Synthesis of meso-substituted corroles and porphyrins using iodine as a catalyst

Article abstract of DOI:10.1007/s12039-020-01823-z

Abstract: Different types of corroles and porphyrins are synthesized from substituted aldehydes and pyrrole. The current synthetic method involves iodine as catalyst and proceeds at room temperature itself. By varying the amounts of reactants (i.e., pyrrole and aldehydes), the corrole and porphyrins were obtained in good to excellent yields. These products were characterized by ¹H-NMR, UV-visible, and HRMS techniques. The reaction approach utilizes the readily available pyrrole and substituted aldehydes as starting materials and makes this reaction highly attractive in diversity-oriented synthesis. Graphic abstract: Different types of porphyrins and corroles are synthesized from substituted aldehydes and pyrrole using iodine as a catalyst and the reaction proceeds at room temperature itself. By varying the amount of reactants (i.e. pyrrole and aldehydes), the porphyrins and corroles are obtained in good to excellent yields.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s12039-020-01823-z

J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 2 3
Ó I n d ia n A c a d e m y o f S c i en c es
h t tp s :/ / d o i . o r g/ 1 0 . 1 0 0 7 / s 1 2 0 3 9 - 0 2 0 - 0 1 8 2 3 - z Sadhana( 0 1 23 4 5 6 7 8 9( ) . -, v o l V ) F T 3 ] ( 0 1 23 4 5
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REGULAR ARTICLE
Synthesis of meso-substituted corroles and porphyrins using iodine
as a catalyst
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B io - O r g a n i c R e s e a r c h L a b o r a t o r y , D e p a r t m e n t o f C h e m i s tr y , U n iv e r s i t y o f D e l h i , D e l h i 1 1 0 0 0 7 , I n di a
E - m a i l : s h i v e m s c h a u h a n @ y a h o o . c o m
M S r e c e i v e d 1 5 M a r c h 2 02 0 ; r e v i s e d 1 1 J u n e 2 0 2 0; a c c e p t e d 1 2 J u n e 2 0 2 0
Abstract. D i f f e r e n t t y p e s o f c o rr o l e s a n d p o r p h y r i n s a r e s y n t h e s i z e d f r o m s u b s t i tu te d a l d e h y d e s a n d p yr -
r o l e . T h e c u rr e n t s y n t h e t i c m e t h o d i n v o l v e s i o d i n e a s c a t a l y s t a n d p r o c e e d s a t r o o m t e m p e r a t u r e i t s el f . B y
v a r y in g t h e a m o u n t s o f r e a c t a n t s ( i . e . , p y r r o l e a n d a l d e h y d e s ) , t h e c o r r o l e a n d p o r p h y r i n s w e r e o b t a i ne d i n
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g o o d t o e x c e l l e n t y i e l d s . T h e s e p r o d u c t s w e r e c h a r a c t e r i z e d b y H - N M R , U V - v i s ib l e , a n d H R M S t e c h ni q ue s .
T h e r e a c t i o n a p p r o a c h u t i l i z e s t h e r e a d i ly a v a i l a b l e p y r r o l e a n d s u b s t i tu t e d a l d e h y d e s a s s t a r t i n g m a t e r i al s a nd
m ak e s t h i s r e a c t i o n h i g h l y a t t r a c t i v e i n d i v e r s it y - o r i e n t e d s y n t h e si s .
Keywords. P y r r o l e ; a l d e h y d e s ; i o d i n e ; c o r r o l e ; c o r r i n ; p o r p h y r i n .
1. Introduction
a t o m o f p o rp h y r i n s k e l et o n . M o re o v er , i n s o l u t i o n s,
c o r ro l e s a re p r e s e n t i n a ci d – b a s e e q u i l i b ri a a n d l e a d t o
t h e f o r ma t i o n o f c at i o n i c o r a n i o n i c s p e c i e s b y r e a c t i n g
w i t h a ci d o r b a s e . T h e p r e s e n c e o f o n e i m i n e- l i k e a n d
t h re e p y r r o l e- l i k e n i t r o g e n d o n o r a t o m s m ak e t h e m
m o r e a ci d i c ( s t r o n g e r a ci d ) t h an t h ei r p o r p h y ri n a n d
P o r p h y r i ns a r e t h e c l a s s o f t e t r a py r ro li c m a c r o c y c l e s
c o mp r i s i n g o f f o u r p y r ro le r in g s t h a t a r e l i n k e d
1
t h r o u g h t h e m e s o -c a r b o n a t o m s a t m e s o -p o s i t i o n s .
T h e se a r e c o m p ri s e d o f 1 8 p e l e c t ro n i c c o n j u g a t e d
s y s t e m i n w h i ch 1 8p e l e c t ro n s a r e d e l oc a l iz e d o v e r 2 0
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D u e t o t h e a l t e r a t i o n o f l i g a n d s s t ru ct u r e , t h e t r a n -
s i t i o n m et al c o m p l e x e s o f c o r ro l e s s h o w v e r y d i f f er e n t
p r o p er t i es t h an t h e a n a l o g o u s m et al l o p o r p h y ri n s . A s
c o m p a re d t o t h e d i p r o t o n i c p o rp h y r i n s , c o r r o l es
b e h a v e a s t e t r a d e n t a t e t r i an i o n i c l i g a n d s t o w ar d t r a n -
e l ec t r o ns f o r m a p la n a r s t r uc t u r e a n d a r e r e s p o n s i b l e
f o r t h ei r a r o m a t i c i t y. M e t a l l o p or p h y r i n r in g i s c o m -
m o n i n a v a r i e t y o f i m p o r ta n t b i o lo g ic a l s y s t e m w h e r e
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p h y r i ns a r e c o l o r e d i n n a t ur e a n d a r e c h a r a c t e r i ze d b y
t h e i r c h a r a c t e r i s t i c U V - v i s i b l e a b s o r p ti o n p a t t er n .
R ec e n t l y , t h e p o r p h y r in s a n d m e ta ll o p o r p hy ri n s w e r e
s i t i o n m et al i o n s . T h u s , i t h e l p s t h em t o s t ab i l i z e t h e
1 6
u n u s u a l l y h i g h o x i d a t i o n s t at es , s u c h a s c o b a l t ( I V ) ,
1
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C u r re n t l y , m e t a l l at ed
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u s e d i n p h o t o d yn a m ic t he ra p y , s o l a r c e l ls , c h e m i c a l
c o r r o l e s a re u s e d i n b i o c h e mi ca l a p p l i c at i o n s s u c h a s
s e n s o r, a n t i o x i d an t t h er a p y , s o l a r c el l s , d i ab et i c t h e r -
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s e n s o r s, c a t a l ys t s , d y e s a n d p i g m e n t s , l iq u i d c r y s -
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t a ls , e t c . C o r r o l e s a r e f ul l y a r o m a t ic t e t r a -p y r ro l i c
o r g a n i c m a c r oc yc li c c o m p ou n d s t ha t a r e a n a l o g u e s o f
1 9
a p y , a n t i -c a n c e r a g e n t s , a s a c at a l y s t f o r d i f f er e n t
2 0
o x i d a t i o n r e ac t i o n s a n d g e n e r al l y u s e d a s a p o t e n t i a l
1 0
p o r p h y r i ns . I t i s a 1 9 - c a r b o n c o nt a in in g c o m p o u n d
2 1
s e n s i t i z e r i n p h o t o d y n a mi c c an ce r t h er a p y .
F i r s t c o r ro l e w a s s y n t h e s i ze d i n 1 9 6 5 b y J o h n s en
( o n e l e s s t h a n p o rp h y r i n) , w h i c h p o s s e s s e s 1 8 p c o n -
j u g a t e d e l e c t r o n i c s y s t e m . S i m i l a r t o o t h e r p o r -
p h y r i ns a n d t h ei r a n a l o gu e s , c o r ro le s a r e a r o m a t i c i n
1 1
2 2
et al. f o l l o w i n g w h i ch , c o r r o l e s w e re s y n t h e s i z e d b y
v a r i o u s m et h o d s w i t h t h e h e l p o f p y r r o l e a n d a l d e h y -
1 2
n a t u r e. H o w e v e r , c o rr o l e ’s s k e l e t o n p o s s e s s e s a
2 3
d e s u n d er d i ff e r en t r e ac t i o n c o n d i t i o n s s u c h a s A l O
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3
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d i r e c t p y r r o l e –p y r r ol e l in k a g e a t e a c h m e s o - ca r b on
2 4 –2 6
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A c O H ( b y r e flu x i n g ) , T F A ( wi t h
( i n m i c ro w a v e ),
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Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-020-01823-z) contains supple-
mentary material, which is available to authorized users.

1 2 3 P a g e 2 o f 8
J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 2 3
2 8
s o l v en t C H C l ) , H C l ( w it h s o l v e n t , H O a n d
s u b s t i tu t e d b e n z a l d e h y d e s ( 1 m m o l ) a n d f r e s h l y d is t i l le d
p y r r o l e ( 2 m m o l ) w e r e a d d e d a n d s t ir r e d a t r o o m t em p er -
a t u r e . T o t h i s r e a c t io n m i x t u r e , i n s t e a d o f a c i d , i o d in e w a s
a d d e d ( a s a c a t a l y t ic a m o u n t ) a n d t h e c o l o r c h a n g e o f t he
r e a c ti o n m i x t u r e w a s o b s e r v e d . F u r t h e r , t h e r o u n d - bo t t om
fl a s k w a s c o v e r e d w i t h f o il p a p e r a n d c o n t i n u e d s t ir r in g f or
5 – 1 0 m i n . P r o g r e s s o f t h e r e a c t i o n w a s m o n i t o r e d w i t h t he
h e l p o f t h i n l a y e r c h r o m a t o g r a p h y ( T L C ) ( i . e ., i f n o r ea ct a nt
r e m a in s ) . F o l l o w i n g w h ic h , D D Q ( 1 m m o l ) w a s a d d ed a nd
t h e s t ir r i n g w a s c o n t i n u e d f o r a n o t h e r 5 m i n . T h e p ro d uc t
( c o r r o l e ) w a s s e p a r a t e d b y b a s i c a l u m i n a c o l u m n c hr o-
m a t o g r a p h y w i t h h e x a n e / c h l o r o f o r m s o l u t io n . T h e c om -
p o u n d w a s s o l i d i n n a t u r e w i t h p u r p l e c o l o r a n d c or r o le s
w e r e o b t a i n e d i n h i g h y i e l d w i t h 1 : 2 m o l a r r a t i o i n t he
p r o c e s s .
