Simultaneous construction of polymer backbone and side chains by three‐component polycondensation. Synthesis of polyethers with propargyl side chains from dialdehydes, alkylene bis(trimethylsilyl) ethers, and allenyltrimethylsilane

Abstract

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

Synthesis of poly(p-phenylene-vinylene) derivative having amphiphilic substituents by palladium-catalyzed three-component coupling polymerization of p-bromophenylallene and nucleophile containing oligo-oxyethylene units

“…Bromobenzene was distilled prior to use. Tri-o-tolylphosphine (P(o-tolyl) 3 ) was purified by recrystallization from EtOH. Other reagents were used as received.…”

“…After addition of p-bromophenylallene (1, 0.097 g, 0.50 mmol), the reaction mixture was heated at 80°C for 15 h. After addition of water, the product was extracted with chloroform and the chloroform solution was concentrated and precipitated into hexane to give a polymer (3) in an 87% yield (0.19 g, 0.43 mmol).…”

“…Then, palladium acetate (Pd(OAc) 2 , 0.0068 g, 0.030 mmol), P(o-tolyl) 3 (0.036 g, 0.12 mmol), and 1,4-dioxane (2.0 mL) were added and the mixture was stirred for 10 min. After addition of bromobenzene (0.16 g, 1.0 mmol) and phenylallene (0.12 g, 1.0 mmol), the reaction mixture was heated at 80 °C for 15 h. To the resulting mixture, water was added and was extracted three times with diethyl ether.…”

“…Then, Pd(OAc) 2 (0.0034 g, 0.015 mmol), P(o-tolyl) 3 (0.018 g, 0.060 mmol), and 1,4-dioxane (1.0 mL) were introduced and the mixture was stirred for 10 min. After addition of p-bromophenylallene (1, 0.097 g, 0.50 mmol), the reaction mixture was heated at 80°C for 15 h. After addition of water, the product was extracted with chloroform and the chloroform solution was concentrated and precipitated into hexane to give a polymer (3) in an 87% yield (0.19 g, 0.43 mmol).…”

“…The only way to obtain PPV's with good solubility and processability is to design monomers by incorporation of soft lateral substituents. As an alternative approach to obtain polymers with highly functionalized repeating units, we have been working on the development and applications of novel threecomponent polycondensation systems that enable to connect three kinds of building blocks at once [2,3]. For example, on the basis of the palladium-catalyzed threecomponent coupling reaction [4], we have described the polymerization of aromatic bisallenes, aryl dihalides, and nucleophiles or of halophenylallenes and nucleophiles which proved to be effective to design PPV's having functional groups on each vinylene unit [2b, 2d].…”