Use of Unmodified Carbohydrate Reagents for the Polymerization of Dicyanoalkenes and Dicyanoarenes

Kim, Ik‐Bum; Rixman, Monica A.; Tsai, Zo-Hong; Wu, Dorothy; Njus, Jeffrey M.; Stark, J. C.; Hankins, J. M.; Sandman, Daniel J.

doi:10.1021/ma0108160

Cited by 5 publications

(8 citation statements)

References 12 publications

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“…The monomer 6 is also thermally reactive in the solid state. The product of the solid state reaction 46 has a repeat structure that appears to be the same as that obtained in solution synthesis, but the mechanism of initiation appears to involve a tautomeric form of 6 in a reaction that is inhomogeneous throughout the crystal. The crystal structure 47 of the monomer does not allow for a topochemical process leading to the observed product.…”

Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 91%

“…A similar material was also obtained from lithium n-butoxide in n-butanol, and the solid-state 13 C NMR spectrum of this material was particularly revealing. While the NMR spectra of the polymers from 6 and the sugar reagents have resonances 43 near d =100 assignable to the anomeric carbon, a resonance in this region in the polymer from lithium n-butoxide in n-butanol demands a different assignment. A carbon associated with a double bond is feasible, and hence we deduce that this reaction is likely initiated in part by an anion derived from 6.…”

Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 98%

“…Both cyclopolymerization and polymerization at only one of the two (or three) cyano groups were observed. 43 4-Nitrophthalonitrile (3a) reacts 43 with alkaline glucose to give the product of a cyclopolymerization in 26% yield. The electronic spectrum of this material reveals a broad intense band peaking at 703 nm.…”

Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 99%

“…With reference to Figure 4, the electron-releasing property of the R 2 N group results in enhanced electron density at the para-CN group. Addition of a nucleophile at the meta-CN group would result in an anion that would encounter the excess electron density at the CN group para to R 2 N. 2,3-Dicyano-5,7-dimethyl-6H-1,4-diazepine (6) reacts with glucose, 43 sucrose, and lactose 46 to give polymers involving reaction at only one cyano group. These polymers are sparingly soluble in all solvents, and their 13 C NMR spectra were obtained using cross polarization and magic angle spinning (CPMAS) methods.…”

Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 99%

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Conjugated Materials: Problems and Prospects for Synthesis Using Carbohydrate Reagents

Sandman¹,

Kim²,

Rixman³

et al. 2002

Synthesis

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C o n j u g a t e d M a t e r i a l s : P r o s p e c t s f o r S y n t h e s i s U s i n g C a r b o h y d r a t e R e a g e n t s Abstract: General considerations related to the use of sugars and closely related compounds as reagents for molecular and macromolecular synthesis are presented. For the first time, we have used unprotected carbohydrates to initiate polymerizations. A variety of dicyanoalkenes and -arenes react with sugars in the presence of alkali to give conjugated polymers. Both cyclopolymerization and polymerization at only one of two cyano groups are observed, and some qualitative mechanistic issues related to these observations are discussed. In some cases, a sugar alkoxide is the active initiating reagent. Characterization of the resulting polymers is reported. Alkaline sugar reagents have also been used in Knoevenagel reactions to synthesize CN-PPV oligomers and a related conjugated polymer in good yields. The use of the polysaccharide chitosan as a polycation allows the absorption spectrum of the polythiophene HPURET to shift to longer wavelengths than other polycations in electrostatically assembled films.

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Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 91%

Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 98%

Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 99%

Section: Polymerization Of Other Dicyanoalkenes and Phthalonitriles Wmentioning

confidence: 99%

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Conjugated Materials: Problems and Prospects for Synthesis Using Carbohydrate Reagents

Sandman¹,

Kim²,

Rixman³

et al. 2002

Synthesis

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“…We recently [1] described the use of unprotected sugars to polymerize dicyanoalkenes and Àarenes to materials with conjugated backbones. We recently [1] described the use of unprotected sugars to polymerize dicyanoalkenes and Àarenes to materials with conjugated backbones.…”

Section: Introductionmentioning

confidence: 99%

Concentration and Solvent Sensitive Visible Spectra of Poly(tricyanovinyldimethylaniline): Aggregation and Solvatochromism

Kim¹,

Sandman²

2002

J. of Macromolecular Sc., Part A

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This work presents unusual spectral behavior of poly(tricyanovinyldimethylaniline) (1) in dilute solutions. A new conjugated polymer(1) was prepared from p-(tricyanovinyl)N,N-dimethylaniline via the use of a methylglucopyranoside reagent. It is observed that dilute solutions of 1 exhibit spectral features associated with aggregation. The associative interaction is studied by changing the salt concentration of LiBr in DMF solution, by changing the concentration of 1, and by varying the solvents. The association modi®es the visible spectrum of 1 in dilute solution. Spectra of 1 in DMF solution exhibit an intense absorption maximum at 429 nm, which can be assigned to the side group, with tailing past 700 nm. With increasing concentration, a new absorption band arises between 480 nm and 700 nm. LiBr dissociates the aggregate to decrease the additional spectral features. The visible spectrum of 1 varies in dierent solvents. The spectrum of 1 in chloroform solution exhibits two maxima at 490 nm and 550 nm. The associative interaction presumably arises from a dipoleÀdipole interaction among pendant side groups. In DMF solution of 1 in the presence of p-chloranil, the spectrum shows a Downloaded by [University of California, San Francisco] at 22:23 26 December 2014 maximum at 429 nm with a distinct shoulder near 520 nm which does not orginate from 1 and p-chloranil(CA) itself.

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Synthesis and Mesoscopic Order of a Sugar-Coated Poly(p-phenyleneethynylene)

2002

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Use of Unmodified Carbohydrate Reagents for the Polymerization of Dicyanoalkenes and Dicyanoarenes

Cited by 5 publications

References 12 publications

Conjugated Materials: Problems and Prospects for Synthesis Using Carbohydrate Reagents

Conjugated Materials: Problems and Prospects for Synthesis Using Carbohydrate Reagents

Concentration and Solvent Sensitive Visible Spectra of Poly(tricyanovinyldimethylaniline): Aggregation and Solvatochromism

Synthesis and Mesoscopic Order of a Sugar-Coated Poly(p-phenyleneethynylene)

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