78-38-6Relevant articles and documents
Synthesis and selected reactions of 4-(Diethoxyphosphorylmethyl)-3-furoic acid
Pevzner
, p. 404 - 412 (2012)
Reduction of 4-(ethoxycarbonyl)-3-furoyl chloride with sodium borohydride in dioxane-DMF mixture leads to an ethyl 4-hydroxymethylfuran-3-carboxylate. The treatment of the latter with thionyl chloride at boiling yields the corresponding chloromethyl derivative. The obtained chloride reacts with one equivalent of sodium iodide in acetone at room temperature to form iodomethylfuran. Halomethylfurans synthesized are phosphorylated with sodium diethyl phosphite and triethyl phosphite to give ethyl 4- (diethoxyphosphorylmethyl)- 3-carboxylate. The hydrolysis of this substance with one equivalent of potassium hydroxide in ethanol gives the corresponding furoic acid. Treating this substance in succession with ethyl chloroformate and sodium azide yields furoyl azide which while heating in toluene undergoes rearrangement to phosphorus-containing 3- furylisocyanate. Heating the latter with a mixture of acetic acid and acetic anhydride gives N-[4- (diethoxyphosphorylmethyl) furyl-3]acetamide. 4-(Diethoxyphosphorylmethyl)-3- furoic acid reacts with thionyl chloride to form the corresponding furoyl chloride. Its reduction with sodium borohydride in dioxane-DMF mixture leads to the phosphorylated 3-furylmethanol. Aminomethylation of its acetate with dimethylmethyleneiminium chloride in acetonitrile does not proceed at the ring. Instead of that the unstable ester of 3-(dimethylamino) propionic acid and the phosphorylated 3-furylmethanol are formed. In slightly basic medium free Mannich base decomposed to give the starting acetate. Pleiades Publishing, Ltd., 2012.
Use of microwave irradiation for sugar and nucleoside phosphonates synthesis
Peyrottes, Suzanne,Gallier, Franck,Béjaud, Jér?me,Périgaud, Christian
, p. 7719 - 7721 (2006)
Sugar and nucleoside phosphonates have been prepared using a microwave-assisted reaction. The comparison of thermal and microwave experimental conditions of the Michaelis-Arbuzov reaction is reported.
Synthesis and reactions of 3,3-difluoroallylphosphonates and 3,3-difluoroallyltriphenylphosphonium bromide
Qiu, Weiming,Burton, Donald J.
, p. 143 - 148 (1993)
3,3-Difluoroallyltriphenylphosphonium bromide (1) and 3,3-difluoroallylphosphonates, 2, have been prepared by the reaction of CH2=CHCF2Br with phosphites or triphenylphosphine in good yield.Wittig reaction of 1 with aldehydes gave the corresponding dienes (ArCH=CHCH=CF2) 4; however, Wadsworth-Emmons reaction of 2 with aldehydes failed to produce the dienes.
Intensified Continuous Flow Michaelis-Arbuzov Rearrangement toward Alkyl Phosphonates
Monbaliu, Jean-Christophe M.,Toupy, Thomas
supporting information, p. 467 - 478 (2022/02/25)
Herein is described the development of an intensified continuous flow process for the preparation of a library of alkyl phosphonates through a Michaelis-Arbuzov rearrangement. A careful process optimization and thorough analysis of the competitive reactions led to a very attractive protocol with unprecedented productivities (up to 4.97 kg of material per day) and a low environmental footprint with the absence of solvent, additives, catalysts, and waste. In-line low-field 31P NMR monitoring was conveniently implemented for rapid optimization and process monitoring. Two key alkyl phosphonate intermediates were also assessed for the unprecedented diazene dicarboxylate-mediated electrophilic amination under continuous flow conditions toward the α-aminophosphonic acid derivatives of Pphenylalanine and Palanine, bioisosters of the natural amino acids phenylalanine and alanine, respectively.
