Coupling Reactions of Natural Tetrapyrroles
FULL PAPER
dark green solid, m. p. >300°C, yield 152 mg (51%, mixture of
CH3, pyr), 3.63Ϫ3.66 (m, 6 H, COOCH
3
), 3.96Ϫ4.04 (m, 4 H, 131/
1
1
regioisomers). Ϫ H NMR (200 MHz, [D
6
]DMSO): δ ϭ 3.24Ϫ3.42
), 3.57Ϫ3.75 (m, 36 H, CH3 pyr, COOCH ), J ϭ 17.55 Hz, ABX-CHvinyl), 6.95 (d, 2 H, J ϭ 11.27 Hz, J ϭ
), 7.80Ϫ7.88 (m, 1 H, CHvinyl), 17.55, ABX-CHvinyl), 7.33 (d, 2 H, J ϭ 15.97 Hz, AB-CHvinyl), 7.70
.05 (d, 2 H, J ϭ 16.52 Hz, CHvinyl), 8.24 (d, 2 H, J ϭ 8.35 Hz, (d, 4 H, J ϭ 8.04 Hz, CHaryl), 7.88 (d, 4 H, J ϭ 8.04 Hz, CHaryl),
8.04 (d, 1 H, J ϭ 15.97 Hz, AB-CHvinyl), 8.67, 8.76, 8.86, 8.95 (s,
CHβ-pyr], 10.12Ϫ10.17 (m, 4 H, CHmeso), 10.26 (s, 2 H, CHmeso), 4 H, CHmeso-pyr).Ϫ UV/Vis (CH Cl ): λmax (lg ε) ϭ 328 (4.498),
406 (5.305), 542 (4.189), 582 (4.365). Ϫ FAB-MS (nitrobenzyl al-
2
17 -CH ), 5.44 (d, 2 H, J ϭ 11.27 Hz, ABX-CHvinyl), 5.99 (d, 2 H,
2
2
(m, 8 H, 13 /17 -CH
2
3
1
1
4.27Ϫ4.53 (m, 8 H, 13 /17 -CH
2
8
CHaryl), 9.34 (s, 1 H, CHaryl), 9.22Ϫ9.34 [m, 4 H, CHvinyl, 3(8)-
2
2
1
1
3
1
0.49 (s, 2 H, Hmeso). Ϫ 13C NMR (50 MHz, [D
2.31, 12.54, 14.28, 14.57 (q, CH3, pyr), 22.36 (t, 13 /17 -CH
7.78, (t, 13 /17 -CH ), 52.28 (q, OCH
2 3
6
]DMSO): δ ϭ
1
1
ϩ
2
), cohol): m/z (%):856.31 (4) [M ]. Ϫ C52
), 97.64, 98.44, 98.95, C 72.76, H 5.64, N 6.53, found C 72.45, H 5.48, N 6.31.
02.02 (d, CHmeso), 123.99 (d, CHvinyl), 125.71, 126.37, 126.99 (d,
48 4 4
H N O Zn (858.35): calcd.
2
2
Zinc(II)Ϫ3(8)-(4-Vinyl-(E)-Ͱ-styryl)deuteroporphyrin-IX Di-
methyl Ester (10): The reaction was carried out with zinc(II)Ϫ3(8)-
bromodeuteroporphyrin-IX dimethyl ester (5) (306 mg, 0.43
CHaryl), 130.47, 130.86 (d, CHβ-pyr), 134.55 (d, CHvinyl), 137.68 (d,
CHaryl), 137.34, 138.10, 138.63, 139.50, 139.87, 140.06, 140.57,
1
41.29, 147.79, 148.31, 148.64, 148.95, 149.95 (s, Cring), 173.98 (s,
CO CH ). Ϫ UV/Vis (CH Cl ): λmax (lg ε) ϭ 408 (5.421), 544
4.216), 585 (4.234). Ϫ FAB-MS (nitrobenzyl alcohol): m/z (%):
mmol), K
2
CO
3
(297 mg, 2.15 mmol), tetra-n-butylammonium bro-
(10
2
3
2
2
mide (139 mg, 0.43 mmol), LiCl (18 mg, 0.43 mol), Pd(OAc)
2
(
mg, 10 mol-%), 1,4-divinylbenzene (168 mg, 1.3 mmol), and 20 ml
of DMF following the procedure described above. (reaction time
ϩ
1
5
70 8 8 2
330.38 (2) [M ]. Ϫ C74H N O Zn (1330.18): calcd. C 66.82, H
.30, N 8.42, found C 66.58, H 5.23, N 8.27.
