Poly . optically active

Diisocyanobenzene (130) undergoes living polymerization to form the poly(quinoxaline-2,3-diyl)s 131, and the optically active helical polyfquinoxa-line-2,3-diyl) 132 is prepared from 131[123]. 

An interesting aspect of the benzofuran cationic polymerization was uncovered by Natta, Farina, Peraldo and Bressan who reported in 196160,61 that an asymmetric synthesis of an optically active poly(benzofuran) could be achieved by using AlCl2Et coupled with (-)j3-phenylalanine, (+)camphorsulphonic acid or with (-)brucine. The optical activity was definitely due to the asymmetric carbon atoms in the polymer chain, indicating that at least some of the polymer s macromolecules possessed a di-isotactic structure, v/ z.62 ... 

Synthesis of Optically Active Poly(l,l -bi-2-naphthyl) 1654c... 

One-shot techniques, 216, 217, 236-237 Optical fiber waveguide, 271-272 Optically active poly(arylene), synthesis of, 518-519... 

Optically active polymers, 473, 479-480 synthesis of, 509 Optically active poly(phenylene-ethynylene), synthesis of,... 

Polyarylate (PAR), 22 Poly(arylene), optically active, 518-519 Poly(arylene ether ether ketone) (PEEK), 327... 

Polyt/f-esters), 41-43 Poly(l,l -bi-2-naphthyl) (Poly[BINAP]), optically active, 509-510, 513-514... 

Poly(phenyleneethynylene)s, 482 optically active, 516-517 synthesis of, 496-500, 502 Poly(m-phenylene isophthalamide), 136 synthesis of, 185-186 Poly(l,4-phenylene terephthalate) liquid crystalline polymers, 51 Poly(para-phenylene)s, 472. See also Poly (p -pheny lene)... 

Poly(phenylenethylene), dendronized, 522 Poly(phenylenevinylene) optically active, 510-511 synthesis of, 495-496 Poly(/ ara-phenylenevinylene)s, 472 Polypheny lquinoxaline (PPQ) hyperbranched, 312-314 synthesis of, 309-313 Polyphosphoric acid, 333 Polypropylene oxide) polyol, 223 Polypropylene polyols, 220 Poly (pyridine), synthesis of, 503-505 Polyquinoxaline (PQ), synthesis of, 309-313... 

Subsequently, a number of reactions at poly-L-valine coated carbon electrodes 237-243) gj.g reported to yield optically active products. Reductions, e.g. of citraconic acid or l,l-dibromo-2,2-diphenylcyclopropane as well as the oxidation of aryl-alkyl sulfides proceeded with chiral induction at such electrodes... 

The preparation of helically well-ordered polymers with stable screw-sense, which is able to be transmitted to newly formed polymer main-chains effectively, is highly desired for the development of new methodology for the synthesis of optically active helical polymers. An aromatizing polymerization of 1,2-diisocyanobenzenes is promoted by methylpalladium(II) complexes, producing poly(quinoxaline-2,3-diyl)s.146-148 The polymerization proceeds with successive insertion of the two isocyano groups of the diisocyanobenzene to the carbon palladium bond of... 

Fig. 15. Optical activities of poly(propylene imine) dendrimers, functionalized at the periphery with protected phenylalanine or f-butoxy methoxy benzyl acetate groups, depend on the number of end groups [2]...

Vogtle et al. have prepared chiral poly(imine) dendrimers of various generations by condensation of non-racemic 5-formyl-4-hydroxy[2.2]paracyclophane moieties with poly(amine) dendrimers [71]. They have found that the optical activity of these dendrimers was nearly constant with increasing generation number. 

Poly(hydroxyalkanoates) (PHAs), of which poly(hydroxybutyrate) (PHB) is the most common, can be accumulated by a large number of bacteria as energy and carbon reserve. Due to their bio degradability and bio compatibility these optically active biopolyesters may find industrial applications. A general overview of the physical and material properties of PHAs, alongside with accomplished applications and new developments in this field is presented in this chapter. 

The optically active poly(TrMA) shows a large optical activity and intense circular dichroism (CD) due both to the triphenylmethyl group, indicating that this group has a chiral propeller structure, and to the helicity. Poly(TrMA) of degree of polymerization (DP) over 80 is insoluble in common organic solvents. 

Figure 4.2 Comparison of UV absorption spectra of four optically active poly silanes in THF at 30°C poly methyl-(iS )-2-methylbutylsilane (1, a of 0.59), poly -hexyl-(5 )-4-methylpentyl-silane (2, a of 0.75), poly -hexyl-(5 )-3-methylpentylsilane (3, a of 0.92), and poly -hexyl-(5)-2-methyl-butylsilane (4, a of 1.25).

Figure 4.2 shows the UV absorption spectra of four optically active poly(dialkylsilane)s bearing different chiral side groups in THF at 30°C.32a It is evident that as the value of a increases from 0.59 to 1.25, the UV... 

This knowledge and understanding may be helpful to characterize local conformations of other optically active polysilanes in solution. For example, poly(methyl-(-)-(3-pinanylsilane) [(+)-7 Mw = 10,200] prepared by Shinohara and co-workers.281 showed a bisignate CD band at 280 and 303 nm, associated with a broad UV absorption at 300 nm in chloroform at 15°C. Since the spectroscopic features are quite similar to those of i,28d-28e it is possible that the main chain in 7 may contain diastereomeric helical motifs with opposite screw senses and different screw pitches. 

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