- An Efficient Method for Synthesis of 4-(Phosphonomethyl)benzene Derivatives under Solvent-Free Conditions
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A simple, efficient and general method has been developed for synthesis of 4-(phosphonomethyl)benzene derivatives through one-pot reaction of phosphoric acid, 4-substitute benzyl chlorides and hexamethyldisilazane under solvent-free conditions and the following hydrolysis in 2M NH4OH.
- Yang, Ting,Lin, Changxue,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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- The Aza α-aminophosphonate macrocycle
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In order to combine the properties of aza-macrocycles and aminophosphonates, a new tetraaminophosponic macrocyclic molecule has been synthesized. This potential receptor for organic molecules as well as for metal cations was obtained by condensation, hydr
- MLynarz, Piotr,Rydzewska, Agata,Sliwinska, Sylwia,Szymczyk, Monika
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- Synthesis method of tris (trimethylsilyl)phosphite
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The invention discloses a synthesis method of tris (trimethylsilyl)phosphite, and the method comprises the following steps: dissolving phosphorous acid in an organic solvent, dropwisely adding into hexamethyldisilazane, and reacting under the action of a catalyst to obtain the tris (trimethylsilyl)phosphite, wherein the mass ratio of the phosphorous acid to the hexamethyldisilazane is (1: 2.2)- (1: 4.4), the temperature is controlled to be 20-120 DEG C in the dropwise adding process, the temperature is kept at 20-120 DEG C for reaction after dropwise adding is finished, and the catalyst is strongly acidic cation exchange resin. The method has the advantages that the raw materials are easy to obtain, the reaction conditions are mild, and the conversion rate is as high as 90% or above; and 2, direct rectification can be carried out after the reaction is finished, the post-treatment steps are simple, and the yield is high. No waste is generated in the whole synthesis process, and environmental pollution is small.
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Paragraph 0017-0026
(2020/06/24)
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- Preparation method of phosphate or phosphite and secondary battery. (by machine translation)
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The preparation method of the phosphate or phosphite ester disclosed by the invention comprises, the following steps: of: reacting inorganic phosphate or inorganic phosphite 3) with a phosphoric acid ester as shown in a formula (shown in the 1) formula); and preparing 2) the phosphate ester or the. phosphite. ester according to the invention as shown in the invention . (by machine translation)
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Paragraph 0078; 0079
(2019/12/25)
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- Synthetic method of di(trimethylsilyl)phosphite
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A synthetic method of di(trimethylsilyl)phosphite belongs to the technical field of compound synthesis. Trimethylchlorosilane and orthophosphorous acid which are adopted as raw materials undergo a reaction to obtain the di(trimethylsilyl)phosphite. The method comprises the following steps: placing orthophosphorous acid in methanamide, introducing nitrogen, stirring the orthophosphorous acid in methanamide for 15-20 min, adding the trimethylchlorosilane, simultaneously adding benzyltriethylammonium chloride and/or tetrabutylammonium hydrogen sulfate, continuously introducing nitrogen, controlling the reaction temperature to be less than 40 DEG C, and carrying out a one-step reaction to obtain the di(trimethylsilyl)phosphite. The synthetic method has the advantages of simplicity, easiness in operation, mild and stable reaction process, and high yield and high purity of the obtained di(trimethylsilyl)phosphite.
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Paragraph 0053; 0054
(2017/07/19)
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- Preparation of the library of fluorescent aromatic aminophosphonate phenyl and benzyl esters
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Classical hydrophosphonylation of Schiff bases have been used for the preparation of library of diphenyl and dibenzyl aromatic aminomethylphosphonates N-substituted with aromatic moieties. The reaction, although being capricious provided the desired products in satisfactory yields. When using harsh reaction conditions conversion of diphenyl esters into monophenyl ones was observed. On the other hand, the use of more delicate conditions resulted in lack of hydrophosphonylation. The fluorescence studies revealed that the obtained library could be used for the construction of diagnostic microarrays.
- Górny Vel Górniak, Micha?,Kafarski, Pawe?
