756-79-6Relevant articles and documents
Carboranyl Oligonucleotides. 1. Synthesis of Thymidine(3',5')thymidine (o-Carboran-1-ylmethyl)phosphonate
Lesnikowski, Zbigniew J.,Schinazi, Raymond F.
, p. 6531 - 6534 (1993)
Using methyl (o-carboran-1-ylmethyl)phosphonate 6 as a novel and versatile borophosphonylating agent, 5'-O-(monomethoxytrityl)thymidine 3'-O- (8) and thymidine(3',5')thymidine (o-carboran-1-ylmethyl)phosphonate (12) were synthesized.The internucleotide (o-carboran-1-ylmethyl)phosphonate linkage was resistant to cleavage by phosphorodiesterases.The dinucleotide 12 represents a new class of modified lipophilic oligonucleotide-bearing carboranyl residue, designed as a carrier for boron neutron capture therapy and for potential use in antisense oligonucleotide technology.
Molecular interactions of monosulfonate tetraphenylporphyrin (TPPS1) and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) with dimethyl methylphosphonate (DMMP)
Huo, Danqun,Yang, Limin,Hou, Changjun,Fa, Huanbao,Luo, Xiaogang,Lu, Yi,Zheng, Xiaolin,Yang, Jun,Yang, Li
, (2009)
The molecular interactions of monosulfonate tetraphenylporphyrin (TPPS1) and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) with dimethyl methylphosphonate (DMMP) have been investigated by UV-vis and fluorescence spectroscopies. The association
Trimethyl Phosphite Adsorbed on Silica: An NMR and Infrared Study
Gay, Ian D.,McFarlan, A. J.,Morrow, B. A.
, p. 1360 - 1368 (1991)
Infrared spectroscopy and phosphorus-31 magic angle spinning nuclear magnetic resonance spectroscopy have been used to study the adsorption of trimethyl phosphite (TMP) on silica.At 23 deg C TMP reacts rapidly with surface silanol groups to give SiOCH3 as a chemisorbed product and liquid dimethyl phosphite (DMP).However, formation of DMP ceases when about half of the SiOH groups have been consumed because DMP strongly hydrogen bonds to the remaining silanols thereby inhibiting further reaction between TMP and SiOH.TMP also undergoes isomerization to dimethyl methylphosphonate (DMMP) which is catalyzed by SiOH.As the number of initial silanol groups is decreased (by using higher temperatures of vacuum activation) the quantity of DMP produced decreases whereas that of DMMP increases.A mechanism for formation of DMP and DMMP has been suggested.At 100 deg C isomerization does not occur, all SiOH groups are consumed, and the major product is DMP/SiOCH3 accompanied by a small quantity of a chemisorbed phosphorus-containing species having the proposed structure (SiO)2P-H(=O).The latter is stable up to 400 deg C.If TMP is heated with silica from 100 to 400 deg C, in addition to SiOCH3, the major new chemisorbed product of the reaction which can be identified by IR and NMR is (SiO)2P-Me(=O) (Me = CH3).The advantages of a combined IR-NMR approach are discussed.
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.
Challenging synthesis of bisphosphonate derivatives with reduced steric hindrance
Chiminazzo, Andrea,Sperni, Laura,Fabris, Fabrizio,Scarso, Alessandro
, (2021/04/12)
An alternative approach is reported for the synthesis of methyl ester protected bisphosphonate building blocks, such as methylene bisphosphonate, vinylidenebisphosphonate and aryl substituted prochiral vinylidenebisphosphonates, that cannot be obtained directly from dimethyl phosphite and dichloromethane.
METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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Paragraph 0045; 0079, (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
Experimental and computational studies on the formation and biological properties of the simplest polyfluoroalkyl phosphonates
Tokarz, Paulina,Gostyński, Bart?omiej,Tokarz, Pawe?,Zagórski, Piotr M.
, p. 10933 - 10945 (2020/07/15)
A representative set of the simplest dialkyl polyfluoroalkylphosphonates was in silico profiled against their absorption, distribution, metabolism, and excretion with the use of the SwissADME tool. Promising results of the screening led us to attempt to synthesize the title compounds for further biological investigations. Detailed experimental and quantum-theoretical (DFT) investigations were performed to reveal that the studied compounds could not be obtained through the standard Michaelis-Arbuzov or Michaelis-Becker reactions. Kinetic studies showed that trimethyl phosphite undergoes a reaction with 1,1,1-trifluoro-2-iodoethane several orders of magnitude slower than a side reaction. The difficulty was overcome by developing a simple three-step synthesis path that involves only readily available substrates. The newly synthesized substances were tested against several cell lines. The in vitro research revealed that both dimethyl and diethyl (2,2,3,3,3-pentafluoropropyl)phosphonate exhibited toxicity towards glioblastoma cells (U-87 MG) at a considerably lower concentration than known chemotherapeutics. This journal is
Preparation method of cyclic phosphonate flame retardant
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Paragraph 0030-0038, (2020/07/24)
The invention discloses a preparation method of a cyclic phosphonate flame retardant, which relates to the technical field of organic phosphorus flame retardant synthesis. The method comprises the following steps of taking trimethylolpropane and trimethyl phosphite as raw materials with the feed mole ratio of 1: 2-4, selecting methyl benzenesulfonate or methyl p-toluenesulfonate as a catalyst, controlling proper process parameters such as catalyst quantity, temperature, time and the like, and carrying out transesterification and rearrangement reaction to obtain the phosphonate flame retardantwith a cyclic structure and the byproduct dimethyl methylphosphonate flame retardant. The method provided by the invention has the advantages of few raw material varieties, easy source, low cost, rapid reaction, high efficiency, environment-friendly process, energy conservation and consumption reduction; the product prepared by the method is the same as the product prepared by the existing method,but the production period is shortened by 2/3-3/4, the production capacity is greatly improved, and the method is suitable for industrial production.
Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
supporting information, p. 2916 - 2922 (2019/06/18)
Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
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.
