Organische Phosphorverbindungen 44 Darstellung und Eigenschaften von Bis‐(ß‐chloräthyl)‐phosphinsäure‐Derivaten [1]

Abstract Reaction of ClCH 2 CH 2 PCl 2 with ethylene oxide gives the phosphonous acid ester ClCH 2 CH 2 P (OCH 2 CH 2 Cl) 2 which on heating to 120° rearranges to the phosphinic acid ester (ClCH 2 CH 2 ) 2 P(O)OCH 2 CH 2 Cl ( 3 ). Chlorination of 3 with PCl 5 in CCl 4 ‐solution yields the phosphinic chloride (ClCH 2 CH 2 )P(O)Cl ( 4 ), which on treatment with P 2 S 5 at 170° produces the thioderivative, (ClCH 2 CH 2 ) 2 P(S)Cl, ( 5 ). Treatment of 4 and 5 with alcohols, mercaptanes, or amines in the presence of an acid binding agent leads to the corresponding phosphinic and thiophosphinic acid derivatives, (ClCH 2 CH 2 ) P (X)Y, (X = O, S; Y = OR, SR, NR 2 ) ( 6 ). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH 2 = CH) 2 P (X) Y (X = O, S; Y = OR, SR, NR 2 ) ( 7 ). Bis‐(ß‐chloroethyl)‐phosphinates, e. g. (ClCH 2 CH 2 ) 2 P (O) OEt, undergo a Michaelis ‐ Arbuzov reaction when heated with phosphites to 160–170° to give bis‐(phosphonylethyl)‐phosphinates, e.g. (EtO) (O)P[CH 2 CH 2 CH 2 P(O)(OEt) 2 ] 2 ( 8 ), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO 2 P(CH 2 CH 2 PO 3 H 2 ) 2 .