Regioselective Formation of Six- and Seven-Membered Ring by Intramolecular Pd-catalyzed Amination of N-allyl-anthranilamides

A divergent synthesis of quinazolin-4-ones and l,4-benzodiazepin-5-ones by Pd(II)-catalyzed intramolecular amination of tosylated N-allyl-anthranilamides is described. Both kinds of products were available in high yields depending on the different reaction conditions

Conductance and spectroscopic mapping of EDOT polymer films upon electrochemical doping

This paper deals with the electrochemical doping of different poly(ethylenedioxythiophene) (PEDOT)-based active layers performed in an organic electrochemical transistor configuration through the mapping of in situ conductance trends during electrochemical doping and dedoping. The experiments are complemented by UV/Vis/NIR in situ spectroelectrochemistry in the wavelength range from 400 to 1600 nm, which allow monitoring of the development of the neutral and charged redox species. Both electropolymerized EDOT-based layers and solution-processed chemically synthesized PEDOT films are characterized. In addition to pure electropolymerized PEDOT (e-PEDOT), tris(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)phenyl) (TPA-EDOT3) is electrodeposited to generate highly branched networks of P(TPA-EDOT3). The solution-deposited PEDOT films contain poly(ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with ratios of 1:2.5 and 1:6. Overall, we find that e-PEDOT and PEDOT:PSS(1:2.5) behave like classical conjugated polymers with a plateau-like conductance over a wide potential region. In contrast, PEDOT:PSS(1:6) and P(TPA-EDOT3) show rather bell-shaped conductance profiles. The mixed-valence conductivity model is used to interpret the experimental results in terms of the number of accessible redox states. We suggest that the bell-shaped conductance in the case of PEDOT:PSS(1:6) is caused by a high amount of PSS insulator that limits the inter-chain interaction between PEDOT moieties and in the case of P(TPA-EDOT3) by its distorted molecular architecture

One-pot sequential synthesis of isocyanates and urea derivatives via a microwave-assisted Staudinger\u2013aza-Wittig reaction

A fast and efficient protocol for the synthesis of N,N'-disubstituted urea derivatives from alkyl halides and primary or secondary amines has been developed. The synthetic pathway combines nucleophilic substitutions and a Staudinger-aza-Wittig reaction in the presence of polymer-bound diphenylphosphine under 14 bar of CO2 pressure and has been performed in a one-pot two-step process. The protocol has been optimized under microwave irradiation and the scale-up experiment has been conducted under conventional conditions in a Parr reactor. The final compounds were isolated after simple filtration in almost quantitative overall yields which makes this procedure facile and rapid to execute

In Situ Electrochemical Investigations of Inherently Chiral 2,2\u2032-Biindole Architectures with Oligothiophene Terminals

The synthesis and characterization of three new inherently chiral N,N\u2032-dipropyl-3,3\u2032-diheteroaryl-2,2\u2032-biindole monomers, nicknamed Ind2T4, Ind2T6 and Ind2Ph2T4, which differ in the number of thiophenes as terminals, are reported. In addition to a full monomer characterization, stable electroactive oligomeric films were obtained by electro-oxidation upon cycling to potentials which activate the thiophene terminals. Cyclic voltammetry, UV-Vis-NIR spectroelectrochemistry and in situ conductance measurements show that oligomeric films of Ind2T6 present the best stability and electrochromic switching performance. Enantioselective tests with a chiral ferrocene amine clearly show the potential as chiral selectors for analytical and sensing purposes