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b y 2 , 3- di c h l o r o - 5 , 6 - d i cy a no - 1 , 4 -b e n z o q u in on e ( D D Q )
o r p- c h l or on il . R e c e n t ly , c o r ro le s a r e a l s o s y nt h e s i ze d i n
m i c r o w a v e a t h i g h t e m p e r a t u re i n w h ic h i od in e i s u s e d
3 1
i n s t e a d o f a c i d . F u rt h e rm o r e , c o r ro le s a r e a l s o s y n -
t h e s i z ed u n d e r s o l ve n t -f re e c o n d i ti o n s u s i ng e l ec t r o n
3 2
d e fi ci e n t a l d e h y d e s . T h e s e m e th o d s r e q u i re d h i g h
t e m p e r a t u r e a n d s t r o n g o rg a n ic a c i d s . D u ri n g t h e s y n -
t h e s i s o f c o r r o l e s b y p y r ro le a n d a l d e h y d e s v i a t h es e
m e t h o d s , p o r p h y r i n s a r e o b t a i n e d a s a m a jo r p ro d u c t a n d
3 3
c o r r o l es a s b y p r o d u c t. T h e r e f o r e , t he re i s a n e e d t o
d e v e l o p a n e f fi c i e n t m e th o d f or t h e s y n t h e s is o f c o r r o l es .
R e c e n t l y , o u r r e s e a r c h g ro u p h a d d e v e lo p e d n e w e r
e f fi c i e n t m e t h o d o lo g i es f o r t he s y nt h e s i s o f d i ff e r en t
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c al i x[ 4 ] p y r r o l e s , p o r ph o d i m e t he n e, c a l ix p h y ri n s ,
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e t c. W e h a d a l s o s u c c e s s f u l l y s y nt h e s i z e d d i f f er e n t of porphyrin (4a–f)
c o r e - m o di fi e d p o rp h y r i no g e n s , 5 - p or ph o m e t h e n es ,
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5 , 1 0 - po rp ho di m et he ne s , 5 , 15 -p o r p h od i m e the n e s a n d
3 8
p o r p h o t r i m et h en e s . I n c o nt i nu a t i on o f o u r o n g o i n g
s i m il a r t o t h e a b o v e p r o c e s s . T h e o n l y d i f f e r e n c e b et w e e n
t h i s a n d t h e a b o v e p r o c e s s i s t h e e q u im o l a r r a t i o o f r ea ct a n ts
( s u b s ti t u t e d b e n z a l d e h y d e s a n d p y r r o l e ) a n d s o l v e n t q ua n-
t it y . I n t h i s p r o c e s s , s u b s t i tu t e d b e n z a l d e h y d e s ( 1 m m o l)
a n d p y r r o l e ( 1 m m o l ) w e r e u s e d i n e q u i m o l a r r a t i o 1 :1 w i t h
2 0 m L c h l o r o f o r m .
r e s e a r c h, w e h a v e d e v e lo p e d a n e w e r e f fi c ie n t a n d
s i m p l e m et h o d f o r t he s y nt h e s i s o f p o r ph y r in o i d s a n d
t h e i r a n a l o g ue s. H e re , w e h a v e r e p o r te d t h e i o d i n e-
c at a l y z e d s y n t h e s i s o f c o r ro le s a n d p o r ph y r in s f r o m
p y r r o l e a n d a l d e h y d e s i n d i c hl o r o m e t h a n e f o r 5 – 1 0
m i n . T h i s r e a c t i o n d o e s n o t r e q u i re h i g h t e m p e r a t u r e
b u t p r o c e e d s a t r o o m t e m p e r a t u r e i ts e l f . T h e e as i l y
a s s es sa b l e 2 , 3- di c h lo r o -5 , 6- d i c y a n o - 1, 4 - b e n z o q u i no n e
( D DQ ) i s u s e d a s a n o x i da nt i n t he c u rr e n t r e a ct i o n .
T h i s m et h o d d o e s n o t r e q u i re o r g a n i c a c i ds , e x t r e me l y
t o x i c c h e m i c al s, o r c o s t l y c a t a l y s ts f or t he s y nt h e s i s o f
c o r r o l es .
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3 H ) . M S ( E S I ) : m / z = c a l c u l a t e d ( C H N ) , 5 26 . 63 ;
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2. Experimental
2 . 4 5,10,15-Tris(pentafluorophenyl)corrole
(PFC) (3b)
P y r r o l e, s u b st i t u t e d b e n z a l d e h y d e s , i o d i n e , D DQ a n d s o l -
v e n ts ( l i k e a ce t on i t r i l e , m e t h a n o l , d i c h l o r o m e t h a n e ( C H
2
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C l ) a nd c h lo r o f o r m ( C H C l ) ) w e re p u r c h a s e d f r o m
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S p e c tr oc h e m a n d t h e s e a n a l y t i c g r a d e s o l v e n t s w e r e d r ie d
b e f o r e t h ei r u s e. T o c o n fi r m t h e f o r m a t i o n o f c o m p o u n d s ,
3
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( 0 .1 5 ) , 6 0 4 .6 5 n m ( 0 .0 9 ) , H - N M R ( C D C l , 4 0 0 M H z ); d =
3
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J E O L 4 0 0 M H z H - NM R s p e c t r o m e t e r w a s u t i l i z e d , a n d
9 . 1 3 – 9 .1 2 ( d , 2 H ) , 8 . 7 8 – 8 .7 7 ( d , 2 H ) , 8 . 6 0 – 8 . 5 8 ( d, 4 H ),
-2 . 8 3 ( s , 3 H ) . M S ( E S I ) : m / z = c a l c u l a t e d ( C H F N ) ,
t e tr a m e t h y l si l a n e ( T M S) w a s t a k e n a s a n i n t e rn a l s t a n d a r d
s o lv e n t . T h e U V - v i s i b l e s p e c t r u m w a s r e c o r d e d b y P e r k in -
E l m er L A M B D A 9 5 0 h i g h - p e r f o r m a n c e U V - v i s i b l e
s p e c t r o p h o t o m et e r .
3 7 1 1 1 5
4
7 9 6 .4 9 ; o b s e r v e d ( M ?H ) ? 7 9 7 .0 8 .
2 . 5 5,10,15-Tris(2,6-dichlorophenyl)corrole
(DPC) (3c)
2 . 1 General procedure for the synthesis of A3-
corrole (3a–f)
U V - V i s ( C H C l ) : km a x ( l o g e) = 4 0 9 .8 2 ( 0 .8 5 ) , 4 22 . 03
3
1
( 0 .7 9 ) , 5 6 6 .0 9 ( 0 .1 0 ) , 6 0 5 .3 0 ( 0 .0 4 ) , 6 3 3 .0 9 n m ( 0 . 02 ). H -
F o r t h e s y n th e s i s o f c o rr o l e , a r o u n d - b o t t o m fl a s k w i t h N
s a t u r at e d d i ch l o r o m e t h a n e ( 1 0 m L ) w a s u s e d i n w h ic h 8 . 3 6 ( m , 4 H ) , 7 . 7 4 ( m , 6 H ) , 7 . 3 5 ( m , 3 H ) , -1 . 7 2 ( s , 3 H );
N M R ( C D C l , 4 0 0 M H z ) : d = 8 . 9 2 ( d , 2 H ) , 8 . 5 1 ( d, 2 H ),
2
3

J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 2 3
P a g e 3 o f 8
1
2
3
Table 1. O p t i m i z a t i o n o f r e a c t i o n c o n d i t i o n s f o r t h e i o d i n e - c a t a l y z e d c o r r o l e ( 3a) a n d p o r p h y r i n ( 4a) s y n t h e s i s f ro m
p y rr o l e ( 1a) a n d b e n z a l d e h y d e (2a) .
a
b
Y i e l d o f c o r r o l e ( 3 a ) ( % )
b
Y i e l d o f p o r p h y r i n ( 4 a) ( % )
P
y
r
r
o
l
e
/
a
l
d
e
h
y
d
e
r
a
t
i
o
S
o
l
v
e
n
t
1
2
3
4
5
6
7
8
2:1
2 : 1
2 : 1
2 : 1
2 : 1
2 : 1
1:1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
CH2Cl2
C H C l
M e OH
A c e t o n i t r i l e
M e OH ? C H C l
27
2 5
1 0
2 5
2 2
2
0
0
0
0
6
6
4
6
5
\1
24
2 2
9
2 2
1 5
1
3
2
2
T H F
CH2Cl2
C H C l
M e OH
3
9
1 0
1 1
1 2
A c e t o n i t r i l e
M e OH ? C H C l
T H F
0
0
2
2
T h e a cc el e r a t e c at a l y t i c s y s t e m w h i c h i s f u r t h e r a p p l i e d i n t a b l e 2 t o s y n t h e s i z e m o r e d e r i v a ti v e s a r e i n b o l d .
a
R e a ct i o n p r o c e ed s a t r o o m t e m p e r a t u r e .
b
I
s
o
l
a
t
e
d
y
i
e
l
d
.
M S ( E S I ) : m / z = c a l c u l a t e d ( C H N C l ) , 7 2 9 .9 8 ;
3 7 2 0
2
.
8
5
,
1
0
,
1
5
,
2
0
-
T
e
t
r
a
p
h
e
n
y
l
p
o
r
p
h
y
r
i
n
(
T
P
P
)
(
4
a
)
4
6
o b s er v e d ( M ?H ) ? 7 3 0 . 9 6 .
U
V
-
V
i
s
(
C
H
C
l
)
:
k
(
l
o
g
e
)
=
4
1
5
.
8
6
(
1
.
7
4
)
,
5
1
5
.
1
1
3
m
a
x
( 0 .0 6 ) , 5 4 9 .8 8 ( -0 . 0 1 ) , 5 9 0 .1 2 ( -0 . 0 2 ) , 6 4 8 .6 3 ( -0 .0 1 )
1
2 . 6 5,10,15-Tris(4-chlorophenyl)corrole (4-
ClPC) (3d)
n
m
,
H
-
N
M
R
(
C
D
C
l
,
4
0
0
M
H
z
)
:
d
=
8
.
8
4
(
s
,
8
H
)
,
3
8
.
2
2
–
8
.
2
0
(
d
,
8
H
)
,
7
.
7
7
–
7
.
7
2
(
d
,
1
2
H
)
,
-
2
.
7
8
(
s
,
2
H
)
.
