Molecules 2011, 16
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151.82 (C-2), 145.66 (C-8), 131.09 (C-11, C-15), 129.59 (C-10), 129.50 (C-3'), 129.02 (C-2'), 127.83 (C-
5), 114.06 (C-12,14), 55.33 (C-13-OCH3), 44.08 (C-1'), 43.78 (C-4'). LC-MS (m/z): 277 [M+1]+, 100%.
Anal. Calcd. for C16H15N4OCl: C 61.05, H 4.80, N 17.80; Found: C 61.15, H 4.95, N 17.95.
N9-[(E)-4'-Chloro-2'-butenyl-1'-yl]-6-(4-fluorophenyl)purine (18a). A suspension of 6-(4-fluoro-
phenyl) purine (0.5 g, 2.3 mmol), anhydrous potassium carbonate (0.65 g, 4.7 mmol), trans-1,4-
dichloro-2-butene (0.33 g, 2.6 mmol) in DMF (40 mL) was stirred at room temperature under argon
for 22 h. The reaction has been worked-up as described in the general procedureA.The resulting
product was chromatographed on a column of silica gel using ethyl acetate - light petroleumether (1:1)
v/v as an eluent. Fractions of 100 mL were collected. The fractions 3-4 yielded 18a as a cream white
solid, homogeneous on silicagel TLC, mobile phase ethyl acetate-hexane 7:3 v/v, Rf 0.69 (0.4g), 57%
1
yield, m.p. 73–75 °C. H-NMR: δ 8.98 (1H, s, H-2), 8.94–8.91 (2H, m, Ar-H), 8.68 (1H, s, C-8),
7.45–7.42 (2H, m, Ar-H), 6.16–6.12 (1H, m, HC=CH), 5.82–5.79 (1H, m, HC=CH), 5.01–5.0 (2H, d,
1
J = 5.0 Hz, N-CH2), 4.22–4.20 (2H, m, CH2Cl). 13C-NMR: δ 164.80 (d, JCF = 250 Hz, C-13), 152.16
4
(C-4), 151.80 (C-2), 151.43 (C-6),146.27 (C-8), 131.85 (d, JCF = 2.52 Hz, C-10), 131.75 (d,
3JCF = 8.8 Hz, C-11, C-15),129.96 (C-5), 129.59 (C-3'), 128.87 (C-2'),115.71 (d, 2JCF = 21.4 Hz, C-12,
C-14), 44.04 (C-1'), 43.85(C-4'). LC-MS (m/z): 303 [M+1]+, 100%. Anal. Calcd. for C15H12N4FCl: C
59.51, H 4.0, N 18.51; Found: C 59.25, H 4.16, N 18.65.
N9,N9''-bis[(E)-2'-Butenyl-1',4'-diyl]-6-(4-fluorophenyl)purine (18b). From the above chromatography,
fractions 6–10 yielded this dimer 18b, Rf 0.1, brownish white solid, (0.15 g), 13% yield, m.p.
1
217–219 °C. H-NMR: δ 8.95 (2H, s, H-2, H-2''), 8.93–8.90 (4H, m, Ar-H), 8.65 (2H, s, H-8, H-8''),
7.46–7.42 (4H, m, Ar-H), 5.98 (2H, m, HC=CH), 4.97–4.96 (4H, m, 2 × N-CH2). 13C-NMR: δ 164.86
1
(d, JCF = 252 Hz, C-13, C-13''), 152.61 (C-4, C-4''), 151.75 (C-6, C-6''), 151.61 (C-2, C-2''), 144.04
3
4
(C-8, C-8''), 131.44 (d, JCF = 8.8 Hz, C-11, C-11'', C-15, C-15''), 131.32 (d, JCF = 2.52 Hz, C-10,
2
C-10''), 130.06 (C-5, C5''), 127.90 (C-2', C-3'), 115.06 (d, JCF = 21.4 Hz, C-12, C-12'' C-14, C-14''),
43.88 (C-1', C-4'). LC-MS (m/z): 481 [M+1]+, 100%. Anal. Calcd. for C26H18N8F2: C 64.99, H 3.78, N
23.32; Found: C 64.82, H 3.85, N 23.45.
N9-[4'-Chloro-2'-butynyl-1'-yl]-6-(4-methoxyphenyl)purine (19). White solid, 80% yield, m.p.
1
119–121 °C. H-NMR: δ 8.93 (1H, s, H-2), 8.87–8.82 (2H, m, Ar-H), 8.70 (1H, s, H-8), 7.18–7.13
(2H, m, Ar-H), 5.31 (2H, t, J = 3.5 Hz, N-CH2), 4.50 (2H, m, CH2Cl), 3.87 (3H, s, OCH3). 13C-NMR:
δ 161.70 (C-13), 152.67 (C-4), 152.0 (C-2), 151.58 (C-6), 145.19 (C-8), 131.13 (C-11, C-15), 129.49
(C-10), 127.67 (C-5), 114.11 (C-12, C-14), 80.34 (C-3'), 80.28 (C-2'), 55.34 (OCH3), 32.77 (C-1'),
30.55 (C-4'). LC-MS (m/z): 313 [M+1]+, 100%. Anal. Calcd. for C16H13N4OCl: C 61.44, H 4.19, N
17.91; Found: C 61.35, H 4.30, N 17.85.
N9-[4'-Chloro-2'-butynyl-1'-yl]-6-(4-fluorophenyl)purine (20a). Abrownish white solid, 64% yield,
1
m.p. 128–130 °C. H-NMR: δ 9.02 (1H, s, H-2), 8.92–8.89 (2H, m, Ar-H), 8.75 (1H, s, H-8),
7.46–7.42 (2H, m, Ar-H), 5.33 (2H, t, J = 2.0 Hz, N-CH2), 4.50 (2H, t, J = 2.0 Hz, CH2Cl). 13C-NMR:
δ 164.86 (d, 1JCF = 249 Hz, C-13), 151.99 (C-2), 151.83 (C-4), 151.65 (C-6), 145.80 (C-8), 131.79 (d,
4
2
3JCF = 8.8 Hz, C-11, C15), 131.68 (d, JCF = 2.52 Hz, C-10), 129.87 (C-5), 115.75 (d, JCF = 21.4 Hz,