9
1 (58) (Calc. for C H ClN : C, 69.00; H, 4.96; N, 11.49;
58.37; H, 4.22; N, 11.54. C H N O requires C, 58.54; H, 4.09;
12 10 2 4
14
12
2
Found: C, 69.23; H, 5.12; N, 11.37%).
N, 11.38%).
1
3
-Methyl-N -(4-methylphenyl)benzamidine 3l. Mp 88–90 ЊC;
Ethyl 2-amino-6,7-methylenedioxyquinoline-3-carboxylate 5g.
Mp 204–205 ЊC (from EtOAc); νmax/cm 3440 (NH ), 3280
Ϫ1
Ϫ1
νmax/cm 3490, 3300, 1650, 1580, 1510, 1380, 1240, 1100, 1020,
20, 860, 790, 710; δ 2.26 (3H, s, CH ), 2.33 (3H, s, CH ), 5.00
2
9
(NH ), 1680 (CO); δ 1.41 (3H, t, J 7.1, CH ), 4.38 (2H, q, J 7.1,
H
3
3
2
H
3
(
(
1
2H, br s, NH, C᎐NH), 6.75–7.85 (8H, m, ArH); m/z 225
M ϩ 1, 27), 224 (M , 94), 209 (11), 133 (9), 118 (30), 107 (100),
OCH ), 6.03 (2H, s, OCH O), 6.56 (2H, br s, NH ), 6.90 (1H, s,
᎐
2
2
2
ϩ
ArH), 6.95 (1H, s, ArH), 8.46 (1H, s, hetero ArH); m/z 261
ϩ
06 (75), 91 (66), 77 (23) (Calc. for C H N : C, 80.32; H, 7.19;
(M ϩ 1, 20), 246 (M , 100), 232 (6), 215 (9), 214 (11), 188 (72),
15
16
2
N, 12.49; Found: C, 80.54; H, 7.03; N, 12.52%).
161 (7), 160 (20) (Found: C, 60.25; H, 4.51; N, 10.66.
C H N O requires C, 60.00; H, 4.64; N, 10.76%).
1
3
-Methyl-N -phenylbenzamidine 3m. Mp 104–106 ЊC; νmax/
13
12
2
4
Ϫ1
cm 3460, 3320, 1640, 1590 1490, 1390, 1240, 1170, 1020, 840,
00, 770, 720, 695; δH 2.37 (3H, s, CH ), 5.20 (2H, br s, NH,
Isopropyl 2-amino-6,7-methylenedioxyquinoline-3-carboxyl-
Ϫ1
8
ate 5h. Mp 215–217 ЊC (from EtOH); νmax/cm 3380 (NH ),
3
2
C᎐NH), 6.90–7.80 (9H, m, ArH); m/z 211 (M ϩ 1, 19), 210
3200 (NH ), 1680 (CO); δH 1.38 (6H, d, J 6.2, 2 × CH ), 5.26
(1H, J 6.2, OCH), 6.03 (2H, s, OCH O), 6.54 (2H, br s, NH ),
2 2
᎐
2
3
ϩ
(
M , 100), 195 (10), 194 (29), 118 (33), 93 (92), 91 (42), 77 (8)
(
7
Calc. for C H N : C, 79.97; H, 6.71; N, 13.32; Found: C,
9.86; H, 6.87; N, 13.38%).
6.91 (1H, s, ArH), 6.95 (1H, s, ArH), 8.44 (1H, s, hetero ArH);
m/z 275 (M ϩ 1, 6), 274 (M , 94), 232 (9), 215 (11), 214 (9), 188
14
14
2
ϩ
(
100), 187 (38), 161 (6), 160 (25) (Found: C, 61.42; H, 5.07;
General procedure for the synthesis of 2-aminoquinoline-3-
carboxylic acid derivatives 5
A solution of nitrocyano olefins 4 (1 mmol) in THF (3 ml) was
N, 10.32. C H N O requires C, 61.31; H, 5.14; N, 10.21%).
14
14
2
4
n-Propyl 2-amino-6,7-methylenedioxyquinoline-3-carboxylate
Ϫ1
5i. Mp 157–158 ЊC (from EtOH); νmax/cm 3400 (NH ), 3150
2
added carefully to SmI (6 mmol) at room temperature under
(NH ), 1690 (CO); δ 1.03 (3H, t, J 7.2, CH ), 1.25–1.65 (2H, m,
2
2
H
3
nitrogen atmosphere. The mixture was stirred at room temp.