U V - V i s ( C H C l ) : km a x ( l o g e) = 4 1 6 . 2 4 ( 0 . 6 8 ) , 5 1 4 .6 7
3
1
(
0
.
0
5
)
,
5
7
5
.
2
5
(
0
.
1
3
)
,
6
1
6
.
8
7
(
0
.
0
9
)
,
6
4
7
.
8
9
(
0
.
0
7
)
.
H
-
2
.
9
5
,
1
0
,
1
5
,
2
0
-
N
M
R
(
C
D
C
l
,
4
0
0
M
H
z
)
d
=
8
.
9
9
(
d
,
2
H
)
,
8
.
8
5
(
d
,
2
H
)
,
Tetra(pentafluorophenyl)porphyrin (PFP) (4b)
3
8 . 2 7 ( m , 4 H ) , 8 . 1 3 ( d , 2 H ) , 7 . 7 6 ( m , 6 H ), -2 . 9 1 ( s , 3 H ) ; M S
( E S I ) : m / z = c al cu l a t e d ( C H N C l ) , 6 2 8 . 1 0 ; o b s e r v e d U V - V i s ( C H C l ) : km a x ( l o g e) = 4 1 2 .6 0 ( 0 .7 8 ) , 5 06 . 82
3
7
2
3
4
3
3
?
1
( 0 .0 1 ) , 5 8 6 .0 2 ( 0 .0 0 3 ) , 6 5 5 . 0 5 n m ( 0 .0 0 1 ) . H - N M R
(
M
?
H
)
6
2
9
.
1
2
.
(
C
D
C
l
,
4
0
0
M
H
z
)
:
d
=
8
.
9
5
(
s
,
8
H
)
,
-
2
.
9
0
(
s
,
2
H
)
.
3
2 . 7 5,10,15-Tris(4-bromophenyl)corrole (4-
BrPC) (3e)
2 . 1 0 5,10,15,20-Tetra(2,6-
dichlorophenyl)porphyrin (DCP) (4c)
U
V
-
V
i
s
(
C
H
C
l
)
:
k
(
l
o
g
e
)
=
4
1
7
.
9
6
(
1
.
1
0
)
,
5
1
5
.
8
1
3
m
a
x
1
(
0
.
0
5
)
,
5
7
7
.
7
5
(
0
.
1
3
)
,
6
1
5
(
0
.
0
9
)
,
6
4
8
.
6
5
(
0
.
0
8
)
n
m
.
H
-
U
V
-
V
i
s
(
C
H
C
l
)
:
k
(
l
o
g
e
)
=
4
1
8
.
2
9
(
1
.
3
5
)
,
5
1
2
.
6
5
3
m
a
x
N
M
R
(
C
D
C
l
,
4
0
0
M
H
z
)
d
=
9
.
0
2
(
d
,
2
H
)
,
8
.
8
6
(
d
,
4
H
)
4
(
0
.
0
4
)
,
5
5
5
.
1
0
(
0
.
0
2
)
,
5
9
2
.
3
7
(
0
.
0
0
3
)
,
6
5
8
.
2
0
(
0
.
0
0
2
)
n
m
,
3
1
H z ) , 8 . 6 3 ( m , 4 H ) , 8 . 2 7 ( d , 4 H ) , 7 . 9 2 – 8 . 1 6 ( m , 6 H ) , -2 . 8 0
( s, 3 H ) .
H
-
N
M
R
(
C
D
C
l
,
4
0
0
M
H
z
)
;
d
=
8
.
6
9
(
s
,
8
H
)
,
7
.
8
2
–
7
.
7
8
3
(
m
,
8
H
)
,
7
.
7
3
–
7
.
6
8
(
m
,
4
H
)
,
-
2
.
6
5
(
s
,
2
H
)
.

1
2
3
P
a
g
e
4
o
f
8
J. Chem. Sci.
(
2
0
2
0
)
1
3
2
:
1
2
3
Scheme 1. I o d i n e - c a t a l y z e d s y n t h e s i s o f s u b s t i t u t e d c o r r o l e s ( 3a– f) a n d p o r p h y r i n s ( 4a– f) f r o m p y r r o l e ( 1a) a nd
a l de h y d es (2a– f) i n d i c h l o ro m e t h a n e u n d e r n i t r o g e n a t m o s p h e r e a t r o o m t e m p e r a t u r e .
2 . 1 1 5,10,15,20-Tetra(4-chlorophenyl)porphyrin
(4-ClPP) (4d)
2 . 1 2 5,10,15,20-Tetra(4-bromophenyl)porphyrin
(4-BrPP) (4e)
U
V
-
V
i
s
(
C
H
C
l
)
:
k
(
l
o
g
e
)
=
4
1
9
.
0
2
(
1
.
4
4
)
,
5
1
5
.
1
6
U
V
-
V
i
s
(
C
H
C
l
)
:
k
(
l
o
g
e
)
=
4
2
1
.
5
3
(
1
.
6
0
)
,
5
1
5
.
2
2
3
m
a
x
3
m
a
x
1
( 0. 0 7) , 5 5 0 . 2 2 ( 0 . 0 3 ) , 5 9 0 . 1 8 ( 0 . 0 2 ) , 6 4 7 . 7 3 ( 0 . 0 2 ) n m , H - ( 0 .0 8 ) , 5 5 0 .3 3 ( 0 .0 4 ) , 5 9 0 .3 6 ( 0 .0 3 ) , 6 4 7 .2 0 ( 0 .0 2 ) n m , H -
1
N
M
R
(
C
D
C
l
,
4
0
0
M
H
z
)
:
d
=
8
.
