604 JOURNAL OF CHEMICAL RESEARCH 2007
Diethyl
2-(N-(2-oxo-2H-chromen-4-yl)-N-phenylamino)-3-[(t-
_
Ph
H
butylimino)methylene]succinate (9a): Colourless crystals; m.p.
147–148°C, (0.43 g, 89%;). IR (KBr) (νmax, cm-1): 3030 (NH),
2040 (C=C=N), 1720 and 1687 (C=O). Anal. Calcd for C28H30N2O6
(490.55): C, 68.6; H, 6.2; N, 5.7;%. Found: C, 68.5; H, 6.2; N, 5.5%.
H3CO2C
N
C
CO2CH3
O
9a-c
1H NMR (500 MHZ, CDCl3, Me4Si): δ 1.21 (6 H, t, 3JHH = 7 HZ,
2
+
N
CH3), 1.43 (9 H, s, CMe3), 4.17–4.32 (4 H, m, 2 OCH2), 5.79 and
O
R
5.98 (2 H, 2 s, N–CH and C=CH), 6.81–7.63 (9 H, m, arom). 13
C
NMR (125.8 MHZ, CDCl3, Me4Si): δ 14.47 and 14.67 (2 CH3), 30.56
(3 CH3 of t-butyl), 53.18 (N–CH), 60.18 and 60.91 (2 OCH2), 62.75
(C=C=N), 64.66 (C of t-butyl), 103.04, 116.94, 117.64, 123.34,
125.77, 125.90, 127.30, 129.75, 131.21, 147.06, 154.69, 159.87 (10
C aromatic and C=CH), 162.34, 163.07, 170.01, 170.16 (C=C=N
and 3 CO). MS (m/z,%): 490 (M, 1).
10
Scheme 4
chromatography using hexane–ethyl acetate as eluent. The solvent
was removed under reduced pressure to afford the product as a
white powder, m.p. 207–209°C (0.40 g, 97%). IR (KBr) (νmax/cm-1):
3265 (NH), 1730 and 1668 (C=O ester). Anal. Calcd for C22H23NO7
(413.43): C, 63.9; H, 5.6; N, 3.4. Found: C, 64.1; H, 5.7; N, 3.4%.
1H NMR (500 MHz, CDCl3, Me4Si): δ 1.41–1.84 (10 H, m, 5 CH2),
3.71, and 3.75 (6 H, 2 s, 2 OCH3), 3.84 (1 H, m, NCH), 4.73 (1 H,
Dimethyl
2-(N-(2-oxo-2H-chromen-4-yl)-N-phenylamino)-3-
[(cyclohexylimino)methylene]succinate (9b): Colourless crystals;
m.p. 131–132°C, (0.44 g, 92%). IR (KBr) (νmax, cm-1): 2910 (CH),
2055 (C=C=N), 1723 and 1694 (C=O). Anal. Calcd for C28H28N2O6
(488.53): C, 68.8; H, 5.8; N, 5.7%. Found: C, 68.5; H, 5.7; N, 5.8%.
1H NMR (500 MHZ, CDCl3, Me4Si): δ 1.31–1.96 (10 H, m, 5 CH2),
3.69 and 3.75 (6 H, 2 s, 2 OCH3), 3.85(1 H, m, CH), 5.83 and 5.98
(2 H, 2 s, N–CH and C=CH), 6.84–7.34 (9 H, m, arom). 13C NMR
(125.8 MHZ, CDCl3, Me4Si): δ 24.27, 24.30, 25.45, 33.48, and 33.62
(5 CH2), 52.20 and 53.30 (2 OCH3), 58.55 (CH), 61.04 (C=C=N),
64.88 (CH of cyclohexyl), 102.86, 117.58, 117.69, 123.40, 125.81,
125.91, 127.28, 129.86, 131.28, 147.04, 154.71, 155.20 (10 C arom
and C=CH), 162.41, 162.61, 170.44, 170.56 (C=C=N and 3 CO).
MS (m/z,%): 488 (M).
Diethyl 2-(N-(2-oxo-2H-chromen-4-yl)-N-phenylamino)-3-[(cyclo-
hexylimino)methylene]succinate (9c): Colourless crystals; m.p.
130–131°C, (0.48 g, 93%). IR (KBr) (νmax, cm-1): 2905 (CH), 2035
(C=C=N); 1723, 1666 (C=O). Anal. Calcd for C30H32N2O6 (516.58):
C, 69.7; H, 6.2; N, 5.4;%. Found: C, 69.5; H, 6.2; N, 5.5%. 1H
NMR (500 MHZ, CDCl3, Me4Si): δ 1.22 (6 H, m, 2 CH3), 1.32–1.95
(10 H, m, 5 CH2), 3.87 (1 H, m, CH cyclohexyl), 4.18–4.71 (4 H,
m, 2 OCH2), 5.81 and 5.93 (2 H, 2 s, N–CH and C=CH), 6.81–7.38
(9 H, m, arom).13C NMR (125.8 MHZ, CDCl3, Me4Si): δ 14.49, 14.71
(2 CH3), 24.10, 24.15, 25.15, 33.45 and 33.58 (5 CH2), 58.97 (CH),
60.96, 60.98 (2 OCH2), 62.57 (C=C=N), 64.96 (CH of cyclohexyl),
102.79, 117.62, 117.67, 123.37, 125.81, 125.95, 127.34, 129.78,
131.24, 147.21, 154.44, 155.17 (10 C arom and C=CH), 162.43,
163.46, 169.88, 170.07 (C=C=N and 3 CO). MS (m/z,%): 516 (M, 1).
