Supporting Information

Transcription

1 DABCO-bis(sulfur dioxide), DABSO, as a Convenient Source of Sulfur Dioxide for Organic Synthesis: Utility in Sulfonamide and Sulfamide Preparation Holly Woolven, Carlos González-Rodríguez, Isabel Marco, Amber L. Thompson and Michael C. Willis* Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, OX1 3TA, UK. Supporting Information Index I General Experimental Procedures S-2 II Sulfonamide Synthesis(General Procedure A) S-3 III Sulfamide Synthesis (General Procedure B) S-3 IV Synthesis of sulfolene 1 S-4 V Data for Sulfonamides S-5 VI Data for Sulfamides S- VII Spectra S-12 1

2 I. General Experimental Procedures All reactions were performed under an inert atmosphere of nitrogen, in oven or flame dried glassware unless otherwise stated. Nitrogen was passed through a Drierite filled drying tube before use. All chemicals were purchased from Acros, Aldrich, or Strem chemical companies and used without further purification, unless otherwise stated. Tetrahydrofuran was obtained dry from an in-house solvent purification system having passed through anhydrous alumina columns. Acetonitrile were purchased from Sigma Aldrich as anhydrous solvent and used without further purification. Sulfuryl chloride was fractionally distilled before use. DABCO-(SO 2 ) 2 complex, 1 (DABSO), was dried under vacuum and then nitrogen for -15 mins prior to use. Petrol refers to the fraction of light petroleum ether boiling in the range 4- C. Analytical thin layer chromatography was carried out using pre-coated aluminiumbacked silica plates (rck Kieselgel F254) and pre-coated plastic backed silica plates (Polygram Sil G/UV254). Plates were visualised under ultraviolet light (254 nm) or by staining with KMnO4 or vanillin. Flash column chromatography was carried out using rck Kieselgel H silica. Pressure was applied at the column head via hand bellows. lting points were determined using a Büchi 535 melting point apparatus and a Leica Galen III and are reported uncorrected. Infrared measurements were carried out as liquid films on NaCl discs or as a KBr disc using a Perkin-Elmer series FTIR spectrometer and Bruker Tensor 27 FT-IR with internal calibration in the range 4-5 cm-1. Mass spectrometry was carried out either on a Bruker microtof or a Bruker FT-ICR-MS Apex III at the University of Oxford, or using a Micromass Quattro II and a Finnegan MAT 95XP at the EPSRC mass spectrometry service at the University of Wales, Swansea. 1 H and 13 C nuclear magnetic resonance experiments were carried out using a Bruker AV-4 MHz or AV-5 MHz NMR spectrometers. Chemical shifts were reported in parts per million from tetramethylsilane for 1 H and 13 C experiments. The residual solvent peak was used as an internal standard. The multiplicities of the spectra are reported as follows: singlet (s), doublet (d), triplet (t), quartet (q) and multiplet (m). Coupling constants (J) are given in Hz. 1 Nguyen, B.; Emmett, J. E.; Willis, C. M. J. Am. Chem. Soc., 132,

3 !!" Sulfonamide Synthesis!!"#$#%&'()%*+#,-%#(./# R-MX + DABSO i) THF ii) SO 2 Cl 2 iii) NHR'R'' R S R' N R'' R' = H, R'' = H R' = R'' = H A suspension of DABSO complex (151 mg,.63 mmol) in THF (3 ml) was cooled to -4 C. The Grignard reagent (.25 mmol) was added drop-wise and the mixture left for 1 h at -4 C. Then sulfuryl chloride (2 ml,.25 mmol) was added at the same temperature and on warming to room temperature, the amine (2.5 mmol) was added to the mixture. After stirring for 3 h at room temperature, the reaction mixture was quenched with H 2 O (3 ml) and extracted with CHCl 3 (3!3 ml). The combined organic layers were dried over MgSO 4, concentrated in vacuo and purified by column chromatography on silica gel to afford the sulfonamide product. 1 Sulfamide Synthesis!!"#$#%&'()%*+#,-%#(2/( R NH 2 + DABSO CN I 2 R N H H R A suspension of DABSO (24 mg, 1 mmol) in CN (5 ml) was cooled to C. Iodine ( mg,.75 mmol) was then added and left to stir for 15 mins at ºC until it was all dissolved. Then arylamine (.5 mmol) was added and the reaction mixture was warmed to room temperature and stirred overnight. After 12 h, % aq NaOH ( ml) were added and then the ph of the solution was adjusted up to "6 using citric acid. The mixture was extracted with DCM (3!5 ml) and the combined organic layers were washed with 1 M aq HCl (1!5 ml), brine (1!5 ml) and then dried over anhydrous MgSO 4 and concentrated in vacuo. Flash column chromatography afforded the sulfamides. 3

