H
H. Li, H. Deng
Paper
Synthesis
(Z)-2-Phenyl-1-[2-(thiophene-2-sulfonamido)phenyl]diazene
Oxide (3n)
13C NMR (100 MHz, CDCl3): δ = 163.99 (d, JC,F = 252.3 Hz), 163.06 (d,
JC,F = 253.2 Hz), 144.44, 139.22 (d, JC,F = 3.4 Hz), 135.78, 134.08 (d,
JC,F = 1.9 Hz), 129.86, 128.21 (d, JC,F = 8.5 Hz), 126.98, 126.91 (d,
JC,F = 10.4 Hz), 126.86, 115.96 (d, JC,F = 22.6 Hz), 111.18 (d, JC,F = 23.1
Hz), 108.61 (d, JC,F = 27.5 Hz), 21.44.
HRMS (ESI): m/z [M + H]+ calcd for C19H16F2N3O3S: 404.0880; found:
404.0883.
Under the optimal reaction conditions, the desired product 3n (80.4
mg, 0.22 mmol, 56%) was obtained as a pale yellow solid after flash
column chromatography (10% EtOAc in PE, Rf = 0.57); mp 180–182 °C.
IR (KBr): 3119, 3091, 1652, 1539, 1434, 1258, 1163, 1021, 857, 769
cm–1
.
1H NMR (400 MHz, CDCl3): δ = 10.45 (s, 1 H), 8.09–8.06 (m, 3 H), 7.87
(d, J = 8.4 Hz, 1 H), 7.56–7.47 (m, 4 H), 7.44–7.43 (m, 2 H), 7.27 (t,
J = 7.6 Hz, 1 H), 6.90–6.88 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 142.86, 139.46, 132.75, 132.67,
132.28, 131.34, 130.76, 128.92, 127.36, 125.70, 125.05, 124.75,
123.43.
(Z)-1-[4-Chloro-2-(4-methylphenylsulfonamido)phenyl]-2-(4-
chlorophenyl)diazene Oxide (3r)
Under the optimal reaction conditions, the desired product 3r (121.8
mg, 0.28 mmol, 70%) was obtained as a pale yellow solid after flash
column chromatography (20% EtOAc in PE, Rf = 0.51); mp 215–217 °C.
IR (KBr): 3100, 2957, 1635, 1480, 1403, 1307, 1089, 829, 714 cm–1
1H NMR (400 MHz, CDCl3): δ = 10.43 (s, 1 H), 8.06 (d, J = 8.8 Hz, 2 H),
7.98 (d, J = 8.8 Hz, 1 H), 7.78 (s, 1 H), 7.63 (d, J = 8.0 Hz, 2 H), 7.47 (d,
J = 8.8 Hz, 2 H), 7.15–7.13 (m, 3 H), 2.31 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.46, 141.19, 138.58, 136.48,
135.78, 133.06, 129.90, 129.23, 127.14, 127.00, 125.90, 124.42,
122.12, 21.50.
.
HRMS (ESI): m/z [M + H]+ calcd for C16H14N3O3S2: 360.0477; found:
360.0480.
(Z)-1-{2-[4-Chloro-3(trifluoromethyl)phenylsulfonamido]phen-
yl}-2-phenyldiazene Oxide (3o)
Under the optimal reaction conditions, the desired product 3o (129.2
mg, 0.28 mmol, 71%) was obtained as a pale yellow solid after flash
column chromatography (30% EtOAc in PE, Rf = 0.31); mp 162–164 °C.
HRMS (ESI): m/z [M + H]+ calcd for C19H16Cl2N3O3S: 436.0289; found:
IR (KBr): 3055, 1607, 1585, 1488, 1394, 1261, 1166, 960, 828, 761 cm–1
.
436.0288.
1H NMR (400 MHz, CDCl3): δ = 10.08 (s, 1 H), 8.05 (d, J = 8.0 Hz, 2 H),
7. 98 (d, J = 8.4 Hz, 1 H), 7.88 (s, 1 H), 7.78 (d, J = 8.0 Hz, 1 H), 7.70 (d,
J = 8.4 Hz, 1 H), 7.57–7.47 (m, 4 H), 7.35–7.29 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 142.68, 139.51, 137.88, 137.71 (q,
JC,F = 1.6 Hz), 132.43, 132.35, 131.19, 130.83, 130.45, 129.33 (q,
JC,F = 32.3 Hz), 128.98, 126.16 (q, JC,F = 5.2 Hz), 125.93, 125.76, 125.71,
124.83, 124.58, 121.57 (q, JC,F = 272.4 Hz).
(Z)-1-[4-Methyl-2-(4-methylphenylsulfonamido)phenyl]-2-(p-
tolyl)diazene Oxide (3s)
Under the optimal reaction conditions, the desired product 3s (124.9
mg, 0.32 mmol, 79%) was obtained as a pale yellow solid after flash
column chromatography (10% EtOAc in PE, Rf = 0.59); mp 197–199 °C.
