KNOTS FOR MOLECULAR STRINGS OF BEADS

Three alpha,alpha,omega,omega-tetraaryl alpha,omega-diols 10 were synt hesized via Grignard reactions of p-tert-butylbromobenzene with 1,10-b is(p-carbethoxyphenoxy)decane, dimethyl terephthalate, and dimethyl ad ipate (8). The diols 10 were converted to 1,10-bis{p-[bis(p'-tert-buty lphenyl)(p ''-hydroxyphenyl)-methyl]phenoxy}decane (11a), nyl)(4'-amin o-3',5'-dimethylphenyl)methyl]-benzene (11b), and 1,1,6,6-tetrakis(p-t ert-butylphenyl)hexane (12) via carbocation chemistry. Alkylation of 1 1a with 2-(2-chloroethoxy)ethanol yielded 1,10-bis{p-{bis[p'-tert-buty lphenyl) [p ''- '-hydroxyethoxy)ethoxy]phenyl]methy}phenoxy}decane (13 ), containing two tetraarylmethyl groups. 4-Bis[bis(p-tert-butylphenyl )hydroxymethyl]benzene (10b) was reduced to 1,4-bis[bis(p-tert-butylph enylmethyl]benzene (14) by formic acid. The reaction of tetraarylhexan ediol 10c with formic acid produced 1,1,6,6-tetrakis(p-tert-butylpheny l)-1,5-hexadiene (15). Via two S(N)2 reactions in a one-step route, di ethyl bis(p-tert-butylbenzyl)malonate (18) was produced from diethyl m alonate and p-tert-butylbenzyl bromide. A Grignard reaction of p-tert- butylbromobenzene with ethyl acetate generated 1,1-bis(p -tert-butylph enyl)ethanol (20) which was converted to 1, 1-bis(p-tert-butylphenyl)e thene (21) by water elimination. All the intermediates and final produ cts are new compounds. While the bisphenol 11a, bisaniline 11b, diol 1 3, diester 17, and the alkanes 12 and 14 with two reactive protons are suitable difunctional knots for syntheses of rotaxanes and of polyrot axanes via step growth polymerizations, the ethene 21 can be used for polyrotaxanes prepared by chain growth polymerizations.