A novel polyaddition of bifunctional acetylenes containing electron-withdrawing groups. III. Synthesis of polymers having β-alkoxyenoate moieties by the reaction of internal diynes with diols

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 34, Issue 8, 1996, Pages 1597-1604

  Kuroda, Hirofumi ^a   Tomita, Ikuyoshi ^a   Endo, Takeshi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Conjugate addition; Diols; Polyaddition; Tri n butylphosphine catalyst; alkoxyenoates; substituted bispropiolates

Indexed keywords

ACETYLENE; ALCOHOLS; CATALYSTS; CHEMICAL REACTIONS; PROTONS; SYNTHESIS (CHEMICAL);

BETA ALKOXYENOATE MOIETIES; BIFUNCTIONAL ACETYLENE; CONJUGATED ADDITION; DIOLS; ELECTRON WITHDRAWING GROUP; INTERNAL DIYNES; POLYADDITION; TRIBUTYLPHOSPHINE CATALYST; ZWITTERIONIC INTERMEDIATES;

POLYMERIZATION;

EID: 0030165894     PISSN: 0887624X     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1099-0518(199606)34:8<1597::AID-POLA25>3.0.CO;2-2     Document Type: Article

References (13)

1. P. Perlmutter, Conjugate Addition Reactions in Organic Synthesis, Pergamon, Oxford, 1992; B. M. Trost, Comprehensive Organic Synthesis, Pergamon, Oxford, 1991, Vol. 4.
2. P. Perlmutter, Conjugate Addition Reactions in Organic Synthesis, Pergamon, Oxford, 1992; B. M. Trost, Comprehensive Organic Synthesis, Pergamon, Oxford, 1991, Vol. 4.
3. For example: S. Kobayashi and T. Mukaiyama, Chem. Lett., 705 (1974); H. Huang and B. Chen, Synthesis, 480 (1987); K. Mori and H. Mori, Tetrahedron, 43, 4097 (1987).
4. For example: S. Kobayashi and T. Mukaiyama, Chem. Lett., 705 (1974); H. Huang and B. Chen, Synthesis, 480 (1987); K. Mori and H. Mori, Tetrahedron, 43, 4097 (1987).
5. For example: S. Kobayashi and T. Mukaiyama, Chem. Lett., 705 (1974); H. Huang and B. Chen, Synthesis, 480 (1987); K. Mori and H. Mori, Tetrahedron, 43, 4097 (1987).
6. H. Kuroda, I. Tomita, and T. Endo, Macromolecules, 28, 433 (1995).
7. H. Kuroda, I. Tomita, and T. Endo, Macromolecules, 28, 6020 (1995).
8. 3P; 5 mol %).
9. The small peaks at 2.3 ppm can be attributed to the methylene group adjacent to triple bond in end group.
10. The phosphine-catalyzed conjugate addition of benzyl alcohol with methyl 2-butynoate has been reported to produce a product with specifically E-isomer. See: J. Inanaga, Y. Baba, and T. Hanamoto, Chem. Lett., 241 (1993).
11. In the case of the polyaddition of dithiols with internal ynoates, the molecular weights and yields of the obtained polymers decreased by slipping off the stoichiometry of two monomers as is usual for polyaddition reaction, (see Ref. 4). The side-reaction (i.e. the anionic chain reaction of ynoate moieties) might be suppressed completely by faster protonation from the dithiol in this system, because thiols have high acidity compared with alcohols. Thus, the result may be expected to support our hypothesis relating to the side-reaction.
12. 1B did not undertake any side reactions in the presence of tri-n-butylphosphine (20 mol %) in THF (0.5M) and was recovered almost quantitatively. The result suggest the anionic chain polymerization of propiolate moieties was considerably suppressed by the introduction of substituents at the β-position of the propiolate.
13. 1H-NMR spectrum, transesterification units were observed. For instance, protons of the methylene group adjust oxygen atom at vinylether moieties generated by the transesterification was observed at 3.5 ppm in the case of polyaddition of 1B with 2a or 2c (Figs. 1 and 6). The transesterification also took place on the case of 1A (see Ref. 3).