- Synthesis method and synthesis device of diethyl methylphosphite
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The invention relates to a synthesis method and a synthesis device of diethyl methylphosphite. The synthesis method comprises the following steps: (1) mixing methyl phosphine dichloride, absolute ethyl alcohol and a solvent to carry out a synthesis reaction; (2) carrying out reduced pressure deacidification treatment on the reaction solution obtained in the step (1); and (3) separating and purifying the deacidified reaction solution obtained in the step (2) to obtain diethyl methylphosphite. According to the synthesis method, an acid-binding agent is not needed, hydrogen chloride gas generatedby the synthesis reaction can be discharged through reduced-pressure deacidification treatment, the generation of solid waste residues containing acid-binding agent hydrochloride is avoided, the separation and treatment of the solid waste residues are reduced, and the dosage of ethanol is reduced by adding a solvent, so that the ethanol does not need to play a role as a solvent, the energy consumption is reduced, the resources are saved, the process is high in yield, simple to operate and environment-friendly, and the atom economy is good.
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Paragraph 0071-0118
(2020/09/09)
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- Purification method of dialkyl methylphosphite
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The invention relates to the technical field of compound purification, and particularly provides a purification method of dialkyl methylphosphite. The purification method comprises the following steps: adding a weak polar solvent into a reaction solution containing dialkyl methylphosphite, magnesium chloride and an ether solvent, conducting cooling to -10 DEG C to 40 DEG C, adding a nitrogen-containing organic alkali compound, carrying out a heat preservation reaction, and conducting filtering to obtain magnesium chloride and a filtrate; and rectifying the filtrate to obtain a dialkyl methylphosphite product. According to the purification method provided by the invention, the purity and the yield of the dialkyl methylphosphite are improved, the obtained magnesium chloride does not containcrystal water, the nitrogen content in the magnesium chloride is 0.01-0.5%, and the purity of the anhydrous magnesium chloride can reach 97% or above; and the purity of the obtained dialkyl methylphosphite product can reach 97% or above, and the yield can reach 85% or above. The method has the advantages of simple process, no need of special equipment, mild reaction conditions and no need of high-temperature distillation or low-temperature brine treatment process, and is suitable for large-scale industrial production.
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Paragraph 0041-0043; 0047-0052; 0059-0067; 0074-0083
(2020/12/15)
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- A method for preparing methyl asia phosphine acid diethyl ester (by machine translation)
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The invention discloses a method for preparing methyl asia phosphine acid diethyl ester, aims to solve the problems in the existing method, when using ammonia gas as acid, pH value of the reaction solution in the need to control the 7.0 - 8.5 between, accurate control of the pH value is very difficult, and is lower than the pH value, will produce a large number of methyl inferior phosphine acid ethyl ester by-product, the use of the organic amine do capture, there is caused a large toxicity, high price, the recovery process is tedious, the recovery rate is low. The present invention relates to methyl-phosphine, ethanol and calcium oxide as the main raw material, process for preparing methyl asia phosphine acid diethyl ester is obtained, which is a low-cost, is suitable for the industrial production of methyl asia phosphine acid diethyl ester preparation method. The invention in the preparation of the methyl asia phosphine acid diethyl ester, for the first time the adoption of the calcium oxide to replace the ammonia or organic amine as capture, effectively reduces the production cost, and the calcium oxide is non-toxic, is friendly to the environment, and has a good economic value and social value. (by machine translation)
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Paragraph 0028-0032
(2019/07/06)
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- A method for preparing methyl asia phosphine acid diethyl ester
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The invention provides a method for synthesizing diethyl methyl-phosphonite. The method comprises technological steps as follows: firstly, a ternary complex is prepared from phosphorus trichloride, aluminium trichloride and chloromethane as raw materials, the ternary complex is reduced by powdered aluminium and reacts with absolute ethyl alcohol, a crude diethyl methyl-phosphonite product is obtained and subjected to reduced-pressure distillation, and a pure product is obtained. According to the method, diethyl methyl-phosphonite is directly prepared from the ternary complex, an intermediate methyl phosphonic dichloride is not needed, and dangerous level of industrial production is reduced; compared with a traditional technology for preparing diethyl methyl-phosphonite from the intermediate methyl phosphonic dichloride, ethyl alcohol and sodium chloride through a reaction, the reaction conditions are milder, waste residue rate is obviously reduced, and yield is as high as 85%.
