- Trialkyl Phosphite Addition to the Bis(benzene)-iron(II) and -ruthenium(II) Dications: Catalysed Hydrolysis to Dialkyl Phosphites
-
Phosphite addition to 2+ (M = Fe,Ru) yields cyclohexadienyl phosphonium and phosphonate adducts that catalyse the conversion of excess of phosphite into HP(O)(OR)2 and RP(O)(OR)2.
- Sweigart, Dwight A.
-
-
Read Online
- Stability of phosphite coordinated to ruthenium(II) in aqueous media
-
Changes in the reactivity of phosphorus(III) esters, which are promoted by coordination to the ruthenium(II) metal centre, were the focus of this study. Nuclear magnetic resonance data, which were acquired as a function of time, suggest that the phosphite coordination to the ruthenium(II) centre stabilises these molecules in terms of hydrolysis. This stabilisation is greater when the coordination occurs to the trans-[Ru(H2O)(NH3) 4]2+ rather than to the trans-[Ru(NO)(NH3) 4]3+ fragment, and these results are interpreted considering the 4dπ(RuII) → 3dπ(P(III)) back-bonding interactions. The correlation between the data on alkyl phosphite hydrolysis constants in trans-[Ru(NO)(NH3)4P(III)]n + (P(III) = P(OEt)3, P(O)(OEt)2, P(O iPr)3 and P(OBu)3) complexes and the δ13C data show that the hydrolysis of phosphites that are coordinated to Ru(II) preferably occurs via the Michaelis-Arbuzov mechanism. Only the nitrosyl complex, where P(III) = P(OMe)3, did not exhibit this correlation, which suggests that the hydrolysis likely occurs via the Aksnes mechanism in this case.
- Truzzi, Daniela R.,Franco, Douglas W.
-
-
Read Online
- Synthesis and characterization of new symmetrical bisphosphonates
-
In order to search for new chelating agents, widely employed methodologies in the chemistry of organophosphorus compounds such as the Michaelis-Arbuzov and Michaelis-Becker reactions were used to synthesize new bisphosphonates in high yields. The importance of the synthesis of these compounds resides in their potential capability of complexing different metals, all the more so because bisphosphonates have been widely employed in the diagnosis and therapy of several bone diseases, such as osteoporosis and hypercalcemia, as extracting agents for alkaline, alkaline earth, and transition metals, and also as reaction catalysts. All bisphosphonates synthesized were characterized by IR, 1H-NMR, 13C-NMR, 31P-NMR, and mass spectroscopy.
- Marques Rodrigues, Janaina,DaCosta, Joao Batista Neves
-
-
Read Online
- METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
-
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
- -
-
Paragraph 0086; 0094
(2020/05/02)
-
- Method for preparing phosphite diester by transesterification
-
The invention discloses a method for preparing phosphite diester by transesterification. Dimethyl phosphite and monohydric alcohol which are used as raw materials are stirred, reacted and rectified under the action of a basic catalyst to prepare the phosphite diester, so the problems of high deice requirements and large amount of acid-containing three wastes in the process of producing the phosphite diester by reacting phosphorus trichloride with alcohol are avoided. The method has the advantages of low raw material toxicity, simple process, mild reaction conditions, low device requirements, low pollution, high raw material conversion rate, high product selectivity, stable supply of the raw materials, provision of the phosphite diester used for fine chemical engineering or medical intermediates by dimethyl phosphite production enterprises, high added values of the product, and provision of a new way for the synthesis of the phosphite diester.
- -
-
Paragraph 0023
(2020/01/25)
-
- 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
-
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.
- Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
-
supporting information
p. 2916 - 2922
(2019/06/18)
-
- Synthesis of phosphonates in a continuous flow manner
-
The synthesis of dialkyl H-phosphonates and α-aminophosphonates was studied in a continuous flow microwave reactor. Depending on the conditions, the alcoholysis of dialkyl H-phosphonates could be fine-tuned towards the mixed and the fully transesterified products. The continuous flow synthesis of α-aryl-α-aminophosphonates was elaborated utilizing the aza-Pudovik reaction of imines and dialkyl H-phosphonates, as well as the by the Kabachnik-Fields condensation of primary amines, benzaldehyde and > P(O)H reagents.
