- New look into the synthesis of polyhalogenoarylphosphanes
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The present study shows new aspects of the synthesis of polyhalogenoarylphosphanes. The sterically hindered anions Ph(R)P-Y- (1a-c, Y = O, lone pair; R = Ph, But) have been used to show the complexity of the reaction between phosphorus nucleophiles and hexahalogenobenzenes or 9-bromofluorene (E3). The Ph(But)P-O-(1a) anion reacts with hexachlorobenzene (E1), hexafluorobenzene (E2), or E3 to give Ph(R)P(O)X (4a-c, X = F, Cl, Br) with the release of the corresponding carbanion as a nucleofuge, followed by side reactions. In contrast, the lithium phosphides Ph(R)PLi (1b,c) react with hexahalogenobenzenes to give the corresponding diphosphanes 5a,b as the main product and traces of P-arylated products, i.e., Ph(R)P-C6X 5 (10a,b, X = Cl, F). Unexpectedly, Ph(But)PLi (1b) reacts with an excess of 9-bromofluorene to give only halogenophosphane Ph(Bu t)P-X. Taylor & Francis Group, LLC.
- Nycz, Jacek E.
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experimental part
p. 2605 - 2612
(2010/08/06)
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- Process for preparing tertiary phosphines
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The invention relates to a process for synthesizing tertiary phosphines by reacting halophosphines with organomagnesium compounds in the presence of copper compounds and optionally of salts.
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- P/O ligand systems: Facile synthesis, structure, and catalytic tests of 2′-phosphanyl-1,1′-bipheny 1-2-ols and 2′-phosphanyl-1,1′-binaphthyl-2-ols
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A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-l,1′-binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveal the presence of P...H-O bridging bonds in the more basic /BuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearance of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanylphenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands. WILEY-VCH Verlag GmbH, 1997.
- Kadyrov, Renat,Heinicke, Joachim,Kindermann, Markus K.,Heller, Detlef,Fischer, Christine,Selke, Ruediger,Fischer, Axel K.,Jones, Peter G.
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p. 1663 - 1670
(2007/10/03)
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- o-Hydroxyarylphosphines and diphosphines: Metallation-rearrangement versus P-O reduction of o-halogenoaryloxyphosphines by sodium
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o-Bromo-and o-chloroaryloxyphosphines 1 may react with sodium in two competing ways: (i) metal halogen exchange followed by rapid intramolecular 1,3-rearrangement to give sodium o-hydroxylato-arylphosphines 2, later converted to their OSiMe3 de
- Heinicke, Joachim,Kadyrov, Renat
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p. 131 - 137
(2007/10/03)
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- P/O ligand systems: Synthesis, reactivity, structure of tertiary o-phosphanylphenol derivatives
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Reactions of C,O-dilithium reagents 1 (M = M′ = Li) or C,O-lithium-sodium reagents 1 (M = Li, M′ = Na) with chlorophosphanes afford C,O-disubstitution products 2 or phosphanylphenolates 3 which are treated subsequently with ClSiMe3 to give 4-me
- Heinicke, Joachim,Kadyrov, Renat,Kindermann, Markus K.,Koesling, Manuela,Jones, Peter G.
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p. 1547 - 1560
(2007/10/03)
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