C, 68.92; H, 4.47; N, 18.27%. Found: C, 68.82; H, 4.51; N,
8.11%.
¢-Amino-5-chloro-3¢-methyl-2-oxo-1¢-phenyl-1¢H-spiro[in-
J = 7.5 Hz, 1H), 6.84 (d, J = 6.9 Hz, 1H), 7.09 (t, J = 7.5 Hz,
1H), 7.72 (br s, 2H, NH , D O exchangeable) 10.19 (s, 1H, NH,
O exchangeable). C NMR (DMSO-d , 75 MHz): d 13.5,
1
2
2
1
3
6
D
2
6
doline-3,4¢-pyrano[2,3-c]pyrazole]-5¢-carbonitrile (5i). White
27.1, 28.2, 32.3, 47.1, 51.1, 59.3, 76.7, 108.6, 113.5, 120.9, 122.6,
◦
crystalline solid (yield: 96%); mp: 232–234 C. nmax (KBr):
127.5, 136.7, 144.3, 159.1, 160.8, 162.8, 168.1, 180.4, 195.3. MS
-
1
1
+
3
(
1
2
1
440, 3264,3172, 2196, 1698, 1652, 1576, 1174 cm . H NMR
DMSO-d , 300 MHz): d 1.58 (s, 3H, CH ), 6.96 (d, J = 8.4 Hz,
H), 7.34–7.42 (3H, m), 7.52 (t, J = 8.2 Hz, 2H), 7.63 (br s,
H, NH , D O exchangeable), 7.78 (d, J = 8 Hz, 2H), 10.89 (s,
H, NH, D O exchangeable). C NMR (DMSO-d
(m/z): 383 [M+H] . Anal. calcd for C21
H
22
N
2
5
O : C, 65.96; H,
6
3
5.80; N, 7.33%. Found: C, 65.72; H, 6.01; N, 7.47%.
Ethyl 2-amino-5¢,7,7-trimethyl-2¢,5-dioxo-5,6,7,8-tetrahydro-
spiro[chromene-4,3 indoline]-3-carboxylate (7b). White crys-
2
2
1
3
◦
2
6
, 75 MHz):
talline solid (yield: 95%); mp: 282–284 C. nmax (KBr): 3402,
-
1
1
d 11.8, 47.9, 56.4, 96.5, 109.6, 118.1, 120.2, 125.4, 126.6, 129.5,
29.6, 131.7, 132.3, 137.3, 139.2, 144.1, 145.0, 161.0, 177.5. MS
3280, 3209, 2930, 1696, 1652, 1614, 1220 cm . H NMR
(DMSO-d , 300 MHz): d 0.82 (t, J = 7.2 Hz, 3H, CH ), 0.99 (s,
3H, CH ), 1.02 (s, 3H, CH ), 2.04 (d, J = 16.2 Hz, 1H, CH), 2.19
(d, J = 16.2 Hz, 1H, CH), 2.2 (s, 3H, CH ), 2.56 (d, J = 6.2 Hz,
2H, CH ), 3.68 (q, J = 7.2 Hz, 2H, CH ), 6.66 (d, J = 7.6 Hz,
1H), 6.75 (s, 1H), 6.84 (d, 1H, J = 6.9 Hz), 7.74 (br s, 2H, NH
1
6
3
+
(
m/z): 404 [M+H] . Anal. calcd for C21
H
14ClN
5
O
2
: C, 62.46; H,
.49; N, 17.34%. Found: C, 62.48; H, 3.47; N, 17.35%.
¢-Amino-5-bromo-3¢-methyl-2-oxo-1¢-phenyl-1¢H-spiro[in-
3
3
3
3
6
2
2
doline-3,4¢-pyrano[2,3-c]pyrazole]-5¢-carbonitrile (5j). White
2
,
◦
13
crystalline solid (yield: 94%); mp: 242–244 C. nmax (KBr):
D
2
O exchangeable) 10.21 (s, 1H, NH, D
2
O exchangeable). C
-
1
1
3
(
1
NH
436, 3269, 3168, 2198, 1706, 1650, 1576, 1168 cm . H NMR
DMSO-d , 300 MHz): d 1.58 (s, 3H, CH ), 6.91 (d, J = 7.6 Hz,
H), 7.42–7.54 (4H, m), 7.28 (t, J = 7.9 Hz, 1H), 7.64 (br s, 2H,
, D O exchangeable), 7.79 (d, J = 7.8 Hz, 2H), 10.90 (s,
H, NH, D
d 12.1, 47.9, 56.4, 96.7,110.6, 118.2, 120.9, 125.8, 126.6, 129.5,
29.6, 131.7, 132.3, 137.3, 139.2, 144.1, 145.0, 161.0, 178. MS
NMR (DMSO-d , 75 MHz): d 13.5, 27.2, 21.1, 28.5, 32.3, 47.2,
6
6
3
51.4, 59.2, 76.8, 108.6, 113.7, 121.1, 122.6, 127.5, 136.7, 144.4,
+
159.2, 160.8, 162.8, 168.8, 180.5, 195.4. MS (m/z): 397 [M+H] .
