- Novel application of simple molybdates: Catalytic hydrolysis of an organophosphate neurotoxin under mild aqueous conditions
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A novel protocol for hydrolyzing phosphonothioate neurotoxins has been developed that uses a readily available, inexpensive and non-toxic molybdate (MoO42?). The target organophosphate is O,S-diethylphenyl phosphonothioate (1), a mod
- Kuo, Louis Y.,Dill, Kristina M.,Shari'ati, Yusef A.,Bright, Emily K.,McCormick, Theresa
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- METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
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PROBLEM TO BE SOLVED: To provide a method whereby, a phosphate compound selected from the group consisting of orthophosphoric acid, phosphonic acid, phosphinic acid, and anhydrides of them is used as raw material and, by one stage reaction, a corresponding phosphoester compound is produced. SOLUTION: To an aqueous solution of a phosphate compound, added is an organic silane or siloxane compound having an alkoxy group or an aryloxy group, and the mixture is subjected to a heating reaction, thereby producing a corresponding phosphoester compound without requiring a catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0023; 0029-0031
(2021/09/27)
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- Selective esterification of phosphonic acids
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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.
- Brodzka, Anna,Koszelewski, Dominik,Ostaszewski, Ryszard,Trzepizur, Damian
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- Selective hydrolysis of phosphorus(v) compounds to form organophosphorus monoacids
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An azide and transition metal-free method for the synthesis of elusive phosphonic, phosphinic, and phosphoric monoacids has been developed. Inert pentavalent P(v)-compounds (phosphonate, phosphinate, and phosphate) are activated by triflate anhydride (Tf2O)/pyridine system to form a highly reactive phosphoryl pyridinium intermediate that undergoes nucleophilic substitution with H2O to selectively deprotect one alkoxy group and form organophosphorus monoacids.
- Ash, Jeffrey,Cordero, Paula,Huang, Hai,Kang, Jun Yong
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p. 6007 - 6014
(2021/07/21)
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- B(C6F5)3-catalyzed O-H insertion reactions of diazoalkanes with phosphinic acids
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A highly efficient base-, metal-, and oxidant-free catalytic O-H insertion reaction of diazoalkanes and phosphinic acids in the presence of B(C6F5)3has been developed. This powerful methodology provides a green approach towards the synthesis of a broad spectrum of α-phosphoryloxy carbonyl compounds with good to excellent yields (up to 99% yield). The protocol features the advantages of operational simplicity, high atom economy, practicality, easy scalability and environmental friendliness.
- Jiang, Jun,Zhang, Xinzhi,Zhang, Yangyang,Zhao, Jincheng
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supporting information
p. 5772 - 5776
(2021/07/12)
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- Synthesis of phosphonates from phenylphosphonic acid and its monoesters
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Possibilities for the mono- and diesterification of phenylphosphonic acid were evaluated considering the microwave(MW)-assisted direct esterification, and the alkylating esterification. It was found that regarding the monoesterification, the reaction with 15-fold alcohol excess in the presence of [bmim][BF4] additive utilizing MWs is superior than the approach by alkylation. At the same time, for the conversion of the monoester intermediate to the diester, the reaction with alkyl halides in the presence of triethylamine as the base, again under MW irradiation, was found to be the method of choice. Phosphonates with both identical and different alkoxy groups were made available.
- Henyecz, Réka,Kiss, Adrienn,Mórocz, Virág,Kiss, Nóra Zsuzsa,Keglevich, Gy?rgy
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supporting information
p. 2642 - 2650
(2019/08/08)
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- Cu(II)/Proline-Catalyzed Reductive Coupling of Sulfuryl Chloride and P(O)-H for P-S-C Bond Formation
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A considerably improved method for the Cu-catalyzed coupling of sulfuryl chloride with P(O)-H was described. Using commercially available l-proline as the ligand decreased the precatalyst loading, broadened the substrate scope and greatly promoted the efficiency of the coupling reaction. Moreover, gram-scale preparation, easy-to handle and recyclable catalyst featured this transformation.
- Zhang, Xinghua,Wang, Dungai,An, Duo,Han, Boshi,Song, Xiang,Li, Liang,Zhang, Gaoqi,Wang, Lixian
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supporting information
p. 1532 - 1537
(2018/02/10)
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- Phosphonamide pyrabactin analogues as abscisic acid agonists
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A four step synthesis towards novel phosphonic pyrabactin analogues is presented. Via a stomatal closure and germination assay, the ability of the analogues to selectively induce the ABA-signaling pathway was demonstrated.
- Van Overtveldt,Heugebaert,Verstraeten,Geelen,Stevens
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p. 5260 - 5264
(2015/05/13)
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- Phosphinate ruthenium complexes
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Provided herein are ruthenium complexes of Formula I, and processes of preparation thereof. Also provided are methods of their use as a metathesis catalyst.