4 "#$!%&'()*+,+!-.!/&1,!%21.-'*!3 3! DABSO (1 Eq.) 48h, 1 ºC 6 Eq. % 1 SO 2 2,3-Dimethyl-1,3-butadiene ( ml, 8.8 mmol) was added to DABSO (363 mg, 1.5 mmol) in a sealed tube under an nitrogen atmosphere. The mixture was heated at 1 C over h. Once cooled to RT, EtOAc (3 ml) was added to the mixture, was filtrated to remove any excess DABCO and then concentrated in vacuo to afford 3,4-dimethyl-2,5- dihydrothiophene 1,1-dioxide 7 as a white solid (175 mg, %). 1 H NMR (4 MHz, CDCl 3 )! 3.73 (s, 4H), 1.78 (s, 6H); 13 C NMR ( MHz, CDCl 3 )! (2!C),.7 (2!CH 2 ), 14.6 (2!CH 3 ) ; m/z (ESI, CN); 2, 132, 169 (M+Na) +. 2 Yao, Q. Org Lett 2, 4,

5 V. %4*(561!76(6!-.!%21.-'68,9*+ 4-Tosylmorpholine, (Table 1, Entry 1) 3 O General procedure A was conducted using p-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and morpholine (.22 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:4) afforded the sulfonamide as a white solid (4 mg, 67%). 1 H NMR (4 MHz, CDCl 3 )! 7.64 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 3.75 (t, J = 4.5 Hz, 4H), 2.99 (t, J = 4.5 Hz, 4H), 2.45 (s, 3H); 13 C NMR ( MHz, CDCl 3 )! (C), 13 (C), (2!CH), (2!CH), 66.1 (2!CH 2 ), 4 (2!CH 2 ), 22.6 (CH 3 ),; m/z (ESI, CN); 192, 214, 264 (M+Na) +. 1-Tosylpyrrolidine, (Table 1, Entry 2) 4 General procedure A was conducted using p-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and pyrrolidine (.21 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:4) afforded the sulfonamide as a white solid (45 mg, %). 1 H NMR (4 MHz,CDCl 3 )! 7. (d, J = 8.1 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), (m, 4H), 2.42 (s, 3H), (m, 4H); 13 C NMR ( MHz, CDCl 3 )! (C), (C), (2!CH), (2!CH), 47.5 (2!CH 2 ), 24.8 (2!CH 2 ), 21.1 (CH 3 ); m/z (ESI, CN); 195, 226, 248 (M+Na) +. 1-thyl-4-tosylpiperazine, (Table 1, Entry 3) 5 N General procedure A was conducted using p-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and 1-methylpiperazine (.28 ml, 2.5 mmol). Flash column chromatography (DCM/OH 9:1) afforded the sulfonamide as a white solid (52 mg, 81%). m.p o C; IR (neat) # max 285, 2797, 1345, 1287, 1167, 1151 cm -1 ; 1 H NMR (4 MHz, CDCl 3 )! 7.62 (d, J = 8.1 Hz, 2H), 7. (d, J = 8.1 Hz, 2H), (bs, 4H), 2.46 (t, J = 4.7 Hz, 4H), 2.41 (s, 3H), 2.25 (s, 3H); 13 C NMR ( MHz, CDCl 3 )! (C), (C), (2!CH), (2!CH), 5 (2!CH 2 ), 45.9 (2!CH 2 ), De Luca, L.; Giacomelli, G. J. Org. Chem. 8, 73, ZHu, S.; Jin, G.; Xu, Y. Tetrahedron, 3, 59, Huang, J.; Zhou, Z.; Chan, T. H. Synthesis, 9, 14,

6 (CH 3 ), 21.4 (CH 3 ); HRMS (ESI) calculated for [M+H] + -C 12 H 19 N 2 O 2 S + : , found N,N-diethyl-4-methylbenzenesulfonamide, (Table 1, Entry 4) 6 General procedure A was conducted using p-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and diethylamine (.25 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfonamide as a white solid (28 mg, 5%). 1 H NMR (4 MHz, CDCl 3 )! 7. (d, J = 8.1 Hz, 2H), 7.29 (d, J = 8.1 Hz, 2H), 3.23 (q, J = 7.1 Hz, 4H), 2.42 (s, 3H), 1.13 (t, J = 7.1, 6H); 13 C NMR ( MHz, CDCl 3 )! (C), (C), (2!CH), 12 (2!CH), 4 (2!CH 2 ), 21.5 (CH 3 ), 14.1 (2!CH 3 ); m/z (ESI, CN); 192, 228 (M+H) +, 25 (M+Na) +. N-Allyl-4-methylbenzenesulfonamide, (Table 1, Entry 5) 3 H General procedure A was conducted using p-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and allylamine (.19 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 3:2) afforded the sulfonamide as a white solid (32 mg, %). 1 H NMR (4 MHz, CDCl 3 )! 7.75 (d, J = 8.1 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), (m, 1H), (m, 2H), 4.57 (t, J = 5.6 Hz, 1H), 3.58 (t, J = Hz, 2H), 2.43 (s, 3H); 13 C NMR ( MHz, CDCl 3 )! (C), (C), (CH), (2!CH), (2!CH), (CH 2 ), 45.8 (CH 2 ), 21.5 (CH 3 ); m/z (ESI, CN); 234 (M+Na) +. N-Cyclohexyl-4-methylbenzenesulfonamide, (Table 1, Entry 6) 7 H General procedure A was conducted using p-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and cyclohexylamine (.29 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfonamide as a white solid (38 mg, %). 1 H NMR (4 MHz, CDCl 3 )! 7.76 (d, J = 8.1 Hz, 2H), 7.29 (d, J = 8.1 Hz, 2H), 4.37 (d, J = 7.5 Hz, 1H), 3.-6 (m, 1H), 2.43 (s, 3H), (m, 5H), (m, 5H). 13 C NMR ( MHz, CDCl 3 )! (C), (C), (2!CH), 6 Pandya, R; Murashima, T; Tedeschi, L. Barrett, G. M. A. J. Org. Chem. 3, 68, Zhang, J.; Yang, C-G.; He, C. J. Am. Chem. Soc, 6, 128,

7 126.9 (2!CH), 52.5 (CH), 3 (2!CH 2 ), 25.1 (2!CH 2 ), 24.6 (CH 2 ), 21.5 (CH 3 ). m/z (ESI, CN); 242, 276 (M+Na) +. 4-thyl-N-morpholinobenzenesulfonamide, (Table 1, Entry 7) 1 H N O General procedure A was conducted using p-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and 4-aminomorpholine (.24 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:4) afforded the sulfonamide as a white solid (17 mg, 26%). m.p. 128!129 o C (DCM); IR (neat) # max 35, 3178, 2956, 2854, 13, 1164, 96 cm -1 ; 1 H NMR (4 MHz, CDCl 3 )! 7.85 (d, J = Hz, 2H), 7.31 (d, J = Hz, 2H), 5.43 (s, 1H), (m, 1H), (m, 1H), 2.43 (s, 3H); 13 C NMR ( MHz, CDCl 3 )! 14 (C), (C), (2!CH), (2!CH), 66.6 (2!CH 2 ), 56.8 (2!CH 2 ), 21.6 (CH 3 ); m/z (ESI, CN); 179, 2, 279 (M+Na) +. 4-thyl-N-morpholinobenzenesulfonamide, (Table 1, Entry 8) S N General procedure A was conducted using m-tolyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and and morpholine (.22 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:2) the sulfonamide as a yellow oil (3 mg, 66%); IR (neat) # max 2924, 1668, 1586, 1279, 62 cm -1 ; 1 H NMR (4 MHz, CDCl 3 )! (m, 2H), (m, 2H), (m, 4H), (m, 4H), 2.43 (s, 3H). 13 C NMR ( MHz, CDCl 3 )! (C), (C), (CH), 12 (CH), (CH), 12 (CH), 6 (2!CH 2 ), 4 (2!CH 2 ), 21.4 (CH 3 ). HRMS (ESI) calculated for [M+Na] + -C 11 H 15 NNaO 3 S: 26665, found O 4-(Phenylsulfonyl)morpholine, (Table 1, Entry 9) 6 General procedure A was conducted using phenyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and morpholine (.22 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) the sulfonamide as a white solid (42 mg, 74%). 1 H NMR (4 MHz, CDCl 3 )! 7.75 (d, J = 7.3 Hz, 2H), (m, 3H), 3.75 (t, J = 4.5 Hz, 4H), (t, J = 4.5 Hz, 4H); 13 C NMR ( MHz, CDCl 3 )! (C), O 7

8 133.4 (CH), (2!CH), (2!CH), 66.4 (2!CH 2 ), 46.3 (2!CH 2 ); m/z (ESI, CN); 228 (M+H) +. 1-(Phenylsulfonyl)piperidine, (Table 1, Entry ) 6 General procedure A was conducted using phenyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and piperidine (.25 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) the sulfonamide as a white solid (42 mg, 75%). 1 H NMR (4 MHz, CDCl 3 )! (m, 2H), (m, 3H), ( m, 4H), (m, 4H), (m, 2H). 13 C NMR ( MHz, CDCl 3 )! (C), (CH), (2!CH), (2!CH), 46.9 (2!CH 2 ), 25.1 (2!CH 2 ), 23.5 (CH 2 ); m/z (ESI, CN); 186, 217, 248 (M+Na) +. N,N-Diethyl-1-phenylmethanesulfonamide, (Table 1, Entry 11) S N General procedure A was conducted using benzyl magnesium chloride solution (1 M in THF,.25 ml,.25 mmol) and diethylamine (.25 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfonamide as a white solid (45.6 mg, %). m.p. -85 o C; IR (neat) # max 2976, 2876, 1456, 13, 1186, 1146, 1123, 19 cm -1 ; 1 H NMR (4 MHz, CDCl 3 )! 7.37 (m, 5H), 4. (s, 2H), 9 (q, J = 7.1 Hz, 4H), 8 (t, J = 7.1 Hz, 6H). 13 C NMR ( MHz, CDCl 3 )! 1.7 (2!CH), (C), (2!CH), (CH), 58.4 (CH 2 ), 42.5 (2!CH 2 ), 14.8 (2!CH 3 ); HRMS (ESI) calculated for (M+Na) + -C 11 H 17 NNaO 2 S + : 25872, found (Allylsulfonyl)morpholine, (Table 1, Entry 12) General procedure A was conducted using allyl magnesium bromide solution (1 M in THF,.25 ml,.25 mmol) and morpholine (.22 ml, 2.5 mmol). Flash column chromatography (Et 2 O) afforded the sulfonamide as a pale yellow oil ( mg, 64%). IR (neat) # max 2859, 1639, 1327, 1148, 1112, 95 cm -1 ; 1 H NMR (4 MHz, CDCl 3 )! (m, 1H), (m, 2H), (m, 6H), 3.32 (t, J = 4.5, 4 H); 13 C NMR ( MHz, CDCl 3 )! (CH), (CH 2 ), 66.7 (2!CH 2 ), 54.5 (CH 2 ), 46.3(2!CH 2 ); HRMS (EI) calculated for C 7 H 13 NO 3 S: 19616, found O

