Efficient synthesis of meso-tetraarylporphyrins using i2 as catalyst and ibx as oxidant

Article abstract of DOI:10.1080/00397910902883595

meso-Tetraarylporphyrins are synthesized from pyrrole and substituted benzaldehydes by a catalytic amount of I2 as catalyst and o-iodoxybenzoic acid (IBX) as oxidant in two steps and one flask. The advantages of this method include the use of inexpensive and easily available catalyst, avoidance of heavy consumption of CH2Cl2, innocuous oxidant, and good yields.

Full text of DOI:10.1080/00397910902883595

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Efficient Synthesis of meso-
Tetraarylporphyrins Using I2 as
Catalyst and IBX as Oxidant
Fenghua Liu a , Le Duan a , Yu-Lu Wang a , Qian
Zhang a & Jin-Ye Wang b
a College of Chemical and Environmental Science,
Henan Normal University, Xinxiang, Henan, China
b Biomedical Engineering, Shanghai JiaoTong
University, Shanghai, China
Version of record first published: 16 Oct 2009.
To cite this article: Fenghua Liu , Le Duan , Yu-Lu Wang , Qian Zhang & Jin-Ye
Wang (2009): Efficient Synthesis of meso-Tetraarylporphyrins Using I2 as Catalyst
and IBX as Oxidant, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 39:22, 3990-3998
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Synthetic Communications1, 39: 3990–3998, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902883595
Efficient Synthesis of meso-Tetraarylporphyrins
Using I2 as Catalyst and IBX as Oxidant
Fenghua Liu,1 Le Duan,1 Yu-Lu Wang,1 Qian Zhang,1
and Jin-Ye Wang2
1College of Chemical and Environmental Science, Henan Normal
University, Xinxiang, Henan, China
2Biomedical Engineering, Shanghai JiaoTong University,
Shanghai, China
Abstract: meso-Tetraarylporphyrins are synthesized from pyrrole and substituted
benzaldehydes by a catalytic amount of I2 as catalyst and o-iodoxybenzoic
acid (IBX) as oxidant in two steps and one flask. The advantages of this method
include the use of inexpensive and easily available catalyst, avoidance of heavy
consumption of CH2Cl2, innocuous oxidant, and good yields.
Keywords: Aldehydes, IBX, meso-tetraarylporphyrins, pyrrole, synthesis
The synthesis of porphyrins attracts widespread interest because of their
potential applications as catalysts[1] and in energy conversion,[2] photody-
namic cancer therapy,[3] molecular electronic devices,[4] and modeling of
enzymes.[5] Tetraarylporphyrins were first synthesized by Rothemund[6]
in 1939. Then Adler et al.[7] proposed a simplified synthetic method for
meso-tetraarylporphyrin. Later, Lindsey et al.[8] published an improved
method for sensitive meso-tetraarylporphyrins in a two-step, one-flask
synthesis. Recently, synthetic methods for tetraarylporphyrins include
the use of various acids,[9] clays,[10] silica chloride,[11] ionic liquids,[12]
and cation exchange resins[13] as catalysts and 2,3-dichloro-5,6-dicyano-1,
Received October 16, 2008.
Address correspondence to Yu-Lu Wang and Jin-Ye Wang, College of Chemi-
cal and Environmental Sciences, Henan Normal University, Xinxiang, Henan
453007, China. E-mail: wyl@henannu.edu.cn; jinyewang@sjtu.edu.cn
3990