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Page/Page column 56; 57
(2015/09/23)
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- Phosphonothioate hydrolysis by molybdocene dichlorides: Importance of metal interaction with the sulfur of the thiolate leaving group
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The metallocene bis(cyclopentadienyl)molybdenum(IV) dichloride Cp 2MoCl2 hydrolyzes O,S-diethyl phenylphosphonothioate (1) with only P-S scission to yield a phosphonate under mild aqueous conditions. In terms of degrading phosphonoth
- Kuo, Louis Y.,Baker, Devon C.,Dortignacq, Adria K.,Dill, Kristina M.
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p. 4759 - 4765
(2013/09/24)
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- Synthesis of phosphaisocoumarins through rhodium-catalyzed cyclization using alkynes and arylphosphonic acid monoesters
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A rhodium-catalyzed cyclization using alkynes and arylphosphonic acid monoesters for the synthesis of phosphaisocoumarins is reported. A number of arylphosphonic acid monoesters were selectively cyclized in high yields with functional group tolerance. In addition, unsymmetrical alkynes are applied in high regioselectivity.
- Seo, Jungmin,Park, Youngchul,Jeon, Incheol,Ryu, Taekyu,Park, Sangjune,Lee, Phil Ho
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supporting information
p. 3358 - 3361
(2013/07/26)
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- Ruthenium-catalyzed C-H activation/cyclization for the synthesis of phosphaisocoumarins
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An efficient and cost-effective ruthenium-catalyzed oxidative cyclization of phosphonic acid monoesters or phosphinic acids with alkynes has been developed for the synthesis of a wide range of phosphaisocoumarins in good to excellent yields under aerobic conditions. A multitude of arylphosphonic acid monoesters and arylphosphinic acids having electron-donating and -withdrawing groups were oxidatively cyclized. Various diarylacetylenes, dialkylacetylenes, and alkylarylacetylenes effectively underwent the ruthenium-catalyzed oxidative cyclization. A substrate possessing benzoic acid as well as a phenylphosphonic monoester moiety was smoothly cyclized with hex-3-yne to afford a compound having both isocoumarin and phosphaisocoumarin moieties. Alkenylphosphonic monoester afforded phosphorus 2-pyrone through oxidative cyclization with alkyne. Competition experiments between diaryl- and dialkylalkynes and between diarylacetylenes having p-methoxy and p-chloro groups gave results which showed that the present oxidative cyclizations were not affected by the electronic effects of alkynes. Mechanistic studies revealed C-H bond metalation to be the rate-limiting step.
- Park, Youngchul,Jeon, Incheol,Shin, Seohyun,Min, Jiae,Lee, Phil Ho
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p. 10209 - 10220
(2013/11/06)
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- Design, synthesis and evaluation of new α-nucleophiles for the hydrolysis of organophosphorus nerve agents: Application to the reactivation of phosphorylated acetylcholinesterase
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A series of new α-nucleophiles including oximes and amidoximes have been synthesized, and their ability to efficiently and selectively cleave the P-S bond of organophosphorus nerve agents has been evaluated. The relationship between the chemical structure
- Saint-Andre, Geraldine,Kliachyna, Maria,Kodepelly, Sanjeevarao,Louise-Leriche, Ludivine,Gillon, Emilie,Renard, Pierre-Yves,Nachon, Florian,Baati, Rachid,Wagner, Alain
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experimental part
p. 6352 - 6361
(2011/09/19)
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- A HTS assay for the detection of organophosphorus nerve agent scavengers
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A new pro-fluorescent probe aimed at a HTS assay of scavengers is able to selectively and efficiently cleave the P-S bond of organophosphorus nerve agents and by this provides non-toxic phosphonic acid has been designed and synthesised. The previously described pro-fluorescent probes were based on a conventional activated P-Oaryl bond cleavage, whereas our approach uses a self-immolative linker strategy that allows the detection of phosphonothioase activity with respect to a non-activated P-Salkyl bond. Further, we have also developed and optimised a high-throughput screening assay for the selection of decontaminants (chemical or biochemical scavengers) that could efficiently hydrolyse highly toxic V-type nerve agents. A preliminary screening, realised on a small α-nucleophile library, allowed us to identify some preliminary "hits", among which pyridinealdoximes, α-oxo oximes, hydroxamic acids and, less active but more original, amidoximes were the most promising. Their selective phosphonothioase activity has been further confirmed by using PhX as the substrate, and thus they offer new perspectives for the synthesis of more potent V nerve agent scavengers.
