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

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Abstract
Reaction of ClCH2CH2PCl2 with ethylene oxide gives the phosphonous acid ester ClCH2CH2P (OCH2CH2Cl)2 which on heating to 120° rearranges to the phosphinic acid ester (ClCH2CH2)2P(O)OCH2CH2Cl (3). Chlorination of 3 with PCl5 in CCl4‐solution yields the phosphinic chloride (ClCH2CH2)P(O)Cl (4), which on treatment with P2S5 at 170° produces the thioderivative, (ClCH2CH2)2P(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, (ClCH2CH2) P (X)Y, (X = O, S; Y = OR, SR, NR2) (6). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH2 = CH)2P (X) Y (X = O, S; Y = OR, SR, NR2) (7).Bis‐(ß‐chloroethyl)‐phosphinates, e. g. (ClCH2CH2)2P (O) OEt, undergo a Michaelis‐Arbuzov reaction when heated with phosphites to 160–170° to give bis‐(phosphonylethyl)‐phosphinates, e.g. (EtO) (O)P[CH2CH2CH2P(O)(OEt)2]2 (8), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO2P(CH2CH2PO3H2)2.