Structure design of multifunctional furoate and pyroglutamate esters of dextran by polymer-analogous reactions

Well-defined multifunctionalized dextran esters bearing photo-crosslinkable and chiral groups as well as small alkyl moieties for the adjustment of the solubility were prepared from two dextran samples with different origin and molecular weight. The examination of side structures of the starting dextran was carried out by different one- and two-dimensional NMR techniques. The main synthesis path via in situ activation of furan-2-carboxylic- and pyroglutamic acid with CDI under mild conditions gives highly functionalized dextran derivatives possessing a degree of polymerization in the range of the starting polysaccharide. The subsequent reaction with propionic anhydride leads to completely substituted, CHCl(3) soluble derivatives useful for the determination of the particular degree of substitution. By variation of the molar ratios of polymer to reagent with photo-crosslinkable- and chiral moieties during the reaction and even by subsequent peracylation, multifunctional dextran derivatives with adjustable properties like the hydrophilic/hydrophobic balance were obtained that may form biocompatible spherical nanoparticles.     

o‐Carboxybenzoylferrocene. Bioactivity and chemical Modifications

The antitumor activity of o‐carboxybenzoylferrocene sodium salt ( 1 ) was studied in vivo . Interaction between o‐carboxybenzoylferrocene ( 2 ) and N,N′‐carbonyldiimidazole in boiling methylene dichloride leads to 3‐(N‐imidazolyl)‐3‐ferrocenylisobenzofuran‐1(3H)‐one ( 5 ). The structure of compound 5 was established by X‐ray analysis. Aminolysis of compound 5 in toluene gave rise to ferrocenoylbenzamides ( 6a – d )–derivatives of dimethylamine, piperidine, pyrrolidine and morpholine. Copyright © 2008 John Wiley & Sons, Ltd.     

Storage stability and curing behavior of epoxy‐dicyandiamide systems with carbonyldiimidazole‐Cu (II) complexes as the accelerator

The reaction between carbonyldiimidazole (CDI) and copper (II) nitrate produces a new Cu (II) complex with nitrate as the counter anion. TGA, UV, and FTIR analyses confirmed that the coordination number of CDI in this complex is two. The acceleration effect of the complex in epoxy‐dicyandiamide (DICY) curing systems has been evaluated by DSC and TMA, and the increasing viscosity of the mixture was monitored during the storage. The results revealed that the complex is not only very effective for the acceleration of epoxy‐DICY systems, leading to a rapid gelation within 21 min at 120 °C, but it is also chemically stable at ambient temperature. This is reflected by the slow increase of viscosity of the accelerated curing systems stored at 35 °C, even over 56 days. In addition, the effects of the [Cu(CDI)₂]²⁺ complex with different counter anions, that is, bromide, chloride, nitrate, sulfate, phthalate, and acetate, were compared using a series of tests. By comparing with N,N‐dimethyl‐N′‐phenylurea (fenuron), the widely used latent accelerator for DICY‐epoxy curing systems, the complexes with bromide and nitride were found to be better, both regarding storage stability and for their acceleration effect. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3470–3476     

Efficient accelerating effect of carbonyldiimidazole on epoxy‐dicyandiamide curing system

Carbonyldiimidazole (CDI) was inventively used as an accelerator for the curing reaction of diglycidyl ether of bisphenol A (DGEBA) with dicyandiamide (DICY) and a high acceleration more effective than imidazole in double usage was observed. This result implies the accelerating role of CDI in the curing process is complex and involved not only the release of imidazole. To detail the accelerating mechanism of CDI, a series of curing reactions was studied by differential scanning calorimetry (DSC), NMR, IR, and viscosity monitoring. The results suggested that the accelerating mechanism of CDI involves (1) acylation of DICY with CDI to give the corresponding adduct with enhanced solubility, (2) the consequent release of imidazole that can react with epoxide, and (3) abstraction of proton of DICY by the alkoxide moiety to give the corresponding DICY anion endowed with enhanced nucleophilicity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010