- Louise-Leriche, Ludivine,Paunescu, Emilia,Saint-Andre, Geraldine,Baati, Rachid,Romieu, Anthony,Wagner, Alain,Renard, Pierre-Yves
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experimental part
p. 3510 - 3523
(2010/07/06)
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- Resolution of chiral phosphate, phosphonate, and phosphinate esters by an enantioselective enzyme library
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An array of 16 enantiomeric pairs of chiral phosphate, phosphonate, and phosphinate esters was used to establish the breadth of the stereoselective discrimination inherent within the bacterial phosphotriesterase and 15 mutant enzymes. For each substrate,
- Nowlan, Charity,Li, Yingchun,Hermann, Johannes C.,Evans, Timothy,Carpenter, Joseph,Ghanem, Eman,Shoichet, Brian K.,Raushel, Frank M.
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p. 15892 - 15902
(2007/10/03)
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- Interesting by-products in the synthesis of chiral α- aminophosphinates from enantiopure sulfinimines
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A new reaction of enantiopure sulfinimines and ethyl phenylphosphinate is given. Several unexpected products were isolated and identified, their mechanism of formation is proposed.
- Szabó, Andrea,Jászay, Zsuzsa M.,T?ke, László,Petneházy, Imre
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p. 1991 - 1994
(2007/10/03)
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- Product selectivities and third-order rate laws for solvolyses of ethyl phenylphosphonochloridate in aqueous alcohols
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Rate constants and product selectivities (S) for solvolyses of ethyl phenylphosphonochloridate [PhP(=O)OEtCl] in aqueous ethanol and methanol at 0°C are reported; S = ([ester product]/[acid product]) x ([water]/[alcohol solvent]). The results show trends
- Bentley, T. William,Ebdon, David N.
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p. 759 - 763
(2007/10/03)
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- Intramolecular Hydrogen-bond Participation in Phosphonylammonium Salt Formation
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equation presented A series of phosphonochloridates and phosphonyl dichlorides were prepared, and their reactivity with triethylamine has been investigated using 31P NMR spectroscopy. Taken together these studies provide evidence that an intram
- Smith III, Amos B.,Ducry, Laurent,Corbett, R. Michael,Hirschmann, Ralph
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p. 3887 - 3890
(2007/10/03)
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- Reactions of aryl sulfides and phosphorus(V) esters of thiols with acidic hydrogen peroxide
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Oxidations of sulfides and phosphorus(V) esters of thiols by H2O2 are catalyzed by H2SO4 and HClO4. Sulfides are 4-ZC6H4SMe, 1a-1e, respectively, Z = MeO, Me, H, Cl, NO2; PhSCH2CH2Cl, 2, Ph2S, 3, and the esters are Ph(R)PO·SEt, 4a, 4b, R = Ph, EtO. Electron donation by Z moderately accelerates reaction, but the sulfides are much more reactive than the esters. Reactions are first order in H2O2 and substrate, and second-order rate constants, k2, in H2SO4 are related to excess acidity, X. Plots of log 'k2 against X have slopes in the range 0.61-0.85. Rate constants are similar for given concentrations of H2SO4 and HClO4, except that with greater than 50 wt.% H2SO4 peroxymonosulfuric acid is formed and the observed rate constants then increase. Methanesulfonic acid is a less effective catalyst than the mineral acids. Oxidations of the sulfides are also catalyzed by strongly acidic ion-exchange resins.
- Bunton,Foroudian,Gillitt,Kumar
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p. 895 - 902
(2007/10/03)
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- Oxidative hydrolysis of phosphorus(V) esters of thiols by peroxymonosulfate ion. Reactions of peroxymonosulfate ion with phosphorus(V) esters of thiols
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Peroxymonosulfate ion, HSO5-, as Oxone, readily converts phosphorus(V) esters of thiols into the phosphorus(V) and sulfonic acids. The esters were Ph2PO·SC6H4R(p) with R=MeO (1a), Me (1b), H (1c), Cl (1d) and NO2 (1e), (EtO)2PO·SPh (2), Ph2OI·SEt (3) and PhPO(OEt)SEt (4). Reactions are first order in each reactant and second-order rate constants, k2, for 1a-e fit the Hammett equation with ρ=-0.46. The rate constants increase markedly with increasing water content of H2O-MeCN, the activation enthalpies are low and the entropies are negative. Despite the low value of -ρ, these esters are much less reactive than thiol ethers, but the rate constants of reactions of these compounds and acyl thiols qualitatively follow the ionization potentials of the ethers and the esters.
- Blasko, Andrei,Bunton, Clifford A.,Kumar, Anurag
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p. 427 - 434
(2007/10/03)
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- Fragmentation of a phenylphosphonamidic acid as a new technique for the generation of phenyl dioxophosphorane
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N-(1-Adamantyl) phenylphosphonamidic acid (3), an easily prepared solid, on heating in toluene or 1,2-dichloroethane gave the crystalline adamantylamine salt of the anhydride PhP(O)(NHAd)-O-PPh(O)(OH). The mechanism is proposed to involve first the fragmentation of 3 to form phenyl dioxophosphorane, PhPO2, which then acts as a phosphorylating agent to unreacted 3. This mechanism was supported by the observation of first-order kinetics for the consumption of 3. When the phosphonamidic acid was fragmented in the presence of an alcohol, the intermediate PhPO2 was trapped as the monoalkyl phenylphosphonate. The OH groups on the surface of silica gel were also phosphonylated by PhPO2. The acidic OH group of a phosphoric acid monoester (thymyl phosphate) was phosphonylated to give Thy-O-P(O)(OH)-O-PPh(O)(OH). It is concluded from this study that N-(1-adamantyl) phenylphosphonamidic acid is a useful precursor of phenyl dioxophosphorane, which can perform valuable phosphonylation operations.
- Quin, Gyoengyi Szakal,Jankowski, Stefan,Quin, Louis D.
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- Kinetic Study on the Alkaline Hydrolysis of Some Tetracoordinate PV Esters of 2,4-Dinitrophenol
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The alkaline hydrolysis of 2,4-dinitrophenyl esters of benzylphosphinic, benzylphosphonic and benzylphosphonamidic acid does not proceed through a carbanion-promoted dissociative mechanism, a possible alternative pathway to the usual SN2(P) process; this is a further indication of the clear preference for associative displacement at phosphorous.
- Cevasco, Giorgio,Thea, Sergio
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p. 1103 - 1106
(2007/10/02)
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- Use of Carbohydrate Derivatives for Studies of Phosphorus Stereochemistry. Part 8. Preparation and Some Reactions of 1,3,2-Oxazaphospholidine-2-ones and -2-thiones derived from 2-Deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose
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The four cyclic phosphorus esters from the reaction of MePSCl2 with 2-deoxy-3,4,6-tri-O-methyl-2-methylamino-D-glucopyranose (1) have been separated with difficulty, and structures assigned.Ring-opening of the isomers and subsequent detachment of the chir
- Hall, C. Richard,Inch, Thomas D.,Pottage, Colin,Williams, Nancy E.,Campbell, Malcolm M.,Kerr, Patrick F.
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p. 1967 - 1975
(2007/10/02)
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- SILICON-PHOSPHORUS ANALOGIES. PARTICIPATION OF EXTERNAL NUCLEOPHILES TO ACTIVATED PROCESSES OF RACEMIZATION AND HYDROLYSIS OF CHLOROPHOSPHONO DERIVATIVES
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Kinetic and stereochemical studies show nucleophilic assistance by dimethylformamide (DMF), dimethylacetamide (DMA), hexamethylphosphotriamide (HMPT) and N-methylimidazole (NMI) in racemization and solvolysis of menthylchloro(phenyl)phosphonate, 1a, and O-ethylchloro(phenyl)thiophosphonate, 2.Similar orders of nucleophilic reactivity (Nu = NMI >> HMPT > DMF> DMA), and identical rate laws (vrac = k 2 and vH2O = k') are consistent with a common mechanism, governed by entropy (-60 u.e/= -40 u.e.).Analogies between reaction mechanisms at silicon and phosphorus are clearly evidenced.A two step process, involving rate-determining attack on a pentacoordinate complex is discussed.
- Corriu, R. J. P.,Lanneau, G. F.,Leclercq, D.
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p. 1617 - 1626
(2007/10/02)
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- Photoreduction and Photoarylation of O-Ethyl S-n-Propyl Phenylphosphonothioate
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U.v. irradiation (254 nm) of O-ethyl S-n-propyl phenylphosphonothioate (1) in EtOH leads to a rapid photoreductive cleavage of the phosphorus-sulphur (Φ = 0.14) or the sulphur-carbon (Φ = 0.05) bond, as evidenced by the formation of O-ethyl phenylphosphinate, n-propanethiol, O-ethyl phenylphosphonothioic acid, and propane as the major products.The concomitant photo-oxidation of EtOH to acetaldehyde is also observed.The rate of photoreduction of (1) is independent of the hydrogen-donor capacity of the solvent (MeOH, EtOH, or PriOH).Hence the reaction proceeds without prior hydrogen abstraction, probably by direct homolysis of the excited state of (1).In accordance with this, in situ spin-trapping experiments show the intermediacy of the phosphonyl radical EtO(Ph)P(O).Sensitizers with a triplet energy 80 kcal mol-1 sensitize the photoreduction of (1).Sensitization by aromatic hydrocarbons, e. g. benzene, in found to be complicated by simulataneous photoarylation of (1), which leads to the formation of O-ethyl diphenylphosphinate.
- Benschop, Hendrik P.,Konings, Cornelis A. G.,Platenburg, Dominique H. J. M.,Deen, Rudolf
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p. 198 - 205
(2007/10/02)
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