Halogenophosphines phosphinous acids

As this area was not covered in Volume 31, the present chapter provides an overview of the literature published over the two years between July 1998 and June 2000. The report is structured in terms of the principal classes of tervalent phosphorus acid derivatives, viz halogenophosphines, tervalent phosphorus esters, and amides. Attempts have been made to minimise the extent of overlap with other chapters, in particular those concerned with the synthesis of nucleic acids and nucleotides to which the chemistry of tervalent phosphorus esters and amides contributes significantly (see Chapter 4), the use of known halogenophosphines as reagents for the synthesis of phosphines (see Chapter 1), and the reactions of dialkyl- and diaryl-phosphite esters, in which the contribution of the phosphonate tautomer, (R0)2P(0)H, is the dominant aspect. 

Tetra- and pentachloro- and tetrabromo-complexes of Tc(IV) containing different phosphines were prepared by reaction of technetium tetrahalogenide with the pertinent phosphine [356] or by refluxing TcOj with the phosphine in ethanol in the presence of hydro-halogenic acid [386]. Halogenophosphine complexes are summarized in Table 12.12. A. 

A rationalization of the reactions between )8-keto-alcohols and halogenophosphines has been presented by a Russian group. In particular, the reaction between dichloro(phenyl)phosphine (26) and diacetone alcohol to give the oxide (27) has been shown to occur in stages (Scheme 9), and physical and chemical evidence has been presented for the initial formation of mesityl oxide (28) and the acid (29), followed by the addition product (30). A less detailed study of the analogous reaction of chlorodiphenyl-phosphine (5) with diacetone alcohol has also been published. ... 

The phenolic phosphines (58) are easily accessible by acid-cleavage of the related methyl ethers. The reactions of the enyne-phosphines (60) with Grignard or alkylsilver reagents lead to the allenic phosphines (61). The thienylphosphines (62) are formed in the reactions of thiophenes with halogenophosphines in the presence of zinc. ... 

Phosphines and Phosphonium Salts Quinquecovalent Phosphorus Compounds Halogenophosphines and Related Compounds Phosphine Oxides and Related Compounds Tervalent Phosphorus Acids Quinquevalent Phosphorus Acids Phosphates and Phosphonates of Biochemical Interest Nucleotides and Nucleic Acids Ylides and Related Compounds Phosphazenes Physical Methods. 

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