An Easy and Multigram-Scale Synthesis of Pillar[5]quinone by the Hypervalent Iodine Oxidation of 1,4-Dimethoxypillar[5]arene

Kilingaru I. Shivakumar; Gangadhar J. Sanjayan

doi:10.1055/s-0032-1318390

Synthesis, Inhaltsverzeichnis

Synthesis 2013; 45(7): 896-898
DOI: 10.1055/s-0032-1318390

short paper

An Easy and Multigram-Scale Synthesis of Pillar[5]quinone by the Hypervalent Iodine Oxidation of 1,4-Dimethoxypillar[5]arene

Kilingaru I. Shivakumar

Division of Organic Chemistry, National Chemical Laboratory, Pune 411 008, India Fax: +91(20)25902629 eMail: gj.sanjayan@ncl.res.in

,

Gangadhar J. Sanjayan*

Division of Organic Chemistry, National Chemical Laboratory, Pune 411 008, India Fax: +91(20)25902629 eMail: gj.sanjayan@ncl.res.in

› Institutsangaben

Abstract

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Dedicated to Prof. K. N. Ganesh on the occasion of his 60^th birthday

Abstract

Pillar[5]quinone (P[5]Q), a potential molecule for anion recognition and supramolecular host-guest chemistry, has not as yet been used for practical purposes, presumably due to the synthetic difficulties in obtaining it in large amounts. Herein, we reveal an easy-to-operate and chromatography-free synthetic strategy that can furnish P[5]Q on a multigram scale; its success relies on the utility of hypervalent iodine, generated in situ from Oxone/iodobenzene, as an efficient oxidant. Pillar[5]quinone was obtained in multigram quantities by oxidation of 1,4-dimethoxypillar[5]arene with Oxone/iodobenzene and simple purification by crystallization from 1,1,2,2-tetrachloroethane, thus opening up the opportunity to explore the properties of this interesting macrocyclic quinone.

Key words

supramolecular chemistry - macromolecules - pillararenes - hypervalent iodine oxidation

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Referenzen

References
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22 We have used 1,4-dimethoxypillar[5]arene, crystallized from boiling chlorobenzene. We have found that chlorobenzene is a very good solvent for crystallizing large quantities of 1,4-dimethoxypillar[5]arene, since a substantial amount of 1,4-dimethoxypillar[5]arene can be dissolved in boiling chlorobenzene, from which it crystallizes out on cooling.
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24 We have observed that if MeOH washing is avoided, about 2.5 equiv of 1,1,2,2-tetrachloroethane is adsorbed onto P[5]Q, as evident from its ¹H NMR integration (see ¹H NMR spectrum). However, MeOH washing helps in removing adsorbed 1,1,2,2-tetrachloroethane.
25 TLC pattern, ¹H NMR, and mass spectra suggest that the recovered off-white compound is the starting material (1,4-dimethoxypillar[5]arene).

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