CH ), 4.26 (2H, t, J 6.6, OCH ), 6.01 (2H, s, OCH O), 6.50 (2H,
2
2
2
under N atmosphere until the reaction was complete. The reac-
br s, NH ), 6.88 (1H, s, ArH), 6.92 (1H, s, ArH), 8.42 (1H, s,
hetero ArH); m/z 275 (M ϩ 1, 6), 274 (M , 92), 232 (10), 215
2
2
ϩ
tion mixture was poured into 10% K CO (50 ml) and extracted
2
3
with CHCl (4 × 30 ml). The combined extracts were washed
(12), 214 (10), 188 (100), 187 (39), 161 (6), 160 (25) (Found: C,
61.51; H, 5.03; N, 10.31. C H N O requires C, 61.31; H, 5.14;
3
with saturated aqueous Na S O (15 ml), saturated aqueous
2
2
3
14 14
2
4
NaCl (15 ml), and dried over anhydrous Na SO . After evapor-
N, 10.21%).
2
4
ating the solvent under reduced pressure, the crude product was
purified by preparative TLC on silica gel using ethyl acetate–
cyclohexane (1:1) as eluent.
Butyl 2-amino-6,7-methylenedioxyquinoline-3-carboxylate 5j.
Ϫ1
Mp 148–149 ЊC (from EtOH); νmax/cm 3480 (NH ), 3200
2
(NH ), 1680 (CO); δH 1.00 (3H, t, J 6.8, CH ), 1.21–1.78 (4H,
2
3
Methyl 2-aminoquinoline-3-carboxylate 5a. Mp 139–140 ЊC
m, CH CH ), 4.32 (2H, t, J 6.4, OCH ), 6.02 (2H, s, OCH O),
2
2
2
2
24
Ϫ1
(
(
from EtOH, lit., 140–141 ЊC); νmax/cm 3380 (NH ), 3200
6.55 (2H, br s, NH ), 6.89 (1H, s, ArH), 6.93 (1H, s, ArH), 8.42
2
2
ϩ
NH ), 1700 (CO); δ 3.93 (3H, s, OCH ), 6.80 (2H, br s, NH ),
(1H, s, hetero ArH); m/z 289 (M ϩ 1, 17), 288 (M , 90), 232
2
H
3
2
7
.03–7.68 (4H, m, ArH), 8.66 (1H, s, hetero ArH).
Ethyl 2-aminoquinoline-3-carboxylate 5b. Mp 134–135 ЊC
(11), 216 (7), 215 (11), 188 (100), 187 (31), 161 (8), 160 (23)
(Found: C, 62.37; H, 5.68; N, 9.60. C H N O requires C,
62.49; H, 5.59; N, 9.72%).
15
16
2
4
24
Ϫ1
(
from EtOH, lit., 135 ЊC); νmax/cm 3450 (NH ), 3180 (NH ),
2
2
1
700 (CO); δH 1.41 (3H, t, J 7.2, CH ), 4.40 (2H, q, J 7.2,
3
OCH ), 6.68 (2H, br s, NH ), 7.10–7.82 (4H, m, ArH), 8.69
2
2
ϩ
(
(
1H, s, hetero ArH); m/z 217 (M ϩ 1, 14), 216 (M , 100), 171
18), 170 (32), 144 (75), 143 (65), 116 (36), 89 (23).
Acknowledgements
We are grateful to the National Natural Science Foundation
of China (Project No. 294938004 and 29672007) and the
Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Chinese Academy of Science for
financial support.
Isopropyl 2-aminoquinoline-3-carboxylate 5c. Mp 160–161 ЊC
Ϫ1
(
from EtOH); νmax/cm 3415 (NH ), 3150 (NH ), 1690 (CO);
2
2
δH 1.41 (6H, d, J 6.2, 2 × CH ), 5.28 (1H, J 6.2, OCH), 6.66
3
(
2H, br s, NH ), 7.24–7.70 (4H, m, ArH), 8.65 (1H, s, hetero
2
ϩ
ArH); m/z 231 (M ϩ 1, 15), 230 (M , 81), 188 (5), 171 (14),
44 (100), 143 (51), 117 (21), 116 (32) (Found: C, 67.62;
H, 6.20; N, 12.25. C H N O requires C, 67.78; H, 6.13;
1
13
14
2
2
References
N, 12.16%).
1
(a) P. Girard, J. L. Namy and H. B. Kagan, J. Am. Chem. Soc., 1980,
02, 2693; (b) J. L. Namy, P. Girard and H. B. Kagan, Nouv.
