Vol. 26, No. 22 (2014)
Synthesis of PhenylcarbamicAcid and (4-substituted phenylimino)indolin-1-yl]acetohydrazide Derivatives 7667
-
1
powder, m.p.: 209-210 °C; yield 78 %: IR (KBr, νmax, cm )
3
Methyl 2-(4-bromophenylcarbamoyl)phenylcarbamate
(4c): The product was obtained as a white crystal, m.p.: 190-
1
316, 3132 (NH), 1679, 1653 (C=O), 1586 (C=N). H-NMR
DMSO-d ): δ (ppm) 4.34 (s, 2H, NCH CO), 6.90 (d, J = 8.00,
H), 7.01-7.06 (m, 2H, Ar), 7.17-7.22 (m, 2H, Ar), 7.41 (d, J
7.32 Hz, 2H), 9.41 (s, NH), 9.69 (d, NH), 10.44 (d, NH);
43
(
6
2
192 °C; yield: 58 % (method A); 80 % (method B). (lit. m.p.
-1
2
198 °C; yield 95 %). IR (KBr, νmax, cm ): 3295, 3192 (NH),
1
=
1717, 1659, 1591 (C=O). H-NMR (DMSO-d
(s, 3H, COOCH ), 7.20 (t, J = 8.04 Hz, 1H), 7.54-7.56 (m,
3H), 7.70 (d, J = 8.8 Hz, 2H), 7.80 (d, J = 8.04 Hz, 1H), 8.03
6
): δ (ppm) 3.65
13
C-NMR (DMSO-d
21.23, 124.6, 126.2, 138.8, 160.1, 165.32. Anal. Calcd for
Br: C, 51.49; H, 3.51; N, 15.01. Found: C, 51.61;
H, 3.60; N, 15.35
6
): δ (ppm) 39.0, 108.2, 116.5, 120.8,
3
1
13
C
16
H N O
13 4 2
(d, J = 8.08 Hz, 1H), 10.08 (s, CONH), 10.55 (s, CONH); C-
NMR (DMSO-d ):δ (ppm) 52.6, 116.4, 120.7, 123.1, 123.3,
6
2-[3-(4-Methoxyphenylimino)-2-oxoindolin-1-yl]-
acetohydrazide (3d): The product was obtained as a yellow
129.3, 129.5, 132.1, 132.8, 138.6, 138.8, 154.1, 167.7
(CONH).
-1
powder, m.p.:214-216 °C; yield 64 %. IR (KBr, νmax, cm ):
Methyl 2-(4-methoxyphenylcarbamoyl)phenylcar-
bamate (4d): The product was obtained as a white crystal,
m.p.:172-174 °C; yield: 80 % (method A); 90 % (method B).
1
3
311, 3133 (NH), 1677, 1652 (C=O), 1587 (C=N). H-NMR
DMSO-d ) : δ (ppm) 3.36 (s, 3H, C OCH ), 4.34 (s, 2H,
CO), 6.90 (d, J = 8.04 Hz, 2H), 7.01-7.03 (m, 2H, Ar),
(
6
H
6 4
3
-
1
NCH
2
IR (KBr, νmax, cm ): 3306, 3100 (NH), 1714, 1649, 1603
1
(C=O). H-NMR (DMSO-d
7.17-7.22 (m, 2H, Ar), 7.41 (d, J = 7.92 Hz, 2H), 9.40 (s,
NH), 9.68 (d, NH), 10.44 (d, NH); C-NMR (DMSO-d
6
3
): δ (ppm) 3.46 (s, 3H, OCH ),
1
3
6
) : δ
ppm) 39.5, 53.6, 108.3, 115.7, 116.6, 121.0, 121.4, 121.8,
3.70 (s, 3H, COOCH ), 6.93 (d, J = 9.15, Hz, 2H), 7.11 (t, J =
3
(
7.8 Hz, 1H), 7.53 (t, J = 7, 8 Hz, 1H,), 7.61 (d, J = 9.15 Hz,
2H), 7.82 (d, J = 7 Hz, 1H), 8.10 (d, J = 8 Hz, 1H), 10.36 (s,
124.7, 126.3, 127.8, 138.9, 160.2, 165.5, 165.71. Anal. Calcd
1
3
for C17
H
16
4 3
N O : C, 62.95; H, 4.97; N, 17.27. Found: C, 63.17;
CONH); C-NMR (DMSO-d
119.0, 121.4, 121.7, 122.1, 128.2, 1301.0, 131.6, 138.1, 153.0,
55.5, 166.3.
General procedure for synthesis of 5a-d: A mixture of
4a-d) (0.1 mol) and hydrazine hydrate (99 %, 0.4 mol) in
6
): δ (ppm ) 20.1, 54.7, 113.3,
H, 5.05; N, 17.53.
1
General procedure for synthesis of [2-arylcarbamoyl
phenyl]carbamic acid methyl ester (4a-d)
(
43
Conventional method (A) : Solution of m-chloroper-
benzoic acid (m-CPBA, 2.4 mmol) in the methanol (25 mL)
was added dropwise to a vigorously stirred solution of the
absolute ethanol (10 mL) was subjected to microwave irra-
diation at 80 °C/400 watts for 2 min. After completion of the
reaction mixture the crude product was treated with hot ethanol
to afford the pure products 5a-d.
3
imine (3a-d) (2 mmol) in CH OH (25 mL) at 0 °C. After 3 h at
0
°C, the reaction mixture was allowed to warm up to room
N-[2-(Phenylcarbamoyl)phenyl]hydrazinecarbo-
xamide (5a): The product was obtained as a white powder,
temperature and continued stirring for 24 h. The solvent was
removed and the crude product was recrystallized from
methanol.
-1
m.p.: 200-202 °C; yield 99 %. IR (KBr, νmax, cm ): 3323, 3187
1
(NH), 1726, 1646, 1591 (C=O). H-NMR (DMSO-d
5.50 (s, 2H, NH ), 7.19-7.23 (m, 7H), 7.65 (t, J = 7.32 Hz,
1H,), 7.94 (d, J = 7.36 Hz, 1H), 11.06 (s, CONH); C-NMR
(DMSO-d ): δ (ppm) 113.9, 115.7, 115.9, 123.0, 123.2, 127.4,
127.5, 135, 135.1, 138.7, 149.0, 159.7. Anal. calcd for
: C, 62.21; H, 5.22; N, 20.73. Found: C, 62.50; H,
5.29; N, 20.94.
N-[2-(p-Tolylcarbamoyl)phenyl]hydrazinecarbo-
6
): δ (ppm)
Microwave method (B): A solution of the imine (3a-d)
2
13
(
3
2 mmol) and m-CPBA (2.4 mmol) in CH OH (5 mL) was
microwave irradiated for 5 min at 80 °C/600 W. The crude
product washed with cooled methanol to afford the pure
products 4a-d.
6
14 14 4 2
C H N O
Methyl-2-(phenylcarbamoyl)phenylcarbamate (4a):
The product was obtained as a white crystal, m.p.:176-178 °C;
43
yield %: 50 % (method A); 78 % (method B). (lit. m.p. 183-
xamide (5b): The product was obtained as a white powder,
-1
m.p.: 260-262 °C; yield 80 %. IR (KBr, νmax, cm ): 3324, 3128
-1
1
1
84 °C; yield 83 %). IR (KBr, νmax, cm ): 3244, 3200 (NH),
1
1
(NH), 1728, 1660, 1613 (C=O). H-NMR (DMSO-d
731, 1652 (C=O). H-NMR (DMSO-d
), 7.13 (t, J = 7.71 Hz, 1H), 7.19 (t, J = 7.68 Hz,1H),
.36 (t, J = 8.04 Hz, 2H), 7.54 (t, J = 8.79 Hz, 1H), 7.71 (d, J
8.04 Hz, 2H), 7.81 (d, J = 8.07 Hz, 1H), 8.05 (d, J = 8.43
6
):δ (ppm) 3.65 (s, 3H,
6
): δ (ppm)
COOCH
3
3
2.37 (s, 3H, CH ), 7.18 (d, J = 8.08 Hz, 2H) 7.21-7.24 (m,
7
2H), 7.55 (t, J = 7.36, 8.04 Hz, 1H), 7.28 (d, J = 8.04 Hz, 2H),
7.70 (t, J = 8.0 Hz, 1H), 7.93 (d, J = 8.08 Hz, 1H), 11.54 (s,
13
CONH). C-NMR (DMSO-d ): δ (ppm) 21.3, 114.9, 115.5,
6
=
1
3
Hz, 1H), 10.16, (s, CONH), 10.46 (s, CONH); C-NMR
DMSO-d ):δ (ppm) 51.4, 119.2, 120.2, 121.7, 121.8, 123.5,
28, 128.2, 131.5, 137.7, 137.9, 152.9, 166.4.
Methyl 2-(p-tolylcarbamoyl)phenylcarbamate (4b):
The product was obtained as a white crystal, m.p.:168-170 °C;
(
6
123.0, 128.1, 129.3, 129.9, 133.6, 135.7, 138.0,140.4, 150.8,
162.8.Anal. Calcd for C15 : C, 63.37; H, 5.67; N, 19.71.
1
16 4 2
H N O
Found: C, 63.66; H, 5.80; N, 19.96.
N-[2-(4-Bromophenylcarbamoyl)phenyl]hydrazine-
carboxamide (5c): The product was obtained as a white
43
yield: 40 % (method A); 70 % (method B) (lit. m.p. 172 °C;
-1
-1
powder, m.p.: 278-280 °C; yield 82 %. IR (KBr, νmax, cm ):
yield 76 %). IR (KBr, νmax, cm ): 3335, 3249 (NH), 1709,
1
656, 1602 (C=O). H-NMR (DMSO-d
1
3427 (NH), 1722, 1620.9 (C=O). H-NMR (DMSO-d
1
CH ), 3.66 (s, 3H, COOCH ), 7.16-7.21 (m, 3H), 7.55 (t, J =
6
):δ (ppm) 2.29 (s, 3H,
6
): δ
(ppm) 7.22-7.25 (m, 2H), 7.32 (d, J = 8.04 Hz, 2H), 7.68-7.73
3
3
13
8
.04 Hz, 1H), 7.60 (d, J = 8.04 Hz, 2H), 7.82 (d, J = 7.36 Hz,
H), 8.09 (d, J = 8.08 Hz, 1H), 10.25 (s, CONH), 10.40 (s,
(m, 3H), 7.94 (d, J = 8.08 Hz, 1H), 11.58 (s, CONH); C-NMR
(DMSO-d ): δ (ppm) 115.8, 118.5, 121.8, 123.1, 128.13, 132.0,
132.4, 135.7, 135.8, 140.4, 150.6, 162.7. Anal. Calcd for
Br (349: C, 48.16; H, 3.75; N, 16.05. Found: C,
48.00; H, 3.86; N, 16.32
1
6
13
CONH); C-NMR (DMSO-d
6
):δ (ppm) 21.1, 52.6, 120.2,
21.4, 122.8, 129.34, 129.6, 132.7, 133.8, 136.6, 139.0, 154.1,
67.5.
1
1
14 13 4 2
C H N O