Yakubovich, A. Ya. published the artcileSynthesis of heteroörganic compounds of the aliphatic series by the diazo method. II. Synthesis of compounds of group V elements-organophosphorus compounds, Synthetic Route of 66197-72-6, the publication is Zhurnal Obshchei Khimii (1952), 1534-42, database is CAplus.
cf. C.A. 47, 8010c; Staudinger and Meyer, C.A. 14, 536. At low temperature CH2N2 (I) and other diazoalkanes react satisfactorily with PX3. PCl3 (200 g.) in 200 ml. dry Et2O was treated with stirring and cooling to -70° with 25 g. I in 750 ml. Et2O which had been dried by freezing 3 hrs. at -70° over solid KOH, and the mixture kept at -55 to -65°; the energetic reaction led to rapid evolution of N (14 l.) and the formation of a colorless precipitate The mixture was allowed to rise gradually to room temperature overnight and the products from 5 such runs were filtered without access of moisture and combined, giving a total of 32 g. product which is hydrolyzed by moisture; it is an organophosphorus compound soluble in H2O and ROH, but insoluble in CHCl3 or C6H6; it can not be recrystallized without decomposition Distillation of the filtrate yielded several fractions up to b140 78°. Redistillation gave: 4.8 g. MeOPCl2 b. 91-2° (uncorrected), b. 94-5° (corrected), d2020 1.3995, nD20 1.4750 (this substance is believed to arise from partial hydrolysis of the PCl3 by moisture in the reagents; the resulting HOPCl2 can then be alkylated by I); 31.3 g. POCl3 (this was apparently introduced as an impurity in the PCl3, as shown by rectification of the PCl3 starting material); and some 40% (175 g.) ClCH2P Cl2 (II), b140 80-1°(corrected), d2020 1.5289, nD20 1.5247; II fumes in air because of hydrolysis by moisture. II (5 g.) in 5 ml. CCl4 treated at 0-5° with 2.5 g. Cl in 10 ml. CCl4 yielded a white precipitate; the solvent removed below 35° in vacuo without access of moisture and filtered and washed with cold CCl4 yielded 5.5 g. ClCH2PCl4, decompose 102-4° (sealed tube), deliquescent in air. Passing 3.7 g. NO2 over 30 min. into 10 g. II in CCl4 at 0° to -5° until the NO2 was no longer decolorized and a reddish color appears owing to the formation of resinous products, blowing with a stream of dry air, and immediately distilling gave 7 g. (60%) ClCH2POCl2, b30 103°, d2020 1.6444, nD20 1.4945 (IV). III from 10 g. II treated in the cold with dry SO2 in CCl4 gave 8.5 g. (80%) IV, b80 102-3°, b2 63°. Adding 2 g. IV gradually to 10 ml. H2O and letting the solution stand over P2O5 in vacuo 7 days gave 100% ClCH2PO(OH)2 (V), needles, m. 92° (from C6H6MeNO2), very hygroscopic, does not lose MeCl on heating with alkalies; Ag salt, soluble in H2O. V (0.5 g.) in C6H6 with excess PhNH2 (2 ml.) let stand 2 days gave 100% ClCH2PO(OH)2-PhNH2, needles, decompose 183° (from EtOH). To 8.3 g. IV in 10 ml. Et2O at 0-5° was added 2.8 g. Na in 55 ml. absolute EtOH until the solution was neutral to Congo red; filtration and distillation gave ClCH2PO(OEt)2, b2.5 86-7° , d2020 1.1909, nD20 1.4360. To l90g. PCl3in 200 ml. dry Et2O at -70° was added 30 g. MeCHN2 in 800 ml. Et2O in N atm.; after treatment as above the combined products of 4 runs gave distillate b. up to b50 62.5°, and a little material b7 70°; redistillation gave some 52 g. POCl3, b. 107-9° (corrected); some 22 g. EtOPCl2, b100 51-2°, b. 117-18° (corrected), d2020 1.3300, nD20 1.4640 [the impure product was further identified by treatment with EtOH in Et2O in presence of Et2NPh, yielding (EtO)3P, b12 49°, nD20 1.41-30]; and some 100 g. (35%) MeCHClPCl2 (VI), b50 61.5-2.5° (uncorrected), b50 63.5-4.5° (corrected), d2020 1.4232, nD20 1.5090, which fumes in air and a piece of cotton moistened with it ignites on exposure to air. VI (5 g.) chlorinated at -5° in CCl4 as above gave a colorless precipitate, which, worked up as above yielded MeCHClPCl4, very hygroscopic crystals. To 16.5 g. VI in 15 ml. CCl4 was added with ice-NaCl cooling 7.5 g. Cl in 50 ml. CCl4 and the mixture treated directly with dry SO2 until the precipitate dissolved and 10 min. longer; distillation gave 90-5% MeCHClPOCl2 (VII), b8 70°, d2020 1.5424, nD20 1.4930. VII (2 g.) hydrolyzed with 3 ml. H2O and evaporated in vacuo gave 100% MeCHClPO(OH)2, needles, m. 99-100° (from C6H6-MeNO2); Ag salt, soluble in H2O. Adding 5 g. PhNH2 to 2 g. VII in C6H6, letting the mixture stand overnight, gave, after filtering off the PhNH2.HCl, washing the filtrate with acidified H2O, evaporating, dissolving the residue in EtOH, and diluting with H2O gave ClCH2PO(NHPh)2, m. 154-5° (from dilute EtOH). To 3 g. absolute EtOH and 9 g. Et2NPh in 50 ml. dry Et2O was added dropwise 5.4 g. VII in Et2O with ice cooling, and the mixture filtered after 24 hrs., and