1
2 h). Chromatographic separation gave 209 mg (67%, pure re-
1
Reaction of Zinc(II)Ϫ3(8)-Bromodeuteroporphyrin-IX Dimethyl
gioisomer) of a green solid, m. p. 205Ϫ207°C decomp. Ϫ H NMR
2
2
Ester with 1,2-Divinylbenzene: The reaction of the bromoporphyrin (200 MHz, CDCl
with 1,2-divinylbenzene, following the general procedure de-
CH ), 3.19Ϫ3.28 (m, 6 H, CH3, pyr), 3.43 (s, 3 H, CH3, pyr),
scribed above, resulted in a mixture of the monomeric porphyrin
3.60Ϫ3.66 (m, 9 H, CH3, pyr, COOCH ), 4.05 (t, 4 H, J ϭ 7.55 Hz,
), 5.37 (d, 1 H, J ϭ 11.25 Hz, ABX-CHvinyl), 5.92 (d,
H, J ϭ 17.83 Hz, ABX-CHvinyl), 6.89 (d, 1 H, J ϭ 11.25 Hz, J ϭ
7.83, ABX-CHvinyl), 7.38 (d, 1 H, J ϭ 16.10 Hz, AB-CHvinyl), 7.65
3
, TMS): δ ϭ 3.01 (t, 4 H, J ϭ 7.55 Hz, 13 /17 -
5
2
3
1
1
12 and the dimer 14.
13 /17 -CH
2
1
1
Zinc(II)Ϫ3(8)-[2-Vinyl-(E)-Ͱ-styryl]deuteroporphyrin-IX Di-
methyl Ester (12): The porphyrin 12 was obtained as a green solid,
m. p. 204°C decomp., yield 105 mg (32%, mixture of regioisomers).
(
8
d, 2 H, J ϭ 8.23 Hz, CHaryl), 7.87 (d, 2 H, J ϭ 8.23 Hz, CHaryl),
.14 (d, 1 H, J ϭ 16.10 Hz, AB-CHvinyl), 8.44 [s, 1 H, 3(8)-
1
Ϫ H NMR (300 MHz, CDCl
3
): δ ϭ 3.02 (t, 4 H, J ϭ 7.82 Hz,
1
3
CHβ-pyr], 8.99, 9.07, 9.10, 9.17 (s, 4 H, CHmeso). Ϫ C NMR (50
MHz, CDCl ): δ ϭ 11.43, 11.62, 12.33, 13.26 (q, CH3, pyr), 21.55
2
2
1
3 /17 -CH
.65Ϫ3.67 (m, 6 H, COOCH
), 5.57 (d, 1 H, J ϭ 10.97 Hz, ABX-CHvinyl), 5.92 (d, 1 H, J ϭ
7.31 Hz, ABX-CHvinyl), 7.42 (d, 1 H, J ϭ 10.97 Hz, J ϭ 17.31,
ABX-CHvinyl), 7.53 (d, 1 H, J ϭ 7.39 Hz, CHaryl), 7.61Ϫ7.76 (m,
H, CHaryl, AB-CHvinyl), 7.74 (d, 1 H, J ϭ 7.68 Hz, CHaryl), 7.85
d, 1 H, J ϭ 16.25 Hz, AB-CHvinyl), 8.07 (d, 1 H, J ϭ 7.68 Hz,
CHaryl), 8.38 [s, 1 H, 3(8)-CHβ-pyr], 8.84, 8.96, 9.00, 9.08 (s, 4 H,
meso).Ϫ UV/Vis (CH Cl ): λmax (lg ε) ϭ 406 (5.183), 537 (4.062),
75 (4.177). Ϫ FAB-MS (nitrobenzyl alcohol): m/z (%): 728.12 (24)
2
), 3.14Ϫ3.26 (m, 9 H, CH3, pyr), 3.41 (s, 3 H, CH3, pyr),
1
1
3
3
