T. Gazivoda et al. / Bioorg. Med. Chem. 15 (2007) 749–758
755
4.47 (d, J = 6.63 Hz, 2H, H-60), 5.33 and 5.07 (s, 2H, H-
70 and H-700), 7.37–7.25 (m, 10H, Ph), 4.03 (s, 1H, H-200)
ppm. 13C NMR (DMSO-d6): d 169.03 (C-10), 122.98 (C-
20), 142.27 (C-30), 149.82 (C-40), 103.60 (C-50), 43.32 (C-
60), 157.85 (C-2), 163.68 (C-4), 97.03 (C-5), 149.47 (C-6),
73.98 and 72.88 (C-70 and C-700), 135.75 and 135.40 (C-80
and C-800 Ph), 128.83–127.70 (C–Ph), 83.49 (C-100), 75.08
(C-200) ppm. MS m/z 456.5 (M+Å).
d 11.28 (s, 1H, NH), 7.99 (s, 1H, H-6), 5.64 (t,
J = 6.88 Hz, 1H, H-50), 4.48 (d, J = 6,92 Hz, 2H, H-
60), 5.22 and 5.07 (s, 2H, H-70 and H-700), 7.47–7.32
(m, 10H, Ph), 2.68 (m, 1H, H-100), 5.99 (m, 1H, H-200),
2.21 (m, 6H, H-400, 400 0) ppm. 13C NMR (DMSO-d6): d
162.43 (C-10), 122.74 (C-20), 140.52 (C-30), 145.66 (C-
40), 101.23 (C-50), 43.14 (C-60), 151.83 (C-2), 159.65
(C-4), 104.12 (C-5), 142.16 (C-6), 72.38 and 72.23 (C-
70 and C-700), 135.96 and 135.11 (C-80 and C-800 Ph),
129.46–127.21 (C–Ph), 33.38 (C-100), 119.78 (C-200),
130.16 (C-300), 21.26 and 23.65 (C-400 and C-400 0) ppm.
MS m/z 500.5 (M+Å).
4.2.1.7. 1-(5-Propynyluracil-1-yl)-2-(2,3-di-O-benzyl-
2-butene-4-olidylidene)ethane (7). The procedure was
carried out using (tributylstannyl)-1-propine (789 mg,
2.4 mmol) for 4 h yielding brown oil (55 mg, 32.5%).
1H NMR (DMSO-d6): d 11.40 (s, 1H, NH), 8.13 (s,
1H, H-6), 5.43 (t, J = 6.64 Hz, 1H, H-50), 4.43 (d,
J = 7.01 Hz, 2H, H-60), 5.25 and 4.98 (s, 2H, H-70 and
H-700), 7.56–7.42 (m, 10H, Ph), 2.23 (s, 3H, H-300) ppm.
13C NMR (DMSO-d6): d 164.28 (C-10), 122.87 (C-20),
142.13 (C-30), 144.56 (C-40), 101.54 (C-50), 42.78 (C-
60), 149.77 (C-2), 162.32 (C-4), 100.11 (C-5), 143.73
(C-6), 72.55 and 72.41 (C-70 and C-700), 134.67 and
134.52 (C-80 and C-800 Ph), 128.60–127.44 (C–Ph),
82.33 (C-100), 97.09 (C-200), 24.65 (C-300) ppm. MS m/z
470.5 (M+Å).
4.2.1.11. 1-[5-(2-Bromovinyl)-6-bromouracil-1-yl]-2-
(2,3-di-O-benzyl-2-bromobutene-4-olidylidene)ethane
(11). To a solution of 5-vinyluracil-2,3-di-O-benzyl-L-
ascorbic acid 5 (210 mg, 0.46 mmol) in tetrachlorometh-
ane (15 mL), bromine (147.2 mg, 0.92 mmol) was added
dropwise. Reaction mixture was stirred for 30 min at
room temperature and solvent was evaporated in vacuo.
The oily residue was purified by column chromatogra-
phy (CH2Cl2/MeOH = 50:1) to yield yellow oil
(91.6 mg, 28.6%). 1H NMR (DMSO-d6): d 11.42 (s,
1H, NH), 5.11 (s, 1H, H-60), 5.14 and 5.09 (s, 2H, H-
70 and H-700), 7.33–7.19 (m, 10H, Ph), 7.45 (m, 2H, H-
100), 7.82 (d, J = 3.9 Hz, 1H, H-200) ppm. 13C NMR
(DMSO-d6): d 163.18 (C-10), 122.25 (C-20), 142.33 (C-
30), 148.62 (C-40), 100.87 (C-50), 42.54 (C-60), 148.16
(C-2), 160.11 (C-4), 109.72 (C-5), 132.24 (C-6), 73.27
and 73.16 (C-70 and C-700), 134.19 and 134.06 (C-80
and C-800 Ph), 128.52–127.26 (C–Ph), 132.11 (C-100),
104.88 (C-200) ppm. MS m/z 695.2 (M+Å).
