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Volumn 44, Issue 24, 2006, Pages 7054-7070

Synthesis and Rh(I)-catatyzed polymerization of 1,3-DEphenylyne-calix[4] arene compounds: Novel conjugated, calixarene-based polymers

Author keywords

Calixarene; Catalysis; Conjugated polymers; Cyclopolymerization; Rhodium; Sonogashira coupling

Indexed keywords

CATALYSIS; DERIVATIVES; INITIATORS (CHEMICAL); MOLECULAR WEIGHT; ORGANIC POLYMERS; POLYMERIZATION; SYNTHESIS (CHEMICAL);

EID: 33845965696     PISSN: 0887624X     EISSN: 10990518     Source Type: Journal    
DOI: 10.1002/pola.21797     Document Type: Article
Times cited : (13)

References (73)
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    • For an overview of calixarene nomenclature, see Gutsche, C. D. In Calixarenes 2001; Asfari, Z.; Böhmer, V.; Harrowfield, J.; Vicens, J., Eds.; Kluwer Academic: Dordrecht, 2001; Chapter 1, pp 1-2. For lower rim unsubstituted calix[4]arenes, such as 3 and 4, four main conformations can exist: (1) a cone, with the phenyl groups all syn to one another; (2) a partial cone, with three phenyl groups syn and one anti; (3) a 1,2-alternate, with adjacent pairs of phenyl groups syn and anti; and (4) a 1,3-alternate, with nonadjacent pairs of phenyl groups syn and anti. These four possible conformers, with calix[4]arenes 3 and 4 used as examples, are depicted in Chart S1 in the supplemental material.
    • For an overview of calixarene nomenclature, see Gutsche, C. D. In Calixarenes 2001; Asfari, Z.; Böhmer, V.; Harrowfield, J.; Vicens, J., Eds.; Kluwer Academic: Dordrecht, 2001; Chapter 1, pp 1-2. For lower rim unsubstituted calix[4]arenes, such as 3 and 4, four main conformations can exist: (1) a cone, with the phenyl groups all syn to one another; (2) a partial cone, with three phenyl groups syn and one anti; (3) a 1,2-alternate, with adjacent pairs of phenyl groups syn and anti; and (4) a 1,3-alternate, with nonadjacent pairs of phenyl groups syn and anti. These four possible conformers, with calix[4]arenes 3 and 4 used as examples, are depicted in Chart S1 in the supplemental material.
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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.
    • 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.
    • 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
    • This purification procedure is currently applied during the workup of the Sonogashira reaction.
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    • Merck Molecular Force Field molecular modeling calculations were performed with Spartan' 04 from Wavefunction, Inc, Irvine, CA
    • Merck Molecular Force Field molecular modeling calculations were performed with Spartan' 04 from Wavefunction, Inc. (Irvine, CA).
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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.
    • 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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.