One-pot general synthesis of metalloporphyrins
Anil Kumar,Suman Maji,Prashant Dubey,G.J.Abhilash,z
滩坑水库
Sohini Pandey and Sabyasachi Sarkar *
Department of Chemistry,Indian Institute of Technology Kanpur,Kanpur 208016,India
Received 15June 2007;revid 9August 2007;accepted 13August 2007
Available online 16August 2007
Abstract—A new general one-pot method for the synthesis of various metalloporphyrins has been developed from pyrrole and substituted aldehydes using transition metal salts.This method allows higher working concentrations than tho previously reported.Along with the reported metalloporphyrins,some new metalloporphyrins were synthesized in good yield.Ó2007Elvier Ltd.All rights rerved.
The diver photo-electro and biochemical properties of porphyrins and metalloporphyrins continue to attract the attention of rearchers.Porphyrin rearch has pro-gresd from its pioneering synthesis b
y Fischer 1in 1920s to their u as lective catalysts,2–5in molecular electronic devices,6as photodynamic therapy agents 7and other varied applications in materials chemistry.8Despite such interest,the reported protocols for the preparation of sterically hindered porphyrins result only in low yields even using drastic reaction conditions.9,10Though substituted benzaldehydes bearing multiple functionalities in the meta and para positions are easily converted into the corresponding porphyrins,ortho substituted aldehydes react poorly.Numerous advances in porphyrin synthetic methodology have been made through monopyrrole tetramerisation,11–15dipyrro-methene lf-condensation in organic acid,162+2McDonald dipyrromethane synthesis,17and 3+1synthe-sis with a tripyrrane and a diformylpyrrole.18Most porphyrin synthes proceed by tetramerisation of a monopyrrole.Rothemund 11first synthesized tetra-phenylporphyrin,and subquently Alder–Longo 12reported a simplified synthesis of meso -tetraphenyl-porphyrin.This method has advantages but provided low yields of nsitive porphyrins,reflecting the rather vigorous conditions,and difficult purification problems from the by-products.Recent methods ud in the
synthesis of tetraarylporphyrins via tetramerization of pyrroles include the u of an oxidizing cosolvent,19Lewis acids,20clays,21ionic liquids,22hydrogen peroxide in acetic acid,14microwave assisted synthesis of porphy-rin,23mixtures of xylenes and chloroacetic acid,24vapor pha synthesi
s without the u of solvents or cata-lysts,25and micro-wave assisted synthesis.26In all the methods there are intrinsic disadvantages and most importantly the reaction fails completely with substitu-ents in the ortho position.To date,there is no report available in the literature for the synthesis of metallo-porphyrins directly via a condensation reaction.In this Letter,we report a one-pot synthesis 27of metal-loporphyrins with various aldehydes,which can be ud with a large variety of substituted benzaldehydes including ortho substituted and using different transition metals (Scheme 1).All the porphyrins and metallo-porphyrins were characterized by 1H,13C NMR,and UV–visible spectroscopy.33Spectroscopic data for known compounds were comparable with reported data.The prent reaction conditions were optimized with respect to solvent,temperature,amount of hydrochloric acid,time of the reaction,u of different metal salts,and on the concentration of reactants ud.In solvents such as ethanol,methanol,dichloromethane,and chlo-roform,a precipitate formed just after the addition of HCl and further addition of metal salts,followed by refluxing,yielded only trace amounts of porphyrins/metalloporphyrins.Finally,dimethylformamide was identified as the best solvent to keep the reaction mix-ture homogeneous.It was also obrved that addition of acid prior to the pyrrole and aldehyde in DMF
0040-4039/$-e front matter Ó2007Elvier Ltd.All rights rerved.doi:10.let.2007.08.046
Keywords :Metalloporphyrin;Synthesis.
*Corresponding author.Tel.:+915122597265;fax:+915122597265;e-mail:abya@iitk.ac.in z
Decead.
Tetrahedron Letters 48(2007)
7287–7290
resulted in lower yields than if the acid was added after the aldehyde and followed by pyrrole.Metalloporphyrin yields were lower at room temperature even on long standing.
Benzaldehyde and cupric sulfate were ud to optimize the reaction conditions.In a typical reaction freshly distilled benzaldehyde (1.0ml,9.8mmol)was dissolved in 50ml of argon-purged dimethylformamide.HCl (0.5ml,concentrated)was added followed by dropwi
addition of freshly distilled pyrrole (0.68ml,9.8mmol).The mixture was stirred under argon for 1h and then $2.5equiv of MCl 2(or MSO 4) (M =Cu 2+,Ni 2+,Zn 2+,VO 2+,Co 2+,Fe 2+)were added.The final reaction mixture was refluxed for 8h in air.The solvent was re-moved using a vacuum pump and the crude product was washed veral times with acidic water and dried.The product was dissolved in chloroform and purified by flash chromatography over silica gel using chloro-form as eluent.§The yields of various metalloporphyrins obtained are shown in Table 1.
The best yields of metalloporphyrins were obtained with cupric sulfate and vanadyl sulfate.Using this method,
we have synthesized a variety of metalloporphyrins including complexes with sterically encumbered porphyirns such as 9-anthracenylporphyrin,meso -tetra-kis(2,3-dimethoxyphenyl)porphyrin,and meso -tetra-kis(2,4,6-trimethoxyphenyl)porphyrin in good yields.The porphyrins fail to respond to the Adler-Longo 12procedure,and using the Lindy 13methodology,the product was isolated in very low yield.
Table 2compares yields of various copper porphyrins formed by the methods of Adler and Lindy and tho in the prent study.For some of the free bas synthe-sized by the Adler or Lindy meth
od the corresponding copper complex was not known and therefore an opti-mistic 90%yield of a copper complex from such a ba
Scheme 1.Reaction scheme.
Table 1.Yields of porphyrins with or without metal ions Aldehyde 2H VO 2+Fe 3+Co 2+Ni 2+Cu 2+Zn 2+13244382828443823840a 322828464231822a 551422a 2042433272425343052532a 1815a 20a 38a 25a 61520a 15a 10a 15a 20a 17a 72021a 12121724a 22a 82537a 181820292591827a 1717191917101111a 1112101412113644a 3232354439123240a 22a 28304422a 13
1.8
2.5a
2
—
2
2.5a
2.5a
a
New metalloporphyrins.
CoCl 2Æ6H 2O,NiCl 2Æ6H 2O,CuSO 4Æ5H 2O,and ZnCl 2were ud in the synthesis of CoP,NiP,CuP,and ZnP,respectively,and in the ca of VOP and FePCl,VOSO 4Æ5H 2O and FeCl 2Æ4H 2O were ud,respec-tively.In the ca of free ba porphyrin,no metal salt was ud.
In the ca of free ba,only hot water was ud.§
0.5%Methanol–chloroform mixture was ud in ca of FePCl and methoxy and hydroxy group substituted porphyrins.
7288 A.Kumar et al./Tetrahedron Letters 48(2007)7287–7290
is ud for comparison.From Table2it is apparent that the prent method produces better yields of all the porphyrin systems.
In this method,the intermediate porphyrinogen is di-rectly metallated in the prence of a metal ion to yield metalloporphyrins under aerobic conditions.The advantage of our method is the general nature of the reaction which is valid for any type of substituted alde-hyde.The yield of the metalloporphyrin was reasonably good and the reaction time was shorter than in other methods.Also,higher concentrations of reagents (0.38M)can be employed.
Acknowledgements
A.K.thanks UGC,forfinancial grants as JRF and SRF, S.M.,P.D.and A.G.J.thank the CSIR,for SRF,and S.S.thanks DST,for funding.策划者
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Table2.Comparative yields(%)of reprentative copper porphyrins
from the Adler,Lindy methods and this work
Aldehydes Adler method12Lindy method13This work
11728252844
21428142846
3 4.929 4.92922
41428252834
5—a—a38
618b—a20
7 4.5b—a24
816b—a29
912b—a19
10 1.830 1.83014
111831—a44
122332—a44
130.8—a 2.5
a Data not available.
b Computed value bad on90%yield from the free ba.
A.Kumar et al./Tetrahedron Letters48(2007)7287–72907289
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33.Selected spectral data:1H and13C NMR spectra were
measured in CDCl3at400MHz and100MHz and UV–visible spectra were recorded in chloroform.Co
mpound 2b:k max(log e)425(6.2),548(5.0),586(4.1).FAB-MS: m/z817,IR(KBr pellet,cmÀ1):3062(m Cp–H),3062 (m C–H Bz),1577(m C@C Bz),1449(m Cp–Cp),1446(m Cp–N),1357(m Cp–Cp),1182(d Cp–H),1089(d CCN),C猪脚煲汤
H N(%):Calcd:C,64.65;H,2.96;N,6.85.Found:C,
64.53;H,2.88;N,6.82.
Compound3b:k max(log e)427(5.54),552(4.36),609
(4.04).FAB-MS:m/z744,IR(KBr pellet,cmÀ1)3510(m
O–H),3012(m Cp–H),2920(m C–H Bz),1589(m C–C Bz), 1481(m Cp–Cp),1442(m Cp–N).C H N(%):Calcd:C,
71.06;H,3.8;N,7.53.Found:C,71.01;H,3.68;N,7.49.
Compound5b:k max(log e)429(5.52),464(4.42),550
(4.32).FAB-MS:m/z921,IR(KBr pellet,cmÀ1)2926(m
C–H,OCH3),1605(m C@C Bz),1505(m Cp–Cp),1245(m C@O).C H N(%):Calcd:C,67.90;H,4.82;N,6.09.
Found:C,67.97;H,4.75;N,6.01.
Compound5d:k max(log e)410(5.7),432(4.34),535(3.6).
FAB-MS:m/z913,IR(KBr pellet,cmÀ1)2926(m C–H, OCH3),1605(m C@C Bz),1505(m Cp–Cp),1245(m C–O).
C H N(%):Calcd:C,68.49;H,4.86;N,6.14.Found:C,
68.37;H,4.75;N,6.07.
Compound5e:1H d3.94–4.01(m,12H x,o-OCH3),7.11–
7.36(m,8H,phenyl),7.53–7.74(m,4H,phenyl),8.60–8.63
(s,8H,pyrrole);13C d55.9(o-OCH3),60.7,60.8,60.9(m-OCH3),122.06,127.06,127.28,127.67(meso-C),135.16 (b-C,pyrrole),149.02(a-C,pyrrole),149.16,152.3,112.3, 114.5,131.8,142.5,142.63,142.67;k
max(log e)414(5.39), 527(4.30),559(3.84).FAB-MS:m/z921,C H N(%): Calcd:C,67.90;H,4.82;N,6.09.Found:C,67.97;H,
4.88;N,6.01.
Compound5f:k max(log e)416(5.68),538(4.34),573
(3.60).IR(KBr pellet,cmÀ1)2959,2851(m C–H,OCH3),
1600(m C@C Bz),1505(m Cp–Cp),1260(m C–O).C H N (%):Calcd:C,68.15;H,4.84;N,6.11.Found:C,67.97;H,
4.75;N,6.83.
Compound6b:k max(log e)429(5.52),464(4.42),550
(4.32).IR(KBr pellet,cmÀ1)2948(m C–H,OCH3),1600(m
C@C Bz),1515(m Cp–Cp),1256(m C–O).C H N(%): Calcd:C,67.90;H,4.82;N,6.09.Found:C,67.97;H,
4.75;N,6.01.
Compound6c:k max(log e)381(4.5),422(4.7),510(4.0), 582(3.6),690(3.44).IR(KBr pellet,cmÀ1)2936(m C–H, OCH3),1605(m C@C Bz),1245(m C–O)C H N(%):Calcd: C,66.14;H,4.70;N,5.93.Found:C,66.07;H,4.65;N,
5.87.Compound6d:k max(log e)412(5.7),432(4.34),535(3.6). Compound6e:1H d3.38–3.56(m,12H,o-OCH3),3.77–3.98(m,12H,p-OCH3),
6.68–6.75(m,8H,phenyl),
7.14–7.84(m,4H,phenyl),
8.58(s,8H,pyrrole);13C d55.5 (o-CH3),103.3(meso-C),142.94(a-C,pyrrole),131.56 (b-C,pyrrole),160.9;k max(log e)418(5.12),530(4.00).IR (KBr pellet,cmÀ1)2956(m C–H,OCH3),1600(m C@C Bz), 1248(m C–O).C H N(%):Calcd:C,68.51;H,4.86;N, 6.15.Found:C,68.47;H,4.75;N,6.11.
Compound6g:1H d3.74–3.80(m,12H,o-OCH3),3.9–4.01(m,12H,p-OCH3),6.76–6.80(m,8H,phenyl),7.69–7.81(m,4H,phenyl),8.76(s,8H,pyrrole);13C d55.5 (o-OCH3),55.8(p-OCH3),103.15,116.1,124.5(meso-C), 135.86(b-C,pyrrole),150.5(a-C,pyrrole),105.6,130.74, 131.3,160.15,160.98;k max(log e)422(5.66),549(4.36), 589(4.55).FAB-MS:m/z856,IR(KBr pellet,cmÀ
1):2945 (m C–H,OCH3),1605(m C@C Bz),1248(m C–O).C H N (%):Calcd:C,73.05;H,5.42;N,6.55.Found:C,72.97;H, 5.35;N,6.39.
Compound7b:k max(log e)427(5.41),460(4.52),548 (4.25),660(3.74).FAB-MS:m/z921,IR(KBr pellet, cmÀ1):2926(m C–H,OCH3),1605(m C@C Bz),1245(m C–O).C H N(%):Calcd:C,67.90;H,4.82;N,6.09.Found: C,67.97;H,4.75;N,6.01.
Compound8b:k max(log e)430(5.78),508(3.92),547 (4.61),586(3.90).FAB-MS:m/z921,IR(KBr pellet, cmÀ1)2932(m C–H,OCH3),1582(m C@C Bz),1259(m C–O).C H N(%):Calcd:C,67.90;H,4.82;N,6.09.Found: C,67.97;H,4.75;N,6.01.
Compound9b:k max(log e)429(6.05),550(4.89),592 (4.17).FAB-MS:m/z1041,IR(KBr pellet,cmÀ1)2935(m C–H,OCH3),1578(m C@C Bz),1234(m C–O).C H N(%): Calcd:C,64.67;H,5.04;N,5.39.Found:C,64.57;H, 4.95;N,5.27.
镜子摆放禁忌
Compound10b:k max(log e)429(5.97),550(4.77),587 (3.95).FAB-MS:m/z1041,IR(KBr pellet,cmÀ1)2939(m C–H,OCH3),1607(m C@C Bz),1203(m C–O).C H N(%): Calcd:C,64.67;H,5.04;N,5.39.Found:C,64.57;H, 4.95;N,5.27.
Compound11b:k max(log e)429(4.36),549(3.0),583(2.0). FAB-MS:m/z881,IR(KBr pellet,cmÀ1)3048(m Cp–H), 3026(m C–H,Bz),1578(m C@C Bz).C H N(%):Calcd:C, 81.90;H,4.12;N,6.37.Found:C,81.81;H,4.10;N,6.31. Compound12b:k max(log e)430(5.7),551(4.4),588(3.6). FAB-MS:m/z881,IR(KBr pellet,cmÀ1)3057(m Cp–H), 3026(m C–H,Bz),1578(m C@C Bz).C H N(%):Calcd:C, 81.90;H,4.12;N,6.37.Found:C,81.81;H,4.10;N,6.31. Compound12c:k max(log e)380(4.6),424(4.9),512(41), 583(3.53),665(3.53).
Compound13b:k max(log e)428(6.0),551(4.94),584 (3.74),642(3.32).IR(KBr pellet,cmÀ1)3062(m Cp–H), 3021(m C–H,Bz),1572(m C@C Bz).C H N(%):Calcd:C, 84.41;H,4.11;N,5.19.Found;C84.49,H4.09,N5.14. Compound13f:k max(log e)425(5.55),543(4.63),579 (4.11).IR(KBr pellet,cmÀ1)3048(m Cp–H),3016(m C–H, Bz),1578(m C@C Bz).C H N(%):Calcd:C,84.78;H, 4.12;N,5.20.Found:C,84.73;H,4.09;N,5.15.
7290 A.Kumar et al./Tetrahedron Letters48(2007)7287–7290