3
), 4.05 (t, 4 H, J ϭ 7.82 Hz, 13 /17 -
1
1
2
2
(
9
1
t, 13 /17 -CH
2
), 37.06, 37.20 (t, 13 /17 -CH
5.01, 95.62, 96.09, 99.14 (d, CHmeso), 114.06 (t, CH2, vinyl), 121.49,
21.84 (d, 2ϫ CHvinyl), 126.99, 127.19 (d, 2ϫ CHaryl) 128.20 (s,
2 3
), 52.11 (q, OCH ),
CH
2
1
CHβ-pyr), 131.68 (d, CHvinyl), 137.21 (d, CHvinyl), 141.90, 143.55,
2
(
1
1
44.73, 144.95, 145.15, 145.37, 145.48, 145.61, 145.81, 145.91,
46.36, 146.49 (s, Cring), 173.91, 174.01 (s, CO CH ). Ϫ UV/Vis
Cl ): λmax (lg ε) ϭ 403 (5.447), 534 (4.180), 572 (4.294). Ϫ
FAB-MS (nitrobenzyl alcohol): m/z (%): 728.22 (18) [M ]. Ϫ
Zn (730.18): calcd. C 69.09, H 5.52, N 7.67, found C
2
3
(
CH
2
2
H
2
2
ϩ
5
42 40 4 4
C H N O
ϩ 64
[
M , Zn]. Ϫ C42
H
40
N
4 4
O Zn (730.18): calcd. C 69.09, H 5.52, N
6
8.94, H 5.36, N 7.89.
7.67; found C 68.87, H 5.36, N 7.59.
Bis[(E)-4-{1-[zinc(II)Ϫdeuteroporphyrin-IX dimethyl ester-
(8)-yl]ethen-2-yl}-(E)-Ͱ-styryl]-3,8-zinc(II)Ϫdeuteroporphyrin-
IX Dimethyl Ester (16): A solution of zinc(II)Ϫ3(8)-[4-vinyl-(E)-α-
styryl]deuteroporphyrin-IX dimethyl ester (10) (140 mg, 0.19
mmol), zinc(II)Ϫ3,8-dibromodeuteroporphyrin-IX dimethyl ester
(
E,E)-β,βЈ-Bis[zinc(II)Ϫdeuteroporphyrin-IX dimethyl ester-
3
3
(8)-yl]-1,2-divinylbenzene (14): The dimer 14 was obtained as a
dark green solid, m. p. > 300°C, yield 143 mg (48%, mixture of
1
regioisomers). Ϫ H NMR (200 MHz, [D
6
]DMSO): δ ϭ 3.26Ϫ3.34
), 3.47Ϫ3.70 (m, 36 H, CH3, pyr, COOCH ),
), 7.69Ϫ7.80 (m, 2 H, CHvinyl),
.36Ϫ8.58 (m, 4 H, CHaryl), 8.95Ϫ9.11 [m, 4 H, CHvinyl, 3(8)-
2
2
(
4
8
m, 8 H, 13 /17 -CH
2
3
(
2 3
4) (70 mg, 0.09 mmol), K CO (138 mg, 1 mmol), tetra-n-butylam-
1
1
.04Ϫ4.33 (m, 8 H, 13 /17 -CH
2
monium bromide (64 mg, 0.2 mmol), LiCl (8 mg, 0.2 mmol), and
palladium(II) acetate (4.5 mg, 0.02 mmol) in 10 ml of anhydrous
DMF was heated at 85°C for 24 h under an inert gas atmosphere
CHβ-pyr], 9.91Ϫ10.05 (m, 6 H, CHmeso), 10.37 (s, 2 H, CHmeso). Ϫ
UV/Vis (CH Cl ): λmax (lg ε) ϭ 404 (5.254), 542 (4.140), 578
