Use of 2, 3-Butanedione Monoxime for Homogeneous Precipitation of Nickel (II)

Abstract

The solid monoxime of 2, 3-butanedione is a more convenient material than liquid dione for the homogenous generation of DMG. 2, 3-butanedione dioxime. Determinations of Ni in steels and in pure Ni(II) solutions have shown the optimum pH and order of adding reagents. Gravimetric and/or an EDTA titrimetric finish are possible for a method of reliability within ± 0.2 mg of Ni in 50–150 mg Ni. The solid has the same character and filterability as that from the 1960 dione method of Salesin and Gordon¹.     

An environmentally benign benzylic oxidation catalyzed by hypervalent iodine intermediate in water

An effective and environmentally benign benzylic oxidation for transition of alkylarenes into the corresponding carbonyl compounds was reported.Alkylarenes were mixed and stirred with potassium bromide,m-chloroperbenzoic acid and a catalytic amount of iodobenzene in water at 60 8C for several hours,a series of the corresponding carbonyl compounds was obtained in moderate to good yields.In the reaction,iodobenzene was first oxidized by m-chloroperbenzoic acid into the hypervalent iodine intermediate which then reacted with potassium bromide to form the key radical initiator for the benzylic oxidation.     

1-Butyl-4-aza-1-azoniabicyclo[2.2.2]octane Dichromate (BAAOD): An Efficient and Novel Reagent for Oxidation of Sulfides to the Corresponding Sulfoxides

This article describes an efficient and easy method for oxidation of sulfides 1 to their corresponding sulfoxides 2 with 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane dichromate (BAAOD) under nonaqueous conditions in high yields.     

APICOPHILICITY AND RING-STRAIN IN FIVE-COORDINATE PHOSPHORANES

Abstract

In order to dicuss mechanism in organophosphorus chemistry a number of assumptions have to be made. Among them are: (a) that substitutions at tetrahedral phosphorus proceed via five-coordinate intermediates; (b) these intermediates are trigonal bipyramidal; (c) they are formed by apical attack and decompose by apical loss; and (d) if sufficiently long-lived, they may undergo permutational isomerization, that is the ligands may alter their relative dispositions round the phosphorus, before going on to products or back to reactants.

Assuming that the course of a given substitution is dictated primarily by thermodynamic considerations, in order to understand the course of that substitution one needs to know how to assess the relative stabilities of the four isomeric tbps (trigonal bipyramids) that can be formed initially and of the others that could be formed by subsequent isomerization, the barriers to those isomerizations, and the relative rates of the various product-forming steps. We have concentrated on the first of these factors and this lecture describes our attempts to provide the necessary data.

The energy difference between two isomeric tbps can be analyzed in terms of changes in the relative apicophilicities¹ of the groups occupying apical positions, changes in ring-strain as small rings move between apical-equatorial and diequatorial positions, and changes in steric strain. I shall consider each of these in turn. Ligand subset symmetry may also have to be taken into account.^1,2     

CHIRAL VARIANTS OF ARYLALKYL SULFUR REAGENTS. (R)-CAMPHOR KETIMINES OF OGIOVANNA AMINOTHIOETHERS AND OXIDES

Abstract

Ketimines la-d derived from ortho-aminosubstituted phenylthioethers were prepared in order to determine the degree of chirality transfer from the chiral auxiliary to the sulfur atom in the formation of the sulfoxide or to the α-carbon atom in the reaction of the anion with alkyl halides or benzaldehyde. Oxidation to the sulfoxide occurred with little or no asymmetric induction. The crystalline benzyl sulfone 4c was deprotonated by alkyllithium or Grignard reagents and reacted with alkyl halides and benzaldehyde, in all cases with little to fair transfer of chirality. The major diastereoisomer from methylation of the anion of 4c with methyl iodide, was isolated, and afforded the enantiomerically pure amine 5 after removal of the chiral auxiliary. An X-ray structure determination of 4d allowed the assignment of the absolute configuration of the asymmetric carbon and revealed that the conformation of the ketimine in the crystal state is not homogeneous.     

A Facile Oxidation of Thiols to Disulfides Catalyzed by CoSalen

Abstract

A convenient and facile catalytic oxidation of thiols to the corresponding disulfides is described using CoSalen as the catalyst and air as the oxidizing agent. This new approach provides an efficient method for the preparation of symmetrical disulfides in high yields and under mild conditions.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Spectroscopic Identification of Products 3a–3l.]