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Sapphyrins, derivatives and syntheses

  • US 5,302,714 A
  • Filed: 10/26/1992
  • Issued: 04/12/1994
  • Est. Priority Date: 12/21/1989
  • Status: Expired due to Fees
First Claim
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1. A method for synthesizing sapphyrins comprising the steps of:

  • (A) reacting an alkyl derivativea aldehyde and an n-nitromethylenealkyl derivativeb to produce beta-hydroxynitroalkyl derivativec ;

    (B) reacting the beta-hydroxynitroalkyl derivativec with acetic anhydride to form beta-acetoxynitroalkyl derivativec ;

    (C) reacting the beta-acetoxynitroalkyl derivativec with ethyl isocyanoacetate in the presence of a nonnucleophilic base to form ethyl 3-alkyl derivativea -4-alkyl derivativeb pyrrole-2-carboxylate;

    (D) reacting ethyl 3-alkyl derivativea -4-alkyl derivativeb pyrrole-2-carboxylate with iodine and iodide to form ethyl 3-alkyl derivativea -4-alkyl derivativeb -5-iodopyrrole-2-carboxylate;

    (E) coupling two molecular equivalents of ethyl 3-alkyl derivativea -4-alkyl derivativeb -5-iodo-pyrrole-2-carboxylate in the presence of copper bronze and heat to produce diethyl 4,4'"'"'-dialkyl derivativea -3,3'"'"'-dialkyl derivativeb -2,2'"'"'-bipyrrole-5,5'"'"'-dicarboxylate;

    (F) converting diethyl 4,4'"'"'-dialkyl derivativea -3,3'"'"'-dialkyl derivativeb -2,2'"'"'-bipyrrole-5,5'"'"'-dicarboxylate to 4,4'"'"'-dialkyl derivativea -3,3'"'"'-dialkyl derivativeb -2,2'"'"'-bipyrrole by saponification and decarboxylation;

    (G) reacting 4,4'"'"'-dialkyl derivativea -3,3'"'"'-dialkyl derivativeb -2,2'"'"'-bipyrrole with dimethylformamide and phosphorus oxychloride to form 4,4'"'"'-dialkyl derivativea -5,5'"'"'-diformyl-3,3'"'"'-dialkyl derivativeb -2,2'"'"'-bipyrrole;

    (H) treating benzyl 4-alkyl derivatived -3,5-dimethylpyrrole-2-carboxylate with an oxidizing agent to produce benzyl 5-(X-methyl)-4-alkyl derivatived -3-methylpyrrole-2-carboxylate;

    (I) condensing two molecular equivalents of benzyl 5-(X-methyl)-4-alkyl derivatived -3-methylpyrrole-2-carboxylate with 3-alkyl derivativee -4-alkyl derivativef pyrrole under acidic conditions to produce 2,5-bis(5-benzyloxycarbonyl-3-alkyl derivatived -4-methylpyrrol-2-ylmethyl)-3-alkyl derivativee -4-alkyl derivativef pyrrole;

    (J) hydrogenating 2,5-bis(5-benzyloxycarbonyl-3-alkyl derivatived -4-methylpyrrol-2-ylmethyl)-3-alkyl derivativee -4-alkyl derivativef pyrrole to produce 2,5-bis(5-carboxy-3-alkyl derivatived -4-methylpyrrol-2-ylmethyl)-3-alkyl derivativee -4-alkyl derivativef pyrrole; and

    (K) condensing 4,4'"'"'-dialkyl derivativea -5,5'"'"'-diformyl-3,3'"'"'-dialkyl derivativeb -2,2'"'"'-bipyrrole with 2,5-bis(5-carboxy-3-alkyl derivatived -4-methylpyrrol-2-ylmethyl)-3-alkyl derivativee -4-alkyl derivativef pyrrole under acidic oxidizing conditions to produce a 2,23-dialkyl derivativeb -3,22-dialkyl derivativea -7,18-dimethyl-8,17-dialkyl derivatived -12-alkyl derivativee -13-alkyl derivativef sapphyrin;

    wherein alkyl derivativea, alkyl derivativeb, alkyl derivativec, alkyl derivatived, alkyl derivativee and alkyl derivativef are independently alkane, functionalized alkane, derivatized alkane or derivatized functional alkane and x is a substituent capable of leaving as an anionically stable moiety.

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