5
86
J IRAN CHEM SOC (2013) 10:583–591
1
(
(
(
0.52) nm; H NMR (CDCl ) d: -0.57 (1H, br s, NH), 0.32
(CDCl3) d: -0.14 (1H, br s, NH), 0.36 (1H, br s, NH), 1.74
(3H, d, J = 7.3 Hz, 18-CH ), 1.81 (3H, t, J = 7.6 Hz,
3
1H, br s, NH), 1.51 (3H, d, J = 7.0 Hz, 18-CH ), 1.65
3
3
3H, t, J = 7.6 Hz, 8a-CH ), 1.96–2.08, 2.32–2.39,
3
8-CH ), 1.91–2.01, 2.44–2.54, 2.69–2.80 (all 4H, each m,
3
2
.53–2.61, 2.79–2.88 (each m, all 4H, 17a ? 17b-H), 3.14,
.58, 3.80, 4.34 (each s, each 3H, CH ? OCH ), 3.61 (2H,
17a ? 17b-H), 3.30, 3.61, 3.79 (each 3H, each s,
OCH ? CH ), 4.02 (2H, q, J = 7.6 Hz, 8a-H), 4.34 (1H,
3
3
3
3
3
t, J = 7.6 Hz, 8b-H), 4.78 (1H, q, J = 7.0 Hz, 18-H), 5.26
1H, dd, J = 9.1, 2.6 Hz, 17-H), 6.11 (1H, d, J = 17.8 Hz,
trans-3b-H), 6.24 (1H, d, J = 11.5 Hz, cis-3b-H), 7.80
1H, dd, J = 17.8, 11.5 Hz, 3a-H), 9.53, 9.45 (each s, 2H,
q, J = 7.1 Hz, 18-H), 5.14 (1H, d, J = 7.8 Hz, 17-H), 6.24
(1H, d, J = 11.5 Hz, cis-3b-H), 6.38 (1H, dd, J = 17.8 Hz,
trans-3b-H), 7.87 (1H, dd, J = 17.8, 11.5 Hz, 3a-H), 8.48,
9.68, 10.32 (each 1H, each s, meso-H), 11.06 (s, 1H, CHO);
(
(
?
?
meso-H), MS m/z: 642.2 (M ? H) ; IR (KBr) v: 3460
N–H), 2974, 2237 (C–H), 1741–1691 (C=O), 1685 (C=C),
MS m/z: 593.4 (M ? H) ; IR (KBr) v: 3460 (N–H), 2972,
2939 (C–H), 1741–1697 (C=O), 1662 (C=C), 1583 (chlorin
(
-
1
1
1
5
591 (chlorin skeleton), 1456, 1348, 1176, 1116,
skeleton), 1469, 1384, 1184, 1132, 993 cm . Anal. calcd
for C H N O : C 68.91, H 5.44, N 9.45; found C 68.77,
-
016,781 cm . Anal. calcd for C H ClN O : C 65.46, H
1
3
5
36
5
5
34 32 4 6
.65, N 10.91; found C 65.28, H 5.41, N 10.79.
H 5.61, N 9.58.
3
1
-(1,2-Dibromoethyl)-3-devinyl-N-methoxylpurpurin-
8 imide methyl ester (6)
7-Styryl-N-methoxylpurpurin-18 imide methyl ester (8)
Chlorin 7 (124 mg, 0.209 mmol) and benzyltriphenylpho-
sphonium chloride (100 mg, 0.257 mmol) was dissolved in
50 mL CH Cl and a solution of NaOH (40 mg) in H O
To a dichloromethane solution (50 mL) of 3b (212 mg,
.349 mmol), 65 mg N-bromosuccinimide (0.364 mmol)
0
2
2
2
was added and stirred under nitrogen. The reaction was
monitored by TLC and stopped when starting material
disappeared completely. The mixture was poured into
water, extracted with dichloromethane (2 9 20 mL) and
evaporated to dryness under vacuum. The residue was
purified on chromatography on a silica gel column with
hexane–ethyl acetate (4:1) to give 142 mg 6 (0.185 mmol,
(15 mL) was added with stirring. The solution was stirred
at room temperature under nitrogen for 1 h and poured into
ice water and CH Cl . The aqueous phase was extracted
2
2
with several portions of CH Cl and the combined organic
2
2
phases were acidized with aq. 2 % HCl, washed with aq.