- Tóth, Nóra,Tajti, ádám,Ladányi-Pára, Katalin,Bálint, Erika,Keglevich, Gy?rgy
-
p. 285 - 286
(2019/03/11)
-
- Synthesis and extraction behavior of alkyl and cyclic aminophosphonates towards actinides
-
Alkyl and cyclic substituted aminophosphonates (AmPs) were synthesized and characterized with various spectroscopic techniques. The molecular structures of diphenyl phenyl aminophosphonate (DPhPhAmP) and diphenyl cyclohexyl aminophosphonate (DPhCyAmP) wer
- Das, Dhrubajyoti,Brahmmananda Rao,Sivaraman,Sivaramakrishna, Akella,Vijayakrishna, Kari
-
supporting information
p. 597 - 604
(2018/07/13)
-
- Extraction of actinides by Tri-n-butyl phosphate derivatives: Effect of substituents
-
Tri-n-butyl phosphate (TBP) is most extensively used extractant in the nuclear fuel cycle. The present work investigates the effect of substituents and their role in the basicity of organophosphorus extractant on the uptake of actinides. In this connection, we have synthesized six different analogues of TBP by altering one of its butoxy group. The synthesized TBP derivatives were well characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Pu(IV) and Am(III), as well as acid uptake as a function of nitric acid ranging from 0.01 to 6 M and the data provides the comparison of their extraction behavior with that of 30% (1.1 M) tri-n-butyl phosphate under identical conditions. It was observed that distribution coefficient values strongly depend on the nature and size of the substituents. The presence of electron donating groups enhances the uptake of the actinides and the distribution coefficient values were significantly larger as compared to that of TBP. In addition, the effect of sodium nitrate on the extraction of uranium and enthalpy of extraction were also studied and revealed that the extraction process was exothermic.
- Annam, Suresh,Gopakumar, Gopinadhanpillai,Brahmmananda Rao,Sivaraman,Sivaramakrishna, Akella,Vijayakrishna, Kari
-
p. 123 - 132
(2017/09/18)
-
- Remarkable structural effects on the complexation of actinides with H-phosphonates: A combined experimental and quantum chemical study
-
The structural effects of the carbon chain on the extraction of actinides by organo-phosphorus extractants have been examined experimentally and by computation. Branched butyl H-phosphonates and their linear chain isomer, n-butyl H-phosphonate (DBHP), wer
- Chandrasekar, Aditi,Brahmmananda Rao,Sundararajan, Mahesh,Ghanty, Tapan K.,Sivaraman
-
supporting information
p. 3841 - 3850
(2018/03/21)
-
- Catalytic Phosphite Hydrolysis under Neutral Reaction Conditions
-
Cationic phosphametallocene-based platinum(II) aqua complexes were used as efficient precatalysts for the hydrolysis of aromatic and aliphatic tertiary phosphites under neutral reaction conditions at room temperature, leading to the selective cleavage of one P-O bond of the phosphite. NMR labeling experiments combined with stoichiometric model reactions and theoretical density functional theory calculations, performed with the appropriate model compounds, shed light on the operative catalytic cycle, which comprises intramolecular water molecule transfer to the cis-coordinated phosphite molecule.
- Oberhauser, Werner,Manca, Gabriele
-
supporting information
p. 4824 - 4827
(2018/05/17)
-
- Continuous flow alcoholysis of dialkyl h-phosphonates with aliphatic alcohols
-
The continuous flow alcoholysis of dialkyl H-phosphonates by aliphatic alcohols in the absence of a catalyst was elaborated using a microwave (MW) reactor equipped with a flow cell. By the precise control of the reaction conditions, the synthesis could be fine-tuned towards dialkyl H-phosphonates with two different and with two identical alkyl groups. In contrast to the “traditional” batch alcoholysis, flow approaches required shorter reaction times, and the products became available at a larger scale.