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Paragraph 0036; 0037; 0038; 0039-0045
(2019/05/04)
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- Methyl asia phosphine acid ester compound synthesis and purification method
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The invention relates to a synthesis and purification method of methyl phosphinate compounds. The method concretely comprises the following steps: adding brine to a solution containing a methyldialkyl phosphinate and magnesium chloride mixture in an inert solvent at a low temperature, and separating to obtain methylalkyl phosphinate or methyldialkyl phosphinate. The method solves the post-treatment and purification difficulties of a Grignard reagent method, and has the advantages of industrial production, effective reduction of the generation of methyl phosphonous acid, mild process conditions, and excellent reaction yield and product quality.
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Paragraph 0061; 0062; 0063
(2018/02/04)
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- Preparation method of dialkyl methylphosphonite
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The invention relates to a preparation method of dialkyl methylphosphonite. tertiary amine with pKa greater than 10 is adopted as the acid binding agent, methyl phosphonic dichloride and alcohol react in a solvent, and the mole ratio of the methyl phosphonic dichloride, alcohol and tertiary amine is 1:2.0-2.4:2.0-2.4, the produced tertiary amine hydrochloride is neutralized with a caustic soda aqueous solution, and the solvent and tertiary amine obtained by evaporation is recycled and reused. The alkyl of the dialkyl methylphosphonite is straight chain and side chain alkane or alkene of aliphatic C1-C4, the alcohol refers to methanol, ethanol, propanol, isopropanol, allyl alcohol, n-butanol, isobutanol and the like, the tertiary amine refers to tertiary fatty amine, and also refers to fatty group and aromatic mixed tertiary amine, at the same time, the pKa of the tertiary amine is required to be greater than 10, and the tertiary amine can include triethylamine, tripropylamine and tributylamine.
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Paragraph 0047-0054; 0064-0077
(2018/02/04)
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- A kind of preparation method for treating keratoconjunctival and wherein the intermediate preparation method
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The invention relates to the technical field of pesticides and particularly relates to a method for preparing glufosinate-ammonium and a preparation method for an intermediate thereof. The method is characterized by comprising the following steps of: taking phosphorus trichloride and phosphite ester as raw materials, preparing chlorophosphite ester under the catalysis of the mixture of triethylamine, N,N-dimethylformamide or pyridine and hexamethylphosphoramide, preparing methylmagnesium chloride from chloromethane and magnesium metal, preparing methyl phosphite ester by reacting the chlorophosphite ester with methylmagnesium chloride, carrying out an addition reaction on the methyl phosphite ester and acrolein, carrying out a Strecker reaction on the product of the addition reaction, sodium cyanide, ammonium chloride and ammonia water under the catalysis of montmorillonite-supported lewis acid, and carrying out hydrolyzing and purifying after finishing the Strecker reaction, so as to obtain the high-purity glufosinate-ammonium. The method provided by the invention has the advantages that side reactions are few, products are high in purity and easy to separate, and catalysts and solvents are easy to obtain, regenerate and recycle; and the production cost is lowered, and the method is accordant with the trend of green chemical industry and is suitable for industrial production.
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Paragraph 0117; 0118
(2017/03/08)
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- Synthetic method of methyl phosphite and glufosinate-ammonium
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The invention discloses a synthetic method of methyl phosphite and glufosinate-ammonium. The method comprises the steps: with phosphorus pentasulfide as a starting material, then carrying out vulcanization reaction, chlorination reaction, water washing and distillation purification, then carrying out catalytic hydrogenation to obtain chloride phosphite (III), and next carrying out Grignard reaction to obtain methyl phosphite (IV), wherein R is C1-C4 alkyl. The method comprises the steps: with phosphorus pentasulfide as the starting material, then carrying out vulcanization reaction, chlorination reaction, water washing and distillation purification, then carrying out catalytic hydrogenation to obtain chloride phosphite, next carrying out Grignard reaction to synthesize methyl phosphite (IV), and thus obtaining the final product glufosinate-ammonium through a Strecker route of the prior art. The synthetic yield is increased, methyl phosphorus dichloride and other unstable corrosive intermediates cannot be produced, the discharge of three-waste substances is reduced, and environment-friendly costs and pressure are reduced.
