Jul-Aug 2005
Synthesis and Chemical Reactivity of 3-Oxo-2-Arylhydrazono-Propanenitriles
785
(
(
4-Chlorophenylhydrazono)-(4'-methoxyphenylazo)acetonitrile
7d).
Anal. Calcd. for C H ClN O: C, 48.55; H, 3.17; N, 25.17.
9 7 4
Found C, 48.24; H, 3.11; N, 25.07.
A cold solution of p-methoxybenzene diazonium salt (10
mmol) (prepared as described above) added to a cold solution of
c (10 mmol) in EtOH and DMF containing sodium acetate (3.5
N-[4-(4-Chlorophenylazo)-isoxazol-5-yl)-acetamide (12).
A mixture 11 (0.01 mol) and acetic anhydride (20 ml) was
6
refluxed for 2 h. then poured into H O. The solid that formed was
2
g) the mixture was stirred at r.t. for 1 h and the solid product, so
formed, was collected by filtration and crystallized from ethanol.
This compound was obtained as dark orange crystals; mp. 215-
collected by filtration and crystallized from ethanol to give dark
red crystals, m.p. 185-187 °C; yield 62%; IR (KBr): ν
= 3335
max
-
1
1
(
NH), 3090 (CH aliphatic), 1683 cm (CO); H NMR (d6-
-
1
2
(
2
16 °C; yield 86%; IR (KBr): νmax = 3234 (NH), 2222 cm
DMSO): δ = 2.24 (s, 3H, CH ), 3.17 (br, 1H, NH), 7.40 (s, 1H,
1
3
CN); H NMR (d -DMSO): δ = 3.91 (s, 3H, CH ), 7.12 (d, J=9,
H, Ar-H), 7.40 (d, J=7.8 Hz, 2H, Ar-H), 7.61 (d, J=7.8 Hz, 2H,
6
3
isoxazole-H), 7.66-7.72 (m, 4H, Ar-H); MS (70 eV): m/z = 264
+
(
M , 7.8%), (248, 7.8%), (194, 90%).
Ar-H), 7.82 (br, 1H, NH), 8.07 (d, J=9 Hz, 2H, Ar-H)- MS (70
Anal. Calcd. for C H ClN O : C, 49.92; H, 3.43; N, 21.17.
+
11
9
4 2
eV): m/z = 313 (M , 15.1%), (135, 39.6%), (107, 100%).
Found C, 50.20; H, 3.31; N, 21.09.
Anal. Calcd. for C H ClN O C, 57.42; H, 3.86; N, 22.32.
1
5
12
5
Found C, 57.38; H, 3.80; N, 22.13.
5-Acetyl-1-(4-chloro-phenyl)-1H-pyrazole-3-carbonitrile (13).
A mixture of 6c (0.01 mol), chloroacetone (0.01 mol) and
2
-[(4-Chlorophenyl)-hydrazono]-3-(phenylhydrazono)-propio-
K CO (0.02 mol) in dioxane (20 mL) was refluxed for 2 h. The
nitrile (8).
2
3
solvent was then evaporated under reduced pressure and the
residue poured on water and neutralized by HCl. The product was
collected by filtration and crystallized from ethanol to give
A mixture of 6c (0.01 mol) and phenylhydrazine (0.01 mol) in
ethanol (20 mL) was refluxed for 45 min. then poured into H O.
2
The solid, so formed was collected by filtration and crystallized
from ethanol to give orange crystals; m.p. 203-205 °C; yield
brown crystals; m.p. 180-181 °C; yield 60%; IR (KBr): ν
=
max
-1
1
3
139 (CH aliphatic), 2243 (CN), 1697 cm (C=O); H NMR (d -
6
8
2
7%; IR (KBr): ν
= 3424, 3277 (NH), 3033 (CH aliphatic),
max
DMSO): δ = 2.54 (s, 3H, CH ), 7.52-7.60 (m, 4H, Ar-H), 8.07 (s,
3
219 cm-1 (CN); H NMR (d -DMSO): δ = 7.0-7.91 (m, 9H, Ar-
1
6
13
1
1
(
H, CH); C NMR (d -DMSO): δ = ten signals at 20, 107, 116,
20, 126, 129.6, 131, 135, 136 and 190; MS (70 eV): m/z = 245
6
H), 10.70 (s, 1H, CH), 11.11 (br, 1H, NH), 12.0 (s, 1H, NH); MS
70 eV): m/z = 297 (M , 98.4%), (236, 32.3%), (77, 100%).
Anal. Calcd. for C H ClN : C, 60.51; H, 4.06; N, 23.52.
+
(
+
M , 88%), (230, 100%).
1
5
12
5
Anal. Calcd. for C H N OCl: C, 58.67; H, 3.28; N, 17.10.
1
2 8 3
Found C, 60.15; H, 3.89; N, 23.12.
Found C, 58.56; H, 3.24; N, 17.11.
1
-(4-Chlorophenyl)-4-phenylazo-1H-pyrazol-3-carboxylic Acid
N-[2-(4-Chlorophenyl)-6-cyano-3-oxo-2,3-dihydro-pyridazin-4-
yl)]-benzamide (16).
Amide (10).
A mixture of 6c (1.5 mmol) in dry DMF (1 ml) was added
the Vilsmeier-Haack reagent (0.9 g, 3 mmol) [1 mol= 300 g,
A mixture of 6c (0.01 mol), hippuric acid (0.01 mol) and acetic
anhydride (15 ml) refluxed for 2 h. then poured into H O, the
2
from POCl (150 g, 1 mol) and DMF (150 g, 2 mol)] and the
3
solid so formed was collected by filtration and crystallized from
ethanol to give brown crystals m.p. 220-222 °C; yield 71%; IR
mixture was kept at 70 ºC for 1 h. After cooling the mixture
was poured onto ice. To the clear solution was added carefully
dilute aqueous NaOH solution under cooling until a PH value
of 8-9 was reached. The precipitate was separated and recrys-
tallized from ethanol to give yellow crystals; m.p. 198-200 °C;
-1
1
(
(
7
(
KBr): νmax = 3375 (NH), 2244 (CN), 1709 cm (CO); H NMR
d6-DMSO): δ = 7.55-7.68 (m, 7H, 5H phenyl-H, and 2H Ar-H),
.97 (d, J= 7.2 Hz, 2H, Ar-H), 8.42 (s, 1H, pyridazinyl-H), 10.05
s, 1H, NH)- MS (70 eV): m/z = 350 (M , 8.%), (M 2, 3.2%),
(105, 100%).
Anal. Calcd. for C H ClN O : C, 61.64; H, 3.16; N, 16.97.
+
+
-
1
yield 60%; IR (KBr): ν
= 3116, 3070 (NH ), 1692 cm
max
2
1
(
CO); H NMR (d -DMSO): δ = 7.47 (d, J =8.0 Hz, 2H, aryl-
H), 7.58 (m, 5H, phenyl), 7.76 (d, J=8.0 Hz, 2H, aryl-H), 8.15
s,1H, pyrazole-H), 10.71 (br, 1H, NH ); C NMR (d6-
6
1
8
11
4 2
Found C, 61.25; H, 3.12; N, 15.89.
1
3
(
2
6
-Chloro-cinnoline-3-carboxylic Acid Amide (17).
DMSO): δ = 123.5, 123.6, 123.9, 128.4, 129.3, 129.5, 129.7,
1
3
30.2, 135.0, 137.8, 151.1, 151.2; - MS (70 eV): m/z =
Compound 6c (0.01 mol) was heated with conc. H SO (3-5
2
4
+
25(M , 25.8%), (M+2, 6.7%), (297, 79.2%).
mL) at 198-200 °C for 5 min and kept overnight and then poured
Anal. Calcd. for C H ClN O: C, 58.99; H, 3.71; N, 21.50.
into H O. The solid product, so formed, was collected by filtra-
1
6
12
5
2
Found C, 58.87; H, 3.43; N, 21.21.
tion and crystallized from ethanol. This compound was obtained
as orange crystals, yield 45%; m.p. 285 °C; IR (KBr): ν
=
max
2
-[(4-Chlorophenyl)-hydrazono]-3-hydroxyiminopropionitrile
-
1
1
3
426, 3278 (NH ), 1681 cm (CO);- H NMR (d -DMSO): δ =
2
6
(
11).
A mixture of 6c (0.01 mol), hydroxylamine hydrochloride
0.01 mol), and sodium acetate (0.01 mol) in ethanol (20 ml) was
7
.21 (br, 2H, NH ), 7.67-8.07 (m, 4H, Ar-H, and cinnoline-H);
2
1
3
C NMR nine signals at 120, 124, 125.2, 128.5, 129.1,
+
(
133.7,147.4, 162.6 and 185; MS (70 eV): m/z = 207 (M , 100%),
(164, 77.1%).
refluxed for 15 min. then poured into H O. The solid, so formed
2
was collected by filtration and crystallized from ethanol to give
Anal. Calcd. for C H ClN O: C, 52.07; H, 2.91; N, 20.24.
9
6
3
orange crystals; m.p. 262-263 °C; yield 82%; IR (KBr): ν
=
Found C, 52.10; H, 2.74; N, 20.14.
max
-
1
3
498, 3348 (OH and NH), 2989 (CH aliphatic), 2212 cm (CN);
4
-(4-Chlorophenylazo)-1H-pyrazol-3-ylamine. (18).
1
H NMR (d -DMSO): δ = 7.37 (m, 2H, aryl-H), 7.40 (s, 1H,
6
CH), 7.65 (m, 2H, aryl-H), 7.80 (br, 1H, NH), 11.73 (br, 1H,
A mixture of 6c (0.01 mol) and hydrazine hydrate (0.01 mol)
in ethanol (25 mL) was refluxed for 2 h then poured into H O.
+
OH)- MS (70 eV): m/z =222 (M , 100%), (M+2, 44.5%).
2