The products of the reaction of the hydroxyl radical with 2-ethoxyethyl acetate

The gas-phase reaction products of the OH radical with 2-ethoxyethyl acetate (EEA, CH₃C(O)OCH₂CH₂OCH₂CH₃) have been investigated. 1,2-Ethanediol acetate formate (EAF, CH₃C(O)OCH₂CH₂OC(O)H) and ethyl formate (EF, HC(O)OCH₂CH₃) were identified as the two main products. A third product, ethylene glycol diacetate (EGD, CH₃C(O)OCH₂CH₂OC(O)CH₃), was also observed. EAF, EF, and EGD formation yields were determined to be 0.37 ± 0.03 and 0.328 ± 0.018 and 0.040 ± 0.005, respectively. Proposed reaction mechanisms are discussed and compared with these data. © 1996 John Wiley & Sons, Inc.     

Recent advances toward sustainable flow photochemistry

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Phases of elastic materials

Zusammenfassung Es wird eine Methode beschrieben für die Charakterisierung von Stoff-Phasen durch Angabe der Symmetrie-Gruppe als Funktion der Deformation und Temperatur. Wenn in einem elastischen Stoff die Phase durch Dichte und Temperatur bestimmt wird, dann gelten die meisten der üblichen Resultate für die Gesamt-Symmetrie-Gruppe auch für die Gruppe, die einer gegebenen Phase entspricht.     

On Congruence of Complex Matrices

For each of a standard set of normal forms for (n × n) complex matrices under the relation of congruence, explicit matrices are exhibited which transform, via congruence, the normal form to its transpose.     

Equilibria in complexes ofN-heterocyclic molecules,part XXII. The reaction of triaquo(2,4,6-tri-(2-pyridyl)-1,3,5-triazine) copper(II) and its nickel(II) and cobalt(II) analogues with water and hydroxide ion

Summary The kinetics of the reaction of [Cu(TPT)(H₂O)₃]²⁺ and [Ni(TPT)(H₂O)₃]²⁺ with H₂O have been followed and it has been shown that the formation of covalent hydrates is important in the understanding of these systems. The [Co(TPT)(OH)₃]^– compound and its Ni analogue are attacked by HO^– initially to form pseudo-base species and in, the case of Ni , the ligand then hydrolyses to yield a compound related to the carboximate formed when HO^– reacts with [Cu(TPT)(OH)₃]^–. In this reaction too, the formation of a pseudo-base, involving attack of HO^– at the triazine ring in the ligand is significant.Part XXI, ref. 2.     

Synthesis of N-Benzoyl-4-oxo-1,2,3,4-Tetrahydropyridine and its Ethylene Ketal

Recently we had need for large quantities of N-benzoyl-4-oxo-1,2,3,4-tetrahydropyridine (1), its ethylene ketal derivative 7, and potentially other N-acyl derivatives. Prior to our initial studies, the N-carboethoxy derivative 2 had been prepared by sodium borohydride reduction of N-carboethoxy-4-pyridone.¹.     

Intercalation of trioxatriangulenium ion in DNA: binding,electron transfer,x-ray crystallography,and electronic structure

Trioxatriangulenium ion (TOTA(+)) is a flat, somewhat hydrophobic compound that has a low-energy unoccupied molecular orbital. It binds to duplex DNA by intercalation with a preference for G-C base pairs. Irradiation of intercalated TOTA(+) causes charge (radical cation) injection that results in strand cleavage (after piperidine treatment) primarily at GG steps. The X-ray crystal structure of TOTA(+) intercalated in the hexameric duplex d[CGATCG](2) described here reveals that intercalation of TOTA(+) results in an unusually large extension of the helical rise of the DNA and that the orientation of TOTA(+) is sensitive to hydrogen-bonding interactions with backbone atoms of the DNA. Electronic structure calculations reveal no meaningful charge transfer from DNA to TOTA(+) because the lowest unoccupied molecular orbital of TOTA(+), (LUMO)(T), falls in the gap between the highest occupied molecular orbital, (HOMO)(D), and the (LUMO)(D) of the DNA bases. These calculations reveal the importance of backbone, water, and counterion interactions, which shift the energy levels of the bases and the intercalated TOTA(+) orbitals significantly. The calculations also show that the inserted TOTA(+) strongly polarizes the intercalation cavity where a sheet of excess electron density surrounds the TOTA(+).