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p. 511 - 519
(2016/04/05)
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- Preparation of a novel group of hybrid compounds N-benzyl aminoboronbenzylphosphonic and N,N′-ethylenedi(aminoboronbenzylphosphonic) acids
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Two groups of new boronic acids containing aminophosphonate functions were synthesized and characterized by NMR spectroscopy and ESI-MS. Both groups of compounds were obtained by simple reactions of prepared in situ tris(trimethylsilyl) phosphite with a corresponding imine. The synthesized compounds may serve as a potential new class of building blocks, BNCT agents and supramolecular host molecules.
- M?ynarz, Piotr,Rydzewska, Agata,Pok?adek, Ziemowit
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experimental part
p. 457 - 460
(2011/02/28)
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- Radiolabelled bisphosphonates and method
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The present invention relates to 32P or 33P-labelled bisphosphonates as radiotherapeutic radiopharmaceuticals. The 32P- or 33P-labelled bisphosphonates, which are chemically identical to the unlabelled agent, are expected to target the lesion site in an identical manner, but also deliver a significant radiocytotoxic effect to the surrounding cells. This should result, given the favorable energetics of the β particle emission from the 33P nuclide, in a loss of proliferative capacity of cells associated with the tumor lesion. The relative stability and in vivo localisation of bisphosphonates makes them good candidates as 32P/33P delivery vehicles.
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- Application of silicon-phosphorus based reagents in synthesis of aminophosphonates. Part 2: Reactions of N-(Triphenylmethyl)-aldimines with the silylated phosphorus acid esters
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Reactions of silylated phosphorus acid esters with N-triphenylmethylaldimines (N-tritylaldimines) were investigated. N-Tritylmethaneimine reacts at room temperature with a mixture of P(OMe)3 and Me3SiBr forming the corresponding aminophosphonate derivatives in high yield. Other N-tritylimines are resistant toward the silylated reagents at room temperature, but undergo a similar phosphorylation reaction at elevated temperatures to form the expected aminophosphonic acids.
- Boduszek,Soroka
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p. 1105 - 1111
(2007/10/03)
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- Application of bromotrimethylsilane and trialkyl phosphites for convenient and effective synthesis of aminophosphonic acids and corresponding monoalkyl and dialkyl esters
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Application of bromotrimethylsilane (Br-TMS) in a mixture with trialkyl phosphite for synthesis of various aminophosphonic acids and esters was investigated. It was found, that appropriate mixtures of Br-TMS and trimethyl phosphite or triethyl phosphite were effective reagents for phosphorylation of various aldimines, obtained from aromatic and heteroaromatic aldehydes. Products of these reactions were corresponding aminophosphonic acids, or corresponding dialkyl or monoalkyl esters, respectively.
- Boduszek
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p. 663 - 672
(2007/10/03)
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- Synthesis of novel pyrone, chromone and coumarin derivatives of aminomethanephosphonic acid
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Novel pyrone, chromone and coumarin derivatives of aminomethanephosphonic acid were obtained in a one-step process, by treatment of a mixture of heterocyclic aldehyde and amine with tris(trimethylsilyl)phosphite, and a subsequent solvolysis of the formed silylated product with methanol.
- Boduszek, Bogdan,Uher, Michal
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p. 1749 - 1754
(2007/10/03)
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- Aminophosphonic derivatives of chromone. synthesis of novel chromone-3-(α-amino) methanephosphonic acids
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Reactions of 3-formylchromones with benzyl carbamate and triphenyl phosphite in acetic acid lead to the corresponding diphenyl chromone-3-[α(-N-benzyloxycarbonyl)amino]methanephosphonates 2 in high yields. Deprotection of the Z-substituted diphenyl esters 2 by means of acetic hydrogen bromide solution and the subsequent hydrolysis by means of 20% aq. HCl, lead to the final chromone-3-(a-amino)methanephosphonic acids 4. Attempts of synthesis of the corresponding chromone-2- aminophosphonic derivatives by this way, have failed. On the other hand, chromone-2-(α-amino)methanephosphonic acid (6) was successfully obtained by an addition of tris(trimethylsilyl) phosphite to the aldimine, which was formed from the 2-formylchromone.
- Boduszek, Bogdan,Lipinskp, Margin,Kowalska, Maria W.
