1746-03-8Relevant academic research and scientific papers
Microwave synthesis of vinylphosphonic acid and its derivatives
Zotov,Tuzhikov,Tuzhikov,Khokhlova
, p. 639 - 643 (2012)
Microwave Pyrolysis of β-substituted ethylphosphonic acid derivatives was studied. The resulting mixture of vinylphosphonic acid derivatives is similar to that obtained by convective heating.
Wet and dry processes for the selective transformation of phosphonates to phosphonic acids catalyzed by br?nsted acids
Li, Chunya,Saga, Yuta,Onozawa, Shun-Ya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
, p. 14411 - 14419 (2020/12/29)
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.
METHOD FOR PRODUCING PHOSPHONIC ACID DERIVATIVE
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Paragraph 0051-0052, (2020/10/27)
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
Zwitterionic pyrrolidene-phosphonates: Inhibitors of the glycoside hydrolase-like phosphorylase: Streptomyces coelicolor GlgEI-V279S
Veleti, Sri Kumar,Petit, Cecile,Ronning, Donald R.,Sucheck, Steven J.
, p. 3884 - 3891 (2017/07/10)
We synthesized and evaluated new zwitterionic inhibitors against glycoside hydrolase-like phosphorylase Streptomyces coelicolor (Sco) GlgEI-V279S which plays a role in α-glucan biosynthesis. Sco GlgEI-V279S serves as a model enzyme for validated anti-Tuberculosis (TB) target Mycobacterium tuberculosis (Mtb) GlgE. Pyrrolidine inhibitors 5 and 6 were designed based on transition state considerations and incorporate a phosphonate on the pyrrolidine moiety to expand the interaction network between the inhibitor and the enzyme active site. Compounds 5 and 6 inhibited Sco GlgEI-V279S with Ki = 45 ± 4 μM and 95 ± 16 μM, respectively, and crystal structures of Sco GlgE-V279S-5 and Sco GlgE-V279S-6 were obtained at a 3.2 ? and 2.5 ? resolution, respectively.
Joint production method of ethephon and vinylphosphonic acid
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Paragraph 0015; 0016, (2018/02/04)
The invention discloses a joint production method of ethephon and vinylphosphonic acid. The joint production method comprises the following steps of acylating bis(2-chloroethyl)-2-chloroethyl phosphonate by phosgene or thionyl chloride under the action of a catalyst to obtain a mixture of vinyl phosphonic chloride and 2-chloroethyl phosphonic chloride; separating the vinyl phosphonic chloride from the 2-chloroethyl phosphonic chloride in a reduced pressure distillation mode; hydrolyzing the vinyl phosphonic chloride and the 2-chloroethyl phosphonic chloride to obtain the vinylphosphonic acid and the ethephon. According to the joint production method disclosed by the invention, two products of the ethephon and the vinylphosphonic acid are synthesized by using the bis(2-chloroethyl)-2-chloroethyl phosphonate; a process is simple, and the purities of the two products are improved.
Highly selective markovnikov addition of hypervalent H-spirophosphoranes to alkynes mediated by palladium acetate: Generality and mechanism
Han, Li-Biao,Ono, Yutaka,Xu, Qing,Shimada, Shigeru
supporting information; experimental part, p. 1086 - 1099 (2010/11/05)
Palladium acetate efficiently catalyzes the addition of an H-spirophosphorane (pinacolato)2PH to alkynes to give Markovnikov addition products highlyselectively. The addition products can be easily converted to the corresponding alkenylphosphonates and phosphonicacids viasimple hydrolysis or thermal decomposition. This new reaction isa general method for the introduction of phosphorus functionality to the internal carbons of terminal alkynes, resolving the problem of the regioselectivity associated with hydrophosphorylation reactions so far reported. Mechanistic studies confirmed that (a) palladium acetate was reduced to metallic palladium by H-spirophosphorane, (b) the P-H bond of H-spirophosphorane could be activated by zero-valent platinum complexes to give the corresponding hydridoplatinum complexes, and (c) an alkenylpalladium species was identified from the reaction of palladium acetate with H- spirophosphorane and diphenylacetylene. These results support a reaction mechanism that palladium acetate was first reduced by H-spirophosphorane to give zero-valent palladium. This zero-valent palladium might insert into the P-H bond of the H-spirophosphorane to give a hydridopalladium species which then added to alkyne via the addition of H-Pd bond to form an alkenylpalladium species with the hydrogen atom added to the terminal carbon of alkynes. Reductive elimination of the alkenylpalladium affords the addition product.
