P. He, S. Zhu / Tetrahedron 62 (2006) 549–555
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(3ca). Colorless oil. H NMR (CDCl3, 300 MHz): d 5.87
for C13H17F8NO4S: C, 35.87; H, 3.94; N, 3.22%. Found: C,
36.06; H, 3.93; N, 3.23%.
(1H, tt, JZ3.0, 52.8 Hz), 4.29 (2H, q, JZ7.2 Hz), 3.52–3.48
(1H, m), 2.14–2.05 (2H, m), 1.86–1.61 (6H, m), 1.35 (3H, t,
JZ7.2 Hz). 19F NMR (CDCl3, 282 MHz): d K81.2 (2F, t,
JZ13.1 Hz, CF2O), K89.0 (2F, m, OCF2), K118.0 (2F, s,
4.1.8. 1-Cyclohexyl-1-ethoxy-meth-(Z)-ylidene-perfluoro-
butylsulfonyl imine (3db). Colorless oil. 1H NMR (CDCl3,
300 MHz): d 4.29 (2H, q, JZ7.2 Hz), 3.17–3.07 (1H, m),
2.02–1.42 (8H, m), 1.36 (3H, t, JZ7.2 Hz), 1.33–1.20 (2H,
m). 19F NMR (CDCl3, 282 MHz): d K81.0 (3F, t, JZ
10.0 Hz, CF3), –114.1 (2F, t, JZ15.1 Hz, CF2), –121.1 (2F,
m, CF2S), –126.2 (2F, m, CF2). IR (KBr) cmK1: 2939, 2862,
1584, 1359, 1238, 1140, 1012. MS: m/z (%) 437 (MC, 2),
354 (MCKC6H11, 4), 110 (MCC1KRfSO2–EtO, 100), 83
(C6HC11, 78). Anal. Calcd for C13H16F9NO3S: C, 35.70; H,
3.69; N, 3.20%. Found: C, 35.74; H, 3.79; N, 3.55%.
CF2S), K137.9 (2F, d, JZ52.7 Hz, HCF2). IR (KBr) cmK1
:
2968, 2879, 1583, 1359, 1326, 1144, 1010, 907. MS: m/z
(%) 421 (MC, 1), 380 (MCKC3H5, 8), 352 (MCKC5H9,
18), 96 (MCC1KRfSO2–EtO, 100), 69 (C5H9C, 54). Anal.
Calcd for C12H15F8NO4S: C, 34.21; H, 3.59; N, 3.32%.
Found: C, 34.32; H, 3.59; N, 3.27%.
4.1.4. 1-Cyclopentyl-1-ethoxy-meth-(Z)-ylidene-per-
fluorobutylsulfonyl imine (3da). Colorless oil. H NMR
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(CDCl3, 300 MHz): d 4.30 (2H, q, JZ7.2 Hz), 3.53–3.48
(1H, m), 2.12–2.06 (2H, m), 1.85–1.64 (6H, m), 1.36 (3H, t,
JZ7.2 Hz). 19F NMR (CDCl3, 282 MHz): d K81.2 (3F, t,
JZ8.5 Hz, CF3), K114.4 (2F, t, JZ13.8 Hz, CF2), K121.3
(2F, t, JZ4.8 Hz, CF2S), K126.5 (2F, t, JZ14.1 Hz, CF2).
IR (KBr) cmK1: 2967, 2878, 1583, 1360, 1237, 1140, 1012.
MS: m/z (%) 382 (MCKC3H5, 12), 354 (MCKC5H9, 25),
96 (MCC1KRfSO2–EtO, 100), 69 (C5HC9 , 93). Anal.
Calcd for C12H14F9NO3S: C, 34.05; H, 3.33; N, 3.31%.
Found: C, 34.14; H, 3.36; N, 3.31%.
4.2. General procedure for the reaction of aryl azides
with cycloalkenyl ether
To a 10 mL round-bottom flask containing 1-ethoxy-
cycloheptene 2b (227 mg, 1.62 mmol) in 2 mL anhydrous
toluene was added 4-nitro phenyl azides 4a (0.246 g,
1.5 mmol) at room temperature under N2. Then the mixture
was continuously stirred and heated to 80 8C. After 48 h
TLC analysis showed the azide 4a was not consumed
completely. The solvent was evaporated and the residue
was chromatographed on a silica column using petroleum
ether–ether (20/3 v:v) as eluant to give pure product 5ab as a
yellowish solid (253 mg, 83%). Meanwhile, 80 mg of
4-nitro-phenyl azides 4a was recycled.
4.1.5. 1-Cyclohexyl-1-ethoxy-meth-(Z)-ylidene-(50-iodo-
30-oxa-octafluoropentyl)-sulfonyl imine (3ab). Colorless
oil. 1H NMR (CDCl3, 300 MHz): d 4.29 (2H, q, JZ7.2 Hz),
3.16–3.09 (1H, m), 2.01–1.42 (8H, m), 1.36 (3H, t, JZ
7.2 Hz), 1.32–1.20 (2H, m). 19F NMR (CDCl3, 282 MHz): d
K65.1 (2F, t, JZ5.8 Hz, ICF2), K81.3 (2F, t, JZ13.3 Hz,
CF2O), K85.7 (2F, m, OCF2), K117.5 (2F, s, CF2S). IR
(KBr) cmK1: 2938, 2861, 1584, 1332, 1292, 1186, 1146,
915. MS: m/z (%) 561 (MC, 1), 478 (MCKC6H11, 3), 227
(IC2FC4 , 8), 110 (MCC1KRfSO2–OEt, 100), 83 (C6H1C1,
65). Anal. Calcd for C13H16F8INO4S: C, 27.82; H, 2.87; N,
2.50%. Found: C, 27.89; H, 2.93; N, 2.46%.
