Efficient synthesis of free-base 2-formyl-5,10,15,20-tetraarylporphyrins, their reduction and conversion to [(porphyrin-2-yl)methyl]phosphonium salts

被引:72
作者
Bonfantini, EE
Burrell, AK
Campbell, WM
Crossley, MJ [1 ]
Gosper, JJ
Harding, MM
Officer, DL
Reid, DCW
机构
[1] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia
[2] Massey Univ, IFS Chem, Nanomat Res Ctr, Palmerston North, New Zealand
[3] Los Alamos Natl Lab, Los Alamos, NM 87545 USA
关键词
porphyrins; periphery functionalization; formylporphyrins; porphyrin phosphonium salt; side-chain reduction;
D O I
10.1142/S108842460200083X
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A highly efficient synthesis of 2-formyl-5,10,15,20-tetraarylporphyrins, 1 and 2, that can be carried out on multi-gram scales is reported. The key steps in the sequence involve use of copper(II) chelation to ensure very efficient electrophilic substitution, and the demetalation of the intermediate iminium salt that results from Vilsmeier-Haack formylation of the copper(II) porphyrins prior to base-catalyzed. hydrolysis of the salt to the corresponding free-base 2-formylporphyrin. This sequence avoids the formation of by-products that inevitably result when the formyl group is subjected to acidic conditions. Borohydride reduction of (metallo)-2-formylporphyrins give the corresponding 2-hydroxymethyl-porphyrins in quantitative yield. Catalytic reduction of copper(II) 2-hydroxymethyl-5,10,15,20-tetraphenylporphyrin 15 with hydrogen under acidic conditions affords 2-methyl-5,10,15,20-tetraphenylporphyrin 20 in 60% yield. Treatment of 2-hydroxymethylporphyrins with thionyl chloride in dry pyridine yields the corresponding 2-chloromethyl-porphyrins in good yields. The 2-chloromethyl-porphyrins give the corresponding triphenyl[(porphyrin-2-yl)methyl]phosphonium chlorides in 90% yield on treatment with PPh3 in boiling chloroform. These salts are useful building blocks for the synthesis of conjugated porphyrin dimers and higher oligomers. Copyright (C) 2002 Society of Porphyrins & Phthalocyanines.
引用
收藏
页码:708 / 719
页数:12
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