Bifunctional Synzymes Via Alternating Copolymerization
Bifunctional Synzymes Via Alternating Copolymerization
Vanderbilt, David Paul
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The reac- tion scheme along with yields obtained in this laboratory is outlined below. -OH 43% 0OCOC1 DMF, Et 3 N MeOH bromo- benzene 160°C ■OCOPh II 825 13 Carboxylic Acid --Maleimides The carboxylic acid group has been incorporated into synzymes 55,56 and also plays a key role in the "charge-relay system" of the natural 57 enzyme chymotrypsin. We attempted the synthesis of carboxylic acid containing maleimide monomers for two reasons: evaluation of bifunc- tional synzymes containing the carbo...xylic acid residue, and conversion of the carboxylic acid group via its N-hydroxysuccinimide ester to a hydroxamic acid group. 68 The direct dehydration of maleanilic acids 22 and 23 were unsuc- cessfully carried out using the following reagents: Ac-O/NaOAc, 49 50 59 DCC/DMF,^ DCC/CH 2 C1 2 , J:7 and refluxing xylene. 60 On the other hand, maleanilic acid 15 was cleanly dehydrated to maleimide 16 in 83% yield using AcpO/NaOAc. 0M NH 0=/ \=0 CH 2 C0 2 H 23 Clearly, the presence of the second carboxyl group in 22 and 23^ is in some way responsible for the inability to effect dehydration.
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