158 Padmavathi et al.
TABLE 2 1H NMR Spectral Data for 2–9
δ1 H in ppm (J in Hz)
2a 4.14 (dd, 1H, HX), 4.32 (dd, 1H, HM, JMX = 10.54), 4.88 (dd, 1H, HA,JAM = 12.61, JAX = 5.50), 6.65 (d, 1H, HC),
6.92–7.42 (m, 11H, Ar-H and HD, JCD = 14.13), 9.92 (bs, 1H, N-H).
2c 4.38 (dd, 1H, HX,), 4.45 (dd, 1H, HM, JMX = 10.56), 4.95 (dd, 1H, HA, JAM = 12.58, JAX = 5.51), 6.68 (d, 1H, HC),
6.98–7.52 (m, 10H, Ar-H and HD, JCD = 14.24), 9.94 (bs, 1H, N-H).
ꢁ
3a 4.15 (dd, 1H, HX), 4.36 (dd, 1H, HM,JMX = 10.64), 4.92 (dd, 1H, HA, JAM = 12.60, JAX = 5.56), 3.86 (dd, 1H HX ,), 4.08
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
(dd, 1H, HM , JM X 10.61), 4.24 (dd, 1H, HA , JA M = 12.58, JA X = 5.54), 6.98–7.44 (m, 10H, Ar-H), 10.00 (bs, 2H,
N-H).
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
3c 4.23 (dd, 1H, HX ), 4.43 (dd, 1H, HM , JM X = 10.64), 4.94 (dd, 1H, HA, JAM = 12.68, JAX = 5.52), 4.00 (dd, 1H HX ,), 4.15
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
(dd, 1H, HM , JM X 10.63), 4.32 (dd, 1H, HA ,JA M = 12.64, JA X = 5.52), 7.01–7.62 (m, 9H, Ar-H), 9.99 (bs, 2H, N-H).
4a 3.10 (dd, 1H, HX), 3.30 (dd, 1H, HM, JMX = 10.63), 5.92 (dd, 1H, HA, JAM = 12.70, JAX = 5.53), 6.62 (d, 1H, HC),
7.0–7.68 (m, 11H, Ar-H and HD, JCD = 14.15), 10.26 (bs, 1H, N-H).
4b 2.25 (s, 3H, Ar-CH3), 3.20 (dd, 1H, HX), 3.36 (dd, 1H, HM, JMX = 10.60), 5.98 (dd, 1H, HA, JAX = 5.52, JAM = 12.62),
6.68 (dd, 1H, HC), 7.02–7.58 (m, 10H, Ar-H and HD, JCD = 14.18), 10.25 (bs, 1H, N-H).
ꢁ
ꢁ
5a 3.16 (dd, 1H, HX ), 3.32 (dd, 1H, HM, JMX = 10.54), 5.93 (dd, 1H, HA, JAM = 12.68, JAX = 5.51), 3.93 (dd, 1H, HX ,),
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
4.09 (dd, 1H, HM , JM X 10.62), 4.28 (dd, 1H, HA , JA M = 12.68, JA X = 5.51), 6.92–7.58 (m, 10H, Ar-H), 9.96 (bs,
1H, N-H), 10.21 (bs, 1H, NH).
ꢁ
5c 3.16 (dd, 1H, HX), 3.35 (dd, 1H, HM, JMX = 10.60), 5.92 (dd, 1H, HA, JAM = 12.62, JAX = 5.56), 3.98 (dd, 1H, HX ,), 4.12
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
(dd, 1H, HM , JM X = 10.63), 4.30 (dd, 1H, HA , JA M = 12.64, JA X = 5.52), 6.92–7.61 (m, 9H, Ar-H), 9.94 (bs, 1H,
N-H), 10.22 (bs, 1H, N-H).
6a 1.32 (ddd, 1H, HN), 1.48 (ddd, 1H, HM), 2.78 (ddd, 1H, HB, JBM = 5.55, JBN = 10.12), 2.88 (ddd, 1H, HA, JAB = 5.72,
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
JAN = 6.58, JAM = 8.55), 3.14 (dd, 1H, HX ), 3.33 (dd, 1H, HM , JM X = 10.71), 5.95 (dd, 1H, HA , JA M = 12.64,
ꢁ
ꢁ
JA X = 5.54), 7.05–7.62 (m, 10H, Ar-H), 10.53 (bs, 1H, N-H).