- Bálint, Erika,Tajti, ádám,Tóth, Nóra,Keglevich, Gy rgy
-
-
- Oxidation of phosphine with quinone and quinoid redox polymers in alcohol solutions of copper
-
New quinoid redox polymers were obtained by chemical modification of commercial weakly basic anion exchangers with quinone and its derivatives. The redox properties of quinone and quinoid redoxites with respect to phosphine were studied in alcohol solutions of copper complexes.
- Polimbetova,Mukhitdinova,Ergozhin,Borangazieva,Khakimbolatova, K. Kh.,Tasmagambet,Dauletkulova,Ibraimova, Zh. U.
-
p. 2344 - 2349
(2017/11/09)
-
- Hydrophosphonylation of Alkynes with Trialkyl Phosphites Catalyzed by Nickel
-
The use of simple and inexpensive NiCl2?6 H2O as a catalyst precursor for C?P bond formation in the presence of commercially available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu, SiMe3) along with several alkynes is presented. Control experiments showed the in situ formation of (RO)2P(O)H as the species that undergo the addition into the C≡C bond at the alkynes to yield the product of P?H addition. The hydrophosphonylation of diphenylacetylene with P(OEt)3, P(OiPr)3, and P(OSiMe3)3 proceeds in high yields (>92 %) without the need of a specific solvent or ligand. This method is useful for the preparation of organophosphonates for both phenylacetylene as a terminal alkyne model and internal alkynes in yields that range from good to modest.
- Islas, Rosa E.,García, Juventino J.
-
p. 4125 - 4131
(2017/10/09)
-
- Novel dialkylphosphorylhydrazones: Synthesis, leishmanicidal evaluation and theoretical investigation of the proposed mechanism of action
-
As part of a program to develop new drugs for the treatment of neglected diseases, new dialkylphosphorylhydrazones were synthesized and evaluated against the trypanosomatid parasites Leishmania braziliensis and Leishmania amazonensis. The synthesis of these compounds proved satisfactory with yields ranging from moderate to good. The most active compounds against L. braziliensis presented IC50 values in the 10-2 μM range, similar to that of the reference drug pentamidine. Two compounds, 4m and 4n, showed a significant dose dependent decrease in the infection index of L. amazonensis infected macrophages and caused a complete healing of nodules and ulcers when tested in vivo against L. amazonensis-infected mice, but the control of parasite burden at the inoculation site was statistically significant only in the case of treatment with 4n. A target fishing (reverse docking) approach using molecular docking with 15 enzymes of L. braziliensis indicated that the probable target of the active compounds was hexokinase, the first enzyme of the glycolytic pathway.
- Da Matta, Carolina Barbosa Brito,De Queiroz, Aline Cavalcanti,Santos, Mariana Silva,Alexandre-Moreira, Magna Suzana,Gon?alves, Vinicius Tomaz,Del Cistia, Catarina De Nigris,Sant'Anna, Carlos Mauricio R.,DaCosta, Jo?o Batista N.
-
-
- Phosphine-catalyzed addition of P(O)-H compounds to ethyl phenylpropiolate
-
An efficient PBu3-catalyzed α-addition of the P(O)-H bond to ethyl phenylpropiolate has been developed. This strategy offers a facile method for the preparation of synthetically useful alkenyl phosphonates and phosphinates proceeding under neut
- Salin, Alexey V.,Il'in, Anton V.,Shamsutdinova, Fanuza G.,Fatkhutdinov, Albert R.,Galkin, Vladimir I.,Islamov, Daut R.,Kataeva, Olga N.
-
supporting information
p. 6282 - 6286
(2015/10/20)
-
- Tamiphosphor monoesters as effective anti-influenza agents
-
Oseltamivir is a potent neuraminidase inhibitor for influenza treatment. By replacing the carboxylate group in oseltamivir with phosphonate monoalkyl ester, a series of tamiphosphor derivatives were synthesized and shown to exhibit high inhibitory activities against influenza viruses. Our molecular modeling experiments revealed that influenza virus neuraminidase contains a 371-cavity near the S1-site to accommodate the alkyl substituents of tamiphosphor monoesters to render appreciable hydrophobic interactions for enhanced affinity. Furthermore, guanidino-tamiphosphor (TPG) monoesters are active to the oseltamivir-resistant mutant. TPG monohexyl ester 4e having a more lipophilic alkyl substituent showed better cell permeability and intestinal absorption than the corresponding monoethyl ester 4c, but both compounds showed similar bioavailability. Intranasal administration of TPG monoesters at low dose greatly improved the survival rate of mice infected with lethal dose of H1N1 influenza virus, whereas 4c provided better protection of the infected mice than oseltamivir and other phosphonate congeners by oral administration.
- Chen, Chun-Lin,Lin, Tzu-Chen,Wang, Shi-Yun,Shie, Jiun-Jie,Tsai, Keng-Chang,Cheng, Yih-Shyun E.,Jan, Jia-Tsrong,Lin, Chun-Jung,Fang, Jim-Min,Wong, Chi-Huey
-
p. 106 - 118
(2014/06/09)
-
- Synthesis of H-Phosphonate Intermediates and Their Use in Preparing the Herbicide Glyphosate
-
The esterfication of hypophosphorous acid is followed by reaction with another molecule of alcohol under the action of a nickel catalyst to provide a green method for the preparation of H-phosphonate diesters. This method avoids the need for any stoichiometric chlorine unlike those based on phosphorous trichloride.
- -
-
Paragraph 0034; 0044
(2014/10/16)
-
- Catalytic enantioselective hydrophosphonylation of aldehydes using the iron complex of a camphor-based tridentate Schiff base [FeCl(SBAIB-d)]2
-
An iron(III)-Schiff base-catalyzed, highly enantioselective hydrophosphonylation of various aldehydes is described. Under the optimized reaction conditions, 5 mol% of the iron/camphor-based tridentate Schiff base complex [FeCl(SBAIB-d)]2 produces high yields (up to 99%) of α-hydroxy phosphonates in excellent enantioselectivities (up to 99%). The merits of this catalytic system are an easily synthesizable catalyst, inexpensive starting materials, practically simple aerobic reaction conditions, and low catalyst loading (5 mol%). Copyright
- Boobalan, Ramalingam,Chen, Chinpiao
-
supporting information
p. 3443 - 3450
(2013/12/04)
-
- Catalytic method of synthesis of phosphorus acids esters from zinc phosphide and alcohol
-
Ecologically safe effective catalytic method for preparing phosphorous and phosphoric acid esters by oxidation of zinc phosphide with oxygen in the solution of copper(II) halides in butanol at 50-70 C is developed. It is found that in the presence of Cu(II) chloride a mixture of dibutyl hydrogen phosphite and tributyl phosphate is formed, while at the catalysis with Cu(II) bromide tributyl phosphate is mainly obtained. Promoting action of hydrogen chloride on the reaction rate and yield of organophosphorus compounds is established. Optimal reaction conditions are found and redox mechanism of catalytic process is assumed.
- Polimbetova,Ibraimova,Borangazieva
-
p. 1081 - 1086
(2013/08/23)
-
- Organophosphorus chemistry without PCl3: A bridge from hypophosphorous acid to H-phosphonate diesters
-
A process for the conversion of hypophosphorous acid (H3PO 2, HPA) and alcohols into various H-phosphonate diesters [(RO) 2P(O)H] is described. The new reaction provides a missing bridge between HPA and important H-phosphonates, completely avoiding the use of PCl3. Nickel chloride or nickel on silica catalyze the oxidative phosphorylation of alkyl phosphinates with various alcohols or water. The reaction is atom economic and avoids the formation of waste products. The previous need for both chlorine and base is completely avoided. Esterification of hypophosphorous acid followed by reaction with another molecule of alcohol under the action of a nickel catalyst provides a green method for the preparation of H-phosphonates. This method entirely avoids the need for any stoichiometric chloride unlike those based on phosphorus trichloride. Copyright
- Fisher, Henry C.,Prost, Lucie,Montchamp, Jean-Luc
-
p. 7973 - 7978
(2014/01/06)
-
- Convenient preparation of long-chain dialkyl phosphates: Synthesis of dialkyl phosphates
-
Reaction of phosphorus oxychloride with a primary alcohol (1.8 equiv) and triethylamine (1.8 equiv) in toluene, followed by filtration and treatment with steam, gives dialkyl phosphates in good yield and essentially free from trialkyl phosphate contamination. Georg Thieme Verlag Stuttgart · New York.