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p. 179 - 189
(2007/10/03)
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- Inhibition of human immunodeficiency virus type 1 replication by phosphonoformate- and phosphonoacetate-2',3'-dideoxy-3'-thiacytidine conjugates
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The synthesis of potential 'combined prodrugs' where phosphonoformic acid (PFA) or phosphonoacetic acid (PAA) was attached to the 5'-O or N4 position of 2',3'-dideoxy-3'-thiacytidine (BCH-189) is described. The anti-HIV-1 activity of 11 analogues which included carboxylic ester or phosphoric ester linkages of PFA or PAA to BCH-189 was determined in MT-4 cells. Of these compounds, the IC50 of analogues 3, 4, 6, and 7 ranged from 0.2 to 100 μM, while IC50 for BCH-189 in this system was 0.1 μM. In vitro hydrolysis of the various esters or amides in human plasma indicated that these agents were relatively stable in the presence of plasma esterases with t( 1/2 ) values of up to 120 min. Moreover, lipophilicity of these compounds (partition coefficient) was determined in order to establish correlation between lipophilicity and diffusion of BCH-189 analogues into the cells. The active compounds may exert their effects by extracellular or intracellular hydrolysis to the corresponding antiviral agent BCH-189, but intrinsic anti- HIV-1 activity of some of PAA and PFA adducts, themselves, may also be involved.
- Charvet,Camplo,Faury,Graciet,Mourier,Chermann -,Kraus
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p. 2216 - 2223
(2007/10/02)
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- Synthesis, hydrolytic behavior, and anti-HIV activity of selected acyloxyalkyl esters of trisodium phosphonoformate (foscarnet sodium)
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The synthesis and anti-HIV activity of selected (acyloxy)-alkyl esters of trisodium phosphonoformate (foscarnet sodium) are described. The conversion of bis(trimethylsilyl) (alkoxycarbonyl)phosphonates 11a-d to the corresponding disilver salts 12a-d and their subsequent reaction with iodoalkyl acrylates 4a-c gave the desired bis(acyloxyalkyl) phosphonates 6- 9(a-c). Of the analogs tested, only the dichlorophenyl analog 9a showed a dose-dependent inhibition of HIV activity in H9 cells. Using 31P-NMR, bioreversibility has been investigated in an attempt to rationalize these results.
- Iyer,Boal,Phillips,Thakker,Egan
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p. 1269 - 1273
(2007/10/02)
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- REACTION OF TRIS(TRIMETHYLSILYL)PHOSPHITE WITH EPIHALOHYDRINS
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The reaction of tris(trimethylsilyl) phosphite with halohydrins does not lead to an Arbuzov product but to bis(trimethylsilyl) esters of 3-halo-2-trimethylsiloxypropylphosphonic acids.Methanolysis and neutralization affords the 3-halo-2-hydroxypropylphosphonic acids and their salts.Key words: Tris(trimethylsilyl) phosphite; epichlorohydrin; epibromohydrin; 3-halo-2-hydroxypropylphosphonic acids.
- Serves, Spyros V.,Teloniati, Anthi G.,Sotiropoulos, Demetrios N.,Ioannou, Panayiotis V.
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p. 181 - 184
(2007/10/02)
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- Synthesis of acyloxyalkyl acylphosphonates as potential prodrugs of the antiviral, trisodium phosphonoformate (foscarnet sodium)
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Bis(trimethylsilyl) acylphosphonates via their silver salts couple with iodoalkyl esters to provided an efficient synthesis of the corresponding acyloxyalkyl esters as potential prodrugs of the antiviral agent, trisodium phophonoformate. These compounds were tested as inhibitors of HIV-1 in chronically infected H9 cells.
