Category: 66197-72-6

Yakubovich, A. Ya. published the artcileSynthesis of hereto-organic compounds of the aliphatic series by means of the diazo derivatives. Syntheses of compounds of group V elements, Related Products of bromides-buliding-blocks, the publication is Doklady Akademii Nauk SSSR (1950), 303-5, database is CAplus.

Chlorides of the type MCl₃ (As, Sb, and Bi) react with diazoalkanes, RCHN₂, yielding progressively RCHClMCl₂, (RCHCl)₂MCl, and (RCHCl)₃M at 0-5°; the extent of reaction is somewhat controlled by the reagent ratios used; over-all yields of 30-50% are attained. The reactions with PCl₃ and PBr₃ at low temperatures (-50° to -60°) are analogous and yield (average) 40% of the corresponding dihalophosphines. Reactions of dihalophosphines with diazoalkanes or the reactions of PX₃ at higher temperatures yield solid organophosphorus compounds of more complex nature. POCl₃ and POBr₃ do not react with diazoalkanes, but PCl₅ reacts easily, forming di- and trisubstitution products. The necessary diazo compounds were prepared in Et₂O or C₆H₆ and were dried by freezing at -70° over solid KOH, followed by standing over Na wire; these were added to the desired halide in Et₂O or C₆H₆ with stirring and when N evolution ceased and the color was discharged the products were distilled The following were obtained: (MeCHCl)₂AsCl, b₁ 51.5°, d₂₀²⁰ 1.553, n_D²⁰ 1.5870. (MeCHCl)₃As, b₂ 81-2°, d₄²⁰ 1.445, n_D²⁵ 1.5307. ClCH₂BiO (the chloride originally formed hydrolyzes under the conditions used), easily decomposed, with explosive violence at times. ClCH₂SbCl₂, m. 36-8°, b₂ 86.5°, d₂₀²⁰ 2.677. (ClCH₂)₃Sb, b₃ 105°, d₂₀²⁰ 2.038. (ClCH₂)₃SbBr₂, m. 90-90.5°. (MeCHCl)₂SbCl, b₁ 69.5°, d₂₀²⁰ 1.831. (MeCHCl)₂SbO(OH), does not m. 190°. ClCH₂PCl₂, b₁₄₀ 80°, d₂₀²⁰ 1.5289, n_D²⁰ 1.5247. MeCHClPCl₂, b₃₀ 64°, d₂₀²⁰ 1.4232, n_D²⁰ 1.5090. ClCH₂PCl₄, decompose 102-4°, is readily chlorinated to Cl₃CPCl₄, which with water yields stable Cl₃CPO(OH)Cl, m. 79°; hydrolysis of Cl₃CPO(OMe)₂ or the di-Et analog with HCl in sealed tube yields Cl₃CPO(OH)₂.H₂O. m. 87°, also obtainable by hydrolysis of the above semichloride. MeCHClPCl₄ decompose at an unstated temperature ClCH₂POCl₂ b₃₀ 103°, d₂₀²⁰ 1.6444, n_D²⁰ 1.4945. MeCHClPOCl₂ b₈ 70°, d₂₀²⁰ 1.5424, n_D²⁰ 1.4930. PrCHClPOCl₂ b₂₅ 84°, d₂₀²⁰ 1.3236, n_D²⁰ 1.5010. ClCH₂PO(OH)₂ m. 92°; its (monoaniline salt), decompose 183°. MeCHClPO(OH)₂ m. 100°. ClCH₂PO(OEt)₂ b₃ 86°, d₂₀²⁰ 1.1909, n_D²⁰ 1.4360. MeCHClPO(OEt)₂ b₅ 93°, d₂₀²⁰ 1.1474, n_D²⁰ 1.4370. MeCHClPO(NHPh)₂ m. 154-5°. BrCH₂PBr₂ b₄ 70°, d₂₀²⁰ 2.6357. BrCH₂POBr₂ m. 38°, b₂ 112°, d₂₀²⁰ 2.7030, n_D²⁰ 1.6120. BrCH₂PO(OH)₂.PhNH₂ decompose 187°. BrCH₂PO(OEt)₂ b₁ 99°, d₂₀²⁰ 1.4474, n_D²⁰ 1.4587. (ClCH₂)₃PO m. 100.5° (hydrate, m. 88-9°; cf. Hoffman, C.A. 24, 3986). (Cl₃C)₃P(OH)Cl, decompose 203°, solid. (MeCHCl)₂PO(OH) m. 107°; monoaniline salt, decompose 160°. (Cl₃C)₃PO m. 53°.

Doklady Akademii Nauk SSSR 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 C15H20BNO3, Related Products of bromides-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

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, n_D²⁰ 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, n_D²⁰ 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, n_D²⁰ 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, b_2.5 86-7° , d₂₀²⁰ 1.1909, n_D²⁰ 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, n_D²⁰ 1.4640 [the impure product was further identified by treatment with EtOH in Et₂O in presence of Et₂NPh, yielding (EtO)₃P, b₁₂ 49°, n_D²⁰ 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, n_D²⁰ 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, n_D²⁰ 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, n_D²⁰ 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, n_D²⁰ 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, n_D²⁰ 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, n_D²⁰ 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

Evans, Genevieve L. published the artcileAnthranilate phosphoribosyltransferase: Binding determinants for 5′-phospho-alpha-D-ribosyl-1′-pyrophosphate (PRPP) and the implications for inhibitor design, Synthetic Route of 66197-72-6, the publication is Biochimica et Biophysica Acta, Proteins and Proteomics (2018), 1866(2), 264-274, database is CAplus and MEDLINE.

Phosphoribosyltransferases (PRTs) bind 5′-phospho-α-D-ribosyl-1′-pyrophosphate (PRPP) and transfer its phosphoribosyl group (PRib) to specific nucleophiles. Anthranilate PRT (AnPRT) is a promiscuous PRT that can phosphoribosylate both anthranilate and alternative substrates, and is the only example of a type III PRT. Comparison of the PRPP binding mode in type I, II and III PRTs indicates that AnPRT does not bind PRPP, or nearby metals, in the same conformation as other PRTs. A structure with a stereoisomer of PRPP bound to AnPRT from Mycobacterium tuberculosis (Mtb) suggests a catalytic or post-catalytic state that links PRib movement to metal movement. Crystal structures of Mtb-AnPRT in complex with PRPP and with varying occupancies of the two metal binding sites, complemented by activity assay data, indicate that this type III PRT binds a single metal-coordinated species of PRPP, while an adjacent second metal site can be occupied due to a sep. binding event. A series of compounds were synthesized that included a phosphonate group to probe PRPP binding site. Compounds containing a “bianthranilate”-like moiety are inhibitors with IC₅₀ values of 10-60 μM, and K_i values of 1.3-15 μM. Structures of Mtb-AnPRT in complex with these compounds indicate that their phosphonate moieties are unable to mimic the binding modes of the PRib or pyrophosphate moieties of PRPP. The AnPRT structures presented herein indicated that PRPP binds a surface cleft and becomes enclosed due to re-positioning of two mobile loops.

Biochimica et Biophysica Acta, Proteins and Proteomics 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 C5H12BrO3P, Synthetic Route of 66197-72-6.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary