A. Ryokawa, H. Togo / Tetrahedron 57 22001) 5915±5921
5919
4.3.8. 2-Methylamino-40-¯uorobiphenyl 2d. Oil; IR #neat)
3430, 3020, 2920 cm21 1H NMR #400 MHz, CDCl3)
4.3.13. 2,6,9-Trimethyl-6H-dibenzo[c,e][1,2]thiazine-5,5-
dioxide 3f. Mp 145±1468C; IR #KBr) 3030, 2920, 1330,
;
d2.80 #3H, s), 3.83 #1H, bs), 6.69 #1H, d, J7.9 Hz),
6.77 #1H, t, J7.5 Hz), 7.05 #1H, dd, J1.6, 7.4 Hz), 7.12
#2H, t, J8.8 Hz), 7.27 #1H, dt, J1.6, 7.9 Hz), 7.37 #2H,
dd, J5.5, 8.8 Hz); 13C NMR #100 MHz, CDCl3) d30.7
#p), 109.9 #t), 115.7 #t, JC±F21.7 Hz), 116.9 #t), 126.5 #q),
128.9 #t), 130.1 #t), 131.1 #t, JC±F8.3 Hz), 135.3 #q,
JC±F3.1 Hz), 146.2 #q), 162.1 #q, JC±F246.2 Hz); MS
#FAB): m/z 201; HRMS #FAB) Found: m/z 201.0949,
Calcd for C13H12FN: M1201.0954.
1190, 1170 cm21
;
1H NMR #400 MHz, CDCl3) d2.44
#3H, s), 2.50 #3H, s), 3.36 #3H, s), 7.22 #1H, d, J8.3 Hz),
7.28 #1H, dd, J1.6, 8.6 Hz), 7.34 #1H, d, J7.6 Hz), 7.74
#1H, s), 7.77 #1H, s), 7.87 #1H, d, J8.0 Hz); 13C NMR
#100 MHz, CDCl3) d21.0 #p), 21.9 #p), 33.2 #p), 120.0
#t), 122.6 #t), 124.0 #q), 125.7 #t), 125.8 #t), 128.9 #t),
131.0 #t), 131.6 #q), 132.4 #q), 134.4 #q), 137.4 #q), 142.9
#q); MS #EI): m/z 273; HRMS #FAB) Found: m/z 273.0789,
Calcd for C15H15NO2S: M1273.0824.
4.3.9. 2-Fluoro-6-methyl-6H-dibenzo[c,e][1,2]thiazine-
5,5-dioxide 3d. Mp 145±1468C; IR #KBr) 3080, 2950,
4.3.14. N-Methyl-N-ꢀ4-methylphenyl)-p-toluenesulfon-
amide 4f. Mp 59±59.58C #lit. 29 Mp 608C); IR #KBr)
1340, 1170 cm21
;
1H NMR #400 MHz, CDCl3) d3.45
2980, 2920, 1340, 1170 cm21 1H NMR #400 MHz,
;
#3H, s), 7.26 #1H, dt, J2.5, 7.9 Hz), 7.31 #1H, d,
J7.7 Hz), 7.35 #1H, d, J8.1 Hz), 7.54 #1H, dt, J1.5,
7.8 Hz), 7.62 #1H, dd, J2.5, 10.2 Hz), 7.93 #1H, dd,
J1.5, 8.1 Hz), 8.01 #1H, dd, J2.5, 8.7 Hz); 13C NMR
#100 MHz, CDCl3) d32.7 #p), 112.2 #t, JC±F23.8 Hz),
115.7 #t, JC±F23.8 Hz), 119.5 #t), 123.1 #q, JC±F
2.1 Hz), 124.8 #t), 125.4 #t, JC±F9.3 Hz), 125.6 #t), 130.4
#q, JC±F3.1 Hz), 131.1 #t), 135.3 #q, JC±F9.3 Hz), 139.7
#q), 164.9 #q, JC±F252.4 Hz); MS #EI): m/z 263; HRMS
#FAB) Found: M1H 264.0484, Calcd for C13H11FNO2S:
M1H264.0495.