Selective esterification of phosphonic acids
Brodzka, Anna,Koszelewski, Dominik,Ostaszewski, Ryszard,Trzepizur, Damian
, (2021/09/27)
Here, we report straightforward and selective synthetic procedures for mono-and diesteri-fication of phosphonic acids. A series of alkoxy group donors were studied and triethyl orthoacetate was found to be the best reagent as well as a solvent for the performed transformations. An important temperature effect on the reaction course was discovered. Depending on the reaction temperature, mono-or diethyl esters of phosphonic acid were obtained exclusively with decent yields. The sub-strate scope of the proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small-and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30?C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic acid). At higher temperatures, similar intermediate forms give diesters or stable and detectable pyrophosphonates which were also consumed to give diesters.31P NMR spectroscopy was used to assign the structure of pyrophosphonate as well as to monitor the reaction course. No need for additional reagents and good accessibility and straightforward purification are the important aspects of the developed protocols.
Microwave-assisted ionic liquid-catalyzed selective monoesterification of alkylphosphonic acids—an experimental and a theoretical study
ábrányi-Balogh, Péter,Drahos, László,Harsági, Nikoletta,Henyecz, Réka,Keglevich, Gy?rgy
, (2021/09/07)
It is well-known that the P-acids including phosphonic acids resist undergoing direct es-terification. However, it was found that a series of alkylphoshonic acids could be involved in mo-noesterification with C2–C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol–1) that may be overcome only by MW irradiation. The major role of the [bmim][BF4] additive is to increase the absorption of MW energy. The specific chemical role of the [BF4] anion of the ionic liquid in an alternative mechanism was also raised by the computations.
Preparation method of phosphorus flame retardant diethyl ethylphosphonate
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Paragraph 0018-0021, (2020/04/22)
The invention provides a preparation method of a phosphorus-based flame retardant diethyl ethylphosphonate, and the method comprises the following steps: mixing phosphorus trichloride, organic amine and petroleum ether, dropwisely adding absolute ethyl alcohol, and carrying out heat preservation reaction to obtain diethyl ethylphosphonate after the reaction is finished. The method is low in reaction temperature, short in reaction time and low in raw material cost, so that compared with the prior art, the method has the advantages of low energy consumption and low production cost.
METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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Paragraph 0044; 0056-0068; 0079-0081, (2020/05/02)
PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
Solvent-Free Michaelis-Arbuzov Rearrangement under Flow Conditions
Jasiak, Aleksandra,Mielniczak, Grazyna,Owsianik, Krzysztof,Koprowski, Marek,Krasowska, Dorota,Drabowicz, Józef
, p. 2619 - 2625 (2019/02/26)
The first solvent- and catalyst-free procedure for the Michaelis-Arbuzov reaction under flow conditions was developed. A variety of alkylphosphonic esters could be obtained using this protocol starting from the corresponding trialkyl phosphites and even catalytic amounts of alkyl halides with very short reaction times (8.33-50 min) and excellent conversions. In general, this protocol works effectively when the alkyl halide is used in catalytic amounts as low as 5-10% only if it concerns the synthesis of homo alkylphosphonates. One equivalent and an excess of alkyl halides should be used in the reaction with alkyl phosphite if the alkyl group of the selected substrates differ. Thus, it provides a sustainable, fast alternative to the existing methods for the preparation of alkylphosphonates. The isolation of the reaction products is straightforward due to the lack of solvents and a high purity of the obtained products (conv ≥ 99%), and notably, in the catalytic procedures there are only traces of alkyl halides formed after the reaction is complete. The reactions conducted using a glass microreactor chip with an internal volume of 250 μL allow the production of 1.6-1.95 g of organophosphorus esters per hour.
ZWITTERIONIC NANOPARTICLES
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Paragraph 0191-0202, (2019/12/24)
The present invention relates to a zwitterionic nanoparticle, the zwitterionic nanoparticle comprising at least one nanoparticle and a zwitterionic case enclosing the nanoparticle. Furthermore, the present invention relates to a composition, a method of binding a zwitterionic nanoparticle and the use of a zwitterionic nanoparticle.
