358-74-7Relevant academic research and scientific papers
Direct, oxidative halogenation of diaryl- or dialkylphosphine oxides with (dihaloiodo)arenes
Eljo, Jasmin,Murphy, Graham K.
supporting information, p. 2965 - 2969 (2018/06/30)
The oxidative halogenation of diaryl- or dialkylphosphine oxides with the hypervalent iodine reagents (difluoroiodo)toluene (p-TolIF2, 1) and (dichloroiodo)benzene (PhICl2, 2) is reported. Phosphoric fluorides could be recovered in 32–75% yield, or they could be trapped with EtOH to give the corresponding phosphinate in typically good yield. Phosphoric chlorides were not readily isolable, and were trapped with alcohol and amine nucleophiles, giving diaryl- or dialkylphos-phinates and phosphinamides in up to 90% yield.
Diethyl fluoronitromethylphosphonate: Synthesis and application in nucleophilic fluoroalkyl additions
Opekar, Stanislav,Pohl, Radek,Beran, Pavel,Rulisek, Lubomir,Beier, Petr
supporting information, p. 1453 - 1458 (2014/04/03)
Diethyl fluoronitromethylphosphonate (3), a previously unknown compound, was synthesized by electrophilic fluorination of diethyl nitromethylphosphonate with Selectfluor. Base-induced decomposition of 3 was studied by NMR spectroscopy, which identified diethyl fluorophosphate and fluoronitromethane as the main decomposition products. C H acidities [pKa values in dimethyl sulfoxide (DMSO)] of 3, 1-fluoro-1-phenylsulfonylmethanephosphonate (1; McCarthy's reagent), tetraethyl fluoromethylenebisphosphonate (2), and some nonfluorinated phosphonates were computed, and a good correlation between calculated and experimental pKa values was found. The calculated C-H acidities increased in the sequence 2a,b-unsaturated carbonyl compounds, sulfones, and nitro compounds allowed access to variously modified diethyl 1-fluoro-1-nitrophosphonates.
Synthetic and mechanistic aspects of halo-F-methylphosphonates
Flynn, Richard M.,Burton, Donald J.
experimental part, p. 815 - 828 (2011/10/08)
The synthesis of a variety of new halo-F-methylphosphonates has been achieved by a Michaelis-Arbuzov type reaction between a halo-F-methane and a trialkyl phosphite. This synthesis has proved to be of wide scope and utility for the high yield preparation of a number of heretofore unknown compounds. The 1H, 19F, 13C and 31P NMR spectroscopic properties are reported in detail. The mechanism for the formation of bromodifluoromethylphosphonates has been shown to proceed through the intermediacy of difluorocarbene:CF2. The phosphonate products have been shown to react with a wide variety of reagents. Fluoride and alkoxide ions react by attack at phosphorus with cleavage of the carbon-phosphorus bond and formation of [:CF2] from the bromodifluoromethylphosphonates and the CFBr2- anion from the dibromofluoromethylphosphonates. Iodide ion and tertiary phosphines react by attack at the ester carbon to give stable phosphonate salts. Hydrolysis of the phosphonate esters with 50% aqueous HCl gives the expected phosphonic acids. Trimethylsilyl bromide attacks phosphoryl oxygen to afford the bis(trimethylsilyl) esters.
Interaction of α,α-difluoroazides with trivalent phosphorus compounds and triphenylantimony
Lermontov,Polivanova,Shkavrov
experimental part, p. 1646 - 1651 (2011/02/18)
α,α-Difluoroazides react with triphenylantimony and various compounds of trivalent phosphorus according to the oxidative fluorination scheme. In the case of trivalent phosphorus compound the primary products are phosphazenes, phosphazides or difluorophosphoranes that may undergo further transformations to the corresponding fluorine derivatives of pentavalent phosphorus. Pleiades Publishing, Ltd., 2010.