CDCl3)2.33 #3H, s), 2.42 #3H, s), 3.14 #3H, s), 6.96 #2H,
d, J8.5 Hz), 7.09 #2H, d, J8.5 Hz), 7.24 #2H, d,
J8.2 Hz), 7.44 #2H, d, J8.5 Hz).
4.3.15. 2-Methylamino-5-¯uoro-40-methylbiphenyl 2g.
;
Oil; IR #neat) 3430, 3030, 2920 cm21 1H NMR
#400 MHz, CDCl3) d2.40 #3H, s), 2.76 #3H, s), 2.93
#1H, bs), 6.58 #1H, dd, J4.7, 8.8 Hz), 6.83 #1H, dd,
J3.1, 9.1 Hz), 6.95 #1H, dt, J3.1, 9.1 Hz), 7.25 #2H, d,
J8.0 Hz), 7.28 #2H, d, J8.0 Hz); 13C NMR #100 MHz,
CDCl3) d21.2 #p), 31.4 #p), 110.7 #t, JC±F7.2 Hz), 114.4
#t, JC±F21.7 Hz), 116.8 #t, JC±F21.7 Hz), 128.8 #q,
JC±F10.3 Hz), 129.0 #t), 129.7 #t), 135.4 #q), 137.4 #q),
142.5 #q), 155.5 #q, JC±F235.7 Hz); MS #EI): m/z 215;
HRMS #FAB) Found: m/z 215.1096, Calcd for C14H14N:
M1215.1110.
4.3.10. 2-Methylamino-40-chlorobiphenyl 2e. Oil; IR
;
#neat) 3430, 3040, 2920 cm21 1H NMR #400 MHz,
CDCl3) d2.79 #3H, s), 3.85 #1H, bs), 6.69 #1H, d,
J8.1 Hz), 6.77 #1H, td, J1.1, 7.5 Hz), 7.05 #1H, dd,
J1.7, 7.3 Hz), 7.27 #1H, td, J1.7, 7.7 Hz), 7.35 #2H, d,
J7.6 Hz), 7.41 #2H, d, J7.6 Hz); 13C NMR #100 MHz,
CDCl3) d30.8 #p), 110.1 #t), 117.1 #t), 126.4 #q), 129.0 #t),
129.1 #t), 130.0 #t), 130.8 #t), 133.1 #q), 137.9 #q), 145.9 #q);
MS #FAB): m/z 217; HRMS #FAB) Found: m/z 217.0656
#35Cl), 219.0648 #37Cl), Calcd for C13H1235ClN: M1
217.0658, C13H1237ClN: M1219.0632.
4.3.16. 9-Fluoro-2,6-dimethyl-6H-dibenzo[c,e][1,2]thia-
zine-5,5-dioxide 3g. Mp 184±1868C; IR #KBr) 3090,
;
2920, 1320, 1170, 1150 cm21 1H NMR #400 MHz,
CDCl3) d2.52 #3H, s), 3.35 #3H, s), 7.17 #1H, dt, J2.9,
8.4 Hz), 7.28 #1H, dd, J5.0, 9.1 Hz), 7.40 #1H, d,
J8.1 Hz), 7.64 #1H, d, J2.9 Hz), 7.67 #1H, s), 7.88
#1H, d, J8.1 Hz); 13C NMR #100 MHz, CDCl3) d21.9
#p), 34.0 #p), 112.0 #t, JC±F23.8 Hz), 117.2 #t,
JC±F23.0 Hz), 122.1 #t, JC±F9.0 Hz), 122.9 #t), 125.9
#t), 126.0 #q), 129.8 #t), 131.3 #q, JC±F2.5 Hz), 131.6 #q),
136.0 #q, JC±F2.5 Hz), 143.3 #q), 159.8 #q, JC±F
244.5 Hz); MS #EI): m/z 277; HRMS #FAB) Found: M1H
278.0629, Calcd for C14H13FNO2S: M1H278.0651.