2
2
Anal. calcd for C22
H
24
N
2
5
O : C, 66.65; H, 6.10; N, 7.07%. Found:
1
3
1
2
O exchangeable). C NMR (DMSO-d , 75 MHz):
6
C, 66.82; H, 6.01; N, 7.27%.
Ethyl 2-amino-5¢-chloro-7,7-trimethyl-2¢,5-dioxo-5,6,7,8-tet-
rahydrospiro[chromene-4,3-indoline]-3-carboxylate (7c). White
1
+
◦
(
m/z): 448 [M+H] . Anal. calcd for C21
H
14BrN
5
O
2
: C, 56.27; H,
.15; N, 15.62%. Found: C, 56.17; H, 3.21; N, 15.60%.
¢-Amino-3¢-methyl-5-nitro-2-oxo-1¢-phenyl-1¢H-spiro[indo-
crystalline solid (yield: 93%); mp: 292–294 C. nmax (KBr):
-
1
1
3
3401, 3284, 3218, 2935, 1698, 1658, 1610, 1226 cm . H NMR
(DMSO-d , 300 MHz): d 0.82 (t, J = 7.2 Hz, 3H, CH ), 0.98
(s, 3H, CH ), 1.01 (s, 3H, CH ), 2.07 (d, J = 16.4 Hz, 1H, CH),
2.2 (d, J = 16.4 Hz, 1H, CH), 2.56 (d, J = 6.2 Hz, 2H, CH ),
3.67 (q, J = 7.4 Hz, 2H, CH ), 6.68 (d, J = 7.4 Hz, 1H), 6.76
(s, 1H), 6.85 (d, J = 7.2 Hz, 1H), 7.74 (br s, 2H, NH , D
O exchangeable) C NMR
, 75 MHz): d 13.6, 27.2, 28.5, 32.3, 47.2, 51.4, 59.2,
6
6
3
line-3,4¢-pyrano[2,3-c]pyrazole]-5¢-carbonitrile (5k). White crys-
3
3
◦
talline solid (yield: 95%); mp: 226–228 C. nmax (KBr): 3446,
2
-
1
1
3
(
1
7
269, 3176, 2208, 1710, 1650, 1576, 1178 cm . H NMR
DMSO-d , 300 MHz): d 1.59 (s, 3H, CH ), 7.12 (d, J = 8.4 Hz,
H), 7.38–7.55 (m, 3H), 7.68 (br s, 2H, NH , D O exchangeable),
.78 (m, 2H), 7.98 (d, J = 6.8 Hz, 2H), 11.44 (s, 1H, NH, D
2
6
3
2
2
O
1
3
2
2
exchangeable) 10.19 (s, 1H, NH, D
(DMSO-d
2
2
O
6
1
3
exchangeable). C NMR (DMSO-d
5
1
6
, 75 MHz): d 12.3, 47.9,
6.4, 96.5, 109.6, 118.1, 120.2, 125.4, 126.6, 132.0, 132.6, 131.7,
34.3, 137.3, 139.2, 144.9, 145.0, 161.2, 178.8. MS (m/z): 415
: C, 60.87; H, 3.41; N,
0.28%. Found: C, 60.76; H, 3.47; N, 20.29%.
¢-Amino-3¢,5,7-trimethyl-2-oxo-1¢-phenyl-1¢H-spiro[indo-
76.8, 108.6, 113.7, 116.9, 121.9, 128.4, 136.9, 145.8, 159.2, 160.4,
+
162.8, 168.7, 180.6, 195.3. MS (m/z): 417 [M+H] . Anal. calcd
for C21
H
21ClN
2
O
5
: C, 60.51; H, 5.08; N, 6.72%. Found: C, 60.72;
+
[
M+H] . Anal. calcd for C21
H
14
N
6
O
4
H, 5.01; N, 6.55%.