Process for production of vinylphosphonic acids and silyl esters thereof
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Page 3, (2008/06/13)
A process for preparing vinylphosphonic acid compounds and silyl esters thereof in which a bis(haloalkyl) vinylphosphonate is reacted with an organosilyl halide to produce a silyl ester which can then be converted to the acid by reaction with a proton donor.
Dealkylation of phosphonate esters with chlorotrimethylsilane
Gutierrez,Prisbe,Rohloff
, p. 1299 - 1302 (2007/10/03)
Chlorotrimethylsilane completely dealkylates phosphonate esters at elevated temperature in a sealed reaction vessel. These conditions are tolerated by a variety of functional groups and lead to high conversions of dimethyl, diethyl and diisopropyl phosphonates to their corresponding phosphonic acids.
Reactions of phosphonates with organohaloboranes: New route to molecular borophosphonates
Mortier, Jacques
, p. 4266 - 4275 (2008/10/08)
Phosphonates RPO(OR′)2 (R = Me, R′ = Et (1); R = CH2Ph, R′ = Et (2); R = CH double bond CH2, R′ = Et (3); R = CH2-CH double bond CH2, R′ = Me (4); R = CH2N3, R′ = Et (5)) react with CyBCl2 (6; Cy = C6H11) in a 1:1 molar ratio in toluene at -30 °C to form the primary adducts CyBCl2·O double bond PR(OR′)2 (7-11). These products undergo a thermally induced bis-chlorodealkylation with the formation of mixtures of oligomers [-O-PR(O-)-O-BCy(O-)]n (22-26) having isovalent P-O-B groupings. Under electron impact mass spectral conditions, the ions [RPO3BCy]4-Cy, which may be attributed to tetramers [RPO3BCy]4 (22′-26′), are detected. Compounds 22′-26′ presumably possess a central cubic M4O12P4 framework that is analogous to those found in alumino- and gallophosphate materials. NMR monitoring shows that [CyBCl(μ2-O)2PR(OR′)]2 (12-16) are formed as intermediates in these reactions. These unstable dimers 12-16 possess a cyclic core analogous to the single-four-ring (4R) secondary building units (SBUs) found in zeolites and phosphate molecular sieves. Hydrolysis of 12-16 and 22-26 with methanol at 30 °C gave respectively RPO(OH)(OR′) (17-21) and RPO(OH)2 (27-31). NMR monitoring reveals that the cyclic dimer [Me2B(μ2-O)2P(CH2Ph)(OEt)]2 (35a) is the primary adduct in the reaction of PhCH2PO(OEt)2 (2) with Me2BBr (34). Heating or prolonged storage at room temperature leads to a mixture of 35a, cyclic borophosphonate Me2BC(μ2-O)2P(CH2Ph)(OEt) (35b), and the mixed anhydride of benzylphosphonic acid and dimethylborinic acid (35c).
MECHANISM OF THE PHOSPHORYLATION REACTION OF 2-HALOALKYLPHOSPHONIC ACIDS
Segall, Yoffi,Toia, Robert F.,Casida, John E.
, p. 191 - 194 (2007/10/02)
2-Haloalkylphosphonic acids require aqueous solutions of suitable pH to react as phosphorylating agents.Reaction rates are slow at pH1, moderate at pK12 (monoanion) and fast at pH>pK2 (dianion).The end products in water are phosphoric acid (major) and 2-hydroxyalkyl- and vinylphosphonic acids (minor).The dianinon is stable in non-aqueous solutions.The order of reactivity is bromo>chloro>>fluoro.Dehydrohalogenation is the major patway with mono- and diesters.In contrast, 2-chloroethylphosphonothioic acid dianion is stable even at pH 13.These findings are consistent with a mechanism involving a bimolecular process rather than an SN1 pathway via a metaphosphate intermediate.