s, CH), 7.27–7.72 (4 H, m, aromatic protons), 8.73 (1 H, s, NH). 13
C
NMR (125.8 MHz, CDCl3, Me4Si): δ 24.8, 24.9, 25,8, 33.9, and 34.1
(5 CH2), 36.7 and 51.1 (2 CH), 51.6 and 53.1 (2 OCH3), 72.5, 103.4,
and 114.0 (3 C), 117.5, 122.4, 125.0, and 133.1 (4 CH), 153.2, 155.3,
158.7, 161.1, 169.7, and 173.5 (3 C and 3 CO). MS, m/z (%): 413
(M+., 35).
Diethyl 2-cyclohexylamino-5-oxo-4H,5H-pyrano[3,2-c]chromene-
3,4-dicarboxylates (4b): White powder, m.p. 166–167°C (0.42 g,
90%). IR (KBr) (νmax/cm-1): 3230 (NH), 1736, 1727, 1689 (3 C=O).
Anal. Calcd for C24H27NO7 (441.47): C, 65.3; H, 6.2; N, 3.2. Found:
C, 65.3; H, 6.4; N, 3.1%. 1H NMR (500 MHz, CDCl3, Me4Si):
δ 1.20–2.09 (16 H, m, 5 CH2 and 2 CH3), 3.88 (1 H, m, N–CH),
4.17 (4 H, m, 2 OCH2), 4.72 (1 H, s, CH), 7.28–7.72 (4 H, m, arom),
8.72 (1 H, s, NH). 13C NMR (125.8 MHz, CDCl3, Me4Si): δ 14.6 and
14.9 (2 CH3), 24.8, 24.9, 25,8, 33.9, and 34.2 (5 CH2), 36.9 and 51.0
(2 CH), 60.2 and 61.8 (2 OCH2), 72.7, 103.5, and 114.1 (3 C), 117.5,
122.4, 124.9, and 133.0 (4 CH), 153.2, 155.3, 158.5, 161.2, 169.4,
and 173.4 (3 C and 3 CO). MS, m/z (%): 441 (M+., 15).
Di-tert-butyl
2-cyclohexylamino-5-oxo-4H,5H-pyrano[3,2-c]
chromene-3,4-dicarboxylates (4c): White powder, m.p. 79–81°C,
(0.44 g, 90%). IR (KBr) (νmax/cm-1): 3235 (NH), 1732, 1717, 1676
(3 C=O). Anal. Calcd for C28H35NO7 (497.58): C, 67.6; H, 7.1; N,
1
2.8. Found: C, 67.3; H, 7.1; N, 2.7%. H NMR (500 MHz, CDCl3,
Me4Si): δ 1.20–1.96 (28 H, m, 5 CH2 and 6 CH3), 3.82 (1 H, m,
N–CH), 4.55 (1 H, s, CH), 7.04–7.70 (4 H, m, arom), 8.66 (1 H, s,
NH). 13C NMR (125.8 MHz, CDCl3, Me4Si): δ 25.1, 25.2, 25.9, 34.0,
and 34.4 (5 CH2), 28.3 and 29.0 (6 CH3 of tert-butyl groups), 38.3
and 51.1 (2 CH), 80.3 and 81.7 (2 OC of t-butyl groups), 74.2, 103.9,
and 114.2 (3 C), 117.3, 122.4, 124.8, and 132.8 (4 CH), 153.1, 155.2,
158.4, 161.1, 169.1, and 172.9 (3 C and 3 CO). MS, m/z (%): 497
(M+., 7).
Diethyl 2-tert-butylamino-5-oxo-4H,5H-pyrano[3,2-c]chromene-
3,4-dicarboxylates (4d): White powder, m.p. 191–193°C (0.37 g,
90%). IR (KBr) (νmax/cm-1): 3235 (N–H), 1719, 1679, 1643(3 C=O).
Anal. Calcd for C22H25NO7 (415.43): C, 63.6; H, 6.1; N, 3.4. Found:
C, 63.5; H, 6.0; N, 3.4%. 1H NMR (500 MHZ, CDCl3, Me4Si):
δ 1.23 and 1.28 (6 H, 2 t, 3JHH = 7.1 HZ, 2 CH3), 1.52 (9 H, s, CMe3),
4.11–4.22 (4 H, m, 2 OCH2), 4.71 (1 H, s, CH), 7.34–7.83 (4 H, m,
arom), 9.01 (1 H, s, NH). 13C NMR (125.8 MHz, CDCl3, Me4Si):
δ 14.16 and 14.46 (2 CH3), 30.60 (CH), 59.98 and 61.47 (2 OCH2),
63.06 (C of t-butyl), 73.25, 103.16 and 113.62 (3 C), 117.22, 122.37,
124.61, and 132.63 (4 CH), 152.76, 155.06, 159.48 (=C–N and
2=C–O),160.85,169.19and172.99(3CO).MS,m/z(%):415(M+.,25).
Received 12 September 2007; accepted 30 October 2007
Paper 07/4837
doi: 10.3184/030823407X256145
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PAPER: 07/4837