Synthesis and Reaction of Coumarinyl Crotononitriles
J. Chin. Chem. Soc., Vol. 52, No. 6, 2005 1197
collected by filtration and crystallized from the proper sol-
vents to give 15a-f.
13d: recrystallized from methanol to give red crystals
in 76% yield, m.p. 162 °C. Anal. C21H13N4O2Br (433.25),
Calcd.: C, 58.21%; H, 3.02%; N, 12.93%; Br, 18.44%; Found:
C, 58.00%; H, 3.20%; N, 13.00%; Br, 18.50%.
12a: recrystallized from acetic acid to give grey crys-
tals in 70% yield. Anal. C26H15N5O3 (445.42), Calcd.: C,
70.10%; H, 3.39%; N, 15.72%; Found: C, 70.00%; H, 3.40%;
N, 15.60%.
13e: recrystallized from ethanol to give red crystals in
66% yield, m.p. 168% °C. Anal. C21H14N4O2 (354.36), Calcd.:
C, 71.17%; H, 3.98%; N, 15.87%; Found: C, 70.90%; H,
4.10%; N, 15.95%.
12b: recrystallized from ethanol to give brown crystals
in 65% yield, m.p. 175 °C. Anal. C26H14N5O3Br (524.31),
Calcd.: C, 59.55%; H, 2.69%; N, 13.41%; Br, 15.23%. Anal.
Found: C, 59.40%; H, 2.70%; N, 13.50%; Br, 15.20%.
12c: recrystallized from ethanol to give yellow crystals
in 75% yield, m.p. 203 °C. Anal. C28H19N5O3 (473.47),
Calcd.: C, 71.09%; H, 4.04%; N, 14.79%; Found: C, 70.90%;
H, 4.10%; N, 14.85%.
13f: recrystallized from ethanol to give red crystals in
70% yield, m.p. 171 °C. Anal. C21H13N4O2Br (433.25),
Calcd.: C, 58.21%; H, 3.02%; N, 12.93%; Br, 18.44%; Found:
C, 58.10%; H, 3.10%; N, 12.80%; Br, 18.55%.
Synthesis of 3-(1-aryl-5-cyanopyridazin-6-one-4-yl)
coumarin derivatives 15a-f
12d: recrystallized from dioxane to give yellow crys-
tals in 75% yield, m.p. 211 °C. Anal. C28H18N5O3Br (552.37),
Calcd.: C, 60.88%; H, 3.28%; N, 12.67%; Br, 14.46%;
Found: C, 61.00%; H, 3.30%; N, 12.50%; Br, 14.55%.
12e: recrystallized from dioxane to give yellow crystals
in 60% yield, m.p. 265 °C. Anal. C28H19N5O3 (473.47), Calcd.:
C, 71.09%; H, 4.04%; N, 14.79%; Found: C, 71.20%; H,
3.80%; N, 14.85%.
A solution of each of 13a-f (0.01 mol.) in acetic acid
(30 mL) was refluxed for 2 hrs. The reaction mixture was
poured into crushed ice. The solid products that separated out
were crystallized from the proper solvents to give 15a-f.
15a: recrystallized from acetic acid to give yellow crys-
tals in 75% yield, m.p. 262 °C. Anal. C20H11N3O3 (341.31),
Calcd.: C, 70.37%; H, 3.24%; N, 12.31%; Found: C, 70.25%;
H, 3.40%; N, 12.20%.
12f: recrystallized from ethanol to give yellow crystals
in 65% yield, m.p. 204 °C. C28H18N5O3Br (552.37), Calcd.:
C, 60.88%; H, 3.28%; N, 12.67%; Br, 14.46%; Found: C,
60.70%; H, 3.30%; N, 12.50%; Br, 14.60%.
15b: recrystallized from ethanol to give yellow crystals
in 75% yield, m.p. 194 °C. Anal. C20H10N3O3Br (420.20),
Calcd.: C, 57.16%; H, 2.39%; N, 10.00%; Br, 19.01%; Found:
C, 57.00%; H, 2.45%; N, 10.20%; Br, 18.90%.
Synthesis of 3-(1,1-dicyano-3-arylhydrazopropenyl)
coumarin derivatives 13a-f
15c: recrystallized from ethanol to give grey crystals in
76% yield, m.p. 193 °C. Anal. C21H13N3O3 (355.34), Calcd.:
C, 70.97%; H, 3.68%; N, 11.82%; Found: C, 71.00%; H,
3.55%; N, 11.90%.
A solution of aryl diazonium chloride, namely phenyl,
o-tolyl and p-tolyl diazonium chloride (0.01 mol.), was added
gradually while stirring to a cold solution of 2a,b (0.01 mol.)
in acetic acid (50 mL) containing sodium acetate (5 g). The
reaction mixture was left overnight in an ice-bath. The solid
product that formed was collected by filtration and crystal-
lized from the proper solvents to yield compounds 13a-f.
13a: recrystallized from ethanol to give red crystals in
86% yield, m.p. 145 °C. Anal. C20H12N4O2 (340.43), Calcd.:
C, 70.56%; H, 3.58%; N, 16.45%; Found: C, 70.70%; H,
3.40%; N, 16.55%.
15d: recrystallized from methanol to give yellow crys-
tals in 65% yield, m.p. 200 °C. Anal. C21H12N3O3Br (434.22),
Calcd.: C, 58.08%; H, 2.78%; N, 9.67%; Br, 18.40%; Found:
C, 58.10%; H, 2.65%; N, 9.55%; Br, 18.50%.
15e: recrystallized from acetic acid to give yellow crys-
tals in 60% yield, m.p. 208 °C. Anal. C21H13N3O3 (355.34),
Calcd.: C, 70.97%; H, 3.68%; N, 11.82%; Found: C, 70.80%;
H, 3.75%; N, 11.70%.
15f: recrystallized from ethanol to give yellow crystals
in 75% yield, m.p. 192 °C. Anal. C21H12N3O3Br (434.22),
Calcd.: C, 58.08%; H, 2.78%; N, 9.67%; Br, 18.40%; Found:
C, 58.20%; H, 2.75%; N, 9.80%; Br, 18.35%.
13b: recrystallized from methanol to give red crystals
in 81% yield, m.p. 143 °C. Anal. C20H11N4O2Br (419.23),
Calcd.: C, 57.29%; H, 2.64%; N, 13.36%; Br, 19.05%; Found:
C, 57.40%; H, 2.50%; N, 13.50%; Br, 18.90%.
13c: recrystallized from methanol to give orange crys-
tals in 85% yield, m.p. 171 °C. Anal. C21H14N4O2 (354.36),
Calcd.: C, 71.17%; H, 3.98%; N, 15.87%; Found: C, 71.10%;
H, 4.00%; N, 16.00%.
Synthesis of 4-cyano-3-(coumarin-3-yl)-6-oxo-pyridazino-
[1,6-a]quinazoline 16
A solution of diazonium chloride of anthranilic acid
(0.01 mol.) was added gradually while stirring to a cold solu-