Three-component coupling polymerization of bisallene, aryl dihalides, and nucleophiles via π-allylpalladium complex. II. Effect of nucleophiles on polymerization

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 35, Issue 7, 1997, Pages 1211-1218

  Miyaki, Nobuyuki ^a   Tomita, Ikuyoshi ^a   Endo, Takeshi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Aryl dihalides; Bisallene; Nucleophiles; Palladium catalyst; Three component polycondensation; allylpalladium complex

Indexed keywords

AMINES; CATALYSTS; COMPOSITION EFFECTS; HALOGEN COMPOUNDS; OLEFINS; PALLADIUM; POLYCONDENSATION;

ARYL DIHALIDES; BISALLENES; NUCLEOPHILES; PALLADIUM CATALYSTS;

ORGANIC POLYMERS;

EID: 0031139211     PISSN: 0887624X     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1099-0518(199705)35:7<1211::AID-POLA6>3.0.CO;2-4     Document Type: Article

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21. 1H-NMR spectra.
22. 3h and 3i are insoluble in 1,4-dioxane. Thus, DMSO was used as a solvent for the polymerizations with these nucleophiles.
23. The nucleophiles having low pKa such as 3g and 3i required longer polymerization time, which may indicate the slower nucleophilic attacks. However, these nucleophiles increased the contents of the Z units. Up to now, the reason for the increase of Z units in these cases is not clear.
24. Attempts to use molpholine and acyclic secondary amines were unsuccessful. They may not have either enough basicity or the nucleophilicity in comparison with 3j-3l.
25. The decrease of the exo-unit by increasing the ring number of cyclic amine can be explained by the increase of the steric hindrance (and the decrease of the nucleophilcity) in 3. However, the lower Z-selectivity in the cases of 3h and 3l can not be explained fully by the proposed idea.