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8.22 and 8.07 (AB system, JAB = 7.8 Hz, 8 H, m-Ph and o-Ph, respec- CDCl3/CD3OD 2:1, v/v, 25 °C): δP = 26.82 ppm. IR (neat): νmax = 1607
˜
tively), 4.28–4.22 (m, 2 H, CH2O), 4.04–3.97 (m, 2 H, CH2O), 3.91 (s,
(m), 1559 (m), 1539 (w), 1522 (m), 1517 (w), 1507 (m), 1499 (w),
1472 (m), 1458 (m), 1440 (m), 1384 (w), 1352 (w), 1312 (m), 1302
(w), 1292 (m), 1249 (s, P=O), 1225 (w), 1204 (m, P=O), 1184 (w),
1172 (s), 1156 (w), 1105 (m), 1086 (m), 1073 (w), 1059 (m), 1039 (m),
6 H, OCH3), 1.13 (t, 3JH,H = 7.1 Hz, 6 H, CH3) ppm. 31P NMR (600 MHz,
CDCl3/CD3OD 2:1, v/v, 25 °C): δP = 26.16 ppm. IR (neat): νmax = 1717
˜
(s, C=O), 1606 (s), 1549 (w), 1524 (m), 1471 (m), 1435 (s), 1418 (w),
1401 (w), 1390 (w), 1353 (w), 1308 (w), 1271 (s, P=O), 1226 (m), 1201 1009 (m, P–O), 993 (s, P–O), 982 (s, P–O), 974 (s, P–O), 958 (w), 892
(s, P=O), 1178 (m), 1155 (m), 1110 (s), 1098 (s), 1063 (m), 1041 (m), (s), 876 (m), 858 (s), 846 (s), 808 (s), 800 (s), 788 (w), 778 (m), 773
987 (s, P–O), 960 (s, P–O), 893 (s), 865 (s), 819 (s), 789 (s), 758 (s),
734 (s), 716 (s), 700 (s), 671 (w), 666 (m), 636 (m), 579 (s), 574 (s),
(s), 758 (m), 741 (s), 717 (m), 700 (s), 668 (m), 645 (w), 608 (s), 578
(s), 568 (s), 553 (s) cm–1. UV/Vis (CHCl3/CH3OH 95:5, v/v): λmax [log (ε/
555 (s) cm–1. UV (CHCl3): λmax [log (ε/
M
–1 cm–1)] = 420 (5.45), 546
M
–1 cm–1)] = 420 (5.33), 550 (4.24), 586 (4.06) nm. HRMS (ESI): m/z
(4.24), 580 (3.95) nm. HRMS (ESI): m/z calcd. for C40H33N4NaO7PZn
calcd. for C38H33N4NaO5PZn [M + Na]+ 743.13777; found 743.16632.
[M + Na]+ 799.12760; found 799.12538.
[10-(Diethoxyphosphoryl)-5,15-dimesitylporphyrinato(2–)]zinc
(Zn3f): This compound (Table 1, Entry 11) was prepared from a
Zn2f/Zn4f mixture (1.28 g, molar ratio of 10:6) and diethyl H-phos-
phonate. The reaction mixture was chromatographed with a
CH2Cl2/MeOH mixture (99.5:0.5, v/v) as an eluent to give phosphon-
ate Zn3f as a red-purple solid in 56 % yield (745 mg). Porphyrins
Zn1f [Rf = 0.92 (TLC, SiO2, CH2Cl2/MeOH 95:5, v/v)] and Zn5f [Rf =
0.18 (TLC, SiO2, CH2Cl2/MeOH 95:5, v/v)] were also formed in the
reaction according to 1H NMR and MALDI-TOF analyses of the reac-
tion mixture. Compounds Zn1f and Zn5f were not isolated in pure
form.
[10-(Diethoxyphosphoryl)-5,15-bis(4-cyanophenyl)porphyrin-
ato(2–)]zinc (Zn3d): This compound (Table 1, Entry 9) was pre-
pared from a Zn2d/Zn4d mixture [96 mg, also containing Zn1d
(Zn2d/Zn1d/Zn4d molar ratio of 10:2.8:1.9)] and diethyl H-phos-
phonate. The reaction mixture was chromatographed with CHCl3 as
an eluent to give phosphonate Zn3d as a red-purple solid in 59 %
yield (50 mg). Porphyrins Zn1d [Rf = 0.90 (TLC, SiO2, CHCl3/MeOH
95:5, v/v)] and Zn5d [Rf = 0.17 (TLC, SiO2, CHCl3/MeOH 95:5, v/v)]
1
were also formed in the reaction according to H NMR and MALDI-
TOF analyses of the reaction mixture. Compounds Zn1d and Zn5d
were not isolated in pure form.
