stirring was continued for a longer reaction time, as shown in
Table 2. After the usual work up and purification by column
chromatography, the bis-alkylated products were characterised
by NMR spectra.†
(CDCl3, d ppm-1 relative to TMS): 3.73 (3H, s, OCH3); 3.93 (2H, d, J =
=
4.5 Hz, –NCH2); 4.46 (2H, s, –NCH2); 5.18 (2H, t, J = 8.4 Hz, CH2);
=
=
5.83–5.92 (1H, m, CH); 6.68 (2H, d, J = 9 Hz, 2 CH, 2 aromatic
=
proton); 6.78 (2H, d, J = 9 Hz, 2 CH, 2 aromatic proton); 7.23–
7.33 (5H, m, 5 aromatic protons). 13C NMR (CDCl3, d ppm-1): 53.8
(–NCH2); 54.9 (–NCH2Ph); 55.7 (OCH3); 114.4–116.4 (aromatic car-
bons); 126.8–128.5 (aromatic carbons); 134.2 ( CH, aliphatic); 139.3
=
(>C<, aromatic); 143.6 (>C<, aromatic); 151.6 (>C<, aromatic).
N-benzyl-4-chlorobenzenamine; Table 3, Entry 7: 1H NMR (CDCl3,
d ppm-1 relative to TMS): 3.96 (1H, br s, NH); 4.19 (2H, s, –NCH2Ph);
Acknowledgements
We are grateful to the Department of Science and Technology,
New Delhi for financial support (Grant No. SR/S1/OC-
49/2006). S. P. thanks CSIR, New Delhi for awarding senior
research fellowship.
=
6.44 (2H, d, J = 8.7 Hz, 2 CH, 2 aromatic proton); 7.04 (2H, d,
=
J = 8.7 Hz, 2 CH, 2 aromatic proton); 7.10–7.27 (5H, m, 5 aromatic
13
-1
=
proton). C NMR (CDCl3, d ppm ): 48.2 (–NCH2); 113.8 (2 CH,
2 aromatic carbon); 121.9 (>C<); 127.3–129.0 (aromatic carbons);
138.9 (>C<); 146.6 (>C<). N-benzyl-4-chloro-N-pentylbenzenamine;
Table 3, Entry 8: 1H NMR (CDCl3, d ppm-1 relative to TMS): 0.89
(3H, d, J = 6.9 Hz, CH3); 1.31 (4H, s, 2 –CH2); 1.61 (2H, s, CH2);
3.35 (2H, t, J = 7.5 Hz, –NCH2); 4.51 (2H, s, –CH2Ph); 6.56 (2H, d,
J = 8.1 Hz, 2 aromatic proton); 7.09 (2H, d, J = 8.4 Hz, 2 aromatic
proton); 7.17–7.30 (5H, m, 5 aromatic proton). 13C NMR (CDCl3,
d ppm-1): 14.1 (–CH3); 22.6 (–CH2 CH3); 26.7 (–CH2CH2CH3); 29.3
(–CH2CH2CH2CH3); 51.6 (–NCH2CH2); 54.6 (–NCH2Ph); 113.1–138.6
(aromatic carbons).
Notes and references
† 1H and 13C NMR spectral data of some selected compounds: N-allyl-
1
4-methoxybenzenamine; Table 2, Entry 9: H NMR (CDCl3, d ppm-1
relative to TMS): 3.65–3.84 (6H, m, –OCH3, –NH, –NCH2); 5.12–
=
=
5.29 (2H, m, CH2); 5.89–5.98 (1H, m, CH); 6.58 (2H, d, J =
8.7 Hz, 2 aromatic proton); 6.77 (2H, d, J = 8.7 Hz, 2 aromatic
protons). 13C NMR (CDCl3, d ppm-1): 47.6 (–NCH2); 55.8 (–OCH3);
=
=
114.4 (2 CH, 2 aromatic carbon); 114.9 (2 CH, 2 aromatic carbon);
1 (a) A. Seayad, M. Ahmed, R. Jackstell and T. Gross, Science, 2002,
297, 1676; (b) M. Johannsen and K. A. Jorgensen, Chem. Rev., 1998,
98, 1689.
=
=
116.2 ( CH); 135.8 ( CH2); 142.3 (>C<); 152.3 (>C<). N,N-diallyl-
4-methoxybenzenamine; Table 2, Entry 9: H NMR (CDCl3, d ppm-1
1
relative to TMS): 3.74 (3H, s, OCH3); 3.85 (4H, d, J = 4.8 Hz, 2CH2N–);
2 (a) C. Brielles, J. J. Harnett and E. Doris, Tetrahedron Lett., 2001, 42,
8301; (b) D. H. R. Barton and E. Doris, Tetrahedron Lett., 1996, 37,
3295; (c) S. Yuvaraj, V. V. Balasubramanian and M. Palanichamy,
Appl. Catal., A, 1999, 176, 111; (d) Y. Yoshida and Y. Tanabe,
Synthesis, 1999, 10, 1739; (e) S. Narayanan and K. Deshpande, Appl.
