Issue 5, 2002

Abstract

Fourteen new derivatives of ortho-carborane, 1,2-C2B10H12, have been prepared containing functionalized aryl groups attached to one or both of the boron atoms (B9 and B12) antipodal to the carbon atoms, in order to test the suitability of such species for use in the preparation of new categories of phenylene ether carboranylene ketone (PECK) polymers. Model compounds prepared from 9-iodo-ortho-carborane 1 to test synthetic procedures and reactions included the mono-substituted carboranes 9-R1-1,2-C2B10H11 in which the boron attached group R1 was p-tolyl (2), p-HO2CC6H43, p-MeOC6H4COC6H44, p-PhOC6H45 or p-PhCOC6H4OC6H46 (C6H4 represents para-phenylene throughout). Formation of 3 from 2 by CrO3 oxidation showed the capacity of the boron–aryl link to withstand strongly oxidizing conditions. Formation of 4 from 3 and anisole, PhOMe, in trifluoromethane sulfonic acid (TFSA), and of 6 from 5 and benzoic acid, PhCO2H, in TFSA showed such systems could undergo the acylation reactions that would allow polymer formation from suitable diarylcarborane monomers. Compound 7, 9-(3-PhCO-4-PhO-C6H3)-1,2-C2B10H11 an isomer of 6, was also obtained during the synthesis of 6 from 5 and benzoic acid. The diarylcarboranes 9,12-R22-1,2-C2B10H10 with R2 = p-tolyl 9, p-HO2CC6H410 or p-MeOC6H4COC6H411, bearing identical functionalised aryl groups attached to both antipodal boron atoms, were prepared from 9,12-I2-1,2-C2B10H108. Further series of diarylcarboranes 1,9- and 1,12-R32-1,2-C2B10H10, bearing identical aryl groups R3 on one carbon atom (C1) and on the antipodal boron atom (B12), or on the boron atom (B9) antipodal to the unsubstituted carbon atom (C2), have also been prepared and characterized, with R3 = p-tolyl 12, 13, p-HO2CC6H414, 15 or p-MeOC6H4COC6H416, 17.

Graphical abstract: Model compounds and monomers for phenylene ether carboranylene ketone (PECK) polymer synthesis: preparation and characterization of boron-arylated ortho-carboranes bearing carboxyphenyl, phenoxyphenyl or benzoylphenyl substituents

Article information

Article type
Paper
Submitted
27 Sep 2001
Accepted
24 Jan 2002
First published
14 Mar 2002

J. Mater. Chem., 2002,12, 1301-1306

Model compounds and monomers for phenylene ether carboranylene ketone (PECK) polymer synthesis: preparation and characterization of boron-arylated ortho-carboranes bearing carboxyphenyl, phenoxyphenyl or benzoylphenyl substituents

M. A. Fox and K. Wade, J. Mater. Chem., 2002, 12, 1301 DOI: 10.1039/B108721E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements