75765-60-5Relevant academic research and scientific papers
Dipole-Moment-Driven Cooperative Supramolecular Polymerization
Kulkarni, Chidambar,Bejagam, Karteek K.,Senanayak, Satyaprasad P.,Narayan,Balasubramanian,George, Subi J.
, p. 3924 - 3932 (2015)
While the mechanism of self-assembly of π-conjugated molecules has been well studied to gain control over the structure and functionality of supramolecular polymers, the intermolecular interactions underpinning it are poorly understood. Here, we study the mechanism of self-assembly of perylene bisimide derivatives possessing dipolar carbonate groups as linkers. It was observed that the combination of carbonate linkers and cholesterol/dihydrocholesterol self-assembling moieties led to a cooperative mechanism of self-assembly. Atomistic molecular dynamics simulations of an assembly in explicit solvent strongly suggest that the dipole-dipole interaction between the carbonate groups imparts a macro-dipolar character to the assembly. This is confirmed experimentally through the observation of a significant polarization in the bulk phase for molecules following a cooperative mechanism. The cooperativity is attributed to the presence of dipole-dipole interaction in the assembly. Thus, anisotropic long-range intermolecular interactions such as dipole-dipole interaction can serve as a way to obtain cooperative self-assembly and aid in rationalizing and predicting the mechanisms in various synthetic supramolecular polymers. (Graph Presented).
New radical reactions of S-alkoxycarbonyl xanthates. Total synthesis of (±)-cinnamolide and (±)-methylenolactocin
Forbes, Judith E.,Saicic, Radomir N.,Zard, Samir Z.
, p. 3791 - 3802 (2007/10/03)
Irradiation with visible light of S-alkoxycarbonyl xanthates derived from various alcohols gives rise to alkoxycarbonyl radicals with bifurcate reactivity: loss of carbon dioxide leads to deoxygenated derivatives (i.e. alkyl xanthates) whereas intramolecular addition to a suitably located double bond produces lactones; these new reactions were applied to the total synthesis of (±)-cinnamolide and (±)-methylenolactocin.
Reduction et photoreduction de derives de l'acide carbonique influence de l'hexamethylphosphorotriamide
Dembele, Albert,Deshayes, Henri,Pete, Jean-Pierre
, p. 671 - 680 (2007/10/02)
Photoreduction and reduction of carbonic acid derivatives in HMPT have been compared.The highest yield of alkane was obtained from N,N-dimethylthiocarbamates either by the photochemical method or by reduction with a dissolved metal.Competitive reactions have been characterized: - during the photoreduction not only the alkane but products of a photo-Fries rearrangement and products of a homolytic cleavage were detected; - basic reactions can compete with the reduction of carbonic acid derivatives by sodium in HMPT.
Radical-initiated Reduction of Chloroformates to Alkanes by Tri-n-propylsilane. A Method for Removal of Unwanted Hydroxy-Groups from Organic Molecules
Jackson, Richard A.,Malek, Farideh
, p. 1207 - 1211 (2007/10/02)
Chloroformates of primary and secondary alcohols, produced by the reaction of the alcohol with phosgene, are reduced to the corresponding alkane in excellent yields by reaction with tri-n-propylsilane in the presence of t-butyl peroxide at 140 deg C.Unusually large amounts of initiator are required tO)2 per mol of RO*CO*Cl>.The results are rationalized in terms of a free-radical reaction scheme.
