G. Kaupp et al. / Tetrahedron 59 (2003) 3753–3760
3759
4.7. General procedure for the preparation of 13
4.8.4. 2-Amino-3-cyano-7,7-dimethyl-4-(4-nitrophenyl)-
5-oxo-5,6,7,8-tetra-4H-chromene (14g). Mp 183–1858C,
lit.38 174–1768C; 1H NMR (CDCl3/DMSO-d6), d¼8.14
(cd, 2H), 7.42 (cd, 2H), 6.50 (br s, 2H, NH2), 4.48 (s, 1H,
H-4), 2.52 (br s, 2H, H-8), 2.26 (H-6a, JAB¼16.0 Hz), 2.16
(H-6b, JAB¼16.0 Hz), 1.14 (s, 3H), 1.03 (s, 3H); 13C NMR
(CDCl3), d¼195.2 (CvO), 162.1 (C-8a), 158.1 (C-2),
150.9, 146.2, 128.1 (2C), 123.1 (2C), 118.1 (CN), 112.2
(C-4a), 58.5 (C-3), 49.9 (C-6), 40.1 (C-8), 35.4 (C-4), 31.6
(C-7), 28.2, 27.0.
The stoichiometric mixtures of 1a,b (2.00 mmol) with 12
(2.00 mmol) were melted under vacuum in a 50 mL flask in
a drying oven at the temperatures reported in Table 2 for the
times given. 13a and 13b were quantitatively obtained after
drying at 808C in a vacuum and did not require purifying
workup. The products 13a,b were identical in all respects
with those described in the literature (see Table 2).
4.7.1. 4-Dimethylaminobenzylidene methylcyanoacetate
(13a). Mp 141–1438C, lit.29 140–1418C; 1H NMR (CDCl3/
DMSO-d6), d¼8.10 (s, 1H), 7.94(cd, 2H), 6.70 (cd, 2H), 3.90
(s,3H),3.11(s,6H);13C NMR (CDCl3), d¼164.8, 154.7, 153.7,
134.1 (2C), 119.4, 117.5, 111.5 (2C), 93.6, 52.7, 40.0 (2C).
Acknowledgements
This work was supported in part by the Deutsche
Forschungsgemeinschaft. We thank Mrs Ludmila Hermann
for her reliable help in the experimental work and the Zoz
Ltd, Wenden, Germany, for a loan of the Simoloyerw 2 L
ball-mill.
4.7.2. 4-Hydroxybenzylidene methylcyanoacetate (13b).
Mp 208–2108C, lit.31 2118C; 1H NMR (CDCl3/DMSO-d6),
d¼10.18 (br s, OH), 8.17 (s, 1H), 7.93 (cd, 2H), 6.95 (cd,
2H), 3.92 (s, 3H); 13C NMR (CDCl3), d¼163.7, 162.8,
154.9, 133.8 (2C), 122.8, 116.4 (2C), 116.3, 97.0, 52.8.
4.8. General procedure for the preparation of 14
References
The stoichiometric mixtures of 11b,e,f,g (2.00 mmol) with
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the case of 11b) at the temperatures reported in Table 3 for
the times given. 14b,e,f,g was obtained after drying at 808C
in a vacuum with 100% yield and did not require purifying
workup.
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