IR (KBr): 2922, 2360, 1635, 1586, 1375, 1339, 1169, 1091, 816, 736
cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C19H14ClF3N3O3S: 456.0396; found:
456.0396.
1H NMR (400 MHz, CDCl3): δ = 10.37 (m, 1 H), 7.99 (d, J = 8.4 Hz, 2 H),
7.85 (d, J = 8.4 Hz, 1 H), 7.55 (d, J = 8.4 Hz, 3 H), 7.28 (d, J = 8.0 Hz, 2
H), 7.04 (d, J = 8.0 Hz, 2 H), 6.96 (d, J = 8.8 Hz, 1 H), 2.43 (s, 3 H), 2.39
(s, 3 H), 2.24 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 143.83, 142.93, 141.31, 140.75,
135.96, 131.29, 129.59, 129.40, 126.79, 125.71, 125.42, 124.34,
123.52, 21.58, 21.44, 21.36.
(Z)-1-[2-(Methylsulfonamido)phenyl]-2-phenyldiazene Oxide (3p)
Under the optimal reaction conditions, the desired product 3p (61.7
mg, 0.21 mmol, 53%) was obtained as a pale yellow solid after flash
column chromatography (10% EtOAc in PE, Rf = 0.62); mp 131–133 °C.
IR (KBr): 3063, 2930, 1718, 1582, 1486, 1331, 1161, 971, 877, 760 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C21H22N3O3S: 396.1382; found:
396.1383.
1H NMR (400 MHz, CDCl3): δ = 10.35 (s, 1 H), 8.23 (d, J = 8.4 Hz, 1 H),
8.16 (d, J = 8.4 Hz, 2 H), 7.81 (d, J = 7.6 Hz, 1 H), 7.56–7.45 (m, 4 H),
7.26 (t, J = 8.4 Hz, 1 H), 3.05 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 142.82, 132.67, 132.17, 130.81,
128.95, 125.72, 125.19, 123.94, 120.49, 40.10.
(Z)-1-[4-Isopropyl-2-(4-methylphenylsulfonamido)phenyl]-2-(4-
isopropylphenyl)diazene Oxide (3t)
Under the optimal reaction conditions, the desired product 3t (143.8
mg, 0.30 mmol, 75%) was obtained as a pale yellow solid after flash
column chromatography (20% EtOAc in PE, Rf = 0.43); mp 205–207 °C.
HRMS (ESI): m/z [M + H]+ calcd for C13H14N3O3S: 292.0756; found:
292.0755.
IR (KBr): 2961, 1726, 1600, 1383, 1346, 1284, 1166, 1074, 863, 705
(Z)-1-[4-Fluoro-2-(4-methylphenylsulfonamido)phenyl]-2-(4-
fluorophenyl)diazene Oxide (3q)
cm–1
.
1H NMR (400 MHz, CDCl3): δ = 10.45 (s, 1 H), 8.05 (d, J = 8.0 Hz, 2 H),
7.92 (d, J = 8.4 Hz, 1 H), 7.64 (s, 1 H), 7.59 (d, J = 7.6 Hz, 2 H), 7.37 (d,
J = 8.8 Hz, 2 H), 7.08–7.02 (m, 3 H), 3.01–2.96 (m, 2 H), 2.26 (s, 3 H),
1.33–1.29 (m, 6 H), 1.27–1.24 (m, 6 H).
13C NMR (100 MHz, CDCl3): δ = 153.66, 152.07, 143.88, 141.04,
136.00, 131.53, 129.56, 126.99, 126.81, 125.86, 124.49, 122.99,
122.63, 122.62, 120.76, 34.17, 33.99, 23.69, 23.45, 21.39.
Under the optimal reaction conditions, the desired product 3q (103.2
mg, 0.27 mmol, 64%) was obtained as a pale yellow solid after flash
column chromatography (20% EtOAc in PE, Rf = 0.49); mp 201–203 °C.
IR (KBr): 3313, 2959, 1731, 1633, 1494, 1397, 1345, 1122, 861, 775
cm–1
.
1H NMR (400 MHz, CDCl3): δ = 10.67 (s, 1 H), 8.19–8.16 (m, 2 H),
8.10–8.06 (m, 1 H), 7.66 (d, J = 8.0 Hz, 2 H), 7.49 (dd, J = 9.6, 1.6 Hz, 1
H), 7.21–7.15 (m, 4 H), 6.87–6.82 (m, 1 H), 2.31 (s, 3 H).
HRMS (ESI): m/z [M + H]+ calcd for C25H30N3O3S: 452.2008; found:
452.2012.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 48, A–J