Aldona Szadowiak

A New View of the Mechanistic Pathways in the Iodine Atom Transfer Addition Reaction Involving 1-Iodoalkylphosphonates and Related Nonphosphorus Systems

The title reaction in the initiation step proceeds via two mechanistic pathways involving attack of the isobutyronitrile radical either on the starting iodide or on the starting alkene or alkyne followed by the reaction of the adduct radical with the iodide.

Determination of some thiophosphorus insecticides based on coulometric titration with the anodically generated chlorine: a further insight in the reaction mechanism in aqueous medium

A new method of analytical determination of some thiolo (PS) and thiono (PS) group containing phosphorus insecticides using a coulometric titration with the anodically generated chlorine and biamperometric end-point detection was described. The method worked well for compounds containing one (methamidophos) or two PS bonds (iso-malathion) or one PS bond (fenitrothion) but failed for compounds containing both PS and PS bonds (malathion, dimethoate) or additional sterically hindered CSC bond (fenthion). Based on the found number z of electrons transferred per mol of oxidized compounds, mechanistic pathways for chlorination of PS and PS containing thiophosphorus insecticides with molecular chlorine in aqueous, acidic medium were proposed.

Functions Containing at Least One Phosphorus, Arsenic, Antimony or Bismuth, and No Halogen, Chalcogen or Nitrogen

The chapter describes the methods of synthesis of acyclic and cyclic bisphosphino alkenes published during the years 1995–2003. It also covers the methods of synthesis and transformations of the bisphosphino alkenes containing various combinations of arsenic and antimony as well as metalloids (silicon, germanium, and boron). A major part of this chapter deals with the synthesis of metal derivatives of acyclic and cyclic bisphospino alkenes. Thus, the compounds containing group 1 metals (Li, Na, K), group 2 metals (Mg, Ba, Ca), group 13 metals (Ga, Tl), and group 14 metals (Sn, Pb) are discussed. A special subsection is devoted to the transition metal (group 3–12 metals) complexes with bisphosphino alkenes and their coordination modes.

Alkynylnitrogen and -phosphorus Compounds

This chapter describes preparative approaches for the synthesis of alkynylnitrogen and alkynylphosphorus compounds. The first part of this chapter deals with protocols which have been applied for the preparation of alkynylamines and their salts including primary, secondary, and tertiary ynamines. It is followed by presentation of procedures to obtain alkynylnitrogen compounds with an NY function such as N-methylene ynamines, azoalkynes, alkynyl azides, and alkynyl isocyanates. The second part devoted to alkynylphosphorus compounds begins with a summary of synthetic approaches to alkynylphosphines. It is followed by subchapters presenting the synthetic procedures leading to alkynylphosphonium salts, derivatives with alkynyl-PX2 functions, compounds having alkynyl (R)P-X functions, alkynylphosphine oxides and imides, and finally alkynylphosphonates.