2
Ethyl 2-amino-5¢-bromo-7,7-dimethyl-2¢,5-dioxo-5,6,7,8-tet-
rahydrospiro[chromene-4,3-indoline]-3-carboxylate (7d). White
6
◦
line-3,4¢-pyrano[2,3-c]pyrazole]-5¢-carbonitrile (5l). White crys-
crystalline solid (yield: 98%); mp: 296– 298 C. nmax (KBr):
◦
-1
1
talline solid, (yield 95%); 218–220 C nmax (KBr): 3428, 3264,
3398, 3282, 3209, 2934, 1700, 1662, 1612, 1223 cm . H NMR
(DMSO-d , 300 MHz): d 0.82 (t, J = 7.2 Hz, 3H, CH ), 0.99
(s, 3H, CH ), 1.01 (s, 3H, CH ), 2.06 (d, J = 16.4 Hz, 1H, CH),
2.2 (d, J = 16.4 Hz, 1H, CH), 2.54 (d, J = 6.2 Hz, 2H, CH ),
3.68 (q, J = 7.2 Hz, 2H, CH ), 6.67 (d, J = 7.2 Hz, 1H), 6.76
(s, 1H), 6.86 (d, J = 7.4 Hz, 1H), 7.72 (br s, 2H, NH , D
O exchangeable) C NMR
, 75 MHz): d 13.3, 27.4, 28.5, 32.6, 47.2, 51.5, 59.2,
-
1
1
3
3
CH
171, 2198, 1700, 1652, 1564, 1155 cm . H NMR (DMSO-d
00 MHz): d 1.57 (s, 3H, CH ), 2.24 (s, 3H, CH ), 2.33 (s, 3H,
), 6.84 (s, 1H), 7.02 (s, 1H), 7.39 (t, J = 7.6 Hz, 1H), 7.48 (t,
J = 8.0 Hz, 2H), 7.58 (br s, 2H, NH , D O exchangeable), 7.64 (d,
J = 7.6 Hz, 2H), 10.68 (s, 1H, NH, D O exchangeable). C NMR
DMSO-d , 75 MHz): d 11.9, 19.2, 20.6, 47.9, 56.8, 96.3, 109.6,
18.4, 120.2, 125.4, 126.6, 129.5, 129.8, 131.6, 132.3, 137.3,
6
,
6
3
3
3
3
3
3
2
2
2
2
1
3
2
2
2
O
1
3
(
1
1
6
exchangeable) 10.20 (s, 1H, NH, D
(DMSO-d
2
6
+
39.7, 143.9, 145.0, 161.0, 177. MS (m/z): 398[M+H] . Anal.
: C, 69.51; H, 4.82; N, 17.62%. Found: C,
9.47; H, 4.80; N, 17.56%.
Ethyl 2-amino-7,7-dimethyl-2¢,5-dioxo-5, 6,7, 8-tetrahydro-
76.3, 108.6, 111.7, 118.9, 121.9, 128.5, 136.9, 145.8, 159.7, 161.4,
+
calcd for C23
6
H
19
N
5
O
2
161.9, 168.7, 181.1, 195.6. MS (m/z): 462 [M+H] . Anal. calcd
for C21
H
21BrN
2
O
5
: C, 54.68; H, 4.59; N, 6.07%. Found: C, 54.85;
H, 4.48; N, 5.92%.
spiro[chromene-4,3-indoline]-3-carboxylate (7a). White crys-
Ethyl 2-amino-7,7-dimethyl-5¢-nitro-2¢,5-dioxo-5,6,7,8-tet-
rahydrospiro[chromene-4,3-indoline]-3-carboxylate (7e). White
◦
talline solid (yield: 96%); mp: 278–280 C. nmax (KBr): 3398,
-
1
1
◦
3
(
(
2
3
276, 3212, 2925, 1698, 1652, 1610, 1221 cm . H NMR
DMSO-d , 300 MHz): d 0.82 (t, J = 7.2 Hz, 3H, CH ), 0.98
s, 3H, CH ), 1.01 (s, 3H, CH ), 2.04 (d, J = 16.2 Hz, 1H, CH),
.18 (d, J = 16.2 Hz, 1H, CH), 2.55 (d, J = 6.2 Hz, 2H, CH ),
.69 (q, J = 7.2 Hz, 2H, CH ), 6.65 (d, J = 7.5 Hz, 1H), 6.76 (t,
crystalline solid, (Yield: 93%); mp: 276– 278 C. nmax (KBr):
-
1
1
6
3
3406, 3288, 3212, 2935, 1702, 1662, 1618, 1225 cm . H NMR
(DMSO-d , 300 MHz): d 0.83 (t, J = 7.4 Hz, 3H, CH ), 0.99 (s,
3H, CH ), 1.02 (s, 3H, CH ), 2.07 (d, J = 16.2 Hz, 1H, CH), 2.2
(d, J = 16.2 Hz, 1H, CH), 2.58 (d, J = 6.8 Hz, 2H, CH ), 3.71
3
3
6
3
2
3
3
2
2
This journal is © The Royal Society of Chemistry 2011
Green Chem., 2011, 13, 2135–2145 | 2143