A. Le Pera et al. / Tetrahedron 62 (2006) 6100–6106
6105
d ꢀ14.68. Anal. Calcd for C7H8FN: C, 67.19; H, 6.44; F,
References and notes
15.18; N, 11.19. Found: C, 67.01; H, 6.41; F, 15.23; N,
11.16. IR (liquid film): nmax 3410, 3061, 2935, 1610, 1596,
1. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.;
Wiley: New York, NY, 1978; Vol. 2, pp 309–321.
1509, 1458, 1321 cmꢀ1
.
2. (a) Gibson, M. S. The Chemistry of the Amino Group; Patai, S.,
Ed.; Interscience: London, UK, 1968; Chapter 2, pp 45–62; (b)
Willson, F. G.; Wheeler, T. S.; Organic Syntheses; Wiley: New
York, NY, 1941; Vol. 1, p 102.
4.5.1.6. N-Methyl-o-iodoaniline29 (4f). Yield 92%, dark
oil. GC–MS (EI): m/z 233 [Mꢃ+, 98%]; 232 (100); 203 (3);
127 (10); 106 (25); 105 (37); 104 (43); 91 (17); 79 (29);
1
77 (82); 64 (14); 63 (19). H NMR (CDCl3): d 2.92 (d,
3. (a) Huh, K.-T.; Tsuji, Y.; Kobayashi, M.; Okuda, F.; Watanabe,
Y. Chem. Lett. 1988, 449–452; (b) Watanabe, Y.; Tsuji, Y.; Ige,
H.; Ohsugi, Y.; Ohta, T. J. Org. Chem. 1984, 49, 3359–3363; (c)
Watanabe, Y.; Tsuji, Y.; Ohsugi, Y. Tetrahedron Lett. 1981, 22,
2667–2670; (d) Grigg, R.; Mitchell, T. R. B.; Sutthivaiyakit, S.;
Tongpenyai, N. J. Chem. Soc., Chem. Commun. 1981, 611–
612; (e) Matsuhashi, H.; Arata, K. Bull. Chem. Soc. Jpn.
1991, 64, 2605–2606; (f) Jiang, Y.-L.; Hu, Y.-Q.; Feng, S.-Q.;
Wu, J.-S.; Wu, Z.-W.; Yuan, Y.-C. Synth. Commun. 1996, 26,
161–164.
4. Hayat, S.; Atta-ur-Rahman; Choudhary, M. I.; Khan, K. M.;
Schumann, W.; Bayer, E. Tetrahedron 2001, 57, 9951–9957.
5. (a) Badet, B.; Julia, M.; Ramirez-Munoz, M. Synthesis 1980,
926–929; (b) Ono, T.; Umemoto, T. J. Fluorine Chem. 1996,
80, 163–166; (c) Barton, D. H. R.; Ozbalik, N.; Ramesh, M.
Tetrahedron Lett. 1988, 29, 857–860.
6. (a) Selva, M.; Tundo, P.; Perosa, A. J. Org. Chem. 2001, 66,
677–680; (b) Fu, Z.-H.; Ono, Y. Catal. Lett. 1993, 22, 277–
281; (c) Hari Prasad Rao, P. R.; Massiani, P.; Barthomeuf, D.
Catal. Lett. 1995, 31, 115–120; (d) Selva, M.; Bomben, A.;
Tundo, P. J. Chem. Soc., Perkin Trans. 1 1997, 1041–1045;
(e) Onaka, M.; Ishikawa, K.; Izumi, Y. Chem. Lett. 1982,
1783–1786; (f) Onaka, M.; Umezono, A.; Kawai, M.; Izumi,
Y. J. Chem. Soc., Chem. Commun. 1985, 1202–1203.
7. (a) Santhanalakshmi, J.; Raja, T. Appl. Catal., A 1996, 147, 69–
80; (b) Valot, F.; Fache, F.; Jacquot, R.; Spagnol, M.; Lemaire,
M. Tetrahedron Lett. 1999, 40, 3689–3692.
3H, N–CH3, J¼4.8 Hz); 4.25 (br s, 1H, N–H); 6.46–6.62
(m, 2H, Ar–H); 7.25–7.32 (m, 1H, Ar–H); 7.68–7.73 (m,
1H, Ar–H). 13C NMR (CDCl3): d 29.97; 85.14; 109.98;
118.45; 129.47; 138.83; 148.11. Anal. Calcd for C7H8IN:
C, 36.08; H, 3.46; I, 54.45; N, 6.01. Found: C, 36.21; H,
3.48; I, 54.67; N, 6.05. IR (liquid film): nmax 3419, 3052,
2931, 1612, 1600, 1515, 1455, 1319 cmꢀ1
.
4.5.1.7. N-Methyl-p-nitroaniline30 (4g). Yield 92%, yel-
low solid, mp 149–151 ꢁC. GC–MS (EI): m/z 152 [Mꢃ+,
100%]; 122 (53); 106 (33); 94 (17); 79 (46); 78 (30); 77
1
(84); 65 (49). H NMR (CDCl3): d 2.94 (d, 3H, N–CH3,
J¼4.9 Hz); 4.70 (br s, 1H, N–H); 6.50–6.56 (m, 2H,
Ar–H); 8.07–8.13 (m, 2H, Ar–H). 13C NMR (CDCl3):
d 30.14; 110.69; 126.42; 137.90; 154.22. Anal. Calcd for
C7H8N2O2: C, 55.26; H, 5.30; N, 18.41. Found: C, 55.18;
H, 5.27; N, 18.34. IR (KBr): nmax 3358, 1603, 1550, 1498,
1324, 1302 cmꢀ1
.