9 4-(Butylsulfonyl)morpholine, (Table 1, Entry 13) General procedure A was conducted using butyl magnesium chloride solution (2 M in THF,.13 ml,.25 mmol) and morpholine (.22 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:4) afforded the sulfonamide as a white solid (28 mg, 55%). m.p o C; IR (neat) # max 1341, 1327, 1152, 1114, 95 cm -1 ; 1 H NMR (4 MHz, CDCl 3 )! 3.76 (t, J = 4.8 Hz, 4H), 3.27 (t, J = 4.8, 4H), 2.9 (t, J = 8.1 Hz, 2H), (m, 2H), (m, 2H),.95 (t, J = 7.4 Hz, 3H); 13 C NMR ( MHz, CDCl 3 )! 66.6 (2!CH 2 ), 48.5 (CH 2 ), 45.8 (2!CH 2 ), 24.9 (CH 2 ), 21.7 (CH 2 ), 13.5 (CH 3 ); HRMS (EI) calculated for C 8 H 17 NO 3 S: 929, found 927. O 3-(Pyrrolidin-1-ylsulfonyl)pyridine, (Table 1, Entry 14) 6 Preparation of 1 M pyridin-3-yl magnesium bromide solution To a solution of 3-bromopyridine (.19 ml, 2 mmol) in THF (.7 ml) was added isopropyl magnesium chloride solution (1.15 ml, 1.15 mmol) drop-wise over 5 mins at RT. The mixture was left stirring at RT for mins before being used in the preparation of 3-(pyrrolidin-1-ylsulfonyl)pyridine. N General procedure A was conducted using pyridin-3-yl magnesium bromide solution (.25 mmol) and pyrrolidine (.21 ml, 2.5 mmol). Flash column chromatography (petrol/et 2 O 1:4) afforded the sulfonamide as a white solid (29 mg, 55%). 1 H NMR (4 MHz, CDCl 3 )! 7 (bs, 1H), 8.84 (bs, 1H), 8.12 (d, J = Hz, 1H), (m, 1H), 3.28 (t, J = 6.7 Hz, 4H), (m, 4H); 13 C NMR ( MHz, CDCl 3 )! (CH), (CH), 13 (CH), (C), (CH), 47.9 (2!CH 2 ), 25.3 (2!CH 2 ). HRMS (EI/FI) calculated for C 9 H 12 N 2 O 2 S: 216, found

10 VI. %4*(561!76(6!-.!%21.68,9*+ N,N -Diphenylsulfmaide, (Table 2, Entry 1) 8 S N NH H General procedure B was conducted using aniline (45 ml,.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfamide as a white solid (39 mg, 63%). 1 H NMR (4 MHz, CDCl 3 )! 7.29 (t, J = 7.7 Hz, 4H), 7.15 (t, J = 7.4 Hz, 2H), 9 (d, J = 7.7 Hz, 4H), 6.9 (s, 2H); 13 C NMR ( MHz, CDCl 3 )! (C), (2!CH), (CH), (2!CH); m/z (ESI, CN); 155, 246, 247 (M-1) -. N,N -Bis(4-bromophenyl)sulfamide, (Table 2, Entry 2) 9 Br S N NH H General procedure B was conducted using 4-bromo aniline (86 mg,.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfamide as a white solid (73 mg, 73%). 1 H NMR (4 MHz, CDCl 3 )! 7.39 (d, J = 8.8 Hz, 4H), (s, 2H), 6.95 (d, J = 8.8 Hz, 4H); 13 C NMR ( MHz, CDCl 3 )! 13 (2!C), (2!CH), 122.8(2!CH), (2!C); m/z (ESI, CN); 466, 468 (M+Na+CH 3 CN) +, 4. Br N,N -Bis(4-methoxyphenyl)sulfamide, (Table 2, Entry 3) 8 O S N NH H O General procedure B was conducted using 4-methoxyaniline (63 mg,.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfamide as a white solid (46 mg, %). 1 H NMR (4 MHz, CDCl 3 )! 7-1 (m, 4H), (m, 4H), 6.41 (s, 2H), 3.79 (s, 6H); 13 C NMR ( MHz, CDCl 3 )! (2!C), 12 (2!C), (4!CH), (4!CH), 55.5 (2!CH 3 ); m/z (ESI, CN); 331 (M+Na) +. 8 Spillane, W. J.; Barry, J. A.; Scott, F. L. J. Chem. Soc., Perkin Trans. 2, 1973, Chase, B. H.; Weller, W. T. J. Pharm. Pharmacol., 1964, 16, 163.

11 N,N -bis(4-thylphenyl)sulfamide, (Table 2, Entry 4) 8 S N NH H General procedure B was conducted using p-toluidine (53 mg,.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfamide as a white solid (45 mg, 65%). 1 H NMR (4 MHz, CDCl 3 )! 8 (d, J = 8.2 Hz, 4H), 6.98 (d, J = 8.2 Hz, 4H), 6. (s, 2H), 2. (s, 6H); 13 C NMR ( MHz, CDCl 3 )! (2!C), (2!C), (2!CH), (2!CH),.8 (2!CH 3 ); m/z (ESI, CN); 213, 177, 299 (M+Na) +. N,N -Bis(2-methylphenyl)sulfamide, (Table 2, Entry 5) S N NH H General procedure B was conducted using o-toluidine (53 ml,.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the as a white solid (35 mg, 51%). m.p o C; IR (neat) # max 3275, 16, 1477, 1324, 1151, 9 cm -1 ; 1 H NMR (4 MHz, CDCl 3 )! 7.53 (d, J = 7.9 Hz, 2H), (m, 2H), 7 (d, J = 4.3 Hz, 4H), 6.47 (s, 2H), 1.79 (s, 6H); 13 C NMR ( MHz, CDCl 3 )! (2!C), 1.8 (2!CH), (2!C), (2!CH), (2!CH), (2!CH), 16.7 (2!CH 3 ); HRMS (ESI) calculated for [M+Na] + -C 14 H 16 N 2 NaO 2 S: 29825, found N,N -Bis(2,4,6-trismethylphenyl)sulfamide, (Table 2, Entry 6) N H H General procedure B was conducted using 4-bromo aniline (67 mg,.5 mmol). Flash column chromatography (petrol/et 2 O 1:1) afforded the sulfamide as a white solid (43 mg, 52%). 1 H NMR (4 MHz, CDCl 3 )! 6.88 (s, 4H), 5.83 (s, 2H), 2.32 (s, 12H), 2.26 (s, 6H); 13 C NMR ( MHz, CDCl 3 )! (C), (2!C), 1.9 (C), (2!CH),.9 (CH 3 ), 18.8 (2!CH 3 ); m/z (ESI, CN); 248, 331, 333 (M+H) +. Abramovitch, R. A.; Chellathurai, T.; Holcomb, W. D.; McMaster, I. T.; Vanderpool, D. P. J. Org. Chem., 1977, 42,

12 I. Spectra (Table 1, Entry 1) O C-NMR ( MHz, CDCl 3 )

13 (Table 1, Entry 2) C-NMR ( MHz, CDCl 3 )

14 (Table 1, Entry 3) N C-NMR ( MHz, CDCl 3 )

15 (Table 1, Entry 4) C-NMR ( MHz, CDCl 3 )

16 H (Table 1, Entry 5) C-NMR ( MHz, CDCl 3 )

17 H (Table 1, Entry 6) C-NMR ( MHz, CDCl 3 )

18 H N O (Table 1, Entry 7) C-NMR ( MHz, CDCl 3 )

19 S N O (Table 1, Entry 8) C-NMR ( MHz, CDCl 3 )

20 O (Table 1, Entry 9) C-NMR ( MHz, CDCl 3 )

21 (Table 1, Entry ) C-NMR ( MHz, CDCl 3 )

22 S N (Table 1, Entry 11) C-NMR ( MHz, CDCl 3 )

23 O (Table 1, Entry 12) C-NMR ( MHz, CDCl 3 )

24 (Table 1, Entry 13) O C-NMR ( MHz, CDCl 3 )

25 N (Table 1, Entry 14) C-NMR ( MHz, CDCl 3 )

26 II. Data for new sulfamides S N NH H (Table 2, Entry 1) C-NMR ( MHz, CDCl 3 )

27 Br S N NH H (Table 2, Entry 2) Br C-NMR ( MHz, CDCl 3 )

28 O S N NH H (Table 2, Entry 3) O C-NMR ( MHz, CDCl 3 )

29 S N NH H (Table 2, Entry 4) C-NMR ( MHz, CDCl 3 )

30 S N NH H (Table 2, Entry 5) C-NMR ( MHz, CDCl 3 )

31 S N NH H (Table 2, Entry 6) C-NMR ( MHz, CDCl 3 )

32 1 SO 2 13 C-NMR ( MHz, CDCl 3 )