8
3
(
s
,
8
H
)
,
8
.
1
3
–
8
.
1
0
(
d
,
N
M
R
(
C
D
C
l
,
4
0
0
M
H
z
)
:
d
=
8
.
8
2
(
s
,
8
H
)
,
8
.
0
6
–
8
.
0
4
(
d
,
3
3
8
H
)
,
7
.
7
4
–
7
.
7
2
(
d
,
8
H
)
,
-
2
.
8
9
(
s
,
2
H
)
.
8
H
)
,
7
.
8
9
–
7
.
8
7
(
d
,
8
H
)
,
-
2
.
9
1
(
s
,
2
H
)
.

J. Chem. Sci.
(
2
0
2
0
)
1
3
2
:
1
2
3
P
a
g
e
5
o
f
8
1
2
3
Table 2. S y n t h e s i s o f s u b s t i t u t e d c o r r o l e s ( 3a– f) a n d s u b s t i tu t e d p o r p h y r i n s ( 4a– f) f r o m
p y r r o l e ( 1a) a n d a l d e h y d e s (2a– f) i n d i c h l o r o m e t h a n e u n d e r n i t r o g e n a t m o s p h e r e .
P
y
r
r
o
l
e
A
l
d
e
h
y
d
e
P
r
o
d
u
c
t
Y i e l d ( % )
2 7
R
e
f
e
r
e
n
c
e
a
2
9
,
3
2
1
1a
3a
a
3
2
2
1a
3b
3 5
a
2
9
,
3
2
3
4
1a
1a
3c
3 1
3 0
CHO
Cl
Cl
2c
a
3
2
3d
CHO
Cl
2d
a
a
b
2
9
5
6
7
1a
1a
1a
3e
2
8
3f
–
3
1
,
4
1
4a
2
4

1 2 3 P a g e 6 o f 8
Table 2. (contd)
J. Chem. Sci.
(
2
0
2
0
)
1
3
2
:
1
2
3
P
y
r
r
o
l
e
A
l
d
e
h
y
d
e
P
r
o
d
u
c
t
Y i e l d ( % )
3 4
R
e
f
e
r
e
n
c
e
b
3
9
8
1a
4b
b
3
9
9
1a
1a
4c
3
1
%
CHO
Cl
Cl
2c
b
3
2
,
4
1
1
0
4d
2
9
CHO
Cl
2d
b
4
0
1
1
1a
1a
4e
2 8
b
4
1
1
2
4f
2 0
a
2
:
1
M
o
l
a
r
r
a
t
i
o
o
f
p
y
r
r
o
l
e
(
1
a
)
a
n
d
a
l
d
e
h
y
d
e
s
(
2
a
–
f
)
.
b
1 : 1 M o l a r r a t i o o f p y r r o l e (1a) a n d a l d e h y d e s ( 2a– f) .
3. Results and Discussion
H o w e v e r , t h e m o l a r r a t i o 1 : 1 o f p y r r o l e ( 1a) a n d
a l d e h y d es (2a) g a v e p o rp h y r i n (4a) a s a m a j o r
p r o d u ct . D i f f e re n t t y p e s o f s o l v e n t ( d i c h l o r o m e t h an e,
m et h a n o l , a ce t o n i t ri l e , c h l o ro fo rm , t e t r a h y d r o f u r a n
( T H F ), a n d m i x t u r e o f d i ch l o r o m e t h a n e a n d m e t h a -
n o l ) a r e p r o v i d e d i n T a b l e 1 . F ro m T a b l e 1, i t i s
o b s er v e d t h at i n d i ch l o r o m e t h a n e , b o t h c o r r o l es
( en t r y 1 ) a n d p o r p h y r i n s ( en t r y 7 ) w e re o b t a i n e d i n
m ax i m u m y i el d s . T h e s e r ea c t i o n s w e re p e r fo r m ed a t
r o o m t e m p e ra t u r e w i t h o u t a n y h e a t i n g ( i n m i cr o -
w a v e a n d r e flu x i n g ) a n d t h e p r o g re s s o f t h e r e a ct i o n
w a s m o n i t o r e d v i a t h i n l a y e r c h r o m at o g r a p h y ( T L C ) .
T o e s t a b l i sh a n e f fi c i e n t c a t a l y t i c s y s t e m f o r t h e
s y n t he s i s o f c o r r o l e s ( 3a) a n d p o r p h y ri n s ( 4a) , p y r -
r o l e ( 1a) a n d a l d e h y d e s w e r e s e l e c te d a s a m o d el t o
s c r e e n t h e t h e r e a c t io n p a r a m e te rs ( T a b le 1) . T h e
a m o u nt o f r e a c t a n t s a n d s o l ve n t s p l a y c r u c i a l r o l e i n
t h e s y n t h e s i s o f c o r ro le s a n d p o r ph y r in s . W h e n
p y r r o l e (1a) a n d a l d e h y d e s (2a) w e r e t a k en i n a
m o l a r r a t i o o f 2 : 1 a n d r e a c t io n w a s c a t a l y ze d b y
i o d i n e ( 0 . 1 e q u i v a l e n t) a n d f o l l o w e d b y o x i d a t i o n
w i t h D D Q , c o r r o l e (3a) w a s a m a jo r p r o d u c t .

