1840
N. Hamdi, M. Saoud and A. Romerosa and Rached Ben Hassen
Vol 45
7,7'-[(2,21-Dihydroxy-4,7,10,13,16,19-hexaoxadocosane-1,
compound was obtained as colorless needles,Yield 0.858 g
(75%); mp 145–147ºC. IR spectrum, ꢀ cm–1: 3431 (OH); 2896
(C–H); 1703 (C=ꢁ); 1650 (OC=O); 1624 (ꢂ=ꢂ); 1106 (C–O);
1540 (ꢂ=ꢂarom). 1ꢃ NMR spectrum (CDCl3), ꢀ ppm: 5.20 (1H,
s, OH); 3.19–3.99 (23H, m, H-12–14,16,17,19,20,22,23,25);
4.66 (1H, s, H-3); 7.06–7.83 (4H, m, H-5 + H-6 + H-7 + H-8).
13ꢂ{1H} NMR spectrum (CDCl3), ꢀ ppm: 123.95 (C-10);
154.89 (C-9); 165.49 (C-2); 175.50 (C-4); 74.45 (C-14);
69.91 (C-12); 70.25 (C-13); 72.89 (C-16,17,19,20,22,23,25);
85.97 (C-3); 124.76 (C-5); 121.92 (C-6); 130.21 (C-7);
115.96 (C-8). Mass spectrum, m/z (I, %): 790 [M]+ (100).
Found, %: C 60.6; H 6.80; O 32.5. C40H54O16. Calculated, %:
C 60.75; H 6.83; O 32.41.
4,4'-[(2,33-Dihydroxy-4,7,10,13,16,19,22,25,28,31-decaoxa-
tetratriacontane-1,34-diyl)bis(oxy)]bis(2H-chromen-2-one)
(4c). This compound was obtained as a white solid; yield 0.80 g
(70%); mp 150–160ºC. IR spectrum, IR spectrum, ꢀ cm–1: 3412
(OH); 2875 (C–H); 1722 (C=ꢁ); 1648 (OC=O); 1622 (ꢂ=ꢂ);
1534 (ꢂ=ꢂarom); 1108 (C–O). 1ꢃ NMR spectrum (CDCl3), ꢀ
ppm: 4.52 (1H, s, OH); 3.01–4.10 (23H, m, H-12–
14,16,17,19,20,22,23,25,26,28); 5.56 (1H, s, H-3); 6.98–7.85
(4H, m, H-5–8). 13ꢂ{1H} NMR spectrum (CDCl3), ꢀ ppm:
115.39 (C-10); 154.23 (C-9); 162.94 (C-2); 176.35 (C-4); 73.74
(C-14); 69.19 (C-12); 69.44 (C-13,16,17,19,20,22,23,25,26,28);
89.75 (C-3); 123.88 (C-5); 122.91 (C-6); 132.31 (C-7); 116.42
(C-8). Mass spectrum, m/z (I, %): 878 [M]+ (100). Found, %: C
60.2; H 6.80; O 32.7. C44H62O18. Calculated, %: C 60.13; H 7.06;
O 32.80.
22-diyl)bis(oxy)]bis(4-methyl-2H-chromen-2-one) (3a). Yield
0.82 g (70%); mp 165–170ºC. IR spectrum, ꢀ cm–1: 3430 (OH);
3009 (C-H), 1710 (C=ꢁ); 1632 (C=C), 1490 (ꢂ=ꢂarom), 1120
1
(C–Oalcohol). ꢃ NMR spectrum (CDCl3), ꢀ ppm (J, Hz): 2.40
(3H, s, CH3); 2.92 (1H, s, OH); 3.40–3.72 (8H, m, H-19, 20, 22);
3.92–4.35 (9H, m, H-12–14,16,17); 6.20 (1H, s, H-3); 6.85 (1H,
1
1
s, H-8); 6.90 (1H, d, JHH = 8.57, H-6), 7.52 (1H, d, JHH = 8.75,
H-5). 13ꢂ{1H} NMR spectrum (CDCl3), ꢀ ppm: 18.7 (ꢂH3); 59.2
(ꢂ-13); 68.86 (ꢂ-12, 17, 19, 20, 22); 68.4 (ꢂ-14); 101.7 (ꢂ-8);
113.1 (ꢂ-6); 112.5 (C-3); 113.9 (C-10); 125.6 (ꢂ-5); 152.7 (C-
9); 155.1 (C-4); 161.4 (C-7); 161.5 (C-2). Mass spectrum, m/z (I,
%): 674 [M]+ (100). Found, %: C 60.60; H 6.40; O 33.30.