- Iyer,Phillips,Biddle,Thakker,Egan
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p. 7141 - 7144
(2007/10/02)
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- Protection of Phosphonate Function by Means of Ethoxycarbonyl Group. A New Method for Generation of Reactive Silyl Phosphite Intermediates
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Nucleoside ethoxycarbonylphosphonates were prepared by condensation of appropriately protected nucleosides with ethoxycarbonylphosphonic acid.They were easily converted by treatment with 1 M NaOH followed by trimethylsilylation to highly reactive bis(trimethylsilyl) nucleoside phosphite intermediates which were allowed in situ to react with water, diphenyl disulfide, 2,2'-dipyridyl disulfide, and aldehydes to afford the corresponding nucleoside phosphonates, nucleoside S-phenyl phosphorothioates, nucleoside phosphates, and nucleoside α-hydroxy phosphonates in good yields, respectively.The nucleoside phosphonates were further converted to nucleosides under mild acidic conditions.Thus, the ethoxycarbonyl group proved to serve as a versatile protecting group for not only H-P(O) but also HO-P(O) and hydroxy groups of sugars.
- Sekine, Mitsuo,Mori, Hiroyuki,Hata, Tsujiaki
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p. 239 - 242
(2007/10/02)
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- Organometallic Compounds. XI. Chlorotrimethylsilane / Sodium Bromide - A Simple System for the in situ Generation of Bromotrimethylsilane. Reaction with Ketones, Sulfoxides, and Various Oxygen Containing Substrates
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Bromotrimethylsilane is generated in situ by the addition of chlorotrimethylsilane (2) to a solution or a suspension of sodium bromide (or LiBr, KBr, MgBr2).The reaction of the in situ generated bromotrimethylsilane with ketones, sulfoxides, γ-butyrolactone, triethyl orthoformate, and trialkyl phosphites is described.
- Schmidt, Arthur H.,Russ, Manuel
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p. 1099 - 1110
(2007/10/02)
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- THE MECHANISM OF THE REACTION OF ORGANIC PHOSPHITES WITH TRIALKYLSILYL IODIDE. IODOANHYDRIDES OF PIII ACIDS AS INTERMEDIATES
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The reaction of a trialkyl phosphite with trimethylsilyl iodide, which leads to O-trimethylsilylesters of alkylphosphonic acid, has been shown to involve several steps, all of which are defined.The first step is the formation of the iodophosphite, involving a four centre mechanism in which PIII plays the role of electrophile.This is in contrast to the analogous reaction of phosphites with alkyl halides (the Arbuzov reaction) which begins with nucleophilic attack of the phosphorus.
- Chojnowski, J.,Cypryk, M.,Michalski, J.
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p. 355 - 365
(2007/10/02)
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- Silyl Phosphites. 15. Reactions of Silyl Phosphites with α-Halo Carbonyl Compounds. Elucidation of the Mechanism of the Perkow Reaction and Related Reactions with Confirmed Experiments
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The reactions of silyl phosphites, i.e., tris(trimethylsilyl)phosphite (1), diethyl trimethylsilyl phosphite (11), and bis(trimethylsilyl) ethyl phosphite (12), with a variety of α-halo carbonyl compounds gave the 1:1 carbonyl addition products (6, 13, and 14), enol phosphates (5 and 26), and/or 2-oxophosphonates (4 and 25).Substituents on the phosphites and the α-halo carbonyl compounds have influenced the product ratios.The results of these reactions strongly suggest that the Perkow reaction proceeds via an initial attack of phosphite on the carbonyl carbon of the α-halo carbonyl compound.Treatment of bis(trimethylsilyl) 1--2-halo phosphonates (6) with sodium methoxide in methanol followed by retrimethylsilylation gave bis(trimethylsilyl) 1,2-epoxy phosphonates (17), bis(trimethylsilyl) 2-oxo phosphonates (4), and bis(trimethylsilyl) methyl phosphate (21).On the other hand, diethyl 1-hydroxy-2-halo phosphonates (22) were converted by treatment with different bases to 1,2-epoxy phosphonates (23) predominantly in good yields.When some of tri-n-butyltin alkoxides were used as bases, enol phosphates (26) were obtained selectively.Several bis(trimethylsilyl) esters obtained in the above reactions were successfully converted to the corresponding monoanilinium salts in high yields by treatment with aniline-containing alcohols.
- Sekine, Mitsuo,Okimoto, Kiyomi,Yamada, Khoji,Hata, Tsujiaki
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p. 2097 - 2107
(2007/10/02)
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