- On the tautomerism of secondary phosphane oxides
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The tautomeric behaviour of five secondary phosphane oxides (SPOs) with different electronic properties has been investigated by NMR and IR spectroscopy, density functional theory calculations and X-ray structural analysis. Proof is given that only with s
- Christiansen, Andrea,Li, Chuanzhao,Garland, Marc,Selent, Detlef,Ludwig, Ralf,Spannenberg, Anke,Baumann, Wolfgang,Franke, Robert,Boerner, Armin
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- New synthesis of trimethylsilyl esters of phosphorus(III) acids
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Abstract: A novel synthetically important reaction has been developed for the quick, convenient, and high-yield preparation of trimethylsilyl esters of phosphorus(III) acids, synthetically valuable Michaelis–Arbuzov reaction precursors. Commercially and synthetically available initial compounds used are derivatives of propan-2-ol phosphorylated in the second position capable of long-term storage and available silylating reagents: hexamethyldisilazane, bis(trimethylsilyl)acetamide, and diethyl(trimethylsilyl)amine. Also, a stepwise reaction scheme of the starting compounds with silylating reagents has been proposed. Graphic abstract: [Figure not available: see fulltext.].
- Morgalyuk, Vasily,Strelkova, Tatyana,Brel, Valery
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p. 1993 - 1997
(2019/11/13)
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- Ambident reactivity of chloro(dialkylamino)-(diphenylphosphinoyl)methanes
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The chemical properties of chloro(dialkylamino)(diphenylphosphinoyl) methanes have been studied using the simplest compound of this series, chloro(dimethylamino)(diphenylphosphinoyl)methane, as an example. Chloro- (dimethylamino)(diphenylphosphinoyl)methane shows ambident reactivity when reacting with electrophiles and nucleophiles depending on coreactant nature, it behaves as either electrophilic substrate or phosphorus nucleophile. This fact can be explained by its dissociation in solutions with both C-Cl bond cleavage to give (dimethylamino)- (diphenylphosphinoyl)methyl cation and Cl- anion and C-P bond cleavage to form chloro(dimethylamino)methyl cation and diphenylphosphinite anion. The capability of chloro(dimethylamino) (diphenylphosphinoyl)methane to produce spontaneously Ph2PO-anion allows us to recommend application in organic and organophosphorus synthesis as a synthetic equivalent (synthon) of diphenylphosphinite anion.
- Morgalyuk, Vasilii Petrovich,Strelkova, Tat'Yana Vladimirovna,Nifant'Ev, Eduard Eugenievich
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- Synthesis of polyfunctionalized methylphosphine oxides
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N,N-Dialkylamino(diphenylphosphoryl)chloromethanes, a new type of organophosphorus compounds, were synthesized. On dissolving in polar and low polar solvents, N,N-dialkylamino(diphenylphosphoryl)chloromethanes dissociate spontaneously with the P - C bond cleavage to form the diphenylphosphinite anion Ph2PO-. This was confirmed by the reaction of N,N-dimethylamino(diphenylphosphoryl)chloromethane with electrophilic substrates to form the corresponding addition or substitution products of Ph 2PO-. The capability of spontaneous generating the diphenylphosphinite anion considers accessible N,N- dimethylamino(diphenylphosphoryl)chloromethane as a synthetic equivalent of the diphenylphosphinite anion.
- Morgalyuk,Strelkova,Nifant'Ev
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p. 380 - 385
(2013/06/05)
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- ORGANISCHE PHOTOCHEMIE XLIII. Diphenylphosphinigsaeure, Hetero- und Carbocyclen aus ortho-?-funktionalisierten Aroyl-Diphenylphosphinen durch UV-Bestrahlung in Loesung
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New aroyl diphenyl phosphines (1f-i) substituted with ?-functions in ortho-positions of the aroyl part have been synthesized and photolyzed in benzene.In two cases (1h and i) 1.2- and 1.4-addition products of photochemically formed diphenylphosphinous acid (3) with acetone or phenanthrene quinone (8) are isolated in 59percent yields.Moreover, in neighboring-group participations aroyl radicals formed by competing α-cleavages of 1g-i yield 5- and 6-membered hetero- and carbocycles: xanthone (6), 3,3'-dimethoxy 3,3'-diphthalidyl (7), or the phenanthrene derivative 9, respectively.
- Dankowski, Manfred,Praefcke, Klaus
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p. 131 - 140
(2007/10/02)
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- ORGANISCHE PHOTOCHEMIE, XXXVII PHOTOFRAGMENTIERUNG EINES AROYLDIPHENYLPHOSPHINS IN DIPHENYLPHOSPHINIGSAEURE
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UV irradiation of the new -diphenylphosphine (1) in benzene leads to products via α-cleavage (3) and photosubstitution (4) as well as to the phosphine oxide 2.The genesis of 2 is interpreted by photoinduced 1,2-transfer of oxygen from the carbonyl function onto the phosphorous atom in 1, a novel fragmentation under formation of the phosphine oxide 6 and its addition to aceton.The structure of 2 is based on among other methods X-ray analysis.
- Dankowski, Manfred,Praefcke, Klaus,Lee, Jung-Si,Nyburg, S. C.
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p. 359 - 364
(2007/10/02)
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Phosphinous acid esters of the type (R2PO)nER′4-n (E = Si, Ge, Sn) are prepared by three different methods: 1. reaction of the alkali-phosphinites with R′3ECl, 2. reaction of the sec-phosphine oxides with organo
- Issleib,Walther
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p. 375 - 386
(2007/10/05)
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