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Paragraph 0033; 0052
(2016/11/07)
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- Direct α-chlorination of O,O-dialkyl chalcogenophosphonates with phosphorus oxychloride
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α-Chlorination of phosphonates, and O,O-dialkyl thio- and selenophosphonates involving the direct reaction of their lithiated anion with phosphorus oxychloride is described. The reaction gives good results where previously known methods fail. The role of the chalcogen atom, and the influence of the nature of the alkyl chain with respect to the reactivity are discussed.
- Mons, Stéphane,Sabourault, Nicolas,Klein, Emmanuel,Mioskowski, Charles,Lebeau, Luc
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p. 7547 - 7549
(2007/10/03)
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- Synthesis, NMR, relaxometry and circularly polarised luminescence studies of macrocyclic monoamidetris(phosphinate) complexes bearing a remote chiral centre
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Lanthanide complexes of macrocyclic monoamidetris(phosphinate) ligands are partially hydrated in aqueous solution. Introduction of a chiral centre into the amide group leads to the formation of only two non-interconverting complex diastereoisomers (2:1 for α-phenylethyl and 4:1 for α-1-naphthylethyl). Proton, 31P NMR and circularly polarised luminescence studies indicated that the configuration at the chiral carbon centre determines the helicity of the layout of the pendent arms and the macrocyclic ring conformation, with an RRR or SSS configuration preferred at the phosphorus centres.
- Aime, Silvio,Botta, Mauro,Dickins, Rachel S.,Maupin, Christine L.,Parker, David,Riehl, James P.,Williams, J. A. Gareth
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p. 881 - 892
(2007/10/03)
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- A stereoselective process for the preparation of novel phosphonoalkylphosphinates
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We have devised both a contiguous and a stepwise strategy for the synthesis of the pyridylaminomethane-based class of phosphonoalkylphosphinates (PAPs) that form via the intermediacy of the phosphonoethoxyaminomethane XIa. The PAPs result from condensation of picolines and phosphonoacetals in high chemoselective yield. Following reduction of aminopyridine IIIb, the unprecedented Pt(0)-catalyzed epimerization of the chelated amidine [(hydroxy)methylphosphinyl]-[(3-methyl-2-piperidinyl-idene)amino]methylphosphonic acid (IIIa) yielded a single racemic pair of PAPs (IIIc). The epimerization was found to occur more slowly than amidine formation itself.
- Ebetino, Frank H.,Berk, Jeffrey D.
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p. 135 - 142
(2007/10/03)
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- New syntheses of 1-chloroalkylphosphinates
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Different approaches to the synthesis of 1-chloroalkylphosphinates are described. Initially, we tried to extend a reaction described by Kabachnik for the preparation of chloromethylphosphinic acid chlorides [R1(Cl)P(O)CH2Cl] to C-substituted derivatives. We also considered the possibility of synthesizing the title compounds by routes already described for the formation of diethyl 1-chloroalkylphosphonates. Although these methods have allowed us to obtain several of the desired phosphinates, they suffer from limitations that restrict their synthetic applications. Finally, we have developed a more general approach that allows the formation of a wide range of phosphinates. It involves a selective P-C bond formation by reaction of MeMgCl and PhMgCl with phosphonochloridates, which are prepared by P-chlorination of 1-chloroalkylphosphonates.
- Morise, Xavier,Savignac, Philippe,Denis, Jean-Marc
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p. 2179 - 2185
(2007/10/03)
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- C-fluorinated phosphate analogues
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C-fluorinated phosphinic acid derivatives RP(O)(OEt)CF2Br (R = Ph, Me) 2a, b and 1)>2CF2 (R = Ph, R1 = Et, H) 3, 4 have been prepared via a Michaelis-Arbuzov reaction.The signs of the scalar coupling constants in the AMX spin system of (EtO)2P(O)CHFCOOEt (5) formed by the P, F and H of the P-C(H)F unit were determined using spin-tickling techniques.
