Synthesis and photoinduced deprotection of calixarene derivatives containing certain protective groups

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Abstract
Calixarene derivatives 1a, 1b, and 1c containing pendant tert‐butoxycarbonyl (t‐BOC) groups were synthesized in 81, 93, and 83% yields, respectively, by the reaction of C‐methylcalix[4]resorcinarene (CRA), p‐methylcalix[6]arene (MCA), and p‐tert‐butylcalix[8]arene (BCA) with di‐tert‐butyl dicarbonate using triethylamine as a base in pyridine. Calixarene derivatives 2a, 2b, and 2c containing pendant trimethylsilyl ether (TMSE) groups were obtained in 58, 50, and 82% yields, respectively, by the reaction of CRA, MCA, and BCA with 1,1,1,3,3,3‐hexamethyldisilazane using chlorotrimethylsilane as an accelerator in tetrahydrofuran. Calixarene derivatives 3a, 3b, and 3c containing pendant cyclohexenyl ether (CHE) groups were also prepared in 65, 78, and 84% yields, respectively, by the reaction of CRA, MCA, and BCA with 3‐bromocyclohexene using potassium hydroxide as a base as well as tetrabutylammonium bromide as a phase‐transfer catalyst in N‐methyl‐2‐pyrolidone. The photoinduced deprotection of calixarene derivatives 1a–c was examined with bis‐[4‐(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) as a photoacid generator on UV irradiation followed by heating in the film state, and it was found that the deprotection of the t‐BOC groups of 1a proceeded smoothly in high conversion. The deprotection rates of the t‐BOC groups of 1b and 1c were much lower than that of 1a under the same irradiation conditions. The photoinduced deprotection of calixarenes 2b–c containing tetramethylsilane groups as well as 3a–c containing CHE groups were also examined under similar reaction conditions in the film state, and it was found that the deprotection rates of calixarenes 2b–c and 3a–c were lower than those of the corresponding 1a–c calixarenes. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1481–1494, 2001

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