Catal., A, 1996, 135, 125; (f) P. S. Singh, R. Bandyopadhyay and B. S.
=
=
5.12–5.20 (4H, m, 2 CH2); 5.90–5.78 (2H, m, 2 CH); 6.69 (2H,
d, J = 6.9 Hz, 2 aromatic protons); 6.79 (2H, d, J = 6.9 Hz, 2
aromatic protons). 13C NMR (CDCl3, d ppm-1): 53.6 (2CH2N–); 55.7
=
=
=
(OCH3); 114.5 (2 CH2); 114.6 (2 CH aromatic); 116.1 (2 CH
=
aromatic); 134.6 (2 CH); 143.5 (>C<); 151.5 (>C<). 1-Benzyl-1H-
benzo[d][1,2,3]triazole; Table 2, Entry 27: H NMR (CDCl3, d ppm-1
1
´
relative to TMS): 5.82 (2H, s, –CH2); 7.25–7.41 (8H, m, aromatic
Rao, Appl. Catal., A, 1996, 136, 177; (g) M. Angeles Aramend´ıa, V.
proton); 8.05 (1H, d, J = 7.8 Hz, aromatic proton). 13C NMR (CDCl3,
Borau, C. Jimenez, J. M. Marinas and F. J. Romero, Appl. Catal.,
A, 1999, 183, 73; (h) B. L. Su and D. Barthbomeuf, Appl. Catal.,
A, 1995, 124, 73; (i) I. I. Ivanova, E. B. Pomakhina, A. I. Rebrov,
M. Hunger, Y. G. Kolyagin and J. Weitkamp, J. Catal., 2001, 203,
375; (j) K. Nishamol, K. S. Rahna and S. Sugunan, J. Mol. Catal.
A: Chem., 2004, 209, 89; (k) K. Okano, H. Tokuyamaand and
T. Fukuyama, Org. Lett., 2003, 5, 4987.
-1
=
=
=
d ppm ): 52.2 (CH2); 109.7 ( CH); 120.0 ( CH); 123.9 ( CH);
=
=
=
=
127.4 ( CH, aromatic); 127.6 (2 CH); 128.4 ( CH); 128.9 (2 CH);
1
1
2
2
=
=
=
132.8 ( C); 134.8 ( C); 146.3 ( C). N ,N ,N ,N -tetraallylethane-1,2-
diamine; Table 2, Entry 29: 1H NMR (CDCl3, d ppm-1 relative to TMS):
2.57 (4H, s, 2CH2); 3.10 (8H, d, J = 6.6 Hz, 4CH2); 5.12–5.19 (8H, m,
4
CH2); 5.79–5.92 (4H, m, 4 CH). 13C NMR (CDCl3, d ppm-1): 50.6
=
=
=
=
(2CH2); 57.3 (4CH2); 117.7 (4 CH2); 135.5 (4 CH). N-(prop-2-ynyl)
3 A.-N. Ko, C.-L. Yang, W. Zhuand and H. Lin, Appl. Catal., A, 1996,
134, 53.
4 M. Selva, P. Tundoand and A. Perosa, J. Org. Chem., 2001, 66,
677.
5 (a) R. N. Salvatore, A. S. Nagle and K. W. Jung, J. Org. Chem., 2002,
67, 674; (b) F. Zaragoza and H. Stephensen, J. Org. Chem., 2001,
66, 2518; (c) J. E. Zanetti and J. E. Bashour, J. Am. Chem. Soc.,
1940, 62, 741; (d) M. Shi and Y. Shen, Helv. Chim. Acta, 2001, 84,
3357.
6 (a) T. W. G. Solomons and C. B. Fryhle, Organic Chemistry,
John Wiley & Sons, Inc., New York, 2004, pp. 954-955; (b) J.
March, Advanced organic chemistry: Reactions, Mechanisms, and
Structure, John Wiley & Sons, Inc., New York, 1992, pp. 411-
413.
7 (a) W. J. Hickinbottom, J. Chem. Soc., 1930, 992; (b) S. Caspe, J. Am.
Chem. Soc., 1932, 54, 4457.
8 P. Depreux, H. Aichaoui and I. Lesienr, Heterocycles, 1993,
1051.
9 P. P. Gupta and J. N. Sharma, J. Med. Chem., 1973, 16,
797.
10 (a) C. Gabriel, S. Gabriel, E. H. Grant, B. S. J. Halstead and
D. M. P. Mingos, Chem. Soc. Rev., 1998, 27, 213; (b) R. N. Salvatore,
A. S. Nagle, S. E. Schmidt and K. W. Jung, Org. Lett., 1999, 1,
1893.
benzeneamine; Table 3, Entry 1: 1H NMR (CDCl3, d ppm-1 relative to
≡
TMS): 2.21 (1H, s, CH); 3.93 (2H, s, –NCH2); 4.12 (1H, s, –NH); 6.67–
6.81 (3H, m, 3 aromatic proton); 7.19–7.24 (2H, m, 2 aromatic proton).
C NMR (CDCl3, d ppm ): 33.6 (–NCH2); 71.3 ( CH); 81.0 (>C<);
113.5 (2 CH, 2 aromatic carbon); 118.7 ( CH, aromatic carbon);
13
-1
≡
=
=
=
129.2 (2 CH, 2 aromatic carbon); 146.8 (>C<). N-allyl-N-(prop-2-
ynyl) benzeneamine; Table 3, Entry 2: 1H NMR (CDCl3, d ppm-1 relative
≡
=
to TMS): 2.24 (1H, s, CH); 3.49 (2H, d, J = 6.6 Hz, –CH2C ); 3.88
≡
=
=
(2H, s, –NCH2C ); 5.11–5.06 (2H, m, CH2); 5.95–6.10 (1H, m, CH);
7.10–7.32 (5H, m, 5 aromatic protons). 13C NMR (CDCl3, d ppm-1):
≡
=
≡
≡
34.9 (–NCH2C ); 42.5 (–CH2C ); 72.9 ( CH); 79.4 (–C CH); 115.8
=
(2 CH, 2 aromatic carbon); 122.5–130.3 (aromatic carbons); 135.9
=
=
(
CH); 137.6 ( CH, aromatic carbon); 148.2 (>C<). N-dodecyl-4-
methylbenzenamine; Table 3, Entry 3: 1H NMR (CDCl3, d ppm-1 relative
to TMS): 0.87 (3H, d, J = 7.2 Hz, CH3); 1.26 (18H, s, 9 CH2); 1.57 (2H,
t, J = 6.6 Hz, CH2); 2.23 (3H, s, aromatic CH3); 3.04 (2H, t, J = 7.2 Hz, –
NCH2); 3.35 (1H, br s, –NH); 6.51 (2H, d, J = 8.1 Hz, 2 aromatic proton);
6.95 (2H, d, J = 7.8 Hz, 2 aromatic proton). 13C NMR (CDCl3, d ppm-1):
14.1 (–CH3); 20.4 (–CH2CH3); 22.7 (–CH3, aromatic); 27.3–29.7 (–CH2,
=
aliphatic carbons); 31.9 (–CH2, aliphatic); 44.4 (–NCH2); 112.9 (2 CH,
aromatic carbons); 126.2 (>C<); 129.7 (2 CH, aromatic carbons);
=
146.3 (>C<). N-allyl-N-dodecyl-4-methylbenzenamine; Table 3, Entry
4: 1H NMR (CDCl3, d ppm-1 relative to TMS): 0.86–1.26 (23H, m,
aliphatic CH2, CH3); 2.23 (3H, s, CH3, aromatic); 3.24 (2H, t, J = 7.5 Hz,
11 D. M. Fink, Synlett, 2004, 2394.
=
–NCH2); 3.87 (2H, d, J = 4.8 Hz, –NCH2); 5.10–5.17 (2H, m, CH2);
12 Y. Ju and R. S. Varma, Green Chem., 2004, 6, 219.
13 (a) F. Ullmann, Ber. Dtsch. Chem. Ges., 1903, 36, 2382; (b) I.
Goldberg, Ber. Dtsch. Chem. Ges., 1906, 39, 1691.
14 (a) B. Y. Yang and S. L. Buchwald, J. Organomet. Chem., 1999,
576, 125; (b) J. F. Hartwig, Angew. Chem., Int. Ed., 1998, 37,
2046.
=
5.72–5.98 (1H, m, CH); 6.59 (2H, d, J = 8.4 Hz, 2 aromatic proton);
7.01 (2H, d, J = 8.4 Hz, 2 aromatic proton). 13C NMR (CDCl3, d ppm-1):
14.2 (–CH3, aliphatic); 20.2 (–CH2CH3); 22.7 (–CH3, aromatic); 27.2–
31.9 (–CH2, aliphatic carbons); 51.0 (–NCH2); 53.4 (–NCH2); 112.3 (2
=
=
CH, aromatic carbon); 115.7 ( CH2, allylic); 124.8 (>C<, aromatic);
129.6 (2 CH, aromatic carbon); 134.6 ( CH); 146.3 (>C<, aromatic).
N-allyl-N-benzyl-4-methoxybenzenamine; Table 3, Entry 6: H NMR
=
=
15 L. Shi, M. Yang, C.-A. Fan, F.-M. Zhang and Y.-Q. Tu, Org. Lett.,
1
2003, 5, 3515.
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