J. Chem. Sci.
( 2 0 2 0 ) 1 3 2 : 1 2 3
P a g e 7 o f 8
1
2
3
T h u s , f r o m T a bl e 1, i t i s c l e a r t h a t t h e m o l a r r a t i o Acknowledgements
2 : 1 o f p y r r o l e (1a) a n d a l d e h y d e (2a) i n C H C l
2
2
T h i s r e s e a r c h w o r k i s fi n a n c i a l l y s u p p o r t e d b y U G C -B S R
g r a n t a n d A n s h u D a n d i a i s t h a n k f u l t o U G C f or h er
f e l l o w s h i p .
p r o d u c e d c o r r o l e (3a) a s a m a jo r p r o du c t , w h e r ea s
t h e m o l a r r a t i o 1 : 1 o f p y r ro le ( 1a) a n d a l d eh y d e
(1b) i n C H C l p r o du c e d p o r ph y r in (4a) a s a m aj o r
2
2
p r o d u c t . B o t h t h e s e r e a c t io n s ( s y n t h e s i s o f c o r ro l e
a n d p o r p h y r i n ) w e r e p e rf o r m e d u n d e r n i t r o g e n
a t m o s p h e r e a n d w a s c o m p le t e d w i th i n 5 – 1 0 m i n .
A f t e r g e t t i n g t h e s u i ta bl e c a t a l y t i c s y s t e m i n h a n d ,
w e f u r t h e r b r o a d e n e d t he s c o p e o f t he c a t a l y t i c
References
1 . B ie s a g a M , P y r z y n s k a K a n d T r o j a n o w i c z M 2 00 0
P o r p h y r i n s i n a n a ly ti c a l c h e m is t r y . A r e v ie w Talanta 51
2 0 9
s
y
s
t
e
m
b
y
e
m
p
l
o
y
i
n
g
d if fe re n t
s
u
b
s
t
r
a
t
e
s
( S c h e me 1 ) . T h e r e s u l ts o f t he r e a c t io n a r e s u m -
m a r i z e d i n T a bl e 2 .
2 . F a l k E J 1 9 7 5 Porphyrins and Metalloporphyrins
( E l s e v i e r : N e w Y o r k )
3 . L e s a g e S , X u H a n d D u r h a m L 1 9 9 3 T h e o c c u r r e n c e a nd
r o le s o f p o r p h y r i n s i n t h e e n v ir o n m e n t : p o s s i b l e i m p l i -
c a t i o n s f o r b i o r e m e d i a t i o n Hydrolog. Sci. J. 38 3 43
4 . S p i k e s D J 1 9 7 5 P o r p h y r i n s a n d r e l a t e d c o m p o u nd s a s
p h o to d y n a m ic s e n s i t i z e r s Ann. N. Y. Acad. Sci. 244 4 96
5 . L i L - L a n d D i a u G W E 2 0 1 3 P o r p h y r i n - s e n s it i z e d s o l a r
c e l l s Chem. Soc. Rev. 42 2 9 1
6 . P u r r e l lo R , G u r r i e r i S a n d L a u c e r i R 1 9 9 9 P o rp hy r i n
a s s e m b l i e s a s c h e m ic a l s e n s o r s Coord. Chem. Rev. 190–
192 6 8 3
D i f f e r e n t t y p e s o f e l e c t ro n w i t h d r a w in g a n d
e l ec t r o n d o n a t i n g a l d e h y d e s ( 2b–f) a l o ng w i t h p y r-
r o l e (1a) w e r e e m pl o y e d a s s u bs t ra te s i n S c h em e 1 ,
a n d i t w a s o b s e r v e d t ha t m o s t o f t he e l e c t ro n d e fi -
c i en t a l d e h y d e ( 2b) g a ve m a x i m u m y ie ld . F u r t h er ,
t h e r e a c t i o ns w e r e c o m p le te d w i t h i n 5 – 1 0 m i n w i t h
e l ec t r o n d e fi c i e n t a l d e h y d e s , w h e re a s w i t h e l e ct r o n
d o n a t i n g a l d e h y d e , r e a c t io n w a s p ro lo ng e d u p t o 1 5
m i n . W i t h e l e c t ro n d o n a t in g a l d e h y d e s , o n l y p o r -
p h y r i ns w e r e o b t a i ne d a s t h e fi n a l p r o du c t . A l l t h e
7 . A h ma d S , Y a d a v K K a n d C h a u h a n S M S 2 0 1 2 R o l e o f
h y d r o x y l f u n c t i o n a li z e d i o n i c l iq u i d s i n o x y g e na t i on
a n d o x i d a t io n o f p h e n o l s w i t h H O c a t a l y z ed b y
1
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i r o n ( I I I ) p o r p h y r i n s Current Org. Chem. 16 2 9 8 9
8 . K a n g J G , S o n g C a n d R e n F X 2 0 1 7 T h e o r e t ic al s t u d y
o f z i n c p o r p h y r i n - b a s e d d y e s f o r d y e - s e n s i ti z e d s o l a r
c e l l s J. Photochem. Photobiol. A 333 2 0 0
v i s i b l e a n d H R M S s p e c t ro m e t r y, a n d t he s e c h a r ac -
t e r i z a t i o n d a t a a r e f ul l y s a t is fi e d w i t h l it e ra tu r e d a t a .
