Z. Ren et al. / Tetrahedron 64 (2008) 5156–5161
5159
3.2. Preparation of 4-arylidene-3-methyl-1-phenyl-pyrazolin-
5-ones
J¼9.0, 1H), 3.83 (s, 3H), 3.88 (d, J¼9.0, 1H), 7.13–7.16 (m, 1H), 7.23–
7.24 (m, 2H), 7.28–7.32 (m, 2H), 7.35 (d, J¼7.5, 2H), 7.80 (d, J¼7.5,
2H); 13C NMR (125 MHz, CDCl3) d: 15.2, 37.4, 38.7, 44.9, 53.0, 118.6,
125.1, 128.5, 128.8, 129.3, 130.6, 134.2, 138.1, 156.1, 167.1 168.1; IR
(KBr) n: 3455,1737,1701,1595 cmꢀ1; MS m/z (%) (EI): 370 (Mþþ2, 4),
369 (Mþþ1, 2), 368 (Mþ, 9), 338 (21), 336 (50), 308 (17), 128 (20),
105 (19), 77 (100), 51 (19), 44 (59). Anal. Calcd for C20H17ClN2O3: C,
65.13; H, 4.65; N, 7.60. Found: C, 65.44; H, 4.63; N, 7.66.
These compounds were prepared by condensing 3-methyl-1-phe-
nyl-pyrazolin-5-one with aromatic aldehydes under Knoevenagel
reaction condition. The Z configuration of 4-arylidene-3-methyl-
1-phenyl-pyrazolin-5-one was established from the corresponding
NOESY correlations between the methyl proton and the methylene
proton.
3.3.5. exo-trans-2,3-Dihydro-4-methyl-7-oxo-2,6-diphenyl-5,6-
diaza-spiro[2,4]hept-4-ene-1-carboxylic acid methyl ester (3e)
As a white solid; mp (ꢁC): 120–121 (methylene chloride/
petroleum ether); 1H NMR (500 MHz, CDCl3) d: 2.23 (s, 3H), 3.70 (d,
J¼8.5, 1H), 3.83 (s, 3H), 3.95 (d. J¼8.5, 1H), 7.12–7.15 (m, 1H), 7.29–
7.35 (m, 7H), 7.82–7.83 (m, 2H); 13C NMR (125 MHz, CDCl3) d: 15.2,
37.5, 39.7, 45.0, 52.8, 118.5, 124.9, 128.2, 128.3, 128.7, 129.2, 130.8,
3.3. General procedure for the preparation of compounds 3
A mixture ofpyrazolinone 1 (1 mmol), arsonium salt 2 (1.1 mmol),
and KF$2H2O (284 mg, 3 mmol) was stirred at room temperature in
CHCl3 (5 mL). The completion of the reaction was monitored by TLC.
The solvent was removed under reduced pressure and the residue
was purified by silica gel column chromatography (petroleum ether/
ethyl acetate, 8:1). Triphenylarsine could be recovered and the
desired product 3 was obtained.
138.2, 156.7, 167.2, 168.3; IR (KBr) n: 4354, 1737, 1694, 1596 cmꢀ1
;
MS m/z (%) (EI): 334 (Mþ, 15), 303 (24), 302 (75), 274 (33), 121(27),
115 (32), 102 (33), 77 (100), 51 (35). Anal. Calcd for C20H18N2O3: C,
71.84; H, 5.43; N, 8.38. Found: C, 71.79; H, 5.39; N, 8.36.
3.3.1. exo-trans-2,3-Dihydro-1-benzoyl-2-(4-chlorophenyl)-7-
methyl-5-phenyl-5,6-diaza-spiro[2,4]hept-6-en-4-one (3a)
3.3.6. exo-trans-2,3-Dihydro-2-(4-methoxy-phenyl)-4-methyl-7-
oxo-6-phenyl-5,6-diaza-spiro[2,4]hept-4-ene-1-carboxylic acid
methyl ester (3f)
As a white solid; mp (ꢁC): 159–160 (methylene chloride/
petroleum ether); 1H NMR (500 MHz, CDCl3) d: 2.00 (s, 3H), 4.18 (d,
J¼8.5, 1H), 4.21 (d, J¼8.5, 1H), 7.13–7.16 (m, 1H), 7.28–7.37 (m, 6H),
7.48–7.51 (m, 2H), 7.61–7.64 (m, 1H), 7.86 (d, J¼8.0, 2H), 7.98 (d,
J¼8.0, 2H); 13C NMR (125 MHz, CDCl3) d: 15.0, 38.2, 41.3, 46.5, 118.6,
125.1, 127.2, 128.6, 128.9, 129.2, 129.5, 129.7, 129.9, 130.8, 132.4,
134.2, 134.5, 135.9, 138.3, 156.2, 167.3, 191.7; IR (KBr) n: 3445, 1710,
1679, 1594 cmꢀ1; MS m/z (%) (EI): 416 (Mþþ1, 1), 106 (8), 105 (100),
91 (2), 78 (3), 77 (43), 51 (7), 44 (14), 43 (2). Anal. Calcd for
As a white solid; mp (ꢁC): 126–127 (methylene chloride/petro-
leum ether); 1H NMR (500 MHz, CDCl3) d: 2.25 (s, 3H), 3.40 (d,
J¼9.0, 1H), 3.81 (s, 3H), 3.85 (s, 3H), 3.93 (d, J¼9.0, 1H), 6.86–6.88
(m, 2H), 7.14–7.17 (m, 1H), 7.26 (d, J¼8.0, 2H), 7.34–7.38 (m, 2H),
7.85 (d, J¼8.0, 2H); 13C NMR (125 MHz, CDCl3) d: 15.2, 37.7, 39.6,
45.3, 52.9, 55.2, 113.8, 118.6, 122.6, 124.9, 128.8, 130.4, 138.3, 156.4,
159.5, 167.3, 168.4; IR (KBr) n: 3444, 1735, 1703, 1596 cmꢀ1; MS m/z
(%) (EI): 364 (Mþ, 6), 362 (20), 332 (19), 135 (26), 132 (14), 128 (13),
118 (15), 44 (110), 77 (43). Anal. Calcd for C21H20N2O4: C, 69.22; H,
5.53; N, 7.69. Found: C, 69.60; H, 5.51; N, 7.50.
C
25H19ClN2O2: C, 72.37; H, 4.62, N, 6.75. Found: C, 72.41; H, 4.46; N,
6.83.
3.3.2. exo-trans-2,3-Dihydro-1-benzoyl-7-methyl-2,5-diphenyl-
5,6-diaza-spiro[2,4]hept-6-en-4-one (3b)
3.3.7. exo-trans-2,3-Dihydro-1-(4-chlorophenyl)-2-(2-furoyl)-7-
methyl-5-phenyl-5,6-diaza-spiro[2,4]hepten-4-one (3g)
As a white solid; mp (ꢁC): 131–132 (methylene chloride/
petroleum ether); 1H NMR (500 MHz, CDCl3) d: 2.03 (s, 3H), 4.25 (d,
J¼9.0, 1H), 4.27 (d, J¼9.0, 1H), 7.14–7.17 (m, 2H), 7.34–7.37 (m, 6H),
7.49–7.52 (m, 2H), 7.62–7.66 (m, 1H), 7.86–7.88 (m, 2H), 8.00–8.01
(m, 2H); 13C NMR (125 MHz, CDCl3) d: 15.0, 39.2, 41.3, 46.7, 118.5,
125.0, 128.3, 128.4, 128.6, 129.4, 131.3, 134.4, 136.0, 138.3, 156.4,
167.4, 192.0; IR (KBr) n: 3447, 1690, 1676, 1594 cmꢀ1; MS m/z (%)
(EI): 380 (Mþ, 2),115 (2), 106 (6), 105 (100), 78 (2), 77 (39), 76 (2), 51
(6), 44 (7). Anal. Calcd for C25H20N2O2: C, 78.93; H, 5.30; N, 7.36.
Found: C, 78.79; H, 5.12; N, 7.18.
As a white solid; mp (ꢁC): 151–152 (methylene chloride/petro-
leum ether); 1H NMR (500 MHz, CDCl3) d: 2.14 (s, 3H), 4.14 (d, J¼8.5,
1H), 4.17 (d, J¼8.5, 1H), 6.61–6.62 (m, 1H), 7.14–7.17 (m, 1H),
7.28–7.38 (m, 7H), 7.69 (s, 1H), 7.84–7.86 (m, 2H); 13C NMR
(125 MHz, CDCl3) d: 15.3, 37.9, 41.0, 46.7, 113.1, 118.5, 119.4, 125.1,
128.6, 128.8, 129.8, 130.7, 134.2, 138.2, 148.1, 152.2, 156.4, 167.2,
180.1; IR (KBr) n: 3446, 1694, 1670, 1595 cmꢀ1; MS m/z (%) (EI): 406
(Mþþ2, 2), 405 (Mþþ1, 1), 404 (Mþ, 5), 336 (4), 96 (6), 95 (100), 77
(16), 67 (3), 51 (6), 44 (20). Anal. Calcd for C23H17ClN2O3: C, 68.23;
H, 4.23; N, 6.92. Found: C, 68.37; H, 3.99; N, 6.72.
3.3.3. exo-trans-2,3-Dihydro-1-benzoyl-2-(4-methoxyphenyl)-7-
methyl-5-phenyl-5,6-diaza-spiro[2,4]hept-6-en-4-one (3c)
3.3.8. exo-trans-2,3-Dihydro-1-(4-chlorophenyl)-2-(2-thienoyl)-7-
methyl-5-phenyl-5,6-diaza-spiro[2,4]hepten-4-one (3h)
As a white solid, mp (ꢁC): 144–145 (methylene chloride/
petroleum ether); 1H NMR (500 MHz, CDCl3) d: 2.04 (s, 3H), 3.83 (s,
3H), 4.23 (d, J¼9.0, 1H), 4.27 (d, J¼9.0, 1H), 6.89–6.91 (m, 2H), 7.16–
7.19 (m, 1H), 7.31–7.33 (m, 2H), 7.37–740 (m, 2H), 7.51–7.55 (m, 2H),
7.65–7.68 (m, 1H), 7.90 (d, J¼7.5, 2H), 8.02 (d, J¼7.5, 2H); 13C NMR
(125 MHz, CDCl3) d: 15.0, 39.1, 41.5, 46.9, 55.2, 113.8, 118.5, 123.1,
125.0, 128.6, 128.8, 129.2, 130.6, 134.4, 136.0, 138.4, 156.5, 159.5,
167.5, 192.1; IR (KBr) n: 3448, 1709, 1679, 1596 cmꢀ1; MS m/z (%)
(EI): 411 (Mþþ1, 6), 410 (Mþ,1), 408 (7),106 (8),105 (100), 78 (3), 77
(47), 51 (8), 44 (23). Anal. Calcd for C26H22N2O3: C, 76.08; H, 5.40; N,
6.82. Found: C, 76.35; H, 5.08; N, 6.65.
As a white solid; mp (ꢁC): 140–141 (methylene chloride/petro-
leum ether); 1H NMR (500 MHz, CDCl3) d: 2.09 (s, 3H), 4.12 (d, J¼8.5,
1H), 4.17 (d, J¼8.5,1H), 7.14–7.18 (m, 2H), 7.28–7.37 (m, 6H), 7.75–7.77
(m, 1H), 7.82–7.85 (m, 3H); 13C NMR (125 MHz, CDCl3) d: 15.1, 38.2,
41.9, 46.6, 118.5, 125.1, 128.6, 128.8, 128.9, 129.8, 130.7, 133.8, 134.2,
135.9, 138.2, 143.2, 156.3, 167.3, 184.2; IR (KBr) n: 3445, 1691, 1659,
1595 cmꢀ1; MS m/z (%) (EI): 422 (Mþþ2, 2),113 (6),112 (8),111 (100),
83 (5), 77(13), 51 (6), 44 (16), 42 (3). Anal. Calcd for C23H17ClN2O2S: C,
65.63; H, 4.07; N, 6.66. Found: C, 65.63; H, 3.78; N, 6.50.
3.3.9. exo-trans-2,3-Dihydro-2-(4-chlorophenyl)-4-methyl-7-oxo-
6-phenyl-5,6-diaza-spiro[2,4]hept-4-ene-1-carbonitrile (3i)
As a white solid; mp (ꢁC): 61–62 (methylene chloride/petroleum
ether); 1H NMR (500 MHz, CDCl3) d: 1.28 (s, 3H), 2.93 (d, J¼9.0, 1H),
3.50 (d, J¼9.0, 1H), 7.22–7.24 (m, 1H), 7.38–7.46 (m, 6H), 7.91–7.92
(m, 2H); 13C NMR (125 MHz, CDCl3) d: 16.3, 19.3, 37.0, 41.1, 114.5,
3.3.4. exo-trans-2,3-Dihydro-2-(4-chlorophenyl)-4-methyl-7-oxo-
6-phenyl-5,6-diaza-spiro[2,4]hept-4-ene-1-carboxylic acid methyl
ester (3d)
As a white solid; mp (ꢁC): 190–191 (methylene chloride/
petroleum ether); 1H NMR (500 MHz, CDCl3) d: 2.22 (s, 3H), 3.40 (d,