4.243). Ϫ FAB-MS (nitrobenzyl alcohol): m/z (%): 1330.36 (5)
2
2
(
argon). After cooling the solution to room temp. CH
was added and the organic layer was extracted with water (4 ϫ 150
ml), dried (Na SO ), filtered, and evaporated. To remove the small
amount of starting material the residue was heated twice [with 10
ml of CH Cl /hexane (3:1) with 1% methanol] to reflux and was
2 2
Cl (100 ml)
(
[
ϩ
64
70 8 8 2
M , Zn]. Ϫ C74H N O Zn (1330.18): calcd. C 66.82, H 5.30,
2
4
N 8.42, found C 66.63, H 5.18, N 8.24.
Reaction with 1,4-Divinylbenzene to Form Monomeric Porphyrin-
2
2
Building Blocks Zinc(II)Ϫ3,8-Bis(4-vinyl-(E)-Ͱ-styryl)deutero- decanted after cooling to room temp. The trimeric porphyrin 16
porphyrin-IX Dimethyl Ester (15): The reaction was carried out was obtained as a dark green solid, m. p. > 300°C, yield 154 mg
with zinc(II)Ϫ3,8-dibromodeuteroporphyrin-IX dimethyl ester (4) (83%, pure regioismer). Ϫ H NMR (300 MHz, [D
1
6
]DMSO): δ ϭ
2
2
(
380 mg, 0.5 mmol), K
monium bromide (161 mg, 0.5 mmol), LiCl (21 mg, 0.5 mmol), COOCH
Pd(OAc) (11 mg, 10 mol-%), 1,4-divinylbenzene (156 mg, 1.2
2
CO
3
(345 mg, 2.5 mmol), tetra-n-butylam-
3.20Ϫ3.40 (m, 12 H, 13 /17 -CH
), 4.22Ϫ4.63 (m, 12 H, 13 /17 -CH
AB-CHvinyl), 8.32Ϫ8.43 (m, 8 H, Haryl), 9.13Ϫ9.28 [m, 6 H, AB-
2
), 3.60Ϫ4.03 (m, 54 H, CH3, pyr
,
1
1
3
2
), 7.97Ϫ8.08 (m, 4 H,
2
mmol) and 20 ml of DMF following the procedure described above. CHvinyl, 3(8)-CHβ-pyr], 10.03Ϫ10.28 (m, 8 H, CHmeso), 10.40Ϫ10.55
(
reaction time 15 h). Chromatographic separation gave 246 mg (m, 4 H, CHmeso). Ϫ 13C NMR (75 MHz, [D
6
]DMSO): δ ϭ 12.33,
1
1
1
(57%) of a green solid, m. p. 213Ϫ215°C decomp. Ϫ H NMR (200
2
13.85, 14.33, 14.53 (q, CH3, pyr), 21.83, 22.34 (t, 13 /17 -CH ),
2
2
2
2
MHz, CDCl
3
, TMS): δ ϭ 2.86Ϫ3.25 (m, 16 H, 13 /17 -CH
2
,
37.70, 37.79 (t, 13 /17 -CH
2
), 52.29 (q, OCH
3
), 98.41, 99.14 (d,
1199
Eur. J. Org. Chem. 1998, 1193Ϫ1200