T h e s e r e a c t i o ns w e r e c o n s t a n tl y c a rr i e d o u t a t 1
m m o l s c a l e , a n d s i m i l a r y i e ld s w e r e a l s o o b s er v e d
w i t h 1 0 m m o l s c a l e .
9 . H a k e ta Y , B a n d o Y , S a s a n o Y , T a n a k a H , Y a s ud a N ,
H i s a k i I a n d M a e d a H 2 0 1 9 L i q u i d c r y s ta ls c o m pr i s i n g
I
I
I
p- e l e c tr o n i c i o n s f r o m p o r p h y r i n - A u c o m p l e x es iS-
cience 14 2 4 1
1 0 . H a r e l - A v i v I a n d G r o s s Z 2 0 0 9 A u r a o f c o r r o l e s Chem.
Eur. J. 15 8 3 8 2
4. Conclusion
1 1 . G r o s s Z , G a l i l i N , S i m k h o v i c h L , S a l ts m a n I , B o t o-
s h a n s k y M , B la s e r D , B o e s e R a n d G o ld b e r g I 1 99 9
S o l v e n t - f r e e c o n d e n s a t i o n o f p y r r o l e a n d p e n t afl uo -
r o b e n z a l d e h y d e : a n o v e l s y n t h e t i c p a t h w a y t o c or r o le
a n d o l i g o p y r r o m e t h e n e s Org. Lett. 1 5 9 9
1 2 . P a o l e s s e R , J a q u in o d L , N u r c o J D , M i n i S , S a g on e F ,
B o s c h i T a n d S m it h M K 1 9 9 9 5 , 1 0 , 1 5 - T r i p h en y l c or -
r o le : a p r o d u c t f r o m a m o d i fi e d R o t h e m u n d r ea ct i o n
Chem. Commun. 1 3 0 7
1 3 . H a r r i s o n R H , H o d d e r R J O a n d H o d g k i n C D 1 97 1
C r y s t a l a n d m o l e c u l a r s t r u c t u r e o f 8 , 1 2 - d i et h y l-
2 , 3 , 7 , 1 3 , 1 7 , 1 8 - h e x a m e t h y l c o r r o l e J. Chem. Soc. B 6 40
1 4 . G r y k o D T 2 0 0 2 R e c e n t a d v a n c e s i n t h e s y n t h es i s o f
c o r r o l e s a n d c o r e - m o d i fi e d c o r r o l e s Eur. J. Org. Chem.
2 0 0 2 11 1 7 3 5
1 5 . B a r a t a B F J , N e v e s S M P G M , F a u s t i n o F A M , T o m e
C A a n d C a v a l e i r o S A J 2 0 1 7 S t r a t e g i e s f o r c or r o le
f u n c t io n a l i z a t i o n Chem. Rev. 117 4 3 1 9 2
I n t h i s s t u d y , w e h a v e d e v e lo p e d a n e f fi c ie n t , s i mp l e
a n d c o n v e n i e nt m e th od f o r t he s y n t h e s is o f d i f f er e n t
c o r r o l e s a n d p o r p h y r i ns f ro m e a s i l y a v a i l a b l e s u b -
s t r a t e s . T h e c u r r e n t r e a c t io n d i d n o t r e q u i r e h i g h
t e m p e r at u r e a n d p r oc e e d s a t r o o m t e m p e r a t u r e i t s e l f .
T h e r e a c t i o n r e q u ir e s m i n im a l ( 0. 1 m m o l ) a m o u n t o f
i o d i n e a s a c a t a ly s t . S i m p ly b y c h a n g i n g t h e
a m o u nt s o f t h e r e a c t a n t s , c o r ro le s a n d p o r p h y r i n s
c an b e o b t ai n e d i n g o o d y i e ld . T h e s h or t e r r e ac t i o n
t i me , r o o m t e m p e ra tu r e , s i m p l e w o r k -u p p ro ce d u re ,
h i g h e r p r o d u c t y ie ld , a n d e a s i l y a s s e s s a b le s t ar t i n g
m a t e r i a l s m a k e t h e m e th o d b e t te r t ha n t he o t h e r
r e p o r t e d m e t h o d s .
Supplementary Information (SI)
1 6 . G u il a r d R , G r o s P C , B o l z e F , J e r o m e F , O u Z , S h a o J ,
F i s c h e r J , W e is s R a n d K a d i s h M K 2 0 0 1 A l k y l a nd a ry l
s u b s t i tu t e d c o r r o l e s . 1 . S y n t h e s i s a n d c h a r a c t e r i z a t i on o f
f r e e b a s e a n d c o b a l t c o n ta i n i n g d e r iv a ti v e s . X - ra y
s t r u c t u r e o f ( M e P h C o r ) Co ( p y ) Inorg. Chem. 40 4 84 5
S u p p l e m en t a r y d a ta o f t h i s a r t i c l e c o n t a i n s e x p e r im e n t a l
d e t a i l s , s y n t h e ti c p r o c e d u r e s a n d c h a r a c t e r i z a t i o n d a t a ,
a v a i l a b l e a t w w w . i a s . a c . i n / c h e m s c i .
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