Fitch, Steven J. published the artcileNuclear magnetic resonance study of the P-C(OH)-P to P-CO-P rearrangement: Tetraethyl-I-hydroxyalkylidenediphosphonates, COA of Formula: C5H10Cl3O3P, the publication is Journal of the American Chemical Society (1962), 1876-9, database is CAplus.
Compounds previously reported (Cade, CA 54, 264e) to have the structure RC(OH)[P(O)(OR’)2]2 (I) are found to be isomeric rearrangement products of I, RCH[P(O)(OR’)2] [OP(O)(OR’)2] (II). P31 and H1 nuclear magnetic resonance (N.M.R.) spectra, infrared spectra, and chem. evidence support structure II. MeC(O)P(O)(OEt)2 (30 g.) and 23 g. HP(O)(OEt)2 (III) treated with a drop of NaOEt soluble produced an exothermic reaction. The product, on cooling overnight at 0°, gave hygroscopic crystals of I (R = Me, R’ = Et)(IV), m. 38.0-8.9°, P31 n.m.r. peak (in H2O) at -20.8 p.p.m. (neg. values downfield from 85% orthophosphoric acid standard). The above reaction mixture held 30 hrs. at 50° and distilled gave mainly II (R = Me, R’ = Et) (V), b0.1 130-6°, P31 n.m.r. peaks at -21.1 and + 1.7 p.p.m., previously reported as IV. IV heated 10 min. at 125° with NaOEt gave V. BzP(O)(OEt)2 (242 g.), 138 g. III, and a trace of NaOEt heated 4 hrs. at 105° and distilled gave 55% II (R = Ph, R’ = Et), b0.1 171-4°, n25D 1.4776, small mol. P31 n.m.r. peaks at -16.2 and +1.4 p.p.m. I (R = Ph, R’ = Et) could not be isolated at the lowest usable reaction temperature V, heated with PCl5 in CCl4 and hydrolyzed, gave H3PO4 and MeCHClPO3H2. IV and HCl gave I (R = Me, R’ = H), m. 155° (decomposition), P31 n.m.r. peaks at -23.0 p.p.m. The H1 n.m.r. spectrum of IV showed 2 triplets in the methyl region (J = 7 and 16 cycles/sec.). A double resonance exp. showed that the smaller triplet arose from P-H coupling and that a downfield multiplet was resolved to a quartet. The Me region of V simplified to overlapping triplets and a small doublet under double resonance. The infrared spectrum of IV showed absorption at 3180 (OH), 1260 (P:O) and 1163 (POEt) cm.-1 while anhydrous V had no absorption in the OH region.
Journal of the American 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.
Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics