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Synthesis of 4-Bromo-1,1′:4′,1″-terphenyl and 4-Methyl-1,1′:4′,1″-terphenyl

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Abstract

Possible synthetic routes to 4-bromo-1,1′:4′,1″-terphenyl and 4-methyl-1,1′:4′,1″-terphenyl have been studied. Stevens rearrangement of quaternary ammonium salts containing 3-phenylprop-2-en-1-yl and 3-(4-bromo- or 4-methylphenyl)prop-2-yn-1-yl groups gave 1-(4-bromophenyl)-N,N-dimethyl-4-phenylhex-5-en-1-yn-3-amine, 1-(4-bromophenyl)-N,N-diethyl-4-phenylhex-5-en-1-yn-3-amine, 1-(4-bromophenyl)-4-phenyl-N,N-dipropylhex-5-en-1-yn-3-amine, 1-[1-(4-bromophenyl)-4-phenylhex-5-en-1-yn-3-yl]piperidine, 4-[1-(4-bromophenyl)-4-phenylhex-5-en-1-yn-3-yl]morpholine, 1-[1-(4-methylphenyl)-4-phenylhex-5-en-1-yn-3-yl]piperidine, and 4-[1-(4-methylphenyl)-4-phenylhex-5-en-1-yn-3-yl]morpholine. Vacuum distillation of the resulting amines, by analogy with structurally related compounds, was accompanied by deamination with the formation of 4-bromo-1,1′:4′,1″-terphenyl and 4-methyl-1,1′:4′,1″-terphenyl in high yields. This transformation is a domino reaction involving β-elimination of secondary amine to form conjugated dienyne, electrocyclization of the latter to cyclic allene intermediate, and fast 1,3- or 1,5-hydride shift.

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Authors and Affiliations

  1. Institute of Organic Chemistry, Scientific Technological Center of Organic and Pharmaceutical Chemistry, National Academy of Sciences of Armenia, 0014, Yerevan, Armenia

    E. H. Chukhajian, L. V. Ayrapetyan, K. G. Shahkhatuni & El. H. Chukhajian

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  1. E. H. Chukhajian
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  2. L. V. Ayrapetyan
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  3. K. G. Shahkhatuni
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  4. El. H. Chukhajian
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Correspondence to L. V. Ayrapetyan.

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Chukhajian, E.H., Ayrapetyan, L.V., Shahkhatuni, K.G. et al. Synthesis of 4-Bromo-1,1′:4′,1″-terphenyl and 4-Methyl-1,1′:4′,1″-terphenyl. Russ J Org Chem 56, 1738–1743 (2020). https://doi.org/10.1134/S1070428020100115

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