4.2.1. 8a-Ethoxy-1-(4-nitro-phenyl)-1,3a,4,5,6,7,8,8a-
octahydro-cycloheptatriazole (5ab). Yellowish solid. Mp
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128–130 8C. H NMR (CDCl3, 300 MHz): d 8.25 (2H, dd,
JZ9.0, 0 1.5 Hz, AA0BB0), 7.65 (2H, dd, JZ9.6, 1.5 Hz,
AA0BB ), 4.62 (1H, t, JZ5.4 Hz), 3.19–3.14 (1H, m), 2.93–
2.88 (1H, m), 2.44–1.21 (10H, m), 1.16 (3H, t, JZ7.2 Hz).
IR (KBr) cmK1: 2940, 2859, 1593, 1516, 1493, 1338, 1045,
860. MS: m/z (%) 275 (MCKEt, 5), 259 (MCKEtO, 5),
193 (MCKC2H4–C6H11, 47), 137 (MCKEtO–C6H4NO2,
12), 83 (C6HC11, 93), 55 (C4HC7 , 100). Anal. Calcd for
C15H20N4O3: C, 59.21; H, 6.58; N, 18.42%. Found: C,
59.18; H, 6.78; N, 18.15%.
4.1.6. 1-Cyclohexyl-1-ethoxy-meth-(Z)-ylidene-(50-
chloro-30-oxa-octafluoropentyl)-sulfonyl imine (3bb).
Colorless oil. H NMR (CDCl3, 300 MHz): d 4.28 (2H, q,
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JZ7.2 Hz), 3.16–3.07 (1H, m), 2.01–1.40 (8H, m), 1.36 (3H,
t, JZ7.2 Hz), 1.32–1.19 (2H, m). 19F NMR (CDCl3,
282 MHz): d K74.1 (2F, s, ClCF2), K81.3 (2F, t, JZ
13.7 Hz, CF2O), K87.1 (2F, t, JZ12.6 Hz, OCF2), K117.6
(2F, s, CF2S). IR (KBr) cmK1: 2939, 2862, 1585, 1360, 1305,
1187, 1142, 977. MS: m/z (%) 471/469 (MC, 0.6/1.6), 388/
386 (MCKC6H11, 2/5), 110 (MCC1KRfSO2–OEt, 100), 83
(C6HC11, 71). Anal. Calcd for C13H16ClF8NO4S: C, 33.24; H,
3.43; N, 2.98%. Found: C, 33.23; H, 3.43; N, 2.90%.
4.2.2. 1-(4-Chloro-phenyl)-8a-ethoxy-1,3a,4,5,6,7,8,8a-
octahydro-cycloheptatriazole (5bb). Colorless oil. 1H
NMR (CDCl3, 300 MHz): d 7.46–7.27 (4H, m), 4.50 (1H, t,
JZ5.1 Hz), 3.17–3.11 (1H, m), 2.99–2.93 (1H, m), 2.52–1.23
(10H, m), 1.17 (3H, t, JZ6.9 Hz). IR (KBr) cmK1: 2930,
2856, 1597, 1491, 1455, 1346, 1065, 1039, 829. MS: m/z (%)
295/293 (MC, 1/3), 238/236 (MCKC4H9, 3/9), 182 (MCK
C6H4Cl, 25), 113/111 (ClC6HC4 , 51), 55 (C4H7C, 100). HRMS
(MALDI/DHB) for [MCOH]C: C15H21ClN3O2 Calcd
310.1326. Found: 310.1317.
4.1.7. 1-Cyclohexyl-1-ethoxy-meth-(Z)-ylidene-(10,10,
20,20,40,40,50,50-octafluoro-30-oxa-pentyl)-sulfonyl imine
(3cb). Colorless oil. H NMR (CDCl3, 300 MHz): d 5.87
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(1H, tt, JZ3.0, 52.5 Hz), 4.29 (2H, q, JZ7.2 Hz), 3.17–3.07
(1H, m), 2.01–1.40 (8H, m), 1.36 (3H, t, JZ7.2 Hz),
1.32–1.20 (2H, m). 19F NMR (CDCl3, 282 MHz): d K80.9
(2F, t, JZ12.8 Hz, CF2O), K88.8 (2F, m, OCF2), K117.7
(2F, s, CF2S), K137.66 (2F, d, JZ52.5 Hz, HCF2). IR
(KBr) cmK1: 2939, 2862, 1585, 1358, 1329, 1187, 1009.
MS: m/z (%) 435 (MC, 1), 352 (MCKC6H11, 4), 110
(MCC1KRfSO2–EtO, 100), 83 (C6H1C1, 70). Anal. Calcd
4.2.3. 1-(4-Methoxy-phenyl)-1,4,5,6,7,8-hexahydro-
cycloheptatriazole (6cb). Yellowish solid. Mp
104–106 8C. H NMR (CDCl3, 300 MHz): d 7.32 (2H, dd,
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JZ9.0, 0 2.1 Hz, AA0BB0), 7.02 (2H, dd, JZ9.0, 2.4 Hz,
AA0BB ), 3.87 (3H, s), 2.96 (2H, t, JZ6.0 Hz), 2.69 (2H, t,
JZ5.7 Hz), 1.87–1.67 (6H, m). IR (KBr) cmK1: 2927,
2844, 1515, 1457, 1252, 1233, 1176, 1032, 841. MS: m/z
(%) 243 (MC, 11), 214 (MCKC2H5, 89), 200 (MCKC3H7,