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  • Polymer and Materials Science  (2)
  • N-(aminoalkyl)-9-phenanthrenecarboxamides  (1)
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  • 1
    ISSN: 0894-3230
    Schlagwort(e): N-(aminoalkyl)-9-phenanthrenecarboxamides ; molecular structures ; folded conformations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: ---The molecular structures of three tertiary N-(aminoalkyl)-9-phenanthrenecarboxamides were investigated in solution and the solid state by means of 1H NMR spectroscopy and x-ray crystallography. The tertiary amides exist as a mixture of E and Z isomers in solution and the aminoalkyl groups exist as a mixture extended and folded conformers. A crystalline N-(aminoethyl)amide was obtained as the pure Z isomer in which the phenanthrene and amide planes are nearly perpendicular and the aminoethyl group is folded over the less hindered face of the amide group. Rotation about the Ar-C(O) bond is slow in resolution rendering these molecules chiral on the NMR time-scale. As a consequence, the α-methylene protons display large diasterotopic splittings when the aminoalkyl group is syn to the amide carbonyl. Folded conformations place the Z and E aminoalkyl groups in the deshielding and shielding regions, respectively, of the phenanthrene rings, resulting in large differences in chemical shifts. © 1997 John Wiley & Sons, Ltd.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A novel photoresponsive polymer containing organic chromophores which possess thermal stability as well as substantial and reversible responsiveness upon external photostimulus has been developed. trans-2{4-[2-(Dimethylcarbamoyl)vinyl]phenoxy}ethyl methacrylate (1) was synthesized and copolymerized by free-radical methods with methyl methacrylate giving a copolymer poly[(methyl methacrylate)-co-1] (poly(MMA-co-1)) (2) with cinnamamide moiety chromophores randomly attached as side groups. Photoisomerization and ultraviolet absorbance were used to examine the photostationary states and solubility changes upon photoirradiation. Poly[(methyl methacrylate)-co-1] (90,7 : 9,3 mol%) with 9,3 mol-% cinnamamide content has better solubility in a polar solvent such as acetonitrile (theta temperature ΘPMMA = 30°C) than in a nonpolar solvent such as carbon tetrachloride (ΘPMMA = 27°C). Photoisomerization of the trans-cinnamamide to cis-cinnamamide units significantly shifts the cloud point of poly[(methyl methacrylate)-co-1] (90,7 :9,3 mol-%) in carbon tetrachloride; this cloud point shift is reversible by photoisomerization back to the trans state. However, in a hydrogen-bonding solvent such as tert-butyl alcohol, while photoirradiation of poly[(methyl methacrylate)-co-1] (90,7 :9,3 mol%) yields a significant shift in cloud point, this is not reversible by photoirradiation as hydrogen-bond formation between the tertiary amide and the hydroxylic solvent reduces the isomerization efficiency. Fatigue of the photoreversibility of the copolymer, which is not present in dilute solutions of the cinnamamide chromophore, is noted.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 2625-2635 
    ISSN: 0887-6266
    Schlagwort(e): fluorene ; fluorescence ; quenching ; in situ monitoring ; free-radical polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A new approach for monitoring in situ the progress of an addition polymerization has been developed based on the fluorescence quenching of fluorene. Fluorene is quenched by the enone functionality on acrylates and methacrylates, but is not quenched after the carbon-carbon double bond in this group is broken by incorporation into the polymer backbone. Ethyl (2-fluorenyl)methacrylate was used as a self-quenching comonomer during the 2,2'-pazo bis(2-methylpropionitrile)-initiated free-radical copolymerization of methyl methacrylate at 60°C. The fluorescence intensity increases by 60% up to the onset of the gel effect (defined as the sudden increase in the temperature profile). The system shows sensitivity well into the glassy state, with fluorescence increasing more than two orders of magnitude from the beginning of the reaction. This sensitivity is compared with that of two free-volume-dependent probes, 1,3-bis(1-pyrene)propane and dimethylaminobenzylidenemalononitrile, and to fluorene. The temperature profile of the test-tube-scale reaction was used as an internal reference for characterizing the sensitivity of the probes with respect to the gel effect region. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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