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Caution: Our current procedure uses THF to solubilize the starting material. Because at 120°C a reasonable pressure develops inside the sealed tube (up to 6 atm), considerable care should be taken while the reaction is run, and only appropriate glassware and seals should be used; otherwise, human injury may result. Pressure-rated reaction vials (up to 35 atm) with PTFE-silicon caps were used for this experiment.
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Caution: Our current procedure uses THF to solubilize the starting material. Because at 120°C a reasonable pressure develops inside the sealed tube (up to 6 atm), considerable care should be taken while the reaction is run, and only appropriate glassware and seals should be used; otherwise, human injury may result. Pressure-rated reaction vials (up to 35 atm) with PTFE-silicon caps were used for this experiment.
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Similar results were obtained under microwave irradiation [initial power = 250 W (variable); fixed temperature = 80, 100, or 120°C; time = 10-45 min] with a monomode microwave reactor. Full details of these experiments will be reported elsewhere.
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During the progress of this work, and before this treatment was implemented, it was realized that the polymerization of 1 afforded variable amounts of oligomeric-dimeric fractions that were dependent on the starting monomer batches. As a result, no reproducible interbatch results were sometimes obtained, and this precluded, in turn, any useful comparison between different polymerization systems. Because calix[4]arene 1 was synthesized through procedures that involved the use of Cu and Pd metals, random amounts of these metals in the polymerization mixture would certainly explain the aforementioned results.
-
During the progress of this work, and before this treatment was implemented, it was realized that the polymerization of 1 afforded variable amounts of oligomeric-dimeric fractions that were dependent on the starting monomer batches. As a result, no reproducible interbatch results were sometimes obtained, and this precluded, in turn, any useful comparison between different polymerization systems. Because calix[4]arene 1 was synthesized through procedures that involved the use of Cu and Pd metals, random amounts of these metals in the polymerization mixture would certainly explain the aforementioned results.
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This purification procedure is currently applied during the workup of the Sonogashira reaction
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This purification procedure is currently applied during the workup of the Sonogashira reaction.
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The purity improvement of poly 2 with the dissolution/ precipitation technique was, under the conditions tested, negligible. For that reason, the analyses reported here refer to crude poly 2.
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The purity improvement of poly 2 with the dissolution/ precipitation technique was, under the conditions tested, negligible. For that reason, the analyses reported here refer to crude poly 2.
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