distilled, yielding 3.5 g. MeCHClPO(OEt)2, b5 93°, b7 96°, d2020 1.1474, nD20 1.4370. A solution of 100 g. BuNH2 in 300 ml. H2O at -5° was acidified to methyl red with HCl, treated with 400 g. H2O and 250 g. CO(NH2)2, refluxed 3 hrs., cooled, treated with 120 g. NaNO2 in 300 g. H2O, and added slowly to 95 g. H2SO4 and 600 g. crushed ice with cooling to -5° to 5°; the precipitate of nitrosobutylurea floats and can be readily separated and dried below 10°. This (100 g.) added gradually at -5° to 500 ml. Et2O and 200 ml. 70% KOH gave 25 g. PrCHN2 (estimated by treatment with BzOH) in the red Et2O layer. To 70 g. PCl3 in 100 ml. dry Et2O was added with Dry Ice-Me2CO cooling 22 g. PrCHN2 in 450 ml. Et2O (dried as above), and the mixture distilled yielding 7 g. BuOPCl2, b. 155-7° (decomposition), b30 63-4.5°, d20 1.1661, and 10.5 g. PrCHClPOCl2, (VIII), b25 84°, d2020 1.3236, nD20 1.5010. VIII apparently was formed by oxidation during handling of the primary product, PrCHClPCl2. To 52.7 g. PBr3 in 50 ml. Et2O was added at -50° 2.72 g. I in 150 ml. Et2O (dried by freezing), the mixture was warmed to room temperature, filtered (an amorphous precipitate forms in the reaction), and distilled, yielding after several distillations 9.5 g. (50% based on I) BrCH2PBr2 (IX), b4 70°, d2020 2.6357. At PBr3/I ratios of 2:1 and 1:1 there is a sharp increase of the amount of the precipitate formed and the yield of IX declines to 15-20%. The precipitate hydrolyzes in air, evolving Br; its solubility and characteristics are similar to those of the product formed with PCl3. Passing 4.9 g. dry NO2 25 min. into 17 g. IX in 50 ml. CCl4 at 5-10° and letting the solution stand 0.5 hrs. at room temperature gave 10.8 g. BrCH2POBr2, b7 118-20°, b2 112-13°, d2020 2.7030, nD20 1.5120 (X), which energetically reacts with Hg, forming undistillable products. To 10.8 g. X in 40 ml. Et2O were added with ice cooling 20 ml. Et2O and 3.4 g. absolute EtOH, then 10.3 g. Et2NPh in 50 ml. Et2O and the mixture was allowed to stand overnight at room temperature; filtration and distillation gave 50% BrCH2PO(OEt)2, b1 99°, d2020 1.4474, nD20 1.4585. Hydrolyzing 2 g. X with 3 ml. H2O and drying the product over P2O5, gave the extremely hygroscopic free acid, which had to be isolated as the mono-PhNH2 salt by treatment in C6H6 with excess PhNH2; PhNH2 salt, needles, m. 187° (decomposition; from EtOH containing 1% PhNH2). To 120 g. POCl3 in 50 ml. Et2O was slowly added at -30° 13-14 g. dry CH2N2 in 400 ml. Et2O in the presence of 1 g. CuSO4 (2 addnl. 0.5-g. portions were added in the course of the experiment); after the evolution of N had subsided the temperature was raised to room temperature and the products of 3 runs distilled together, yielding but 6 g. of product, b12 59.5°, identified as MeOPOCl2. Similarly, 15.5 g. POCl3 and 8.5 g. MeCHN2 gave 2.5 g. EtOPOCl2, b. 163-5°; these products were probably produced by alkylation of HOPOCl2 formed from partial hydrolysis of POCl3 in handling. To 10 g. PCl5 in 40 ml. dry Et2O was added at -40° 6 g. I in 200 ml. Et2O (dried by freezing as above); after the N evolution had ceased the cooling bath was removed, the mixture allowed to stand overnight, and the liquid portion decanted from a precipitate and evaporated (the precipitate is also extracted with dry Et2O and the extract evaporated along with the main solution), forming some 6-7 g. needles, m. 100.5° (from petr. ether), which did not contain any Cl hydrolyzable under the usual conditions. The product was identified as (ClCH2)3PO (cf. Hoffmann, C.A. 24, 3986, who described this oxide as the hemihydrate, m. 88-9°). Similar reaction of 10 g. PCl5 with 14-15 g. MeCHN2 at -40° to -50°, followed by standing overnight at room temperature, gave on evaporation 10 g. viscous liquid, containing hydrolyzable Cl; the product could not be distilled without decomposition, but a fraction, b5 55-115° (4.5 g.) hydrolyzed with 5 ml. hot H2O and let stand 2-3 days, then extracted with Et2O, and the dried extract evaporated gave 1.5 g. needles, m. 107° (from C6H6-petr. ether), identified as (MeCHCl)2PO(OH), moderately soluble in H2O, and very soluble in EtOH; Ag salt, soluble in H2O. To 2 g. of this acid was added 3 ml. PhNH2 in C6H6 yielding the PhNH2 salt, 100%, needles, decompose 160°. Reactions of RCHXPX2 with RCHN2 lead to complex solids and not to secondary or tertiary derivatives
Zhurnal Obshchei Khimii published new progress about 66197-72-6. 66197-72-6 belongs to bromides-buliding-blocks, auxiliary class Aliphatic Chain, name is Diethyl (bromomethyl)phosphonate, and the molecular formula is C14H17BClNO2, Synthetic Route of 66197-72-6.
Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary