Bridging chloranilate

Iron(II) chloranilate trihydrate contains zigzag chains in which bidentate chloranilate anions bridge octahedral iron centers, each of which has two cis water ligands. Iron(III) chloranilate is dinuclear, with one chloranilate bridge. " ... 

Scheme 3a gives a representation of the main synthetic procedure for these compounds. It started with the condensation of diformyl-substituted dithiedylethene and benzaldehyde with dipyrrolemethane, followed by oxidation with p-chloranil. The dithienylethene-bridged diporphyrin was given in 19% yield. The other products were synthesized by analogous approaches. 

The mode of reaction of fulvenes with o-quinones varies with structure. As illustrated below, 7,7-disubstituted fulvenes (91) react with o-benzoquinone and alkyl substituted o-quinones to give bridged diones 90,91) (92). The regiochemistry of these reactions was determined by photobisdecarbonylation to 93. Subsequent oxidation with chloranil provided a synthesis of benzofulvenes (94). 

Trifluoromethylpyrroles were also used in the fluorinated porphyrins synthesis [121], Thus, porphyrin 475 was prepared in three steps starting from pyrrole 373a. At first step reduction of carboxyethyl group was performed. Next, intermolecular alkylation takes place to form CH2-bridged precursor of porphyrin under PTSA catalysis. The last step is aromatization under treatment with chloranile. 

Chloranil (Pt) Chloranil (Pt) 0NH2 and other bases HCIO4 LiCl LiCl bridge 3... 

Chloranil Calomel Urea HCIO4 LiClOi LiC104 bridge 25... 

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