4.2.1.8. 1-(5-Allyluracil-1-yl)-2-(2,3-di-O-benzyl-2-bu-
tene-4-olidylidene)ethane (8). The procedure was carried
out
using
(tributylstannyl)-2-propene
(794 mg,
2.4 mmol) for 2 days under reflux to yield yellow oil of
8 (48 mg, 28.2%). 1H NMR (DMSO-d6): d 11.31 (s,
1H, NH), 7.86 (s, 1H, H-6), 5.37 (t, J = 6.68 Hz, 1H,
H-50), 4.43 (d, J = 6,98 Hz, 2H, H-60), 5.22 and 5.06
(s, 2H, H-70 and H-700), 7.36–7.22 (m, 10H, Ph), 2.89
(m, 2H, H-100), 6.02 (m, 1H, H-200), 4.71 (m, 2H, H-300)
4.2.1.12. 1-[5-(5-Bromofuran-2-yl)uracil-1-yl]-2-(2,3-
di-O-benzyl-2-butene-4-olidylidene)ethane (12). To a
13
ppm. C NMR (DMSO-d6): d 165.14 (C-10), 123.06
(C-20), 140.12 (C-30), 147.22 (C-40), 100.76 (C-50),
43.21 (C-60), 155.34 (C-2), 162.88 (C-4), 98.66 (C-5),
142.75 (C-6), 73.21 and 73.07 (C-70 and C-700), 135.74
and 135.28 (C-80 and C-800 Ph), 128.40-127.25 (C-Ph),
33.12 (C-100), 126.23 (C-200), 109.84 (C-300) ppm. MS
m/z 472.2 (M+Å).
solution of 5-furyluracil-2,3-di-O-benzyl-L-ascorbic acid
1 (200 mg, 0.4 mmol) in pyridine (10 mL), N-bromosuc-
cinimide (71.2 mg, 0.4 mmol) was added. The reaction
mixture was stirred for 1 h at 90 ꢁC. Additional amount
of the N-bromosuccinimide (71.2 mg, 0.8 mmol) was
then added and reaction was continued for next 1 h at
90 ꢁC. The reaction mixture was stirred at room temper-
ature overnight and solvent was then evaporated under
reduced pressure. The oily residue was twice purified by
column chromatography (CH2Cl2/MeOH = 50:1) to
4.2.1.9. 1-(5-Alenyluracil-1-yl)-2-(2,3-di-O-benzyl-2-
butene-4-olidylidene)ethane (9). The procedure was car-
ried out using (tributylstannyl)alene (789 mg, 2.4 mmol)
for 2 days which gave orange oil of 9 (72 mg, 42.6%). 1H
NMR (DMSO-d6): d 11.43 (s, 1H, NH), 8.40 (s, 1H, H-
6), 5.52 (t, J = 7,02 Hz, 1H, H-50), 4.42 (d, J = 6,88 Hz,
2H, H-60), 5.18 and 4.96 (s, 2H, H-70 and H-700), 7.55–
7.31 (m, 10H, Ph), 6.06 (s, 1H, H-100), 5.12 (s, 2H, H-
1
yield yellow oil (41.9 mg, 18.3%). H NMR (DMSO-
d6): d 11.68 (s, 1H, NH), 8.10 (s, 1H, H-6), 5.57 (t,
J = 6.47 Hz, 1H, H-50), 4.65 (d, J = 6.44 Hz, 2H, H-
60), 5.31 and 5.16 (s, 2H, H-70 and H-700), 7.43–7.31
(m, 10H, Ph), 6.83 (d, J = 3.36 Hz, 1H, H-300), 6.62 (d,
J = 3.39 Hz, 1H, H-400) ppm. 13C NMR (DMSO-d6): d
163.76 (C-10), 122.89 (C-20), 133.41 (C-30), 142.35
(C-40), 67.40 (C-50), 42.76 (C-60), 150.82 (C-2), 159.57
(C-4), 101.25 (C-5), 145.41 (C-6), 74.04 and 73.00
(C-70 and C-700), 135.76 and 135.42 (C-80 and C-800 Ph),
131.57–128.58 (C–Ph), 148.14 (C-200), 109.11 (C-300),
113.23 (C-400), 134.70 (C-500) ppm. MS m/z 577.4 (M+Å).
13
300) ppm. C NMR (DMSO-d6): d 162.55 (C-10),
121.18 (C-20), 143.26 (C-30), 149.33 (C-40), 102.08
(C-50), 42.54 (C-60), 150.69 (C-2), 160.22 (C-4), 106.80
(C-5), 137.83 (C-6), 74.16 and 73.09 (C-70 and C-700),
134.18 and 133.65 (C-80 and C-800 Ph), 130.75–128.14
(C–Ph), 88.33 (C-100), 182.44 (C-200), 81.08 (C-300) ppm.
MS m/z 470.5 (M+Å).
4.2.1.10. 1-[5-(2-Isopentenyl)uracil-1-yl]-2-(2,3-di-O-
benzyl-2-butene-4-olidylidene)ethane (10). The procedure
was carried out using (tributylstannyl)-3-methyl-2-bu-
tene (862 mg, 2.4 mmol) for 48 h under reflux to yield
4.2.1.13. 1-[5-(5-Chlorofuran-2-yl)uracil-1-yl]-2-(2,3-
di-O-benzyl-2-butene-4-olidylidene)ethane (13). To
solution of 5-furyluracil-2,3-di-O-benzyl-L-ascorbic acid
1 (200 mg, 0.4 mmol) in pyridine (10 mL), N-chlorosuc-
cinimide (104.8 mg, 0.8 mmol) was added. The reaction
a
1
brown oil of 10 (41 mg, 22.8%). H NMR (DMSO-d6):