C34H42O14. Calculated, %: C 60.53; H 6.27; O 33.20.
7,7'-[(2,27-Dihydroxy-4,7,10,13,16,19,22,25-octaoxaocta-
cosane-1,28-diyl)bis(oxy)]bis(4-methyl-2H-chromen-2-one)
(3b). This compound was obtained as colourless needles, Yield
0.95 g (72%); mp 175–180ºC. IR spectrum, ꢀ cm–1: 3436 (OH);
3009 (C–H), 1712 (C=ꢁ); 1632 (C=C); 1497 (ꢂ=ꢂarom), 1123
1
(C–Oalcohol). ꢃ NMR spectrum (CDCl3), ꢀ ppm (J, Hz): 2.40
(3H, s, CH3); 2.88 (1H, s, OH); 3.39–3.65 (10H, m, H-19 + H-20
+ H-22 + H-23 + H-25); 3.96–4.23 (9H, m, H-12–14,16,17);
6.15 (1H, s, H-3); 6.83 (1H, s, H-8); 6.89 (1H, d, 1JHH = 8.57, H-
1
6); 7.50 (1H, d, JHH = 8.75, H-5).13ꢂ{1H} NMR spectrum
(CDCl3), ꢀ ppm: 18.65 (ꢂH3); 59.18 (ꢂ-13); 68.82 (ꢂ-
12,17,19,20,22,23,25); 68.34 (ꢂ-14); 101.67 (ꢂ-8); 112.07 (ꢂ-
6); 112.43 (C-3); 113.88 (C-10); 125.62 (ꢂ-5); 152.68 (C-9);
155.04 (C-4); 161.38 (C-7); 161.49 (C-2). Mass spectrum, m/z
(I, %): 762 [M]+ (100). Found, %: C 60.1; H 6.80; O 33.70.
C38H50O16. Calculated, %: C 59.84; H 6.60; O 33.56.
3-(3-Dimethylaminoacryloyl)-4-hydroxy-2H-chromen-2-
one (5). To a solution of the 3-acetyl-4-hydroxycoumarine-2-
one (1) (2.04 g, 10 mmol) was added DMF–DMA (1.19 g. 10
mmol) in dry toluene (50 mL) and then the reaction mixture was
refluxed for 2 h. The solvent was evaporated under vacuum and
the residual material was triturated with petroleum ether (25
mL), filtered, evaporated under reduced pressure to provide the
product as white needles. Yield 2.20 g (85%); mp 140–145ºC.
IR spectrum, ꢀ cm–1: 3439 (OH); 1700 (CO); 1619 (O–CO
7,7'-[(2,33-Dihydroxy-4,7,10,13,16,19,22,25,28,31-decaoxa-
tetratriacontane-1,34-diyl)bis(oxy)]bis(4-methyl-2H-chromen-
2-one) (3c). This compound was obtained as colorless prisms,
Yield 1.12g (76%); mp 160–165ºC. IR spectrum, ꢀ cm–1: 3440
(OH); 3071, 2896 (C-H), 1713 (C=ꢁ); 1612, 1386 (ꢂ=ꢂarom),
1
1147, 1068 (C–Oalcool). ꢃ NMR spectrum (CDCl3), ꢀ ppm (J,
Hz): 2.37 (3H, s, CH3); 2.78 (1H, s, OH); 3.36–3.78 (10H, m, H-
19,20,22,23,25,26,28); 3.94–4.23 (m, 9-H, H-12–14,16,17); 6.11
1
lactone). ꢃ NMR spectrum (DMSO-D6), ꢀ ppm: 2.50 (6H, s,
(1H, s, H-3); 6.79 (1H, d, 1JHH= 1.94, H-8); 6.88 (1H, dd, 1JHH
=
2CH3); 6.62 (1H, d, Hethyl); 8.32 (1H, d, Hethyl); 18.28 (OH);
7.29–7.95 (5H, m, Harom). 13C {1H} NMR spectrum (DMSO-D6)
ꢀ ppm: 46.2 (CH3); 182.9 (CO); 181.2 (C-4); 158.4 (C-2); 95.3
(C-3); 90.9 (CO–C); 160.9 (C=C–N); 118.8–153.7 (aromatic).