- Boetzel, Ruth,Haegele, Gerhard
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- Unsaturated amino acids
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The invention relates to unsaturated amino acids of the formula I STR1 in which R1 represents hydroxy or etherified hydroxy, R2 represents hydrogen, alkyl, hydroxy or etherified hydroxy, R3 represents hydrogen, alkyl, haloalkyl, hydroxyalkyl, lower alkoxyalkyl, arylalkyl, lower alkenyl, halogen or aryl, R4 represents hydrogen, alkyl or aryl, R5 represents hydrogen or alkyl, R6 represents carboxy or esterified or amidated carboxy, R7 represents amino or amino substituted by alkyl or acyl, A represents unsubstituted or alkyl-substituted α,ω-alkylene having from 1 to 3 carbon atoms or represents a bond, and B represents methylene or a bond, with the proviso that A is other than a bond when B represents a bond, and salts thereof. They can be manufactured, for example, in accordance with the Michaelis-Arbuzov reaction and can be used as pharmacologically active substances.
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- Organophosphorus Compounds. XIX. Synthesis of 2,3-Dihydro-1H-1,2-benzazaphosphole 2-Oxides, Variously Substituted on Nitrogen and Phosphorus, by N-P Cyclization of Zwitterionic Intermediates
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2-Phenyl-2,3-dihydro-1H-1,2-benzazaphosphole 2-oxide (7a) was prepared by thermolysis of the corresponding zwitterionic amino phosphinic acid (4), or its hydrochloride salt (1).Thermolysis of methyl (2-aminobenzyl)phenylphosphinate (5a) was accompanied by intermolecu;ar O->N transmethylation to give, after cyclization, 1-methyl-2-phenyl-2,3-dihydro-1H-1,2-benzazaphosphole 2-oxide (9a); similarly, the ethyl ester (5b) gave the N-ethyl heterocycle (9b). Reaction of 2-phthalimidobenzyl bromide (13a) with diethyl methylphosphonite (14b) gave ethyl (2-phthalimidobenzyl)methylphosphinate 15a).Hydrolysis of (15a) afforded (2-aminobenzyl)-methylphosphinic acid (16), and thermolysis of this produced 2-methyl-2,3-dihydro-1H-1,2-benzazaphosphole 2-oxide (18a). 1-Methyl-2-methoxy-2,3-dihydro-1H-1,2-benzazaphosphole 2-oxide (24) was synthesized in an analogous manner. Base catalyzed N-alkylation of the benzazaphosphole derivatives (7a) and (18a) was readily achieved, and the interconversion of 2-oxides and 2-sulfides was accomplished by conventional methods.
- Collins, David J.,Drygala, Peter F.,Swan, John M.
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p. 2517 - 2536
(2007/10/02)
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- AMINOPHOSPHONIC ACID AND AMINOPHOSPHINIC ACID ANALOGUES OF ASPARTIC ACID
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4-Oxoazetidin-2-ylphosphonates and phosphinates, obtained from Arbusov reactions of 4-acetoxyazetidin-2-one and 4α-acetoxy-3β-phthalimido-2-one with a variety of phosphites and phosphonites, were hydrolysed to β-phosphono- and β-phosphino β-alanine (phosphono- and phosphinoaspartic acid) derivatives.In model studies for their incorporation in peptides, conditions for the selective removal of protecting groups for carboxylic acids, phosphonic and phosphinic acids, and amines, in derived di- and tripeptides were investigated.Alanyl and alanyl alanyl peptide incorporation into bacteria was studied.
- Campbell, Malcolm M.,Carruthers, Nicholas I.,Mickel, Stuart J.
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p. 2513 - 2524
(2007/10/02)
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- The Reaction of 1-Substituted 3,4-Dimethyl-Δ3-phospholens with Diethyl Peroxide: a Correlation Between Rate and 31P Nuclear Magnetic Resonance Shift
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The reactions of a variety of 1-X-3,4-dimethyl-Δ3-phospholens (where X=Br, Me, Ph, NMe2, SEt, H, and OR) with diethyl peroxide are described.The rates of reaction show a broad correlation with the 31P n.m.r. chemical shifts of the starting phospholens, with low field shifts corresponding to the highest reactivity.The results are discussed in terms of the biphilic mechanism for the reaction of trico-ordinate phosphorus compounds with weak ?-bonds.
- Hammond, Philip J.,Scott, Graham,Hall, C. Dennis
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p. 205 - 210
(2007/10/02)
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