- Organophosphorus synthesis without phosphorus trichloride: The case for the hypophosphorous pathway
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The vast majority of organophosphorus compounds is currently synthesized from phosphorus trichloride (PCl3), even though the final consumer products do not contain reactive phosphorus-chlorine bonds. In order to bypass phosphorus trichloride, significant interest has been devoted to functionalizing elemental phosphorus (P4, the precursor to PCl3), red phosphorus (Pred), or phosphine (PH3). Yet, other industrial-scale precursors are hypophosphorous derivatives (H 3PO2 and its alkali salts), but their use as phosphorus trichloride replacements has been completely overlooked. Here, the case is made for an alternative approach to the industrial synthesis of organophosphorus compounds based on hypophosphites.
- Montchamp, Jean-Luc
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- Synthesis of Long-Chain n-Alkylphosphonic Acids by Phosphonylation of Alkyl Bromides with Red Phosphorus and Superbase under Micellar/Phase Transfer Catalysis
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Long-chain n-Alkylphosphonic acids, AlkP(O)(OH)2, are synthesized in up to 91 % yield (mostly 40–60 %) by straightforward phosphonylation of alkyl bromides (AlkBr, Alk=C4–C18) with red phosphorus (Pn) in the multiphase KOH/H2O/toluene system in the presence of 2–10 mol % of cetyltrimethylammonium bromide (CTAB), acting as a micellar/phase transfer catalyst and as a generator/transporter of superbasic hydroxide anions, the intermediate potassium phosphinates being in situ oxidized/neutralized by nitric acid. The key steps of the phosphonylation mechanism are the P?P bond cleavage of Pn polymeric molecules by superbasic ?OH anions, dissolved in the CTAB micelles, and phase transfer of polyphosphide anions to the organic phase and their alkylation with AlkBr.
- Kuimov, Vladimir A.,Malysheva, Svetlana F.,Belogorlova, Natalia A.,Albanov, Alexander I.,Gusarova, Nina K.,Trofimov, Boris A.
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supporting information
p. 1596 - 1602
(2021/03/03)
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- Wet and dry processes for the selective transformation of phosphonates to phosphonic acids catalyzed by br?nsted acids
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A "wet"process and two "dry"processes for converting phosphonate esters to phosphonic acids catalyzed by a Bronsted acid have been developed. Thus, in the presence of water, a range of alkyl-, alkenyl-, and aryl-substituted phosphonates can be generally hydrolyzed to the corresponding phosphonic acids in good yields catalyzed by trifluoromethyl sulfonic acid (TfOH) at 140 °C (the wet process). On the other hand, with specific substituents of the phosphonate esters, the conversion to the corresponding phosphonic acids can be achieved under milder conditions in the absence of water (the dry process). Thus, the conversion of dibenzyl phosphonates to the corresponding phosphonic acids took place smoothly at 80 °C in toluene or benzene in high yields. Moreover, selective conversion of benzyl phosphonates RP(O)(OR′)(OBn) to the corresponding mono phosphonic acids RP(O)(OR′)(OH) can also be achieved under the reaction conditions. The dealkylation via the generation of isobutene of ditert- butyl phosphonate, and the related catalysis by TfOH took place even at room temperature to give the corresponding phosphonic acids in good to high yields. Nafion also shows high catalytic activity for these reactions. By using Nafion as the catalyst, phosphonic acids could be easily prepared on a large scale via a simple process.
