ture of 7:3 v/v light petroleum–dichloromethane; RF (1:3
CH2Cl2–light petroleum) 0.41; λmax/nm (log ε/dm3 molϪ1 cmϪ1
dichloromethane (25 cm3) at 0 ЊC. The mixture was stirred for
)
5 h and simultaneously allowed to warm to room temperature.
The urea was removed by filtration and the solvent removed
under reduced pressure. The products were purified by flash
column chromatography eluting with chloroform on 15 × 3 cm
silica. The product was the first band to elute: recrystallisation
by layering light petroleum (30–40 ЊC) onto a solution of the
product in the minimum volume of dichloromethane yielded 1
(77 mg, 66%) (Found: C, 75.55; H, 7.3; N, 5.25. C67H77F5N4O2
requires C, 75.73; H, 7.24; N, 5.47%); RF (CHCl3) 0.73; λmax/nm
(log ε/dm3 molϪ1 cmϪ1) 410 (5.30), 508 (4.29), 541 (3.70), 575
410 (5.43), 508 (4.34), 541 (3.90), 575 (4.00) and 627 (3.70);
δH (200 MHz) Ϫ2.40 (2H, br s), 1.10 (12H, t, J 7.3), 1.50 (36H,
s), 1.78 (8H, sextet, J 7.4), 2.17 (8H, qn, J 7.4), 2.45 (12H, s),
3.99 (8H, t, J 7.6), 7.80 (2H, t, J 1.7), 7.91 (4H, d, J 1.8) and
10.22 (2H, s); δC(125 MHz) 14.74, 23.91, 27.06, 32.18, 35.65,
36.00, 97.28, 119.65, 121.55, 128.13, 136.94, 141.54, 141.82,
143.48, 145.65 and 150.33; m/z (ϩve FAB) 966.7 (Mϩ). The
second fraction was eluted with 1:1 light petroleum–
dichloromethane and subsequently recrystallised from hot
light petroleum yielding 6 (1.088 g, 42%); RF (1:3 CH2Cl2–light
petroleum) 0.24; λmax/nm (log ε/dm3 molϪ1 cmϪ1) 410 (5.48), 508
(4.43), 542 (3.95), 575 (4.08) and 627 (3.00); νmax(KBr)/cmϪ1
(3.91), 626 (3.15) and 655 (2.83); νmax(KBr)/cmϪ1 1759 (C᎐O);
᎐
δH (500 MHz) Ϫ2.34 (2H, br s), 1.15 (12H, m), 1.56 (18H, s),
1.80 (8H, m), 2.22 (8H, m), 2.51 (6H, s), 2.54 (6H, s), 4.03 (8H,
t, J 7.4), 7.86 (1H, s), 7.96 (2H, s), 8.33 (2H, d, J 7.9), 8.59 (2H,
d, J 8.0) and 10.29 (2H, s); δF (235 MHz) Ϫ152.52 (2F, d, J 20),
Ϫ158.17 (1F, t, J 22.7) and Ϫ162.56 (2F, t, J 21.5); δC(125
MHz) 14.45, 15.35, 23.55, 23.63, 26.73, 31.91, 35.40, 35.73,
97.39, 115.60, 120.18, 121.45, 125.76 (br m), 126.85, 127.75,
129.99, 134.03, 135.51, 137.08, 138.32 (br d, J 251), 141.04,
141.60, 141.77 (br d, J 252), 141.85, 143.48, 143.92, 144.38,
145.65, 150.06, 150.22 and 163.13; m/z (ϩve FAB) 1066.0
(Mϩ).
1720 (C᎐O); δ (500 MHz) Ϫ2.29 (2H, s), 1.18 (6H, t, J 7.4),
᎐
H
1.20 (6H, t, J 7.4), 1.60 (18H, s), 1.84 (8H, sextet, J 7.3), 2.25
(8H, m), 2.55 (6H, s), 2.56 (6H, s), 4.08 (8H, t, J 7.9), 5.65 (2H,
s), 7.49 (1H, t, J 7.5), 7.56 (2H, t, J 7.6), 7.70 (2H, d, J 7.3), 7.91
(1H, t, J 1.8), 8.01 (2H, d, J 1.8), 8.28 (2H, d, J 8.0), 8.56 (2H, d,
J 8.0) and 10.33 (2H, s); δC(125 MHz) 14.24, 14.93, 23.31,
23.41, 26.49, 26.54, 31.69, 35.18, 35.50, 67.11, 97.06, 116.17,
119.74, 121.18, 127.56, 128.44, 128.50, 128.75, 128.89, 129.97,
133.26, 135.60, 136.09, 136.74, 140.89, 141.37, 141.54, 143.18,
143.50, 144.42, 145.35, 147.79, 149.94 and 166.78; m/z (ϩve
FAB) 989.9 (Mϩ). The third fraction was eluted from the col-
umn using dichloromethane yielding 4,4Ј-(2,8,12,18-tetrabutyl-
3,7,13,17-tetramethyl-21H,23H-porphyrin-5,15-diyl)dibenzoic
acid bis(phenylmethyl) ester 5 (0.458 g, 17%); RF (1:3 CH2Cl2–
light petroleum) 0.10; λmax/nm (log ε/dm3 molϪ1 cmϪ1) 410
(5.39), 508 (4.40), 541 (3.90), 576 (4.00) and 626 (3.48); δH (200
MHz) Ϫ2.42 (2H, s), 1.08 (12H, t, J 7.3), 1.71 (8H, sextet, J
7.4), 2.15 (8H, qn, J 7.4), 2.45 (12H, s), 3.97 (8H, t, J 7.5), 5.57
(4H, s), 7.48 (6H, m), 7.63 (4H, dd, J 7.8 and 1.5), 8.17 (4H, d, J
8.1), 8.46 (4H, d, J 8.1) and 10.24 (2H, s); δC(125 MHz) 14.21,
14.89, 23.28, 26.43, 35.46, 67.10, 97.25, 116.69, 128.43, 128.49,
128.73, 128.91, 130.02, 133.13, 135.84, 136.04, 141.52, 143.63,
144.54, 147.52 and 166.71; m/z (ϩve FAB) 1011.4 (Mϩ).
4-[2,8,12,18-Tetrabutyl-3,7,13,17-tetramethyl-15-(3,5-di-tert-
butylphenyl)-21H,23H-porphyrin-5-yl]benzoic acid n-propyl-
amide 10
Oxalyl chloride (2.0 cm3, 16 mmol) was added to a suspension
of 8 (200 mg, 2.2 × 10Ϫ4 mol) in dry dichloromethane (5 cm3)
under nitrogen. It was stirred for 0.5 h and the solvent removed
on the vacuum line. The acid chloride formed was not isolated
1
but could be characterised by H NMR spectroscopy: δH (200
MHz; CDCl3) Ϫ0.98 (4H, s), 1.14 (12H, t, J 7.0), 1.57 (18H, s),
1.76 (8H, m), 2.17 (8H, m), 2.22 (6H, s), 2.26 (6H, s), 3.66 (8H,
t, J 7.3), 7.93 (1H, s), 8.12 (2H, s), 8.48 (2H, d, J 8.0), 8.66 (2H,
d, J 8.0) and 10.27 (2H, s). It was redissolved in dry dichloro-
methane (5 cm3), neutralised with p-dimethylaminopyridine
(0.25 g, 2 mmol) and propylamine (0.131 g, 2.2 mmol) was then
added in dry dichloromethane (1 cm3). After stirring for 15 min
the product was purified by elution through a short silica plug.
Recrystallisation by layering methanol onto a solution of the
product in chloroform yielded 10 (140 mg, 67%); RF (CHCl3)
0.27; λmax/nm (log ε/dm3 molϪ1 cmϪ1) 410 (5.32), 508 (4.20), 541
4-[2,8,12,18-Tetrabutyl-3,7,13,17-tetramethyl-15-(3,5-di-tert-
butylphenyl)-21H,23H-porphyrin-5-yl]benzoic acid 8
Palladium (10%) on charcoal (200 mg) was added to a solution
of 6 (0.800 g, 8.09 × 10Ϫ4 mol) in dry dichloromethane (100
cm3) and the mixture degassed using the water aspirator. It was
then stirred rapidly under an atmosphere of hydrogen gas for
3.5 h and monitored by TLC. The palladium on charcoal was
removed by filtration through Celite and the solvent removed
under reduced pressure. After redissolving in dichloromethane,
the product was separated from the remaining starting
material using a short flash column (10 × 3 cm) eluting initially
with 1% methanol in dichloromethane to remove the reactant
and then with 2% methanol to yield 8 (584 mg, 80%); RF -
(CHCl3) 0.04; λmax/nm (log ε/dm3 molϪ1 cmϪ1) 410 (5.43), 508
(4.34), 541 (3.90), 575 (4.00) and 627 (3.70); νmax(KBr)/cmϪ1
1691 (C᎐O); δ (500 MHz) 1.16 (6H, t, J 7.1), 1.17 (6H, t, J
(3.67), 574 (3.85) and 626 (3.30); νmax(KBr)/cmϪ1 1632 (C᎐O);
᎐
δH (200 MHz; CDCl3) Ϫ2.41 (2H, s), 1.13 (15H, m), 1.50 (9H, s),
1.55 (9H, s), 1.77 (10H, m), 2.16 (8H, br m), 2.45 (12H, s), 3.64
(2H, q, J 6.6), 3.98 (8H, t, J 7.4), 6.48 (1H, t, J 6.7), 7.78 (1H, t,
J 1.8), 7.90 (2H, d, J 1.7), 8.15 (4H, s) and 10.23 (2H, s); m/z
(ϩve FAB) 940.9 (Mϩ).
