Heck reaction poly synthesis

A combination of a Tsuji-Trost and a Heck reaction was also used by Poli and Gi-ambastiani [122] for the synthesis of the aza analogues 6/1-252 of the natural products podophyllotoxin 6/l-247a and etoposide 6/l-247b, which show pronounced... 

J.H. Kim and H. Lee, Synthesis, electrochemistry, and electroluminescence of novel red-emitting poly(p-phenylene vinylene) derivative with 2-pyran-4-ylidene-malononitrile obtained by the Heck reaction, Chem. Mater., 14 2270-2275, 2002. 

The dibromo- (and diiodo-) stilbenes ate potentially useful monomers tor the synthesis of poly(p-phenylenevinylenes) via poly-Heck or poly-Suzuki coupling reactions. ... 

Intramolecular variants of this reaction are often utilized in the synthesis of (poly)cyclic systems, while the intermolecular variant of the transformation is the key step in one of the most frequently studied and utilized carbon-carbon bond forming reactions, the Heck reaction (for details see Chapter 2.2.). 

Chandrasekhar S, Narsihmulu C, Sultana SS et al (2002) Poly(ethylene glycol) (PEG) as a reusable solvent medium for organic synthesis. Application in the Heck reaction. Org Lett 4(25) 439)M401... 

DiazC,AlzateD,RodriguezR,OchoaC,Sierra CA. High yield and stereospecific synthesis of segmented poly(p-phenylene vinylene) by the Heck reaction. Synth Met 2013 172 32-6. 

Ivan T, Vacareanu L, Grigoras M. Synthesis of poly(arylene vinylene)s containing carbazole, triphenylamine, and phenothiazine rings in the backbone by cascade Suzuk-i-Heck reactions. Int JPolym Mater 2013 62(5) 270-6. 

Lamaty and coworkers [148] investigated microwave-assisted Mizoroki-Heck reactions in poly(ethylene glycol) for the synthesis of benzazepines and developed a rapid, generally high-yielding preparation method for differently substituted benzazepines 206 (Scheme 6.61). 

Declerck, V., Ribiere, P, Nedellec, Y. et al. (2007) A microwave-assisted Heck reaction in poly(ethylene glycol) for the synthesis of benzazepines. Eur. J. Org. Chem., 201-8. 

However, we need to note that other chemical routes, rather than oxidation polymerization, can also be applied for conducting polymer synthesis. For example, polymers such as poly(pheny lene vinylene), poly(phenylene ethynylene), and their derivatives are usually synthesized using the Wittig reaction (Wittig and Schollkopf 1954), Heck reaction (Heck and Nolley 1972), and Gilch... 

The wide variety of coupling methods adapted from organic synthesis to condensation polymerization of just one CP can be appreciated from Fig. 5-12. for poly(pheny-lene). Typical condensations and eliminations adapted to syntheses of such CPs as poly(phenylene) and poly(phenylene vinylene) (P(PV)) are illustrated in Fig. 5-13. Fig. 5-14 shows the variety of precursor routes available to P(PV). More recently, the Yu group [86] has demonstrated application of Pd-catalyzed Stille and Heck reactions to the synthesis of poly(thiophene) (P(T)) derivatives (cf. Fig. 5-15. Besides the Grignard couplings such as shown in Eq. 1.6, Chapter 1, P(T) s can also be prepared via a variety of other procedures, such as Friedel-Crafts alkylation [87], and direct oxidation with FeClj as for P(Py) above. 

Heck Reaction Polymerizations. The Heck reaction is readily applicable to the synthesis of poly(arylenevinylene)s and poly(heteroarylvinylene)s. Poly(l,4-phenylenevinylene)s have been prepared with both AA/BB-monomer pairs and AB-monomers. The AA/BB-monomer pairs are typically dihalogenated arenes and ethylene (797) or divinylarenes (798). Bromostj ene (equation 61) is an example of an AB-monomer (799). The molecular weight of the polymer obtained by the polymerization of 4-bromostyrene (equation 61) was limited by its poor solubility (799). 

Substituted polyphenylene vinylenes can be obtained by the Heck reaction (Table I). Table I. Pd-catalyzed synthesis of poly(phenylene vinylene)s... 

The application of Heck coupling polycondensation is not limited to the synthesis of poly(arylene vinylene)s via the alkenylation of haloarenes in simple monomer systems but includes a variety of self- and cross-coupling reactions involving reactants with various functionalities. For instance, the polycondensation of diiodoarene with bis(acrylamido)arene by the Pd(OOCCH3)2—P (o-C6H4—CH3)3 catalyst yields respective aromatic polycinnamamide [106] ... 

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