- Li, Chunya,Saga, Yuta,Onozawa, Shun-Ya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
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p. 14411 - 14419
(2020/12/29)
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- METHOD FOR PRODUCING PHOSPHONIC ACID DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a method for producing a phosphonic acid derivative, in which the reaction proceeds under relatively mild reaction conditions without using hydrogen halide or a metal catalyst. SOLUTION: Provided is a method for producing a phosphonic acid derivative represented by formula (1), comprising a step in which an ester group-containing phosphonic acid derivative is reacted in a solvent or without a solvent in the presence of a superacid catalyst. (In formula (1), R1 and R2 are each independently a substituted or unsubstituted hydrocarbon group that may contain a heteroatom, n is a natural number of 1 to 3, m is a natural number of 0 to 2, o is a natural number of 0 to 1, and n + m + o = 3.). SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0045; 0049; 0052
(2020/10/27)
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- Selective Substitution of POCl 3 with Organometallic Reagents: Synthesis of Phosphinates and Phosphonates
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The selectivity of the substitution reaction of phosphoryl chloride with organometallic reagents was investigated using NMR spectroscopy. This led to the discovery that the selectivity of the substitution reaction can be tuned by choosing a proper organometallic reagent. A phosphinate could be obtained by using a Grignard reagent whereas an organozinc reagent provided a phosphonate. Based on these results, one-pot synthetic methods for the preparation of phosphinates and phosphonates using commercially available starting materials were developed. Both methods allow the synthesis of a broad range of either phosphinate or phosphonate derivatives in a straightforward and general procedure. Moreover, using these one-pot procedures, mixed systems substituted with different alkyl/aryl groups can be prepared.
- Verbelen, Bram,Dehaen, Wim,Binnemans, Koen
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p. 2019 - 2026
(2018/04/14)
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- For metal corrosion inhibiting 1 - octyl phosphine acid synthetic method
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The invention discloses a synthesizing method of 1-octylphosphonate for metal corrosion inhibition and belongs to the field of chemical preparation. The method includes the synthesizing methods that firstly, 1-bromoctane and catalysts are mixed in proportion, triethyl phosphate is dropwise added into a reaction system within the temperature range of 70-120 DEG C, and adding time is 2-3h; then the temperature of the system is raised to 130-160 DEG C and preserved for 2-4 h, and then the reaction continues; secondly, the temperature of the system is lowered to 60-80 DEG C, a hydrogen bromide aqueous solution is dropwise added, and the adding time is 0.5-1 h; then temperature is raised till backflow happens, and the temperature is preserved for 2-4 h for carrying out a reaction; thirdly, the hydrogen bromide aqueous solution in the reaction system is firstly evaporated out at normal pressure, and then vacuumizing is performed so that excessive 1-bromoctane in the reaction can be evaporated out; fourthly, cooling is performed after distilling ends, extraction and liquid separation are performed, and then the 1-octylphosphonate can be prepared. According to the synthesizing method, reaction conditions are moderate, the reaction process is easy to control, the product yield is high, and purity is high.
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Paragraph 0025; 0026; 0027; 0028; 0029; 0030; 0031-0036
(2017/06/23)
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- Method for preparing n-octylphosphonic acid
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The invention provides a method for preparing n-octylphosphonic acid. The method includes the following steps that firstly, n-octylphosphonic acid ester and concentrated hydrochloric acid are added into a reaction kettle, 98% sulfuric acid is added dropwise, stirring is continuously carried out, after sulfuric acid is completely added dropwise, the temperature is raised to 115-118 DEG C and kept for 25-35 hours, the mixture is naturally cooled to 55-65 DEG C, the materials are discharged from the reaction kettle after reaction, the reacted materials are cooled to 25-35 DEG C and is placed for 12 hours or above at the temperature of 25-35 DEG C, and a n-octylphosphonic acid crude product is obtained through centrifugal separation; secondly, the n-octylphosphonic acid crude product is recrystallized to obtain n-octylphosphonic acid. An acid catalyst used in hydrolysis reaction in the preparing process of n-octylphosphonic acid is a mixture of hydrochloric acid and sulfuric acid, is cheap and easy to obtain, and makes hydrolysis of ester thorough.