J. Chim., 1977, 1, 5; (c) H. B. Kagan, New J. Chem., 1990, 14, 453.
2 For reviews see: (a) G. A. Molander and C. R. Harris, Chem. Rev.,
1996, 96, 307; (b) F. Matsuda, Synth. Org. Chem. Jpn., 1995, 53, 987;
(c) G. A. Molander, Org. React., 1994, 46, 221; (d) T. Imamota,
Lanthanides in Organic Synthesis, Academic Press, London, 1994;
ch. 4; (e) M. Shibasaki and H. Sasai, Synth. Org. Chem. Jpn., 1993,
1, 972; ( f ) G. A. Molander, Chem. Rev., 1992, 92, 29; (g) D. P.
Curran, T. L. Fevig, C. P. Jasperse and M. J. Totleben, Synlett, 1992,
43; (h) J. A. Soderquist, Aldrichim. Acta, 1991, 24, 15; (i) G. A.
Molander, Comprehensive Organic Synthesis, ed. B. M. Trost and
I. Fleming, Pergamon, Oxford, vol. 1, 1991, 251; (j) H. B. Kagan,
New J. Chem., 1990, 14, 453; (k) G. A. Molander, in The Chemistry
of the Metal-Carbon Bond; ed. F. R. Hartly, Wiley, Chichester,
n-Propyl 2-aminoquinoline-3-carboxylate 5d. Mp 114–115 ЊC
1
Ϫ1
(
from EtOH); νmax/cm 3400 (NH ), 3280 (NH ), 1690 (CO);
2
2
δ 1.01 (3H, t, J 7.2, CH ), 1.40–1.88 (2H, m, CH ), 4.29 (2H, t,
H
3
2
J 6.6, OCH ), 6.86 (2H, br s, NH ), 7.24–7.69 (4H, m, ArH),
2
2
ϩ
8
.65 (1H, s, hetero ArH); m/z 231 (M ϩ 1, 17), 230 (M , 73),
1
88 (5), 171 (13), 144 (100), 143 (48), 117 (23), 116 (34)
(
Found: C, 67.52; H, 6.21; N, 12.30. C H N O requires C,
13 14 2 2
5
6
7.78; H, 6.13; N, 12.16%).
Butyl 2-aminoquinoline-3-carboxylate 5e. Mp 104–106 ЊC
9
Ϫ1
(
from EtOH); νmax/cm 3380 (NH ), 3150 (NH ), 1690 (CO);
2
2
δH 1.00 (3H, t, J 6.9, CH ), 1.44–1.68 (4H, m, CH CH ), 4.35
3
2
2
(
2H, t, J 6.4, OCH ), 6.79 (2H, br s, NH ), 7.20–7.71 (4H, m,
2 2
ϩ
ArH), 8.66 (1H, s, hetero ArH); m/z 245 (M ϩ 1, 11), 244 (M ,
8), 188 (6), 171 (15), 144 (100), 143 (52), 117 (23), 116 (35)
Found: C, 68.95; H, 6.70; N, 11.38. C H N O requires C,
1
989, vol. 5, ch. 8; (l) H. B. Kagan, M. Sasaki and J. Collin, Pure
Appl. Chem., 1988, 60, 1725; (m) H. B. Kagan and J. L. Namy,
Tetrahedron, 1986, 42, 6573.
6
(
14
16
2
2
6
8.83; H, 6.60; N, 11.47%).
3 (a) Y. Zhang and R. Lin, Synth. Commun., 1987, 17, 329; (b)
J. Souppe, L. Danon, J. L. Namy and H. B. Kagan, J. Organomet.
Chem., 1983, 250, 227; (c) T. Mukaiyama, K. Yoyozu, K. Kato and
T. Yamada, Chem. Lett., 1992, 181.
A. S. Kende and J. S. Mendoza, Tetrahedron Lett., 1991, 32, 1699.
M. J. Burk and J. E. Feaster, J. Am. Chem. Soc., 1992, 114, 6266.
(a) N. R. Natale, Tetrahedron Lett., 1982, 23, 5009; (b) L. Benati,
P. C. Monievecohi, D. Nanni, P. Spagnolo and M. Volta,
Methyl 2-amino-6,7-methylenedioxyquinoline-3-carboxylate
Ϫ1
5
f. Mp 225–227 ЊC (from EtOH); νmax/cm 3400 (NH ), 3150
2
(
NH ), 1680 (CO); δ 3.93 (3H, s, OCH ), 6.05 (2H, s, OCH O),
2 H 3 2
4
5
6
6
.67 (2H, br s, NH ), 6.92 (1H, s, ArH), 6.99 (1H, s, ArH), 8.49
2
ϩ
(
(
1H, s, hetero ArH); m/z 247 (M ϩ 1, 21), 246 (M , 44), 215
27), 214 (45), 188 (44), 187 (100), 161 (12), 160 (30) (Found: C,
J. Chem. Soc., Perkin Trans. 1, 1998
2901