Cadogan, J. I. G. published the artcileReactivity of organophosphorus compounds. V. Reaction of trichloromethyl radicals with trialkyl phosphites, COA of Formula: C5H10Cl3O3P, the publication is Journal of the Chemical Society (1961), 3071-6, database is CAplus.
–From a knowledge of the reactions of benzyl and β,β-dimethylphenethyl radicals evidence was produced in favor of the radical-induced reaction of CCl4 with trialkyl phosphites to give dialkyl trichloromethylphosphonates proceeding by a radical chain reaction involving [(RO)3PCCl3]+ Cl– rather than by decomposition of the phosphoranyl radical (RO)3(Cl3C)P. Evidence concerning the reactivity of phosphoranyl radicals was presented and discussed. Benzyl di-Et phosphite (I) b0.1 70°, n2D5 1.4900. PhCMe2CH2Cl (Ia), b12 101°, n2D1 1.5241, was converted into the alc. as follows: O passed during 3 h. through a solution in Et2O of the Grignard reagent from 250 g. Ia at 0°, and the mixture poured into 2 l. dilute H2SO4, washed, and distilled gave PhCMe2CH2OH (II), b12 110-12°, n24D 1.5248. II (25 g.) and 56.5 g. Et3PO3 kept 4.5 h. at 140°, the alc. formed removed, and the residue distilled gave 27 g. β,β-dimethylphenethyl di-Et phosphite (III), b0.1 98-102°. Attempts to prepare tris(β,β-dimethylphenethyl) phosphite gave oils which readily decomposed when heated. I (5.3 g.) and 0.3 g. Bz2O2 in 15 mL. CCl4 refluxed 18 h. gave 4 fractions: (a) 1.5 g. PhCH2Cl, b. 40-80°, n2D3.5 1.5240; (b) 0.8 g., b. 80-90°, n2D3.5 1.5070; (c) 0.95 g., b. 90-110°, n23.5D 1.4770; and (d) 4.2 g. di-Et trichloromethylphosphonate (IV), b. 120-30°; n2D305 1.4620. Fractions (b) and (c) were mixtures of PhCH2Cl and IV. Bz2O2 (0.44 g.) and 10 g. III in 24 g. CCl4 refluxed 18 h. and evaporated gave a residue, shown by gas chromatog. to contain no Ia. A portion (50%) of the residue distilled gave an unsaturated oil, b12 90-105°, n2D0 1.5208, a 53:47 mixture of 2-methyl-1-phenylpropene and 2-methyl-3-phenylpropene. Distillation of a further portion, attempted at 10-4 mm., gave an oil, b. 110°, n2D4 1.5080. Some decomposition occurred and the product was formulated as impure β,β-dimethylphenethyl Et trichloromethylphosphonate. Et3PO3 (5 g.) and 0.05 mol Bz2O2 in 15 g. CCl4 refluxed 18 h. gave 6.85 g. IV. In a similar experiment, in which CCl4 that had been passed through Al2O3 was used and the reaction carried out in the dark without Bz2O2, 6.94 g. IV was obtained. Ph3PO3 did not react with CCl4 or BrCCl3 under either of the above sets of conditions. The rate of disappearance of Et3PO3 on reaction with CCl4 at 80° was determined by following the reaction by gas-liquid chromatog. The first-order rate constant was 2.2 × 10-4 sec.-1. The experiment was repeated in the presence of Bz2O2 to give a rate constant of 3.5 × 10-4 sec.-1 Et3PO3 (5 g.) and 15 mL. CCl4 degassed and irradiated 1 h. at room temperature in a quartz flask with ultraviolet light gave 70% IV. Et3PO3 and CCl4 did not react in the dark at room temperature in 7 h. tert-Bu2O2 (3.7 g.) in 18.4 g. PhMe and 31.1 g. CCl4 was heated 48 h. at 130° in a sealed tube and the product separated into 2 fractions. Fraction (a) by gas-liquid chromatog. was shown to be largely PhCH2Cl and fraction (b) of 1.2 g., was PhCH2CH2Ph with an unidentified component, possibly PhCH2CCl3. Bis(9-benzyl-9-fluorenyl) peroxide (0.5 g.), m. 170.0-0.5°, was heated 48 h. at 130° in a sealed tube with 2.2 mL. CCl4 and 2 mL. C6H6; gas chromatog. showed the presence of (PhCH2)2 and PhCH2Cl. Et3PO3 (8.3 g.), 15.4 g. CCl4, 9 g. butane-1-thiol, and 0.61 g. Bz2O2 refluxed overnight, evaporated, and the 10.8-g. residue gas-chromatographed indicated tri-Et phosphorothionate, 18%; IV, 22%; and S-Bu di-Et phosphorothioate, 60%. Irradiation of 3.18 g. I in 15 mL. CCl4 under N at room temperature 4 h. followed by fractionation, gave 0.70 g. PhCH2Cl and 1.27 g. IV and left 1.8 g. of residue. Their nature was confirmed by IR spectra.
Journal of the Chemical Society published new progress about 866-23-9. 866-23-9 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is Diethyltrichloromethylphosphonate, and the molecular formula is C5H10Cl3O3P, COA of Formula: C5H10Cl3O3P.
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