Recent developments in the use of polymers as reactants in organic reactions

Abstract

Abstract--In a review article [Accounts ehern. Res., 2, 217 (1969)] is a summation of our work up to 1968. In this review we summarized the activity of polyvinylimidazole and copolymers in esterolytic reactions. We explained the increased reactivity of these polymeric reactants in terms of cooperative effects and electrostatic factors.In 1967, we blundered into the extremely interesting discovery that long-chain esters provided us with enormaus acceleration of rates at room temperature and we have attributed this in "general" terminology to apolar bonding as a third factor to understand the high reactivity of these synthetic macromolecules. Reference 1 describes our recent published work. We are heavily emphasizing the apolar bonding concept.

Optically Active Polyampholytes Derived from L- and D-Carbylanayl-L-histidine

“…The combined 1-butanol fractions were concentrated to yield 5 g of 4a. The product was used without further purification for the synthesis of 5a: yield 13.5 g (51 mmol, 85%); mp 127-128 °C; IR (KBr) 3310 (NH), 1740 (COOCHg), 1650 (NHCO) cm4; NMR (CDgOD) 8.05 (s, 1 H, CHO), 7.65 and 6.90 (2 X s, 2 H, imidazole), 4.55 H, CH), 3.70 (s, 3 H, OCH3), 3.05 (dist d, 2 H, CH2), 1.30 (d, 3 H, CH3).…”

“…(s, 1 H, CHO), 7.95 and 7.10 (2 X s, 2 H, imidazole), 7.80 and 7.35 (2 X d, 4 H, tosyl), 7.35 (br, 1 H, NH), 6.80 (br d, 1 , NH), 4.75 (d of t, Jd = 6 Hz, Jt = 8 Hz, 1 H, CHCH2), 4.60 (d of q, Jd = 8 Hz, Jq = 7 Hz, 1 H, CHCH3), 3.65 (s, 3 H, OCH3), 3.00 (d, 2 H, CH2), 2.45 (s, 3 H, tosyl), 1.20 (d, 3 H, CH3).…”

“…D-Carbylalanyl-Nim-tosyl-L-histidine Methyl Ester (6b). Synthesis was performed as described for 6a: yield 75%; white needles from methanol; mp 134.5-134.6 °C; [a]22678 +18.6°(c 2, chloroform); MS data same as those for 6a; IR (KBr) 3315 (NH), 2149 ± 1 (NC, internal calibration), 1740 (COOCH3), 1670 (NH-CO), 1600,1370, and 1170 (tosyl) cm"1; NMR (CDC13) 8.0 and 7.1 (2 X s, 2 H, imidazole), 7.85 and 7.40 (2 X d, 4 H, tosyl), 8.05 (br d, 1 , NH), 4.80 (d of t,Jd = l Hz, Jt = 5 Hz, 1 H, CHCHj), 4.25 (q, 1 H, CHCH3), 3.65 (s, 3 H, OCR,), 3.10 and 3.075 (2 X d, Jd = 5.3 Hz, 2 H, CH2), 2.45 (s, 3 H, tosyl), 1.60 (d, 3 H, CH3). A finely powdered mixture of 15 mg of 6a and 15 mg of 6b had a melting range from 116 to 118 °C.…”