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single bond due to the adjacent >P=O bond in the formula 111 (as it is the case with carboxylic acid amides), it appears improbable'that such a decrease in intensity of the >C==O band occurs. Thus, this region of the spectrum suggests formula I V as the reaction product. In the range of the I€valency vibrations the reaction product has sever'al absorption maxima. The sharp maxima a t 3.51 p and at 3.40 p with a weak shoulder a t 3.33 p are caused by the methyl groups. 'However, the band a t 3.28 p can no longer be assigned to a methyl group. Because of its longer wave length and sharpness this band cannot be an 0-H band. Therefore, it corresponds to t h e C-H valency vibration of the >C=CH group.gs10 Thus, an additional proof is given for formula IV. In the spectra of isomeric 0,O-dialkyl phosphates and 0,O-dialkyl phosphonates, the maxima d t h e >P=O band are i . 8 and 8.1 p , respectively. The $P=O band of the phosphonates dissolved in CS is split into a doublet, whereas in the phosphates the band is slightly displaced toward a shorter wave length while its form is preserved. The )P== 0 band of the reaction product is at '7.8 p, and after dissolving this substance in CS2 it is split into a doublet a t 7.67 and 7.81 p. Therefore, this region of the spectrum is additional evidence for structural formula IV. This rearrangement of 0,O-dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonateis of considerable theoretical interest as it represents the first reported instance of such transformation of a phosphonate t o a phosphate, The phosphoric acid ester IV is considerably more toxic t o rats, mice and houseflies than the phosphonate 11. Thus, the ~ ~ - value$ 5 0 for IV are: rat oral 25 mg./kg., mouse subcutaneous 25 mg./kg.; and the LD-100 values t o the housefly were: contact 0.01 y and oral 0.005 y, as opposed to 0.1 y and 0.03 y,respectively, for 11. Experimental Part 0,O-Dimethyl 2,2,2-Trichloro-l-hydroxyethylphosphonate (11) was prepared following t h e procedures described by lor en^.^ These differ from t h e method later described , ~ in t h a t a reaction temperature of by Barthel, et ~ l . only 120-130' was used, and t h a t t h e product was recrystallized from water. 0,O-Dimethyl @(2,?-Dichloroethenyl) Phosphate (IV) from Ester I1 by Alkaline Treatment.-One hundred and twenty-nine grams (0.5 m o k ) of 0,O-dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate is dissolved in 500 ml. of water and warmed t o 30". A solution of 20 g. (0.5 mole) of sodium hydroxide in 50 ml. of water is added dropwise with stirring. T h e temperature rises and 0,O-dimethyl 0-(2,2-dichloroethenyl) phosphate (IV) separates as 't colorless oil. T h e oil is dissolved in benzene, washed twice with ice-water and then dried with sodium sulfate (sicc.). On fractionating the benzene solution 54 g. of I V having the boiling point 86-87' a t 3 mm. are obtained; jield 58Yc of the theoretical; n Z o1.4541; ~ d2Or 1.423. Anal. Calcd. for CaHrOaClzP: C1, 32.09; OCH3, 28.08. Found: C1,31.34; OCHI, 28.36. FARBEXFABRIKEX BAYERA G . LEVERKUSEN, GERMANY
T& Tomplete-Itegradation of Cafbon-14 Labeled S.wcinic Acid -and Succinic Anhydride by the Schmidt Reaction' BY E 1; P H A R E 5 A \ D L I A R \ \ !.*O\