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Paragraph 0019
(2016/11/17)
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- Non-metallic compd. Bisphosphonic acid crosslinked layered manufacturing method
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PROBLEM TO BE SOLVED: To provide a novel noncrosslinking type layered phosphonic acid metal compound which has high crystallinity and a uniformly introduced multicomponent phosphonic acid and is free of a fluorine atom, and to provide a method for the production of the same.SOLUTION: The method for the production of the noncrosslinking type layered phosphonic acid metal compound includes a reaction step of reacting two or more monophosphonic acids or derivatives thereof having predetermined conditions with a metal source that can generate a hexacoordinated metal atom ion to be a central atom (M) of a metal oxide octahedron upon reaction in the presence of a sulfuric acid catalyst. The noncrosslinking type layered phosphonic acid metal compound obtained by the production method is also provided.
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- Method for the production of alkylphosphonic acids, esters, and salts by oxidizing alkylphosphonous acids, and use thereof
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The invention relates to a method for producing monocarboxy-functionalized dialkylphosphinic acids, esters, and salts, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to obtain an alkylphosphonous acid, the salt or ester (II) thereof, and b) the obtained alkylphosphonous acid, the salt or ester (II) thereof is reacted with an oxidizing agent or with an oxidizing agent and water or with oxygen and water in the presence of a catalyst B to obtain the alkylphosphonic acid derivative (III), wherein R1, R2, R3, R4 are identical or different from each other and independently represent, inter alia, H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, X and Y are identical or different from each other and independently represent H, C1-C18-alkyl, C6-C18-aryl, C6-C18-aralkyl, C6-C18-alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonated nitrogenous base, and catalysts A and B are transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand.
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Page/Page column 25
(2015/05/05)
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- Novel fluorinated dialkylphosphonatocholines: Synthesis, physicochemical properties and antiprotozoal activities against Acanthamoeba spp.
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The synthesis of four new organophosphorous gemini surfactants is presented. They belong to the class of dialkylphosphonatocholines. Tails are represented with two octyl groups both non or partially fluorinated. The synthesis was performed by reaction of alkylphosphonic acids with choline derivatives in the presence of 2,4,6-triisopropylbenzenesulfonyl chloride. The micellar, surface active, and solubilization properties of new surfactants were studied. Antiprotozoal activities were tested against Acanthamoeba lugdunensis and Acanthamoeba quina.
- Luká?, Milo?,Garajová, Mária,Mrva, Martin,Devínsky, Ferdinand,Ondriska, Franti?ek,Kubincová, Janka
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- A solution-based approach to composite dielectric films of surface functionalized CaCu3Ti4O12 and P(VDF-HFP)
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High permittivity CaCu3Ti4O12/ poly(vinylidenefluoride-co-hexafluoropropylene) P(VDF-HFP) nanocomposites were investigated as dielectrics for film capacitors. CaCu3Ti 4O12 was synthesized by two different soft-chemistry methods, namely, decomposition of a citrate precursor and a recently developed lactate precursor to identify a preferable route to nanometer scale spherical particles with an increased interfacial area. A ball-milling step was applied to break particle agglomerates and to enhance particle distribution in the composite films. To improve the wetting of the CaCu3Ti 4O12 oxide particles and the polymer, a variety of surfactants, e.g. carbonic acid, silane, sulfonic acid and phosphonic acid were investigated. A successful oxide surface functionalization was achieved by 2,3,4,5,6-pentafluorobenzyl phosphonic acid, leading to stable bonds and good structural compatibility between the surfactant and the highly fluorinated polymer matrix. The films were prepared from composite dispersions by a spin-coating technique and can be formed out of powders from both precursors, but the citrate method is preferable due to milder synthesis conditions and improved film homogeneity. The use of ball-milled powders as the oxide component results in homogeneous particle distributions even near to the percolation threshold. In addition, such fine-ground particles lead to homogeneous film thickness and decreased film roughness. Dielectric measurements at different frequencies revealed an enhancement in the relative permittivity by a factor of 5 compared to the pure polymer while the dielectric losses remained very low.
- Ehrhardt, Claudia,Fettkenhauer, Christian,Glenneberg, Jens,Muenchgesang, Wolfram,Leipner, Hartmut S.,Diestelhorst, Martin,Lemm, Sebastian,Beige, Horst,Ebbinghaus, Stefan G.
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p. 2266 - 2274
(2014/02/14)
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- SURFACE-MODIFIED (EFFECT) PIGMENTS
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The invention relates to pigment based on (multiple) coated platelet-shaped substrates comprising an outer layer which is obtained by treatment with a metal oxide/hydroxide and then a phosphate ester, or phosphonate, or a salt thereof, with the proviso that the phosphate ester, or phosphonate do not contain fluorine, to a method for producing said pigments and the use thereof. The outer layer provides a very good photo-stabilisation of the TiO2coated platelet-shaped substrates, such as mica, combined with a good water resistance and an anti-yellowing performance.
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- A novel approach to phosphonic acids from hypophosphorous acid
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A novel access to phosphonic acids via Pd-catalyzed tandem carbon-phosphorus bond formation-oxidation processes was developed. The procedures involve atom-economical and environmentally friendly functionalization reactions of hypophosphorous acid (H3PO2) and H-phosphinic acids [RP(O)(OH)(H)].
- Bravo-Altamirano, Karla,Montchamp, Jean-Luc
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p. 5755 - 5759
(2008/02/09)
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- New mixed phosphonate esters by transesterification of pinacol phosphonates and their use in aldehyde and ketone coupling reactions with nonstabilized phosphonates
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Alkylpinacol phosphonates were prepared by rhodium-catalyzed olefin hydrophosphorylation, and attempted α-deprotonation of the pinacol derived alkyl phosphonates resulted in ring cleavage. The propensity of the alkylpinacol phosphonates to undergo ring opening was exploited to prepare phosphonic acid monomethyl esters in high yield by transesterification in acidulated methanol. Esterification and alkylation with aldehydes or ketones gave β-hydroxy mixed phosphonate esters. tert-Butyl and benzylic phosphonate ester protective groups were introduced to improve the efficiency and functional group compatibility of β-hydroxy phosphonate saponification. The β-hydroxy phosphonic acid monomethyl esters were dehydrated with diisopropylcarbodiimide, which gave oxaphosphetane intermediates that collapse to an olefin. The overall reaction sequence complements the arsenal of Horner-Wadsworth-Emmons-type coupling reactions.
- Reichwein, John F.,Pagenkopf, Brian L.
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p. 1459 - 1463
(2007/10/03)
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- STEREOSPECIFIC INTRAMOLECULAR CYCLIZATION FOR ASYMMETRIC SYNTHESIS OF (Rp)- AND (Sp)-ENANTIOMERS OF 2-OCTYL- AND 2-PHENYL-4H-1,3,2-BENZODIOXAPHOSPHORIN 2-OXIDES
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Our earlier studies established that: 1) 2-octyl- and 2-phenyl-4H-1,3,2-benzodioxaphosphorin 2-oxides (octyl- and phenyl-BDPOs) induce delayed neuropathy in adult hens at 3 and 200 mg/kg, respectively; 2) phenyl-BDPO also significantly potentiates the acute toxicity of the insecticide malathion to mice; 3) the (Rp) and (Sp) enantiomers of these compounds, resolved on a mg scale by chiral HPLC, differ in potency by 92- and 137-fold, respectively, as inhibitors of neuropathy target esterase.In order to further study the stereospecificity in their toxic effects, the individual enantiomers of octyl- and phenyl-BDPOs are prepared here be a general method of asymmetric synthesis from the corresponding TLC-resolved diastereomeric precursors (Rp)- and (Sp)-methyl N- L-prolinates through acid-catalyzed intramolecular cyclization.This occurs under mild conditions in high yields and involves inversion of configuration at phosphorus.HPLC with the CHIRALCEL OC column established their absolute configurations, based on a previously-published assignment, and 97-100percent e.e. for (Rp)- and (Sp)-octyl- and phenyl-BDPOs. Key words: Asymmetric synthesis, 1,3,2-benzodioxaphosphorin 2-oxide, cyclization, NTE inhibitors, L-propinates, stereochemistry.
- Wu, Shao-Yong,Casida, John E.
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p. 177 - 184
(2007/10/02)
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