6c 1.30 (ddd, 1H, HN), 1.45 (ddd, 1H, HM), 2.76 (ddd, 1H, HB, JBM = 5.57, JBN = 10.14), 2.94 (ddd, 1H, HA, JAB = 5.72,
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
JAN = 6.59, JAM = 8.59), 3.17 (dd, 1H, HX ), 3.35 (dd, 1H, HM , JM X = 10.61), 5.97 (dd, 1H, HA , JA M = 12.64,
ꢁ
ꢁ
JA X = 5.54), 7.02–7.78 (m, 9H, Ar-H), 10.21 (bs, 1H, N-H).
7a 1.28 (ddd, 1H, HN), 1.48 (ddd, 1H, HM), 2.74 (ddd, 1H, HB, JBM = 5.58, JBN = 10.14), 2.89 (ddd, 1H, HA, JAB = 5.74,
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
JAN = 6.54, JAM = 8.54), 4.16 (dd, 1H, HX ), 4.32 (dd, 1H, HM , JM X = 10.63), 4.88 (dd, 1H, HA , JA M = 12.58,
ꢁ
ꢁ
JA X = 5.52), 6.95–7.52 (m, 10H, Ar-H), 9.94 (bs, 1H, N-H).
7c 1.32 (ddd, 1H, HN), 1.52 (ddd, 1H, HM), 2.72 (ddd, 1H, HB, JBM = 5.52, JBN = 10.12), 2.92 (ddd, 1H, HA, JAB = 5.72,
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
JAN = 6.59, JAM = 8.55), 4.28 (dd, 1H, HX ), 4.42 (dd, 1H, HM , JM X = 10.60), 4.92 (dd, 1H, HA , JA M = 12.62,
ꢁ
ꢁ
JA X = 5.55), 6.95–7.52 (m, 9H, Ar-H), 9.98 (bs, 1H, N-H).
8a 1.25 (ddd, 2H, HN), 1.58 (ddd, 2H, HM), 2.74 (ddd, 2H, HB, JBM = 5.61, JBN = 10.08), 2.87 (ddd, 2H, HA, JAB = 5.74,
JAN = 6.58, JAM = 8.54), 6.92–7.51 (m, 10H, Ar-H).
9a 1.56 (ddd, 1H, HN), 1.68 (ddd, 1H, HM), 2.75 (ddd, 1H, HB, JBM = 5.52, JBN = 10.12), 2.94 (ddd, 1H, HA, JAB = 5.68,
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
JAN = 6.62, JAM = 8.54), 1.24 (ddd, 1H, HN ), 1.42 (ddd, 1H, HM ), 2.65 (ddd, 1H, HB , JB M = 5.05, JB N = 10.10),
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
2.88 (ddd, 1H, HA , JA B = 5.54, JA N = 6.60, JA M = 8.60), 6.98–7.65 (m, 10H, Ar-H).
(50 ml), and dichloromethane (40 ml) were stirred till
Cyclocondensation of 1 with Hydrazine Hydrate
a clear two-phase system was obtained. To this, ben-
zyltriethylammonium chloride (BTEAC) (100 mg)
was added with continuous stirring for a period of
2–3 h. The reaction was monitored by TLC. After
completion the reaction mixture was diluted with
water. The organic layer was separated and washed
with water and brine solution and then dried (an-
hydrous Na2SO4). Evaporation of the solvent gave a
syrupy substance which solidified on treatment with
2-propanol. Recrystallization from ethanol gave 9.
A similar procedure was adopted for 2 to get 7
and for 4 to get 6.
Compound 1 (0.01 mol) in ethanol (20 ml) and hy-
drazine hydrate (0.02 mol) were refluxed for 2–3 h
and cooled. The solid separated was recrystallized
from ethanol to get pure 4.
Cycloaddition of Diazomethane to 4
To a solution of 4 (0.01 mol) in dichloromethane
(20 ml) an ethereal solution of diazomethane
(100 ml, 0.4 mol) and a catalytic amount of triethy-
lamine were added. This on work up as in 2 resulted
in 5.
Cyclopropanation of 1 (2, 4)
Pyrolysis of 3 and 7 (5 and 6)
with Trimethylsulphoxonium Iodide
A solution of 3 or 7 (.001 mol) and 1,2-ethanediol
(10 ml) was heated at about 200–230◦C for 30–45
min under anhydrous conditions. The contents of
A mixture of 1 (0.01 mol), trimethylsulphoxonium
iodide (0.022 mol), 50% aqueous KOH solution