4.5.1.8. N-Methyl-p-aminoacetophenone31 (4h). Yield
90%, pale yellow solid, mp 106–108 ꢁC. GC–MS (EI): m/z
149 [Mꢃ+, 56%]; 134 (100); 106 (15); 105 (27); 79 (10); 77
1
(14). H NMR (CDCl3): d 2.51 (s, 3H, COCH3); 2.89 (d,
3H, N–CH3, J¼5.0 Hz); 4.40 (br s, 1H, N–H); 6.55–6.61
(m, 2H, Ar–H); 7.82–7.89 (m, 2H, Ar–H). 13C NMR
(CDCl3): d 26.04; 30.07; 110.98; 126.39; 130.76; 153.09;
196.50. Anal. Calcd for C9H11NO: C, 72.46; H, 7.43; N,
9.39. Found: C, 72.22; H, 7.39; N, 9.44. IR (KBr): nmax
8. Oku, T.; Ikariya, T. Angew. Chem., Int. Ed. 2002, 41, 3476–
3479.
3389, 3064, 1662, 1628, 1594, 1528, 1439, 1310, 1283 cmꢀ1
.
9. (a) Yu, L.; McGill, A.; Ramirez, J.; Wang, P. G.; Zhang, Z.-Y.
Bioorg. Med. Chem. Lett. 1995, 5, 1003–1006; (b) Boldrini,
G. P.; Panunzio, M.; Umani-Ronchi, A. Synthesis 1974, 733–
735; (c) Watanabe, Y.; Shim, S. C.; Mitsudo, T.-a.; Yamashita,
M.; Takegami, Y. Bull. Chem. Soc. Jpn. 1976, 49, 1378–1380;
4.5.1.9. Methyl N-methyl-p-aminobenzoate32 (4i).
Yield 95%, pale yellow solid, mp 86–88 ꢁC. GC–MS (EI):
m/z 165 [Mꢃ+, 99%]; 134 (100); 120 (5); 106 (23); 91 (4);
77 (13); 79 (16); 77 (22); 65 (9). 1H NMR (CDCl3): d 2.88
(s, 3H, N–CH3); 3.83 (s, 3H, OCH3); 4.27 (br s, 1H, N–
H); 6.52–6.59 (m, 2H, Ar–H); 7.84–7.91 (m, 2H, Ar–H).
13C NMR (CDCl3): d 30.11; 51.52; 111.04; 118.03;
131.48; 152.90; 167.41. Anal. Calcd for C9H11NO2: C,
65.44; H, 6.71; N, 8.48. Found: C, 65.29; H, 6.74; N, 8.42.
IR (KBr): nmax 3394, 3073, 2948, 1692, 1608, 1583, 1517,
`
(d) Barluenga, J.; Bayon, A. M.; Asensio, G. J. Chem. Soc.,
Chem. Commun. 1984, 1334–1335.
10. Johnstone, R. A. W.; Payling, D. W.; Thomas, C. J. Chem.
Soc. C 1969, 2223–2224.
11. Kadin, S. B. J. Org. Chem. 1973, 38, 1348–1350.
12. Katritzky, A. R.; Rachwal, S.; Rachwal, B. J. Chem. Soc.,
Perkin Trans. 1 1987, 805–809.
1445, 1264, 1244, 1174 cmꢀ1
.
13. Katritzky, A. R.; Drewniak, M.; Aurrecoechea, J. M. J. Chem.
Soc., Perkin Trans. 1 1987, 2539–2541.
4.5.1.10. N-Methyl-m-aminobenzonitrile33 (4j). Yield
90%, brown oil. GC–MS (EI): m/z 132 [Mꢃ+, 99%]; 131
(100); 104 (23); 102 (17); 90 (9); 77 (15); 76 (11); 75
(12). 1H NMR (CDCl3): d 2.82 (s, 3H, N–CH3); 3.73 (br s,
1H, N–H); 6.77–6.73 (m, 2H, Ar–H); 6.94–6.99 (m, 1H,
Ar–H); 7.20–7.27 (m, 1H, Ar–H). 13C NMR (CDCl3):
d 30.34; 112.85; 114.42; 116.95; 119.61; 120.58; 129.83;
149.35. Anal. Calcd for C8H8N2: C, 72.70; H, 6.10;
N, 21.20. Found: C, 72.95; H, 6.07; N, 21.12. IR (liquid
film): nmax 3401, 3062, 2933, 2158, 1602, 1516, 1319,
14. Briggs, E. M.; Brown, G. W.; Jiricny, J.; Meidine, M. F. Synthe-
sis 1980, 295–296.
15. (a) Krishnamurthy, S. Tetrahedron Lett. 1982, 23, 3315–3318;
(b) Hamel, P.; Girard, Y. Tetrahedron Lett. 1994, 35, 8101–
8102.
16. Crochet, R. A., Jr.;DeWittBlanton,C., Jr. Synthesis1974, 55–56.
17. (a) Di Gioia, M. L.; Leggio, A.; Le Pera, A.; Liguori, A.;
Napoli, A.; Siciliano, C.; Sindona, G. J. Org. Chem. 2003, 68,
7416–7421; (b) Leito, I.; Kaljurand, I.; Koppel, I. A.; Yagupol-
skii, L. M.; Vlasov, V. M. J. Org. Chem. 1998, 63, 7868–7874;
(c) Kowalik-Jankowska, T.; Kozloswki, H.; Pawelczak, K.;
1169 cmꢀ1
.