Verfahren zur Herstellung von Phospholin-derivaten

摘要

1,1,1 - Trichloro- or tribromo - phospholines of formula where X is Cl or Br are prepared by reacting a diene which contains a butadiene skeleton of which no carbon atom is part of an aromatic ring and no three carbon atoms belong to the same cyclo-aliphatic ring, with phosphorus trichloride or tribromide. A polymerization inhibitor may be present. The trihalophospholines may be reacted with a compound HYR where Y is oxygen or sulphur and R is hydrogen or unsubstituted or subsubstituted alkyl or aryl, preferably in the presence of a hydrogen halide acceptor, to give a product containing the moity or according to the proportions of reactants, wherein the phosphorus atom is part of a 5-membered ring containing a double bond, i.e. the double bond may shift from the 3-position of the starting materials when conducting further reactions. Salts of the products may be obtained. Examples are given. 1 - Oxo - 1 - chloro - or 1 - oxo - 1 - bromophospholines may also be obtained from the 1,1,1-trihalo compounds by reaction with an acid anhydride such as SO2 or acetic anhydride or by reaction of 1-oxo-1-hydroxyphospholines with, e.g., SOCl2, PCl5 or oxalyl chloride. The halogen in 1-oxo-(or thio)-1-halophospholines may be eliminated as hydrogen halide by reaction with, e.g., alcohols, phenols, mercaptans or, especially, primary or secondary amines, preferably in the presence of tertiary amines. Examples are given. Phosphine oxides are obtained by reacting 1-oxo-1-halophospholines with Grignard reagents (e.g. Example 24, 1-oxo-1-butyl-3-methyl-2-phospholine). 1 - Alkoxy - 1 - oxophospholidines are prepared by hydrogenating the corresponding phospholines. The invention also comprises as novel compounds 1,1,1-trichloro-, 1,1,1-tribromo-, 1-oxo-1-alkoxy, 1-oxo-1-phenoxy and 1-oxo-1-(mono-or disubstituted) amino-phospholines and dihydro derivatives of 1 - oxo - 1 - alkoxyphospholines, with the proviso in each case that none of the phospholine ring carbon atoms is part of an aromatic ring and no three phospholine ring carbon atoms belong to the same cycloaliphatic ring. The various phospholines are stated to have uses as biocides and mineral oil and polymer additives.