Facile syntheses of new cavitands with mixed substituents

The (CH2Br)(4) cavitand 1 and its reactions with NaOAc in varying stoichiom etric ratios have been used to prepare a series of five different (CH2OAc)( 4-n)(CH2Br)(n) cavitands (n = 0-3) 2-6 with mixed substituents, which can b e separated by column chromatography (combined yield >95%) and are thus ava ilable in multi-gram quantities. The substitution reaction is statistical a nd the yields of individual acetates are controlled by the amount of NaOAc relative to 1. Careful hydrolysis of cavitands 2-6 with LiOH in THF-water r esults in the formation of the (CH2OH)(4-n)(CH2Br)(n) cavitands (n = 0-3) 7 -11 in yields of between 70-85%, Treatment of 2-6 with thiourea and NaOH af fords the respective (CH2SH)(4-n)(CH2OH)(n) cavitands (n = 0-3) 12-16 in yi elds of around 90%. Reactions of 2-6 with K-Phthalimide generate the respec tive (CH(2)Pht.)(4-n)(CH2OAc)(n) cavitands (n = 0-3) 17-21, which can be cl eaved with hydrazine hydrate resulting in the (CH2NH2)(4-n)(CH2OH)(n) cavit ands (n = 0-3) 22-26 in an overall yield of 60-70%.