4-{2,8,12,18-Tetrabutyl-3,7,13,17-tetramethyl-15-(3,5-di-tert-
butylphenyl)-5-[4-(N-propylcarbamoyl)phenyl]porphyrinato}-
zinc(II) 10
A mixture of 10 (60 mg, 6.4 × 10Ϫ5 mol) and zinc acetate dihy-
drate (140 mg, 6.4 × 10Ϫ4 mol) were dissolved in chloroform
and heated to reflux for several min. TLC and UV showed the
reaction to be complete after 5 min. The product was purified
by elution through a short silica plug using chloroform.
Recrystallisation from light petroleum (30–40 ЊC) layered onto
a solution of the product in dichloromethane yielded Zn-10 (60
mg, 94%) (Found: C, 76.4; H, 8.65; N, 7.15. C64H83N5OZn
requires C, 76.58; H, 8.33; N, 6.98%); RF (CHCl3) 0.37; λmax/nm
(log ε/dm3 molϪ1 cmϪ1) 412 (5.71), 538 (4.43) and 575 (4.20);
νmax(KBr)/cmϪ1 1641 (C᎐O); δ (500 MHz) 1.15 (15H, m), 1.56
᎐
H
7.1), 1.56 (18H, s), 1.81 (8H, m, J 7.7), 2.24 (8H, quintet, J
7.7), 2.52 (6H, s), 2.56 (6H, s), 4.05 (8H, br t), 7.87 (1H, s),
7.98 (2H, s), 8.32 (2H, d, J 7.7), 8.60 (2H, d, J 7.6) and 10.31
(2H, s); δC(125 MHz) 14.25, 14.94, 23.33, 23.40, 26.52, 31.68,
35.16, 35.50, 97.10, 116.01, 119.80, 121.19, 127.55, 129.16,
129.40, 133.44, 135.52, 136.76, 140.86, 141.39, 141.56, 143.19,
143.58, 144.35, 145.36, 148.66, 149.96 and 171.93; m/z (ϩve
FAB) 899.6 (Mϩ).
4-[2,8,12,18-Tetrabutyl-3,7,13,17-tetramethyl-15-(3,5-di-tert-
butylphenyl)-21H,23H-porphyrin-5-yl]benzoic acid 2,3,4,5,6-
pentafluorophenyl ester 1
Dicyclohexylcarbodiimide (DCC) (21 mg, 0.1 mmol) in dry
dichloromethane (20 cm3) was added dropwise to a solution of
8 (100 mg, 0.1 mmol), pentafluorophenol (22 mg, 1.2 mmol)
and 4-pyrrolidinopyridine (POP) (15 mg, 0.1 mmol) in dry
᎐
H
(9H, s), 1.57 (9H, s), 1.78 (6H, m), 1.83 (4H, m), 2.18 (4H, qn, J
7.6), 2.21 (4H, qn, J 7.6), 2.41 (6H, s), 2.50 (6H, s), 3.61 (2H,
m), 3.94 (4H, d, J 7.2), 4.02 (4H, t, J 7.7), 6.52 (1H, br t), 7.87
(1H, s), 7.99 (2H, s), 8.13 (2H, br d), 8.16 (2H, br d) and 10.20
(2H, s); δC(125 MHz) 11.63, 14.21, 14.83, 15.52, 23.07, 23.31,
23.38, 26.37, 26.49, 31.65, 35.15, 35.46, 42.00, 97.66, 117.71,
J. Chem. Soc., Perkin Trans. 1, 1997
2585