- Aitken, R. Alan,Collett, Chris J.,Mesher, Shaun T. E.
-
scheme or table
p. 2515 - 2518
(2012/09/05)
-
- Synthesis of O,O-dialkyl 2-oxo-2-(4-(selenomorpho-linosulfonyl)phenylamino) ethylphosphonate
-
A series of O,O-dialkyl 2-oxo-2-(4-(seleomorpholinosulfonyl)phenylamino) ethy lphosphonate were synthesized by reactions of 2-chloro-N-(4- (seleomorpholino sulfonyl)phenyl)acetamide with dialkylphosphite in the presence of sodium hydride. The structure of all new compounds has been confirmed by 1H NMR,31P NMR, IR, Mass spectroscopy and elemental analyses. Copyright Taylor & Francis Group, LLC.
- Wang, Fang,Hu, Liming,Li, Xiaopeng,Xu, Xuemei,Du, Hongguang
-
scheme or table
p. 610 - 616
(2009/04/11)
-
- An efficient synthesis of O,O- di propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime and its analogues: A potential marine toxin
-
An efficient method for the synthesis of Ptychodiscus brevis toxin O,O- di n-propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime (TG-1) and its analogues has been developed using thermally stable and recyclable silica gel and Na2SO4 as a condensing agent and water scavenger, respectively. The compounds were evaluated against fish Rasbora daniconius by determining the LC50 and LC90 values. The results of biological evaluation showed that these compounds have high degree of toxicity. Copyright Taylor & Francis Group, LLC.
- Gupta, Arvind K.,Dubey,Parashar,Kaushik
-
scheme or table
p. 1892 - 1910
(2009/08/07)
-
- Process for making a plant growth regulator
-
A method for making a plant growth regulator includes the step of reacting vinyl chloride with a phosphorous reagent.
- -
-
Page/Page column 6
(2008/06/13)
-
- ORGANOPHOSPHORUS COMPOUND HAVING PHOSPHATE-PHOSPHONATE BOND, AND FLAME-RETARDANT POLYESTER FIBER AND FLAME-RETARDANT POLYURETHANE RESIN COMPOSITION EACH CONTAINING THE SAME
-
The present invention provides a phosphate-phosphonate compound which has a low volatility and a high phosphorus content, does not exert adverse influences on the physical properties of a product containing the phosphate-phosphonate compound as a material, and is recyclable and causes substantially no environmental load since a halogen atom such as a chlorine atom or a bromine atom is not included. A phosphorus compound containing a phosphate-phosphonate bond in one molecule and having a specific structure has a high flame retarding property. By using a phosphate-phosphonate compound as a flame retarding agent for a polyurethane or for a polyester, preferable plasticity and flame retarding property are obtained. Such a flame retardant agent exerts substantially no adverse influences on the physical properties of a polyurethane foam or a polyester fiber.
- -
-
Page/Page column 42
(2008/06/13)
-
- Rapid and high yield oxidation of phosphine, phosphite and phosphinite compounds to phosphine oxides, phosphates and phosphinates using hypofluorous acid-acetonitrile complex
-
The hypofluorous acid acetonitrile complex was used as a mild, rapid, and effective agent to oxidize a wide variety of phosphines, phosphites and phosphinites to the corresponding phosphine oxide, phosphate and phosphinate compounds.
- Peng, Weimin,Shreeve, Jean'Ne M.
-
p. 1054 - 1056
(2007/10/03)
-
- Electrocatalytic eco-efficient functionalization of white phosphorus
-
The novel eco-efficient methods to transform white phosphorus into the esters of phosphoric, phosphorous and phosphonic acids, tertiary phosphines and other organophosphorus compounds under conditions of electrochemical catalysis were elaborated. The mechanism of these processes was investigated using the method of cyclic voltammetry and preparative electrolysis.
- Budnikova, Yulia H.,Yakhvarov, Dmitry G.,Sinyashin, Oleg G.
-
p. 2416 - 2425
(2007/10/03)
-
- Reconsideration of the base-free batch-wise esterification of phosphorus trichloride with alcohols
-
Batch-wise esterification of phosphorus trichloride with different alcohols in the absence of base and cleavage of the reaction products by the HCl released in course of the reaction were reinvestigated. The role of the kind of alcohol, mixing order of reagents, temperature, time of reaction, and excursion of gaseous HCl in the proportional composition of the reaction products were studied. Considering the mechanism of esterification and cleavage of the products, the optimized conditions to retain the cleavage process and high-yield production of dialkyl hydrogen phosphonates were determined.
- Fakhraian,Mirzaei
-
p. 401 - 404
(2013/09/05)
-
- Oxidative alkoxylation of zinc phosphide in a butanolic solution of iron(III) chloride
-
Zinc phosphide in a butanolic solution of FeCl3 was oxidized by oxygen at 60 to 90°C into dibutyl phosphite (BuO)2HPO. The kinetics and mechanism of the oxidative alkoxylation of Zn3P 2 in the presence of FeCls
- Ibraimova,Polimbetova,Aleshkova,Borangazieva
-
p. 1265 - 1269
(2007/10/03)
-
- Cu-catalyzed oxidative phosphorylation of alkanols with white phosphorus and H2O2
-
Oxidative phosphorylation of alkanols with white phosphorus in the presence of catalytic amounts of CuCl2 has been effected. The reaction proceeds in the aqueous H2O2-HCl system exothermically to form dialkylphosphites and trialkylphosphates in a total yield of up to 35%. Conditions for selective synthesis of dialkylphosphites in moderate yield have been found.
- Trofimov, Boris,Timokhin, Boris,Gusarova, Nina,Kazantseva, Marina,Golubin, Alexander
-
p. 2385 - 2390
(2007/10/03)
-
- Non-calcemic, antiproliferative, transcriptionally active sulfur-containing analogs of 1α, 25-dihydroxy vitamin D3
-
Novel sulfur-containing analogs of 1α,25-dihydroxy vitamin D3are provided. These analogs are synthesized in a convergent manner by joining A-ring and C,D ring fragments. Each analog with 1α,3β-substituent stereochemistry shows a pharmacologically desirable combination of high antiproliferative and high transcriptional activities in vitro and also low calcemic activity in vivo.
- -
-
-
- Alkylene-bridged alkyl phosphonates
-
Halogen-free, oligomeric or polymeric, alkylene-bridged alkyl phosphonates having the general formula where n is a whole number of from 1 to 20; R1 and R5 are each C1-C6 alkyl; R2 and R4 are each C2-C10 alkyl and R3 is C2-C10 alkyl. The use of such phosphonates as, or in connection with, a flame-retardant (e.g. for polyurethane foams, resins and composites, epoxy resins, phenolic resins, paints, varnishes or textiles).
- -
-
-
- Chlorine free synthesis of organophosphorus compounds based on the functionalization of white phosphorus (P4)
-
Oxidative alkoxylations of P4 in toluene-alcohol solutions are studied. These reactions need oxygen, a catalyst (PdCl2, RuOHCl3, RuCl3) and a co-oxidant (CuCl2, NaNO2, FeCl3, 1,4-benzoquinone, NaBrO3). Trialkylphosphates (RO)3P(O) and dialkylphosphites (RO)2P(O)H are the major products of the reaction. Kinetic experiments concerning the rate of absorption of O2 during these reactions are also reported.