4 % NaHCO and water, dried over Na SO and evapo-
3
2
4
rated in vacuum to dryness. The residue was redissolved in
pyridine (10 mL), to which hydroxylamine hydrochloride
(100 mg) was added. The resulting solution was stirred at
room temperature for 12 h. The reaction mixture was dis-
solved in 20 mL of acetic anhydride, stirred for 4 h, poured
into water and extracted with dichloromethane
(3 9 100 mL). The combined extract was washed with
saturated NaHCO and water, dried over Na SO , meth-
5
3 %) as a red solid: UV–vis m.p. 232–235 °C; UV–vis
(
CHCl ) k : 367 (relative intensity, 0.38), 417 (1.00),
3
max
1
08 (0.05), 547 (0.17), 620 (0.04), 707 (0.92) nm; H NMR
5
(
(
CDCl ) d: -0.52 (-0.64) (1H, each br s, NH), -0.30
-0.39) (1H, each br s, NH), 1.61 (1.62) (3H, t,
3
J = 7.6 Hz, 8-CH ), 1.68 (1.63) (3H, d, J = 7.4 Hz,
3
1
4
3
3
8-CH ), 3.08–3.16, 2.25–2.38, 2.42–2.53, 2.73–2.80 (all
3
3
2
4
H, each m, 17a ? 17b-H), 3.16 (3.18), 3.36 (3.35), 3.60,
.63 (3.61), 4.34 (4.33) (each 3H, each s, CH ? OCH ),
ylated with diazomethane and evaporated to dryness. The
crude product was purified by chromatography on silica gel
column with hexane–ethyl acetate (4:1) to give 9 mg 8
(0.013 mmol, 6 %) as a red solid. m.p. 212–15 °C; UV–vis
(CHCl ) k : 370 (relative intensity, 0.47), 432 (1.00),
3
3
.57 (2H, q, J = 7.6 Hz, 8a-H), 4.07 (4.06) (1H, q,
J = 7.4 Hz, 18-H), 4.32 (4.19) (1H, t, J = 4.2 Hz, 3b-H),
.33 (4.23) (1H, t, J = 9.2 Hz, 3b-H), 5.12 (4.99) (1H, d,
J = 8.6 Hz, 17-H), 6.31 (1H, dt, J = 9.2, 4.4 Hz, 3a-H),
.47 (8.42), 9.25 (9.27), 9.70 (9.69) (each s, each 1H,
meso-H), IR (KBr) v: 3471 (N–H), 2972, 2233 (C–H),
4
3
max
1
4.67 (0.05), 564 (0.17), 6.37 (0.08), 730 (0.56) nm; H
8
NMR (400 MHz. CDCl ) d: 0.53 (1H, br s, NH), 0.47 (1H,
3
br s, NH), 1.55 (3H, t, J = 7.6 Hz, 8-CH ), 1.73 (3H, d,
3
1
1
741–1703 (C=O), 1623 (C=C), 1541 (chlorin skeleton),
J = 7.3 Hz, 18-CH ), 1.90–2.01, 2.43–2.58, 2.80–2.87 (all
3
-
473, 1384, 1222, 1172, 1118, 912 cm . Anal. calcd for
1
4H, each m, 17a ? 17b-H), 3.02, 3.26, 3.60, 4.36 (each
3H, each s, CH ? OCH ), 3.38 (2H, q, J = 7.6 Hz, 8a-H),
C H Br N O : C 54.77, H 4.86, N 9.12; found C 54.60,
5
3
5
37
2
5
3
3
H 5.04, N 9.30.
4.31 (1H, q, J = 7.4 Hz, 18-H), 5.25 (1H, dd, J = 9.6,
.2 Hz, 17-H), 6.12 (1H, d, J = 11.5 Hz, cis-3b-H), 6.22
2
7
-Formylpurpurin-18 methyl ester (7)
(1H, d, J = 17.5 Hz, trans-3b-H), 7.44 (1H, t, J = 7.3 Hz,
Ph-H), 7.53 (2H, t, J = 7.3 Hz, Ph-H), 7.72 (1H, d,
J = 16.5 Hz, 7b-H), 7.78 (1H, dd, J = 17.8, 11.5 Hz,
3a-H), 7.81 (2H, t, J = 7.3 Hz, Ph-H), 8.68 (1H, d,
J = 16.5 Hz, 7a-H), 8.42, 9.32, 9.42 (each 1H, each s,
This compound was obtained in yield of 28 % according to
the method for preparing compound 2. m.p. 215–217 °C;
UV–vis (CHCl3) k max: 412 (relative intensity, 1.00), 546
1
0.14), 634 (0.06), 672 (0.23), 700 (0.19) nm; H NMR
?
(
meso-H), MS m/z: 696.3 (M ? H) ; IR (KBr) v: 3446
1
23