772
RUMYANTSEVA et al.
The porphyrin mixture was separated by column (20.3), 552.2 (10.9), 590.6 (6.8), 647.0 (4.9); mass
+
chromatography using chloroform as an eluent. The first spectrum,
m
/
z
: 939.276 [
М]
;
calculated for
1
fraction was 5ꢀ[4ꢀ(tosyloxy)phenyl]ꢀ10.15,20ꢀtris(4ꢀ C H N O Br, 939.887; HꢀNMR spectrum: 8.91
54
43
4
7
methoxycarbonylphenyl)porphyrin (XIII) and the secꢀ (2 H, m, H3, H7), 8.80 (6 H, m, H2, H8, H12, H13,
ond, 5ꢀ{4ꢀ[2ꢀ(2ꢀ(2ꢀmethoxy)ethoxy)ethoxy]ethoxypheꢀ H17, H18), 8.45 (6 H, m, Н 2), 8.30 (6 H, m, Н 3),
Ph
Ph
nyl}ꢀ10,15,20ꢀtris(4ꢀmethoxycarbonylphenyl)porphyꢀ 8.10 (2 H, m, HOPh2), 7.28 (2 H, m, HOPh3), 4.29 (2 H,
rin (XII). The yield of the target product (XII) was m, Br–CH ), 4.12 (9 H, s, COOCH ), 3.63 (2 H, m,
2
3
–
3
–1
–1
7
4
6
mg (60%). Rf 0.3; EAS,
20.0 (425), 516.4 (17.7), 552.0 (9.6), 591.0 (6.0), (2 H, s, NH).
λ
(
ε
×
10 , М cm ): O–CH ), 2.26ꢀ2.14 (4 H, m, –CH CH –), –2.78
max
2 2 2
+
47.0 (4.4); mass spectrum,
m/z: 951.296 [М + Н] ;
calculated for C H N O 950.35; HꢀNMR specꢀ
trum: 8.91 (2 H, m, H3, H7), 8.81 (6 H, m, H2, H8,
5
ꢀ(4ꢀPyridyl)ꢀ10,15,20ꢀtris(4ꢀmethoxycarbonylpheꢀ
1
5
7
50
4
10
nyl)porphyrin (XVIIa). A round bottom flask was supꢀ
plemented with 180 mg (1.685 mmol) of pyridineꢀ4ꢀ
carbaldehyde (XVIa), 830 mg (5.06 mmol) of
ꢀformylbenzoic acid methyl ester (II), and 20 ml of
propionic acid, boiled with reflux at a temperature of
40 , slowly supplemented in a dropwise manner
with the solution of 452 mg (6.74 mmol) of pyrrole (
in 3 ml of propionic acid, boiled for 30 min, suppleꢀ
mented with 10 ml of methanol, and left overnight at
18 С. The precipitate was filtered and washed with
H12, H13, H17, H18), 8.45 (6 H, m, Н 2), 8.30 (6 H,
Ph
m, Н 3), 8.10 (2 H, m, НОPh2), 7.30 (2 H, m, НОPh3),
Ph
4
4
(
–
3
.42 (2 H, m, О–СН –), 4.12 (9 H, s, COOCH ), 4.06
2
3
2 H, m, –СН ), 3.88 (2 H, m, –СН –), 3.80 (2 H, m,
2 2
1
°С
СН –), 3.75 (2 H, m, –СН –), 3.62 (2 H, m, –СН –),
2 2 2
I
)
.43 (3 H, s, –ОСН3), –2.75 (2 H, s NH).
ꢀ[4ꢀ(Tosyloxy)phenyl]ꢀ10,15,20ꢀtris(4ꢀmethoxꢀ
ycarbonylphenyl)porphyrin (XIII). The solution of
0 mg (0.025 mmol) of 5ꢀ(4ꢀhydroxyphenyl)ꢀ
0,15,20ꢀtris(4ꢀmethoxycarbonylphenyl)porphyrin ( ),
0 mg (0.26 mmol) of tosyl chloride (IX), and 50 mg
5
–
°
methanol. The yield of porphyrin mixture was 240 mg.
2
1
5
V
The mixture obtained was purified on a silica gel
column using chloroform–diethyl ether (94 : 6) as an
eluent. The second fraction was boiled down and
recrystallized. The yield of porphyrin (XVIIa) was
(
0.36 mmol) of potassium carbonate in 7 ml of dry
acetonitrile was boiled with reflux for 4 h and cooled.
The precipitate was filtered, washed with distilled
water, dried, and recrystallized. The yield of the target
9
0 mg (7.5%).
