Katritzky et al.
1H), 8.48 (d, J ) 8.4 Hz, 1H); 13C NMR δ 115.3, 119.9, 121.4,
124.1, 125.5, 128.1, 128.8, 129.2, 130.1, 130.2, 130.3, 132.0, 146.4,
146.9, 153.7.
(s, 3H), 4.67 (s, 2H), 6.58 (d, J ) 7.4 Hz, 2H), 6.73 (d, J ) 8.5
Hz, 2H), 6.89 (d, J ) 8.5 Hz, 2H), 7.18 (d, J ) 8.5 Hz, 2H), 7.30
(d, J ) 7.0 Hz, 2H), 7.37 (t, J ) 7.0 Hz, 2H), 7.44 (d, J ) 7.1 Hz,
2H); 13C NMR δ (3 signals are hidden) 20.7, 46.2, 55.2, 113.5,
122.8, 127.3, 128.1, 128.6, 129.0, 130.0, 139.1, 148.3, 159.9. Anal.
Calcd for C22H22N2O: C, 79.97; H, 6.71; N, 8.48. Found: C, 79.67;
H, 7.07; N, 8.24.
N,N-Diethyl-N′-phenylbenzenecarboximidamide (7e).39 1-[Phe-
nyl(phenylimino)methyl]-1H-benzotriazole (0.149 g, 0.5 mmol) was
dissolved in chloroform (1 mL) in a 10 mL microwave reaction
tube. Aluminum chloride (0.014 g, 0.1 mmol) was added to the
tube, followed by diethylamine (0.073 g, 1 mmol). The tube
containing the reaction mixture was sealed with an aluminum crimp
cap fitted with a silicon septum and then exposed to microwave
irradiation (80 W) for 10 min at 80 °C. The reaction mixture was
diluted with chloroform (20 mL). Aqueous workup gave a residue
that was purified by column chromatography on basic alumina using
hexanes/EtOAc (8:1) as eluent to give a colorless oil: yield, 87%
(0.110 g); 1H NMR δ 1.17 (br s, 6H), 3.35 (br s, 4H), 6.53 (d, J )
7.5 Hz, 2H), 6.68 (t, J ) 7.3 Hz, 1H), 6.96 (t, J ) 7.7 Hz, 2H),
7.07-7.10 (m, 2H), 7.18-7.23 (m, 3H); 13C NMR δ 13.4, 41.8,
120.7, 123.0, 127.9, 128.0, 128.6, 134.3, 151.7, 159.6.
N-Butyl-N′-phenylethanimidamide Acetate (7v). N-[1-(1H-
1,2,3-Benzotriazol-1-yl)ethylidene]aniline (0.118 g, 0.5 mmol),
n-butylamine (0.073 g, 1 mmol), and acetic acid (1 mL) were placed
in a 10 mL microwave reaction tube. The tube containing the
reaction mixture was sealed with an aluminum crimp cap fitted
with a silicon septum and then exposed to microwave irradiation
(120 W) for 10 min at 120 °C. The reaction mixture was diluted
with chloroform (20 mL). Aqueous workup gave a residue that was
purified by column chromatography on basic alumina using
methylene chloride/methanol (20:1) to give pale yellow needles
(from chloroform/hexanes): mp 88-90 °C; yield, 92% (0.115 g);
1H NMR δ 0.89 (t, J ) 7.2 Hz, 3H), 1.25-1.37 (m, 2H), 1.44-
1.51 (m, 2H), 1.96 (s, 3H), 2.15 (s, 3H), 3.20 (q, J ) 6.8 Hz, 2H),
6.64 (br s, 1H) 7.06 (t, J ) 7.3 Hz, 1H), 7.27 (t, J ) 7.8 Hz, 2H),
7.57 (d, J ) 7.7 Hz, 2H), 9.21 (br s, 1H); 13C NMR δ 13.5, 19.8,
22.9, 24.0, 31.3, 39.2, 120.0, 123.8, 128.5, 138.3, 169.3, 170.5.
Anal. Calcd for C14H22N2O2: C, 67.17; H, 8.86; N, 11.19. Found:
C, 66.84; H, 8.86; N, 11.01.
N′-Benzyl-4-methoxy-N-(4-methylphenyl)benzenecarboximi-
damide (7h). N-[1H-1,2,3-Benzotriazol-1-yl(4-methoxyphenyl)-
methylene]-N-benzylamine (0.171 g, 0.5 mmol), p-toluidine hy-
drochloride (0.144 g, 1.0 mmol), and chloroform (1 mL) were
placed in a 10 mL microwave reaction tube. The tube containing
the reaction mixture was sealed with an aluminum crimp cap fitted
with a silicon septum and then exposed to microwave irradiation
(80 W) for 10 min at 80 °C. The reaction mixture was diluted with
chloroform (20 mL), and the insoluble portion was filtered off.
Aqueous workup gave a residue that was purified by recrystalli-
zation from chloroform/hexanes to give white microcrystals: mp
Acknowledgment. We thank Dr. Michael J. Collins for very
helpful discussions and the CEM Corporation for providing the
Discover Microwave Synthesizer.
1
115-117 °C; yield, 91% (0.150 g); H NMR δ 2.21 (s, 3H), 3.74
(37) Thiebaut, S.; Gerardin-Charbonnier, C.; Selve, C. Tetrahedron 1999,
55, 1329.
(38) Sen, M.; Ray, J. N. J. Chem Soc., Abstr. 1926, 646.
(39) Ta-Shma, R.; Rappoport, Z. J. Am. Chem. Soc. 1977, 99, 1845.
(40) Oxley, P.; Short, W. F. J. Chem. Soc., Abstr. 1948, 1514.
(41) Barluenga, J.; Aznar, F.; Liz, R.; Rodes, R. J. Chem. Soc., Perkin
Trans. 1 1980, 12, 2732.
Supporting Information Available: General procedures for the
preparation of N-acylbenzotriazoles 4a-l, amides 5a-Ab, imi-
doylbenzotriazoles 6a-w, and amidines 7a-Aa and characteriza-
tion data for compounds 4b-l, 5b-Ab, 6c-w, and 7a-d,f,g,i-
u,w-Aa. This material is available free of charge via the Internet
(42) Strain, H. T. J. Am. Chem. Soc. 1928, 50, 2218.
(43) Shah, R. C. J. UniV. Bombay, Sci. 1936, 5 (Part 2), 62.
JO052443X
3380 J. Org. Chem., Vol. 71, No. 9, 2006