Compound Zn3d: Rf = 0.37 (TLC, SiO2, CHCl3/MeOH 95:5, v/v). 1H
NMR (600 MHz, CDCl3/CD3OD 2:1, v/v, 25 °C): δH = 10.09 (d, JH,H
Compound Zn3f: Rf = 0.55 (TLC, SiO2, CHCl3/MeOH 95:5, v/v). 1H
3
NMR (300 MHz, CDCl3/CD3OD 2:1, v/v, 25 °C): δH = 9.94 (d, JH,H
=
3
=
4.9 Hz, 2 H, Hꢀ), 9.92 (s, 1 H, Hmeso), 9.03 (d, 3JH,H = 4.4 Hz, 2 H, Hꢀ),
3
3
3
4.8 Hz, 2 H, Hꢀ), 10.08 (s, 1 H, Hmeso), 9.15 (d, JH,H = 4.3 Hz, 2 H,
8.56 (d, JH,H = 4.9 Hz, 2 H, Hꢀ), 8.50 (d, JH,H = 4.4 Hz, 2 H, Hꢀ),
Hꢀ), 8.64 (d, 3JH,H = 4.8 Hz, 2 H, Hꢀ), 8.58 (d, 3JH,H = 4.3 Hz, 2 H, Hꢀ),
7.07 (br. s, 4 H, m-Ph), 4.33–4.19 (m, 2 H, CH2O), 4.81–3.95 (m, 2 H,
3
8.12 and 7.88 (AB system, JAB = 7.9 Hz, 8 H, m-Ph and o-Ph, respec- CH2O), 2.42 (s, 6 H, p-CH3), 1.60 (s, 12 H, o-CH3), 1.15 (t, JH,H
=
tively), 4.30–4.22 (m, 2 H, CH2O), 4.05–3.97 (m, 2 H, CH2O), 1.14 (t, 7.0 Hz, 6 H, CH3) ppm. 31P NMR (300 MHz, CDCl3/CD3OD 2:1, v/v,
3JH,H = 6.9 Hz, 6 H, CH3) ppm. 31P NMR (600 MHz, CDCl3/CD3OD 2:1,
25 °C): δP = 26.96 ppm. IR (neat): νmax = 2956 (w), 2920 (m), 2853
v/v, 25 °C): δP = 25.60 ppm. IR (neat): ν = 2225 (s, C≡ N), 1603 (w), 1610 (w), 1583 (w), 1548 (w), 1522 (m), 1446 (m), 1437 (m),
˜
˜
max
(m), 1559 (w), 1550 (w), 1525 (m), 1506 (w), 1471 (m), 1436 (w),
1412 (w), 1479 (m), 1353 (w), 1307 (w), 1254 (m, P=O), 1224 (s),
1418 (w), 1394 (m), 1384 (m), 1368 (w), 1353 (m), 1312 (w), 1256 1197 (s, P=O), 1160 (m), 1158 (s), 1014 (s, P–O), 993 (s, P–O), 981 (s,
(w), 1222 (m), 1200 (s, P=O), 1174 (w), 1158 (s), 1102 (w), 1092 (m),
1068 (s), 1019 (s, P–O), 991 (s, P–O), 982 (s, P–O), 948 (m), 892 (s),
P–O), 964 (s), 884 (s), 852 (s), 788 (s), 753 (s), 726 (s), 700 (m), 666
(m), 591 (m), 565 (m), 531 (s), 443 (w), 430 (w), 414 (w) cm–1. UV/
875 (w), 866 (m), 857 (s), 804 (w), 798 (s), 778 (s), 753 (s), 738 (s), Vis (CHCl3): λmax [log (ε/
717 (s), 699 (s), 682 (w), 668 (m), 662 (w), 646 (m), 621 (w),
(3.85) nm. HRMS (ESI): m/z calcd. for C42H42N4O3PZn [M + H]+
615 (w), 610 (w), 589 (m), 584 (s), 579 (s), 573 (s), 567 (s), 563 (m), 745.22805; found 745.22844, calcd. for C42H41N4NaO3PZn [M + Na]+
M
–1 cm–1)] = 418 (5.40), 548 (3.93), 581
553 (s) cm–1. UV/Vis (CHCl3): λmax [log (ε/
M
–1 cm–1)] = 418 (5.24), 548
767.21000; found 767.21006.
(4.13), 582 (3.89) nm. HRMS (ESI): m/z calcd. for C38H28N6O3PZn [M
+ H]+ 711.12465; found 711.12158, calcd. for C38H27N6NaO3PZn [M
+ Na]+ 733.10659; found 733.10353.
[5,15-Bis(2,6-Dichlorophenyl)-10-(diethoxyphosphoryl)por-
phyrinato(2–)]zinc (Zn3g): This compound (Table 1, Entry 12) was
prepared from a Zn2g/Zn4g mixture [30 mg, also containing Zn1g
(Zn2g/Zn1g/Zn4g molar ratio 10:1:2)] and diethyl H-phosphonate.
The reaction mixture was chromatographed with a CH2Cl2/MeOH
mixture (99.5:0.5, v/v) as eluent to give phosphonate Zn3g as a red-
purple solid in 57 % yield (17 mg). Porphyrins Zn1g [Rf = 0.91 (TLC,
SiO2, CH2Cl2/MeOH 95:5, v/v)] and Zn5g [Rf = 0.21 (TLC, SiO2,
CH2Cl2/MeOH 95:5, v/v)] were also formed in the reaction according
[10-(Diethoxyphosphoryl)-5,15-bis(4-methoxyphenyl)por-
phyrinato(2–)]zinc (Zn3e): This compound (Table 1, Entry 10) was
prepared from a Zn2e/Zn4e mixture [80 mg, also containing Zn1e
(Zn2e/Zn1e/Zn4e molar ratio 10:0.2:1.8)] and diethyl H-phosphon-
ate. The reaction mixture was chromatographed with CHCl3 as an
eluent to give phosphonate Zn3e. Additional purification by col-
umn chromatography with CHCl3 as eluent yielded pure phosphon-
ate Zn3e as a red-purple solid in 42 % yield (35 mg). Porphyrins
Zn1e [Rf = 0.93 (TLC, SiO2, CHCl3/MeOH 95:5, v/v)] and Zn5e [Rf =
0.04 (TLC, SiO2, CHCl3/MeOH 95:5, v/v)] were also formed in the
reaction according to 1H NMR and MALDI-TOF analyses of the reac-
tion mixture. Compounds Zn1e and Zn5e were not isolated in pure
form.
1
to H NMR and MALDI-TOF analyses of the reaction mixture. Com-
pounds Zn1g and Zn5g were not isolated in pure form. A scale-up
experiment was performed with a mixture of bromides Zn2g and
Zn4g (300 mg, Zn2g/Zn1g/Zn4g molar ratio 10:1:1.5), diethyl H-
phosphonate (40 equiv.), triethylamine (15 equiv.) and Pd(OAc)2/
2 PPh3 catalyst (25 mol-%) in a toluene/ethanol mixture (70 mL, 1:1,
v/v). Porphyrin Zn3g was obtained in 65 % yield (190 mg).
Compound Zn3e: Rf = 0.19 (TLC, SiO2, CHCl3/MeOH 95:5, v/v). 1H Compound Zn3g: Rf = 0.48 (TLC, SiO2, CHCl3/MeOH 95:5, v/v). 1H
3
NMR (600 MHz, CDCl3/CD3OD 2:1, v/v, 25 °C): δH = 10.01 (d, JH,H
=
NMR (300 MHz, CDCl3/CD3OD 2:1, v/v, 25 °C): δH = 10.03 (dd, 3JH,H
=
3
4.8 Hz, 2 H, Hꢀ), 10.00 (s, 1 H, Hmeso), 9.09 (d, JH,H = 4.3 Hz, 2 H,
Hꢀ), 8.75 (d, 3JH,H = 4.8 Hz, 2 H, Hꢀ), 8.70 (d, 3JH,H = 4.3 Hz, 2 H, Hꢀ),
7.87 (d, 3JH,H = 8.3 Hz, 4 H, o-Ph), 7.08 (d, 3JH,H = 8.3 Hz, 4 H, m-Ph),
4.27–4.21 (m, 2 H, CH2O), 4.03–3.97 (m, 2 H, CH2O), 3.90 (s, 6 H,
4.9, 4JP, H = 0.5 Hz, 2 H, Hꢀ), 9.99 (s, 1 H, Hmeso), 9.10 (d, 3JH,H = 4.5 Hz,
3
3
2 H, Hꢀ), 8.54 (d, JH,H = 4.9 Hz, 2 H, Hꢀ), 8.50 (d, JH,H = 4.5 Hz, 2
H, Hꢀ), 7.63–7.58 (m, 4 H, m-Ph), 7.56–7.49 (m, 2 H, p-Ph), 4.34–4.23
3
(m, 2 H, CH2O), 3.84–3.95 (m, 2 H, CH2O), 1.15 (t, JH,H = 7.2 Hz, 6
OCH3), 1.13 (t, JH,H = 7.0 Hz, 6 H, CH3) ppm. 31P NMR (300 MHz,
H, CH3) ppm. 31P NMR (300 MHz, CDCl3/CD3OD 2:1, v/v, 25 °C): δP =
3
Eur. J. Org. Chem. 0000, 0–0
8
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