Mass spectrum, m/z (I, %): 259 [M]+ (100).
The conversion of 3-(3-(dimethylaminoacryloyl)-4-
hydroxy-2H-chromen-2-one (5) to adducts 6a-b. Hydrazine
hydrate (0.048 g, 1.5 mmol) or phenylhydrazine (0.138 g, 1.5
mmol) was added to a solution of (3-dimethylaminoacryloyl)-4-
hydroxy-2H-chromen-2-one (0.001 mol) in toluene (20 mL).
The mixture was refluxed for 6 h. The formed precipitate was
filtered and recrystallized from toluene.
8.78, JHH = 2.42, H-6); 7.47 (1H, d, JHH = 8.83, H-5). 13ꢂ{1H}
NMR spectrum (CDCl3), ꢀ ppm: 18.61 (ꢂH3); 68.77 (ꢂ-13);
69.39 (C-12); 69.48 (C-16,17,19,20,22,23,25,28); 70.80 (C-14);
101.62 (ꢂ-8); 112.01 (ꢂ-6); 112.35 (C-3); 113.82 (C-10); 125.58
(ꢂ-5); 152.61 (C-9); 155.01 (C-4); 161.28 (C-7); 161.48 (C-2).
Mass spectrum, m/z (I, %): 886 [M]+ (100). Found, %: C 60.1; H
6.80; O 33.9. C42H58O18. Calculated, %: C 59.29; H 6.86; O
33.85.
2
1
4,4'-[(2,21-Dihydroxy-4,7,10,13,16,19-hexaoxadocosane-1,
22-diyl)bis(oxy)]bis(2H-chromen-2-one) (4a). This compound
was obtained as colourless needles, Yield 0.74 g (65%); mp
130–135ºC. IR spectrum, ꢀ cm–1: 3435 (OH); 2796 (C–H); 1705
(C=ꢁ); 1655 (OC=O); 1630 (ꢂ=ꢂ); 1108 (C–O). 1ꢃ NMR
spectrum (CDCl3), ꢀ ppm: 5.40 (1H, s, OH); 3.10–4.10 (15H, m,
H-12–14,16,17,19,20,22); 4.62 (1H, s, H-3); 7.10–7.85 (4H, m,
H-5–8). 13ꢂ{1H} NMR spectrum (CDCl3), ꢀ ppm: 124.2 (C-10);
154.7 (C-9); 165.4 (C-2); 176.6 (C-4); 74.4 (C-14); 69.8 (C-12);
70.3 (C-13); 72.2 (C-16,17,19,20,22); 85.9 (C-3); 124.6 (C-5);
121.9 (C-6); 130.3 (C-7); 115.9 (C-8). Mass spectrum, m/z (I,
%): 702 [M]+ (100). Found, %: C 61.60; H 6.70; O 21.60.
C36H46O14. Calculated, %: C 61.53; H 6.59; O 21.45.
4-Hydroxy-3-(1H-pyrazol-3-yl)-2H-chromen-2-one (6a).
This compound was obtained as a yellow solid, Yield 0.273 g
(80%); mp 120–130ºC (CH2Cl2). IR spectrum, ꢀ cm–1: 1735-
1
1755 (CO); 3331 (OH), 1702 (ꢂ=O ester ). ꢃ NMR spectrum
(DMSO-D6), ꢀ ppm: 13.48 (1H, s, OH); 12.51 (1H, s, NH);
7.06–8.00 (5H, m, aromatic ). 13C {1H} NMR spectrum (DMSO-
D6) ꢀ ppm: 160.5 (C-2); 164.6 (C-4); 94.9 (C-3); 146.8 (C=N);
116.6–132.9 (aromatic + C=N); 104.5 (C=C–N). Mass spectrum,
m/z (I, %): 228 [M] + (100). Found, %: C 63.2; H 3.4; O 21.1. N
12.5 Calculated, %: C 63.16; H 3.53; O 21.03. N 12.28;
4-Hydroxy-3-(1-phenyl-1H-pyrazol-3-yl)-2H-chromen-2-
one (6b). This compound was obtained as a white solid, Yield
4,4'-[(2,27-Dihydroxy-4,7,10,13,16,19,22,25-octaoxaocta-
cosane-1,28-diyl)bis(oxy)]bis(2H-chromen-2-one) (4b). This