I2-Catalyzed Synthesis of meso-Tetraarylporphyrins
3991
4-benzoquinone (DDQ)[14] and p-chloranil[10a] as oxidants. There are
numerous advantages in this approach but still disadvantages, such as
poor product yields, expensive catalysts, complex purification proce-
dures, and heavy consumption of dichloromethane.
o-Iodoxybenzoic acid[15] [IBX, l-hydroxy-l, 2-benziodoxol-3(1 H)-one
oxide], a compound first prepared in 1893, is a mild oxidant and can
widely oxidize alcohols to aldehydes and ketones.[16] We now report that
IBX can successfully oxidize porphyrinogen to porphyrin. In our
previous article,[17] we demonstrated that I2 was a great catalyst for tetra-
arylporphyrins. Herein we describe a method (Scheme 1) for preparing
tetraarylporphyrins under milder conditions; pyrrole and benzaldehyde
in the presence of I2 react to form tetraarylporphyrinogen and IBX as
oxidant in one pot, avoiding the use of deleterious and valuable
DDQ[14] or tetrachlorobenzoquinone (TCQ).[18] Under these conditions,
the yields are 25–63%.
Followed our previous research,[17] we mainly investigate the con-
centration of the reactant and the optimal reaction condition of step 1.
We discovered that this method can achieve a good result under these
reaction conditions.
The best CH2Cl2 quantity was studied first (Table 1). The results
apparently show that 15 ml CH2Cl2 is the proper amount for the tetraar-
ylporphyrin synthesis. It is also observed that with more than 15 ml
CH2Cl2, the time of step 1 increased and the yields decreased. On the
other hand, with less than 15 ml CH2Cl2, the reaction time was shorted
but the yield was less.
We found that when IBX was simply suspended in the solution it can
easily oxidize porphyrinogen to porphyrin at 39ꢀC. When the oxidation
step was done at room temperature, it required quite a long time and
the yield was less (entry 6, Table 2). The optimal oxidant quantity of
IBX was also investigated in CH2Cl2 (Table 2). The results distinctly
show that 1 mmol IBX was the appropriate amount of oxidant. The yield
was less when using a small quantity of IBX; meanwhile, the yield did not
distinctly improve when using more IBX.
Scheme 1. Synthesis of meso-tetraarylporphyrins.

3992
F. Liu et al.
a
Table 1. Study of the quantity of CH2Cl2
Time (min)
Entry
CH2Cl2 (ml)
Step 1
Step 2
Yield (%)b
1
2
3
4
5
6
7
2.5
5
30
35
40
50
60
65
120
100
120
180
240
260
280
300
21
28
43
58
54
53
50
10
15
20
25
40
aReactions were performed with 1 mmol pyrrole,
1 mmol benzaldehyde, and 0.025 mmol iodine at rt.
After step 1 was completed, 1 mmol IBX was added to
the solution and refluxed at 39ꢀC.
bIsolated yields.
To investigate the applicable scope of our method, we have
researched a series of benzaldehyde substrates (Table 3), including a
variety of ortho, meta, and para positions, both electron donating and
withdrawing. Various aldehyde substrates can successfully participate
in this two-step, one-flask process, and an increase in steric hindrance and
the existence of electron-withdrawing groups at the benzaldehyde brings
on a general decrease in the yields of porphyrin formation.
Table 2. Study of the quantity of IBXa
Entry
IBX (mmol)
Step 2 time (h)
Yield (%)c
1
2
3
4
5
6b
0.5
0.75
1
1.2
1.5
1
8
5
4
3
2.6
14
45
49
58
58
59
38
aReactions were performed with 1 mmol pyrrole,
1 mmol benzaldehyde, and 0.025 mmol iodine in 15 ml
CH2Cl2 at rt. After step 1 was completed, IBX was
added.
bThe reaction temperature is room temperature.
cIsolated yields.

I2-Catalyzed Synthesis of meso-Tetraarylporphyrins
3993
Table 3. Synthesis of various meso-tetraarylporphyrins
using a one-pot, two-step method
Entry
PhCHOa
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
9
H
5
5
3.5
5.5
6
6
6
3.5
7
5
58
63
60
49
25
48
31
56
30
28
38
40
p-MeO
p-Me
p-Cl
p-F
m-MeO
m-Br
m-Me
m-NO2
o-MeO
o-Br
10
11
12
6
6
o-Cl
aReactions were performed with 1 mmol benzalde-
hyde, 1 mmol pyrrole, and 0.025 mmol iodine in 15 ml
CH2Cl2 at rt. After step 1 was completed, 1 mmol IBX
was added to the solution and refluxed at 39ꢀC.
bIsolated yields.
In conclusion, we have developed a practical and novel procedure for
the synthesis of meso-tetraarylporphyrins in the presence of a catalytic
amount of I2 under IBX oxidation. Our method has the advantages of
facile workup, inexpensive and easily available catalyst, small solvent
quantity, nontoxic oxidant, and ease of purification.
EXPERIMENTAL
CH2Cl2 was distilled from CaCl2. Pyrrole and benzaldehyde were distilled
1
before use; substituted benzaldehydes were used as obtained. H NMR
spectra were recorded on a Bruker AC-400 NMR spectrometer in solutions
of CDCl3 using tetramethylsilane (TMS) a as the internal standard. The
ultraviolet–visible spectra was obtained on a T9 UV-vis spectrophotometer.
Typical Procedure
A standard reaction was performed in a 50-ml, one-necked, round-
bottomed flask equipped with magnetic stirrer. The flask was charged
with 15 ml of distilled CH2Cl2, benzaldehyde (1 mmol, 0.106 g), and I2

