Synthesis of Imidazolyl-group-bearing 5,10,15,20-Tetrakis(a, a, a, a-o-pivalamidophenyl) porphyrinatoiron (II) Derivatives

Kiyoshi Eshima, Etsuo Hasegawa, Yoh Ichi Matsushita, Hiroyuki Nishide, Eishun Tsuchida

Research output: Contribution to journalArticle

Abstract

5,10, 15, 20-Tetrakis(a, a, a, a-o-pivalamidophenyl)porphyrinatoiron(II) derivatives bearing a side chain with a terminal imidazolyl group were synthesized. A formyl group was introduced at the 2-position of the corresponding porphyrinatocopper(II) using Vilsmeier-Haack reaction. The resultant 2-formylporphyrinatocopper(II) was demetallated with sulfuric acid. Treatment of this with sodium borohydride gave the 2-(hydroxymethyl)porphyrin in a quantitative yield. Reaction of this successively, methanesulfonyl chloride, sodium azide, and triphenylphosphine yielded the 2-(aminomethyl)porphyrin. Condensation of the 2-formyl-porphyrin with malonic acid in the presence of piperidine (Knoevenagel reaction) selectively afforded the 2-(trans-2-carboxyethenyl)porphyrin. Using these functionalized porphyrins, 5, 10, 15, 20-tetrakis(a, a, a, a-o-pivalamidophenyl)porphyrinatoiron(II) derivatives bearing a terminal imidazolyl group were prepared.

Original languageEnglish
Pages (from-to)1836-1845
Number of pages10
JournalNippon Kagaku Kaishi
Volume1988
Issue number11
DOIs
Publication statusPublished - 1988

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Bearings (structural)
Porphyrins
Derivatives
Sodium Azide
Sodium chloride
Sulfuric acid
Condensation
Sodium
porphyrinatoiron(II)
Acids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis of Imidazolyl-group-bearing 5,10,15,20-Tetrakis(a, a, a, a-o-pivalamidophenyl) porphyrinatoiron (II) Derivatives. / Eshima, Kiyoshi; Hasegawa, Etsuo; Matsushita, Yoh Ichi; Nishide, Hiroyuki; Tsuchida, Eishun.

In: Nippon Kagaku Kaishi, Vol. 1988, No. 11, 1988, p. 1836-1845.

Research output: Contribution to journalArticle

Eshima, Kiyoshi ; Hasegawa, Etsuo ; Matsushita, Yoh Ichi ; Nishide, Hiroyuki ; Tsuchida, Eishun. / Synthesis of Imidazolyl-group-bearing 5,10,15,20-Tetrakis(a, a, a, a-o-pivalamidophenyl) porphyrinatoiron (II) Derivatives. In: Nippon Kagaku Kaishi. 1988 ; Vol. 1988, No. 11. pp. 1836-1845.
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abstract = "5,10, 15, 20-Tetrakis(a, a, a, a-o-pivalamidophenyl)porphyrinatoiron(II) derivatives bearing a side chain with a terminal imidazolyl group were synthesized. A formyl group was introduced at the 2-position of the corresponding porphyrinatocopper(II) using Vilsmeier-Haack reaction. The resultant 2-formylporphyrinatocopper(II) was demetallated with sulfuric acid. Treatment of this with sodium borohydride gave the 2-(hydroxymethyl)porphyrin in a quantitative yield. Reaction of this successively, methanesulfonyl chloride, sodium azide, and triphenylphosphine yielded the 2-(aminomethyl)porphyrin. Condensation of the 2-formyl-porphyrin with malonic acid in the presence of piperidine (Knoevenagel reaction) selectively afforded the 2-(trans-2-carboxyethenyl)porphyrin. Using these functionalized porphyrins, 5, 10, 15, 20-tetrakis(a, a, a, a-o-pivalamidophenyl)porphyrinatoiron(II) derivatives bearing a terminal imidazolyl group were prepared.",
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AU - Hasegawa, Etsuo

AU - Matsushita, Yoh Ichi

AU - Nishide, Hiroyuki

AU - Tsuchida, Eishun

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AB - 5,10, 15, 20-Tetrakis(a, a, a, a-o-pivalamidophenyl)porphyrinatoiron(II) derivatives bearing a side chain with a terminal imidazolyl group were synthesized. A formyl group was introduced at the 2-position of the corresponding porphyrinatocopper(II) using Vilsmeier-Haack reaction. The resultant 2-formylporphyrinatocopper(II) was demetallated with sulfuric acid. Treatment of this with sodium borohydride gave the 2-(hydroxymethyl)porphyrin in a quantitative yield. Reaction of this successively, methanesulfonyl chloride, sodium azide, and triphenylphosphine yielded the 2-(aminomethyl)porphyrin. Condensation of the 2-formyl-porphyrin with malonic acid in the presence of piperidine (Knoevenagel reaction) selectively afforded the 2-(trans-2-carboxyethenyl)porphyrin. Using these functionalized porphyrins, 5, 10, 15, 20-tetrakis(a, a, a, a-o-pivalamidophenyl)porphyrinatoiron(II) derivatives bearing a terminal imidazolyl group were prepared.

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