- Abdreimova, Rumiya R.,Akbayeva, Dina N.,Polimbetova, Gulshara S.,Caminade, Anne-Marie,Majoral, Jean-Pierre
-
p. 239 - 254
(2007/10/03)
-
- Synthesis of dialkyl phosphites and trialkyl phosphates by oxidation of sodium hypophosphite by copper(II) chloride
-
Sodium hypophosphite oxidazies in alcoholic solution of CuCl2 at 50-80 deg C to give dialkyl phosphite and trialkyl phosphate.The yield of trialkyl phosphate increases with decreasing molecular weight of the alcohol and reaches ca. 100percent for MeOH and EtOH.The optimal conditions were found, and the mechanism of oxidation of NaPH2O2 to (RO)2PHO and (RO)3PO by copper(II) chloride was studied.The reaction proceeds via the formation of alkyl hypophosphite and copper(II) complexes with alkyl hypophosphite and dialkyl phosphite, which undergo inner-sphere two-electron redox decomposition with the liberation of dialkyl phosphite and trialkyl phosphate, respectively.
- Dorfman, Ya. A.,Aleshkova. M. M.
-
p. 515 - 520
(2007/10/03)
-
- Electrosynthesis of aliphatic esters of phosphorus acids from white phosphorus in alcohol solutions, involving radical cations of phenothiazine and triarylamine
-
Aliphatic esters of phosphorus acids can be prepared from white phosphorus by electrolysis of emulsified white phosphorus in alcohol solutions of phenothiazine or triarylamine.
- Budnikova, Yu. G.,Kargin, Yu. M.
-
p. 504 - 507
(2007/10/03)
-
- ELECTROCHEMICALLY INDUCED PROCESSES IN THE FORMATION OF PHOSPHORUS ACID DERIVATIVES. 1. SYNTHESIS OF TRIALKYL PHOSPHATES FROM WHITE PHOSPHORUS
-
An electrochemical method, based on the joint action of nucleophilic and electrophilic reagents on P4, is proposed in order to utilize white phosphorus in the formation of the esters of phosphorus acids.The action of alkoxide ions on white phosphorus in an alcohol medium in the presence of iodine generated at the anode leads to the formation of phosphate esters.A scheme in which the intermediate products are dialkyl and trialkyl phosphites and the side product is dialkyl alkylphosphonate is proposed for the process.Key words: Phosphate esters, white phosphorus, electrosynthesis.
- Romakhin, A. S.,Budnikova, Yu. G.,Zaripov, I. M.,Kargin, Yu. M.,Nikitin, E. V.,et al.
-
p. 1031 - 1035
(2007/10/02)
-
- THE TITANIUM - MEDIATED TRANSESTERIFICATION OF PHOSPHOROUS ESTERS
-
Reactions of alcohols diesters in the presence of titanium tetraalkoxides results in a displacement of both or one ester functions by RO groups of an alcohol used.
- Froneman, M.,Modro, A.
-
p. 3327 - 3330
(2007/10/02)
-
- REACTION OF PHOSPHORUS OXYACID ESTERS WITH p-TOLUENESULFONIC ACID
-
The reaction of primary alkyl esters of phosphorus oxyacids with p-toluenesulfonic acid (TsOH) in refluxing solvents gave the corresponding p-toluenesulfonates (TsOR).We found that the secondary alkyl esters reacted with TsOH at lower temperature (r.t.-40 deg C) to afford TsORs in good yields.It is suggested that sulfonic acids may be useful for the selective dealkylation of mixed esters.Keywords-p-toluenesulfonic acid; p-toluenesulfonate; trialkyl phosphate; trialkyl phosphite; dialkyl phenylphosphonate; transesterification; dealkylation; solvolysis.
- Nitta, Yoshihiro,Arakawa, Yasushi,Ueyama, Naoto
-
p. 2710 - 2718
(2007/10/02)
-