3994
F. Liu et al.
(0.025 mmol, 0.0063 g). The resulting solution was stirred for 5 min at
room temperature (20ꢀC). Then pyrrole (1 mmol, 0.067 g) was added.
The mixture was completed after 50 min of continuous stirring. After-
ward, IBX (1 mmol, 0.280 g) was added, and the reaction mixture was
refluxed for 4 h at 39ꢀC, cooled, and filtered. The filtrate was concen-
trated by rotary evaporation and purified by column chromatography
(silica gel; CH2Cl2=petroleum ether 1:1) to give (1) in 58% yield.
Data
5,10,15,20-Tetraphenylporphyrin (1)
1
This compound was obtained as purple crystals, mp> 300ꢀC; H NMR
(400MHz, CDCl3): ꢁ2.74 (br. s, 2NH), 7.79 (m, 12Ar-H), 8.23 (d,
8Ar-H, J ¼ 1.6 Hz), 8.87 (s, 8-pyrrole-H). Anal. calcd. for C44H30N4: C,
85.97; H, 4.92; N, 9.11. Found: C, 85.79; H, 5.01; N, 8.92. UV-vis (CH2Cl2;
log e) kmax (nm): 424 (5.58), 514 (4.80), 549 (4.33), 590 (4.12), 645 (4.08).
5,10,15,20-Tetrakis(p-methoxyphenyl)porphyrin (2)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3). ꢁ2.73 (br. s, 2NH), 4.13 (s, 12MeO-H), 7.31 (d,
8Ar-H, J ¼ 8.8 Hz), 8.15 (d, 8Ar-H, J ¼ 8.4 Hz), 8.89 (s, 8-pyrrole-H).
Anal. calcd. for C48H38N4O4: C, 78.45; H, 5.21; N, 7.62. Found: C,
78.43; H, 5.19; N, 7.60. UV-vis (CH2Cl2; log e) kmax (nm): 426 (5.61),
518 (4.83), 555 (4.63), 595 (4.33), 650 (4.21).
5,10,15,20-Tetrakis(p-methylphenyl)porphyrin (3)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.75 (br. s, 2NH), 2.73 (s, 12Me-H), 7.57 (d,
8Ar-H, J ¼ 7.6 Hz), 8.12 (d, 8Ar-H, J ¼ 8.0 Hz), 8.88 (s, 8-pyrrole-H).
Anal. calcd. for C48H38N4: C, 85.94; H, 5.71; N, 8.35. Found: C, 85.70;
H, 5.74; N, 8.21. UV-vis (CH2Cl2; log e) kmax (nm): 422 (5.59), 516
(4.81), 551 (4.48), 591 (4.29), 647 (4.13).
5,10,15,20-Tetrakis(p-chlorophenyl)porphyrin (4)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.83 (br. s, 2NH), 7.77 (d, 8Ar-H), 8.15 (d,

I2-Catalyzed Synthesis of meso-Tetraarylporphyrins
3995
8Ar-H, J ¼ 8.4 Hz), 8.87 (s, 8-pyrrole-H). Anal. calcd. for C44H26Cl4N4:
C, 70.23; H, 3.48; N, 7.45. Found: C, 70.20; H, 3.61; N, 7.46. UV-vis
(CH2Cl2; log e) kmax (nm): 424 (5.58), 515 (4.86), 549 (4.45), 590 (4.25),
645 (4.15).
5,10,15,20-Tetrakis(p-fluorophenyl)porphyrin (5)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.85 (br. s, 2NH), 7.76 (d, 8Ar-H, J ¼ 8.4 Hz),
8.18 (d, 8Ar-H, J ¼ 8.4 Hz), 8.86 (s, 8-pyrrole-H). Anal. calcd. for
C44H26F4N4: C, 76.96; H, 3.82; N, 8.16. Found: C, 76.85; H, 3.80; N,
3.91. UV-vis (CH2Cl2; log e) kmax (nm): 424 (5.56), 514 (4.83), 589
(4.24), 644 (4.01).
5,10,15,20-Tetrakis(m-methoxyphenyl)porphyrin (6)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.77 (br. s, 2NH), 4.01 (s, 12MeO-H), 7.35–7.85
(m, 16Ar-H), 8.91 (s, 8-pyrrole-H). Anal. calcd. for C48H38N4O4: C,
78.45; H, 5.21; N, 7.62. Found: C, 78.37; H, 5.24; N, 7.65. UV-vis
(CH2Cl2; log e) kmax (nm): 423 (5.60), 514 (4.27), 548 (4.09), 589 (3.94),
644 (3.83).
5,10,15,20-Tetrakis(m-bromophenyl)porphyrin (7)
This compound was obtained as purple crystals, mp > 300ꢀC; 1H
NMR (400 MHz, CDCl3). ꢁ2.87 (br. s, 2NH), 7.97–7.99 (m,
12Ar-H), 8.40 (s, 4Ar-H), 8.88 (s, 8-pyrrole-H). Anal. calcd. for
C44H26Br4N4: C, 56.81; H, 2.82; N, 6.02. Found: C, 56.89; H, 2.83;
N, 5.94. UV-vis (CH2Cl2; log e) kmax (nm): 424 (5.61), 515 (4.32),
548 (4.04), 591 (3.98), 645 (3.82).
5,10,15,20-Tetrakis(m-methylphenyl)porphyrin (8)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.75 (br. s, 2NH), 2.84 (s, 12Me-H), 7.60–7.92
(m, 16Ar-H), 8.87 (s, 8-pyrrole-H). Anal. calcd. for C48H38N4: C,
85.94; H, 5.71; N, 8.35. Found: C, 85.78; H, 5.72; N, 8.18. UV-vis
(CH2Cl2; log e) kmax (nm): 424 (5.58), 515 (4.39), 549 (4.16), 590 (4.03),
645 (3.95).

3996
F. Liu et al.
5,10,15,20-Tetrakis(m-nitrophenyl)porphyrin (9)
This compound was obtained as purple crystals, mp > 300ꢀC; 1H
NMR (400 MHz, CDCl3): ꢁ2.82 (br. s, 2NH), 8.57–8.75 (m,
16Ar-H), 9.103 (s, 8-pyrrole-H). Anal. calcd. for C44H26N8O8: C,
66.52; H, 3.25; N, 14.28. Found: C, 66.38; H, 3.27; N, 14.22. UV-vis
(CH2Cl2; log e) kmax (nm): 425 (5.60), 516 (4.40), 549 (4.09), 592
(4.01), 645 (3.93).
5,10,15,20-Tetrakis(o-methoxyphenyl)porphyrin (10)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.59 (br. s, 2NH), 3.57–3.64 (m, 12MeO-H),
7.33–7.36 (m, 8Ar-H), 7.75–7.79 (m, 8Ar-H), 8.74 (s, 8-pyrrole-H). Anal.
calcd. for C48H38N4O4: C, 78.45; H, 5.21; N, 7.62. Found: C, 78.39; H,
5.11; N, 7.49. UV-vis (CH2Cl2; log e) kmax (nm): 426 (5.58), 513 (4.37),
546 (4.19), 589 (4.12), 643 (4.05).
5,10,15,20-Tetrakis(o-bromophenyl)porphyrin (11)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.59 (br. s, 2NH), 7.66–7.70 (m, 12Ar-H),
8.04–8.06 (m, 4Ar-H), 8.69 (s, 8-pyrrole-H). Anal. calcd. for
C44H26Br4N4: C, 56.81; H, 2.82; N, 6.02. Found: C, 56.93; H, 2.72; N,
6.10. UV-vis (CH2Cl2; log e) kmax (nm): 426 (5.53), 513 (4.31), 544
(4.05), 589 (3.96), 643 (3.76).
5,10,15,20-Tetrakis(o-chlorophenyl)porphyrin (12)
1
This compound was obtained as purple crystals, mp > 300ꢀC; H NMR
(400 MHz, CDCl3): ꢁ2.63 (br. s, 2NH), 7.67–7.86 (m, 12Ar-H),
8.14–8.19 (m, 4Ar-H), 8.72 (s, 8-pyrrole-H). Anal. calcd. for
C44H26Cl4N4: C, 70.23; H, 3.48; N, 7.45. Found: C, 70.31; H, 3.49; N,
7.37. UV-vis (CH2Cl2; log e) kmax (nm): 426 (5.57), 512 (4.29), 543
(4.08), 587 (3.95), 641 (3.87).
ACKNOWLEDGMENT
This work was supported by the National Program on Key Basic
Research Projects of China (973 Program, 2005 CB724306).

I2-Catalyzed Synthesis of meso-Tetraarylporphyrins
3997
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