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      https://www.ias.ac.in/article/fulltext/jcsc/129/08/1143-1152

    • Keywords

       

      Phosphinite ligands; m-phosphinites; rhodium catalyst; hydroformylation

    • Abstract

       

      Synthesis of meta-substituted phosphinite ligands 3,3' (methoxyphosphanediyl) bis (N,Ndiethylaniline) (4a) and methoxybis(3-methoxyphenyl)phosphane (4b), in high yields, has been demonstrated. Typical phosphorus chemical shift between 110–120 ppm, appearance of methoxy protons and corresponding carbon, as well as ESI-MS spectra unambiguously confirmed the existence of phosphinite ligands 4a and 4b. To demonstrate the synthetic usefulness of 4a and 4b, these ligands were tested in the rhodium catalyzed hydroformylation of 1-octene. The diethylamine substituted ligand 4a was found to be highly active, whereas4bwas less reactive but revealed slightly better regioselectivity of 62% under optimized conditions.Additionally, 4a and 4b were found to catalyze the hydroformylation of styrene, 1-undecenol and 1,1-disubstituted functionalolefin, methyl methacrylate. Both the ligands displayed excellent conversion of styrene, and 4b revealed an excellent branch selectivity of 75%. Although 1-undecenol proved to be amenable to hydroformylation (85–90% conversion to aldehyde), both the ligands failed to discriminate between the linear and branched products. Substrate methyl methacrylate proved to be highly challenging and reduced conversion (between 33–42%) was observed under optimized conditions. Ligand 4a was found to be highly selective towards linear aldehyde (81% linear selectivity).

    • Author Affiliations

       

      SATEJ S DESHMUKH1 SHAHAJI R GAIKWAD1 SWECHCHHA PANDEY1 PRAMOD S MALI2 SAMIR H CHIKKALI1 3

      1. Polymer Science and Engineering Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, Maharashtra 411 008, India
      2. Central NMR facility, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, Maharashtra 411 008, India
      3. Academy of Scientific and Innovative Research (AcSIR), Anusandhan Bhawan, 2 Rafi Marg, New Delhi 110 001, India
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  • Journal of Chemical Sciences | News

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