R
0.68; retention time, 7.45; EAS,
λ
f
max
–3
–1
–1
(ε
×
10 , М cm ): 419.8 (281.0), 514.8 (20.2),
max 549.0 (7.8), 588.8 (6.7), 644.4 (3.4); mass spectrum,
product (XIII) was 18 mg (75%). Rf 0.55; EAS,
λ
–
3
⎯
1
–1
+
(ε
×
10 , М cm ): 419.6 (420), 515.2 (15.1), 549.8
7.1), 590.0 (4.8), 645.6 (2.9); IR spectrum: 1177 (Ts),
723 (COOCH ); mass spectrum, : 959.230 [
Н] ; found, %: C, 70.57; H, 4.73; N, 5.70;
С Н N O S; calculated, %: C, 71.39; H, 4.41;
N 5.84; HꢀNMR spectrum: 8.81 (6 H, s, H2, H8,
H12, H13, H17, H18), 8.76 (2 H, m, H3, H7), 8.45
6 H, m, Н 2), 8.30 (6 H, m, Н 3), 8.12 (2 H, m,
m
/
z
: 790.373 [
M + H] ; calculated 789.851; found, %:
(
1
C, 74.49; H, 4.41; N, 8.54; С Н N О6; calculated,
49
35
5
1
m
/z
М +
3
%: C, 74.51; H, 4.47; N 8.87; HꢀNMR spectrum:
.032 (2 H, d, 5.92, Н 3,Н 5), 8.86 (8 H, s, H2, H3,
H7, H8, H12, H13, H17, H18), 8.47 (6 H, m, Ph),
.32 (6 H, m, Ph), 8.149 (2 H, d,
.14 (9 H, s, COOCH ), –2.65 (2 H, s, NH).
+
9
J
Py
Py
5
7
42
4
1
9
8
4
J 5.92, Н 2,Н 6),
Py Py
3
(
Ph Ph
5
ꢀ(3ꢀPyridyl)ꢀ10,15,20ꢀtris(4ꢀmethoxycarbonylpheꢀ
HОPh2), 7.98 (2 H, m, HОPh3), 7.47 (2 H, m, H 2),
Ts
nyl)porphyrin (XVIIb). A 100ꢀml round bottom flask
was supplemented with 180 mg (1.685 mmol) of pyriꢀ
dineꢀ3ꢀcarbaldehyde (XVIb), 830 mg (5.06 mmol) of
7
.42 (2 H, m, H 3), 4.12 (9 H, s, COOCH ), 2.53
Ts 3
(
3 H, s, CH ), –2.83 (2 H, s, NH).
3
5
ꢀ[4ꢀ(4ꢀBromobutyl)oxyphenyl]ꢀ10,15,20ꢀtris(4ꢀ 4ꢀformylbenzoic acid methyl ester (II), and 15 ml of
methoxycarbonylphenyl)ꢀporphyrin (XV). The suspenꢀ propionic acid, boiled with reflux at a temperature of
sion of 16 mg (0.02 mmol) of 5ꢀ(4ꢀhydroxyphenyl)ꢀ 140 , slowly supplemented in a dropwise manner
0,15,20ꢀtris(methoxycarbonylphenyl)porphyrin ( with 452 mg (6.74 mmol) of pyrrole ( ) in 3 ml of proꢀ
°С
1
V)
I
and 5 mg of anhydrous potassium carbonate in 5 ml of pionic acid boiled for 30 min, cooled, supplemented
dry DMF was supplemented with 0.025 ml with 10 ml of methanol, and left overnight in a freezer.
(
0.21 mmol) of 1,4ꢀdibromobutane (XIV). The reacꢀ The precipitate was filtered and washed with isoproꢀ
tion mixture was mixed at room temperature for 24 h, panol. The resulting porphyrin mixture was separated
supplemented with 10 ml of chloroform, and thorꢀ on a column using chloroform–diethyl ether (5 : 1) as
oughly washed with water. The organic layer was evapꢀ an eluent. The fraction containing the target product
orated; the precipitate was dissolved in a chloroform– was boiled down and recrystallized. The yield of porꢀ
hexane mixture (1 : 1), and chromatographed on silica phyrin (XVIIb) was 40 mg (5.1%). Rf 0.66; retention
gel using chloroform–hexane (5 : 1) as an eluent. The time, 6.50 min; EAS,
λ
max: 420, 515, 550, 589, 645;
1
first fraction was collected, evaporated, and recrystalꢀ
H NMR spectrum: : 9.44 (H, s, H 2), 9.04 (H, s,
Py
lized from a chloroform–petroleum ether mixture. H 4), 8.83 (8 H, s, H2, H3, H7, H8, H12, H13, H17,
Py
The yield of compound (XV) was 17 mg (92%). Rf 0.55
;
H18), 8.47 (H, s, H 6), 7.76 (H, t, H 5), 4.12 (9 H, s,
Py Py
–3
–1
–1
EAS,
λ
(
ε
×
10 , М cm ): 420.0 (380), 516.6 COOCH ), –2.68 (2 H, s, NH).
max
3
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 37
No. 6
2011