CCDC-784897 contains the supplementary
crystallographic data for compound 10a.
These data can be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
<A NAME="RD19710ST-13A">13a</A>
Typical procedure for the synthesis of 4a-l:
A mixture of alkyl isocyanide
(1 mmol), dialkyl acetylene-dicarboxylate (1 mmol)
and 1,3-dicarbonyl compound (1 mmol) in H2O
(5 mL), in the presence of TBAB (10 mol%) was
stirred at 80 ˚C until the reaction was complete as
indicated by TLC. The crude solid product was filtered, washed with
H2O, dried and purified by column chromatography (EtOAc-hexane,
3:7). The products thus obtained were characterized by their IR,
NMR spectroscopic and mass spectrometric data. Dimethyl 2-(cyclohexyl-amino)-5-oxo-4H,5H-pyrano[3,2-c]chromene-3,4-dicarboxylate
(4a): White solid; mp 198-200 ˚C;
IR (CHCl3): 3264.9 (N-H), 1732.6, 1686.3, 1659.4
(C=O) cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 1.37-2.09
(m, 10 H, 5 × CH2), 3.71 (s, 3 H,
OCH3), 3.74 (s, 3 H, OCH3), 3.78-3.87 (m,
1 H, NCH), 4.73 (s, 1 H, CH), 7.30-7.72
(m, 4 H, ArH), 8.70 (s, 1 H, NH); ¹³C
NMR (75 MHz, CDCl3): δ = 24.41, 24.46,
25.3, 33.4, 33.7, 36.3, 50.6, 51.2, 52.7, 72.1, 102.9, 113.5, 117.1,
121.9, 124.6, 132.7, 152.7, 154.9, 158.2, 160.7, 169.3, 173.1. GC/MS: m/z = 413 [M+]
<A NAME="RD19710ST-13B">13b</A>
Typical procedure
for the synthesis of 9: An equimolar mixture of ylidine malononitrile 8 (1 mmol) and 4-hydroxycoumarin (1 mmol)
in H2O (5 mL), in the presence of TBAB (10 mol%)
was stirred at 80 ˚C until the reaction was complete as
indicated by TLC. The solid product was filtered, washed with water,
dried and purified by recrystallization (EtOH-CHCl3,
1:1). The products thus obtained were characterized by their IR,
NMR spectroscopic and mass spectrometric data (9a):
Yellow crystal; mp 240-243 ˚C; IR (KBr):
3430, 3340 (NH2), 1714 (CO), 2181 (CN) cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 1.16 (t,
3 H), 4.08 (q, 2 H), 5.03 (s, CH, 1 H), 6.56
(br s, NH2, 2 H), 7.33-8.13 (m, 8 H,
ArH);
¹³C NMR (75 MHz, CDCl3): δ = 14.2,
35.8, 60.2, 106.4, 113.1, 117.0, 122.3, 123.4, 124.3, 124.6, 129.5,
132.7, 146.7, 151.7, 152.7, 153.6, 158.0, 160.5, 168.2; LCMS (ESI): m/z = 408 [M+].