4.3.11. 2-Chloro-6-methyl-6H-dibenzo[c,e][1,2]thiazine-
5,5-dioxide 3e. Mp 1238C; IR #KBr) 2920, 1320,
1
1170 cm21; H NMR #400 MHz, CDCl3) d3.45 #3H, s),
7.32 #1H, d, J8.3 Hz), 7.35 #1H, t, J7.9 Hz), 7.54 #1H,
dd, J2.0, 8.4 Hz), 7.54 #1H, td, J1.4, 7.8 Hz), 7.94 #1H,
d, J2.0 Hz), 7.94 #1H, d, J8.5 Hz), 7.96 #1H, dd, J7.7,
1.5 Hz); 13C NMR #100 MHz, CDCl3) d32.8 #p), 119.5 #t),
122.9 #q), 124.1 #t), 124.8 #t), 125.5 #t), 125.6 #t), 128.3 #t),
131.1 #t), 132.5 #q), 134.1 #q), 138.8 #q), 140.0 #q); MS #EI):
m/z 279; HRMS #FAB) Found: M1H 280.0192 #35Cl),
282.0164 #37Cl), Calcd for C13H1135ClNO2S: M1H
280.0199, C13H1137ClNO2S: M1H282.0172.
4.3.17. 2-Methyldibenzo[c,e][1,2]thiazine-5,5-dioxide 3h.
Mp 199±2018C; IR #KBr) 3240, 2920, 1320, 1170,
1
1140 cm21; H NMR #400 MHz, CDCl3) d2.53 #3H, s),
7.12 #1H, dd, J1.5, 8.0 Hz), 7.26 #1H, bs), 7.31#1H, dd,
J1.3, 7.5 Hz), 7.38 #1H, d, J7.9 Hz), 7.48 #1H, dt, J1.5,
7.5 Hz), 7.79 #1H, s), 7.90 #1H, d, J8.0 Hz), 8.00 #1H, dd,
J1.3, 8 Hz); 13C NMR #100 MHz, CDCl3) d22.1 #p),
120.8 #t), 122.3 #t), 123.2 #q), 125.2 #t), 125.5 #t), 125.9
#t), 129.2 #t), 130.4 #t), 132.5 #q), 132.6 #q), 135.7 #q),
143.3 #q); MS #FAB): #m1H)/z 246; HRMS #FAB)
Found: M1H 246.0566, Calcd for C13H12NO2S:
M1H246.0589.
4.3.12. 2-Methylamino-40,5-dimethylbiphenyl 2f. Oil; IR
#neat) 3430, 3030, 2920 cm21; 1H NMR #400 MHz, CDCl3)
d2.27 #3H, s), 2.50 #3H, s), 2.77 #3H, s), 3.11 #1H, bs),
6.63 #1H, d, J8.2 Hz), 6.91 #1H, d, J2.2 Hz), 7.07
#1H, dd, J2.2, 8.2 Hz), 7.23 #2H, d, J7.7 Hz), 7.30
#2H, d, J8.1 Hz); 13C NMR #100 MHz, CDCl3) d
20.3 #p), 21.1 #p), 31.3 #p), 110.4 #t), 126.3 #q), 127.9
#q), 128.9 #t), 129.2 #t), 129.5 #t), 130.8 #t), 136.5 #q),
136.8 #q), 143.8 #q); MS #EI): m/z 211; HRMS #FAB)
Found: m/z 211.1355, Calcd for C15H17N: M1
211.1361.
4.3.18. 2-Ethylamino-40-methylbiphenyl 2i. Oil; IR #neat)
3420, 3020, 2920 cm21 1H NMR #400 MHz, CDCl3)
;
d1.16 #3H, t, J7.1 Hz), 2.39 #3H, s), 3.13 #2H, q,
J7.1 Hz), 3.69 #1H, bs), 6.69 #1H, d, J8.2 Hz), 6.74