Polyethers with propargyl side chains were synthesized by the acid-catalyzed reaction of dialdehydes 1, alkylene bis(trimethylsilyl) ethers 2, and allenyltrimethylsilane 4. When ethylene glycol bis(trimethylsilyl) ether was used as 2, only oligomer was obtained. However, the use of 2 with longer carbon chains gave the desired polyethers consisting of 1, 2, and 4 in the molar ratio 1:1:2 in good yields in the presence of 10 mol % triphenylmethyl perchlorate (TrClO 4 ) at À20 8C. This polyether was treated with organometallic reagents such as Co complex or CuCl to give a cross-linked polymer. This polymer synthesis is unusual in that it concurrently constructs both the polymer backbone and the functional side chains from three starting compounds. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5440-5448, 2005
SUMMARY Polyethers with the keto side chains were synthesized by the one-step reaction of dialdehydes (l), alkylene bis(trimethylsily1) ethers (2), and silyl enol ethers (3) in the presence of 10 mol-% of triphenylmethyl perchlorate (trityl perchlorate). The model reactions using monofunctional analogs showed that silyl enol ether 3 h of 4-nitroacetophenone is most effective for the depression of the aldol reaction of the aldehyde with 3. A variety of 1, 2, and 3 h with the molar ratio 1 : 1 : 2 was polymerized at -50 "C to yield polyethers with keto side chains. This polymer synthesis is unusual in that it concurrently constructs both polymer backbone and functional side chains from three starting compounds.
Polyethers with the allenyl side chains were synthesized by the simultaneous acid-catalyzed
reaction of dialdehydes 1, alkylene bis(trimethylsilyl) ethers 2, and 1-trimethylsilyl-2-butyne (4b). Before
polymerization, Lewis acid-catalyzed three-component reactions of aldehydes, alkoxysilanes, and propargylsilanes were studied to find that 4b was effective as an allenyl reagent in this reaction. The
polycondensations of 1, 2, and 4b were carried out in the presence of 10 mol % of triphenylmethyl
perchlorate (TrClO4) at −50 °C to yield the desired polyethers consisting of 1, 2, and 4b with a molar
ratio of 1:1:2 in good yields. This polyether was treated with a cationic catalyst such as BF3OEt2 to give
a cross-linked polymer. This polymer synthesis is unusual in that it concurrently constructs both the
polymer backbone and the functional side chains from three starting compounds.
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