Microwave-assisted synthesis of 5,10,15,20-tetraaryl porphyrins

Article abstract of DOI:10.1081/SCC-100000176

Clean and eco-friendly microwave-assisted cyclocondensation of different aryl aldehydes with pyrrole forms 5,10,15,20 tetraaryl porphyrins in 20 to 43% yields in very low amount of propionic acid in one step is presented.

Full text of DOI:10.1081/SCC-100000176

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MICROWAVE-ASSISTED SYNTHESIS OF 5,10,15,20-
TETRAARYL PORPHYRINS
a
a
a
S. M. S. Chauhan , B. B. Sahoo & K. A. Srinivas
a
Department of Chemistry, University of Delhi, Delhi, 110 007, India
Published online: 09 Nov 2006.
To cite this article: S. M. S. Chauhan , B. B. Sahoo & K. A. Srinivas (2001): MICROWAVE-ASSISTED SYNTHESIS OF
5,10,15,20-TETRAARYL PORPHYRINS, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 31:1, 33-37
To link to this article: http://dx.doi.org/10.1081/SCC-100000176
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SYNTHETIC COMMUNICATIONS, 31(1), 33–37 (2001)
MICROWAVE-ASSISTED SYNTHESIS OF
5,10,15,20-TETRAARYL PORPHYRINS
∗
S. M. S. Chauhan, B. B. Sahoo, and K. A. Srinivas
Department of Chemistry, University of Delhi,
Delhi 110 007, India
ABSTRACT
Clean and eco-friendly microwave-assisted cyclocondensa-
tion of different aryl aldehydes with pyrrole forms 5,10,15,20-
tetraaryl porphyrins in 20 to 43% yields in very low amount of
propionic acid in one step is presented.
Microwave irradiation is an important tool to improve the selectivity, rate
enhancement, and reduction of thermal degradative byproducts in organic synthe-
sis (1,2). Cyclocondensation of aryl aldehydes with pyrrole in propionic acid is
an important method for the synthesis of symmetrical 5,10,15,20-tetraaryl por-
phyrins (3–6) in low yields. The sterically-hindered and electron-withdrawing
groups in the phenyl ring of 5,10,15,20-tetraaryl porphyrins have been prepared
by BF3-etherate and DDQ methods in moderate yields (7–13). Although there have
been recent advances to improve the synthesis of 5,10,15,20-tetraaryl porphyrins,
including solid state and other modifications (14–20), these syntheses suffer from
purification problems and low yields. One of the major disadvantages of the
above methods is the requirement of large amounts of corrosive, acidic, and
∗
To whom correspondence should be addressed.
33
Copyright ꢀC 2001 by Marcel Dekker, Inc.
www.dekker.com

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CHAUHAN, SAHOO, AND SRINIVAS
environmentallyharmfulchlorine-containingsolvents. Optimalyieldsareobtained
only with 0.01 M concentrations of pyrrole and aldehyde. Microwave-assisted or-
ganic synthesis reduces the amount of solvents and time, and leads to high yields.
Hence, we report the microwave-assisted synthesis of 5,10,15,20-tetraaryl por-
phyrins by cyclocondensation of arylaldehydes with pyrrole using a minimum
amount of propionic acid in different reaction conditions.
The microwave-assisted cyclocondensation of benzaldehyde and pyrrole in
propionic acid (5 ml) for 4 min gave 5,10,15,20-tetraaryl porphyrin in 41% yield.
Similarly, the cyclocondensation of arylaldehydes and pyrrole in propionic acid
(3–5 ml) gave 5,10,15,20-tetraaryl porphyrins in microwave irradiation for 3 to
5
min. The yields of various porphyrins and their spectroscopic data are presented
in Table 1. As shown in Table 1, the MW irradiation method gave a remarkably high
yield of 5,10,15,20-tetraaryl porphyrins (3a–h), as compared to other high dilution
methods. The formation of polymeric by-product depends on the solvent used and
the irradiation time. Further, the purification of porphyrins in microwave-assisted
synthesis is easier than solution phase synthesis.
Figure 1 represents the effect of time on the formation of porphyrins in
microwave-assisted porphyrin synthesis. The high dilution conditions are not re-
quired and the chlorin contamination is reduced in microwave-assisted porphyrin
synthesis. Thus, microwave-assisted porphyrin synthesis may be developed into
eco-friendly methods for the synthesis of different heterocycles.
Figure 1. Comparison of maximum yields w.r.t time.

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CHAUHAN, SAHOO, AND SRINIVAS
Scheme 1. One step synthesis of meso-tetraaryl porphyrin.
EXPERIMENTAL
In a typical procedure, benzaldehyde (or its derivatives) (0.1 mol) and pyr-
role (0.1 mol) were added to freshly distilled propionic acid (5 mL) successively.
The well-homogenized mixture was irradiated in a microwave oven (domestic,
the reaction carried out in a pyrex bottle) for 3 to 5 min by 1-min periods, fol-
lowed by cooling to room temperature and homogenization. The cooled reaction
mixture was diluted with H2O (50 mL) and extracted in CHCl2(2 × 50 mL). The
dichloromethane layer was separated and evaporated under reduced pressure and
the residue was passed through Al2O3(Merck aluminium oxide 90, activity II-III,
100 gm) column and eluted with hexane-CH2Cl2. The porphyrin fractions were
collected and evaporated under vaccum. The nitro porphyrins were purified directly
by washing with dichloromethane (3 × 50 mL), without using column chromatog-
raphy. The yield(s) of the reaction product was obtained after recrystallization
from a mixure of CH2Cl2/EtOH, tabulated in Table 1.
ACKNOWLEDGMENTS
We are thankful to Professor R.N. Khanna for providing the microwave
oven. We are also thankful to the Department of Science and Technology (DST)
and Council of Scientific and Industrial Research (CSIR), New Delhi, India, for
financial support.
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Received in the U.K. January 24, 2000

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