydrogen bromide for 5 min. The resulting red solution was refluxed for 16 hr whereupon it turned dark brown. The solution was cooled and poured into water, and the organic components were extracted with chloroform. Usual work-up of this solution gave 0.9 g of a brown oil. Chromatography of this material on neutral alumina afforded, on elution with petroleum ether-ether (3:I), 0.5 g (77.0%) of 12, as a colorless waxy solid, mp ca. 73' (prior softening a t 63"). Molecular distillation of this material a t ca. 120' (0.02 mm) and recrystallization from methanol gave pure 12: mp 68-70'; ?:A: 14.33 p (aromatic system); 310 ( E 20,150), 285 (32,750), and 236 mp (37,400); 7::: 3.16 (singlet, 1 H, vinyl proton), and 2.10-3.05 (complex pattern, 20 H, aromatic protons). Anal. Calcd for C30H21Br: C, 78.09; H, 4.59. Found: C, 77.63; H, 4.21. Photolysis of 1. trans-2,7-Diphenyl-l,6-dithiadispiro[3.0.3.2]deca-2,7-diene 1,1,6,6-Tetraodde (14b).-A stirred solution of 5.1 g (0.027 mol) of 1 in 450 ml of ether ww irradiated under nitrogen with a Hanovia 200 W mercury arc for 5 days. Work-up gave a black oily solid which was chromatographed on neutral alumina. Elution of the column with ether-petroleum ether (1:1) afforded 0.9 g of starting material and 0.5 g (11.9% based on unrecovered 1) of photodimer 14b, mp 231 'dec. An analytical sample of 14b was obtained from acetone: mp 232' dec (sintering " : :A 258 mp 7.62 and 8.64 p (-Sot-); a t ca. 205'); (e 36,900), slight shoulder at 266, and end absorption; ~ ~ 7.27 [multiplet, 4 H, +CHt+], 2.47 (singlet, 10 H, phenyl groups), and 2.10 (singlet, 2 H, vinyl protons). Anal. Calcd for CzoHieO&: C, 62.48; H, 4.20; S, 16.68. Found: C, 62.31; H, 4.29; S, 16.65.
Az'"
Registry No.-2, 16791-00-7; 3,16791-01-8; 4, 1679102-9; 6, 16791-03-0; 8, 16791-04-1; 14b, 16791-05-2. Acknowledgment.-The authors are especially indebted to Professor N. L. Allinger for the dipole moment data.
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