Inorganic anionic oxygen-containing α-nucleophiles - Effective acyl group acceptors: Hydroxylamine ranks first among the α-nucleophile series
Simanenko,Popov,Prokop'eva,Karpichev,Savelova,Suprun,Bunton
, p. 1286 - 1298 (2007/10/03)
Comparative analysis of the nucleophilicity of inorganic oxygen-containing α-nucleophiles (hydroxylamine and ClO-, BrO--, HOO--, NH2O-, and F- ions) covering the pKa range from -2 to 13.81 toward 4-nitrophenyl esters (4-nitrophenyl acetate, 4-nitrophenyl p-toluenesulfonate, diethyl 4-nitrophenyl phosphate, ethyl 4-nitrophenyl ethylphosphonate, and 4-nitrophenyl dimethylcarbamate) in water at 25°C (ionic strength μ 1.0, KCl) was performed in terms of the extrathermodynamic Brosted relation. It was found for the first time that hydroxylamine anion ranks first among the series of α-nucleophiles. It is more reactive than HOO- ion with respect to 4-nitrophenyl acetate (by a factor of ～8), 4-nitrophenyl p-toluenesulfonate (by a factor of ～4) and 4-nitrophenyl dimethylcarbamate (by a factor of ～10). The nucleophilicities of HOO- and NH 2O- ions toward diethyl 4-nitrophenyl phosphate and ethyl 4-nitrophenyl ethylphosphonate are comparable. Taking into account that neutral hydroxylamine exhibits an anomalously high reactivity, as compared to not only common organic but also inorganic α-nucleophiles, it may be regarded as a unique α-nucleophile. Both neutral hydroxylamine and its anion as O-nucleophiles ensure high rates of acyl group transfer throughout a wide range of pH.
A facile conversion of thio- and selenophosphoric acids and their derivatives into fluoridates by means of reaction with silver fluoride
Chworos, Arkadiusz,Wozniak, Lucyna A.
, p. 9337 - 9340 (2007/10/03)
Treatment of numerous thio- or selenophosphorus acids with aqueous silver fluoride in CHCl3 at room temperature results in clean formation of the corresponding fluoridates. Analogous results were obtained with other phosphorothio (seleno)ates such as esters, amidates, or halides.
Reaction of Triethyl Phosphite with Internal Perfluoroolefins and Their Aza Analogs
Rogoza,Furin
, p. 753 - 760 (2007/10/03)
Treatment of perfluoro(2-methylpent-2-ene) with triethyl phosphite gave triethoxydifluorophosphorane and diethyl perfluoro(1-ethylidene-2-methylpropenyl)phosphonate (the latter was also obtained by reaction of triethyl phosphite with perfluorotrimethylallene), while the reactions with other unsaturated perfluorinated compounds involved, together with the Arbuzov reaction, replacement of fluorine at the double bound by an ethyl group with perfluoro(1-ethylcyclohex-1-ene) and by an ethoxy group with perfluoro-(5-azanon-4-ene), perfluoro(1-azacyclohex-1-ene), and perfluoro(3-azapent-2-ene). The reactions pathways and 1H, 13C, 19F, and 31P NMR data are discussed.
New General Synthesis of Organophosphorus P-F Compounds via Reaction of Azolides of Phosphorus Acids with Acyl Fluorides: Novel Route to 2-Deoxynucleosidyl Phosphorofluoridates and Phosphorodifluoridates
Dabkowski, Wojciech,Michalski, Jan,Wasiak, Jacek,Cramer, Friedrich
, p. 817 - 820 (2007/10/02)
Tetra- and tri-coordinate P-N-imidazole derivatives and their structural analogous react smoothly with acyl fluorides to give the corresponding P-F compounds an almost quantitative yield.This method has been successfully applied to produce 2-deoxynucleosidyl phosphorofluoridates and phosphorodifluoridates.
REACTION OF PERFLUOROISOBUTYLENE AND PERFLUOROPROPYLENE WITH N-TRIMETHYLSILYLPHOSPHAZENES
Lermontov, S. A.,Velikokhat'ko, T. N.,Martynov, I. V.
, p. 2582 - 2584 (2007/10/02)
Perfluoroisobutylene and perfluoropropylene react with N-trimethylsilylphosphazenes to give perfluoroalkenylphosphazenes R3P=N-CF=CX-CF3 (R=AlkO, NR2, X=F, CF3).The corresponding dialkyl fluorophosphates (AlkO)2P(O)F, were obtained upon the pyrolysis of the alkoxyphosphazenes.
TRANSFORMATION OF ORGANOPHOSPHORUS S-TRIFLUOROMETHYLTHIOATES RR'P(O)SCF3 INTO FLUORIDES RR'P(O)F. STEREOCHEMICAL ASPECTS OF THIOCARBONYL FLUORIDE EXTRUSION
Lopusinski, Andrezej
, p. 383 - 390 (2007/10/02)
The stereochemical course of the thermal or by nucleophiles catalyzed extrusion reaction of thiocarbonyl fluoride from two diastereomeric (6) and optically active (10) organophosphorus S-trifluoromethylthioates has been investigated.To explain the observed retention of configuration at phosphorus in fluoridates 7 formed in the thermal reactions, a four center transition state for such reactions has been proposed.The lack of the stereoselectivity in the catalyzed reactions of 6, and the observed racemization of the final product 11 are briefly discussed.
