- A CATALYST FOR THE CARBONYLATION OF ALKENES
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The present application relates to a metal complex of Formula (I) and a catalyst composition for the carbonylation of alkenes comprising the metal complex, wherein the metal is a group 10 element such as palladium, platinum or nickel, and the complex comprises a bidentate phosphine ligand. The present invention also relates to a process for the preparation of a dicarboxylic acid or ester thereof from an alkenoic acid or ester thereof, or a process for the preparation of a carboxylic acid or ester thereof from an alkene or alkenoic acid with high selectivity and activity using said metal complex or catalyst composition. The present application also relates to a method of preparing Nylon 6-6 comprising the step of copolymerising adipic acid with hexamethylenediamine.
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Page/Page column 36
(2017/09/02)
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- Highly fluorous bidentate phosphines
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The reaction of tetrachlorodiphosphines [Cl2P(CH 2)nPCl2; n = 2-4] with fluorous aromatic precursors 4-bromo(perfluorohexyl)benzene and 4-(perfluorohexyl)phenol gave a series of fluorous-tagged diphosphines [(p-C6F13C 6H4)2P(CH2)nP(C 6H4C6F13-p)2; n = 2-4] and a new diphosphonite [(p-C6F13C6H 4O)2P(CH2)3P(OC6H 4C6F13-p)2]. The improved synthesis of 1,3-bis(dichlorophosphino)propane (dcpp), involved the facile chlorination of the corresponding primary phosphine with triphosgene. Fluorinated diimines RN=C(CH3)C(CH3)=NR, where R = p-C6H 4C6F13 or P-C6H4C 8F17 have also been prepared, and were found to be air-stable alternatives to the highly air-sensitive phosphorus-containing ligands. All compounds were characterised by a variety of techniques including NMR, IR, MS and microanalysis. The successful reduction of the phosphine-oxides [(p-C6F13C6H4)2P(O) (CH2)nP(O)(C6H4C6F 13-p)2; n = 2,3] with phenylsilane is also presented. Georg Thieme Verlag Stuttgart.
- Berven, Bradley M.,Koutsantonis, George A.
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body text
p. 2626 - 2630
(2009/04/06)
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- Catalyst system and method for carbonylation
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The invention relates to a catalyst system for carbonylating olefinically or acetylenically unsaturated compounds with carbon monoxide and a nucleophile compound, containing (a) palladium; (b) a phosphine and (c) a polymer containing nitrogen which is soluble in the reaction mixture, with the exception of polyvinyl polymers with aromatic radicals containing nitrogen on the polymer chain. The invention also relates to a method for carbonylation in the presence of one such catalyst system.
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Page/Page column 9
(2008/06/13)
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- Medium-ring diphosphines from diphosphabicycloalkanes: stereoselective syntheses, structure and properties
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A series of 1,k+2-diphosphabicycloalkanes 2b-e are prepared by n-BuLi-promoted cyclisation of 1,ω-diphosphinoalkanes, followed by alkylation and cycloalkylation with 1,ω-dihaloalkanes.These compounds appear to be exclusively cis-isomers except 1,6-diphosphabicycloundecane 2e which is a 3:1 cis/trans mixture.Mono-quaternisation of cis-1,k+2-diphosphabicycloalkanes, followed by treatment of the mono-quaternary salts with alkyllithium or Grignard reagents produces cis-1,n-disubstituted-1,n-diphosphacycloalkanes 4 exclusively; examples containing 8-, 9- and 10-membered rings and a range of substituents on phosphorus are described.Di-quaternisation of 1,k+2-diphosphabicycloalkanes, followed by hydrolysis, yields the trans-isomers of 1,n-disubstituted-1,n-diphosphacycloalkane monooxides 6 exclusively; reduction of these with LiAlH4 in benzene gives largely trans-1,n-disubstituted-1,n-diphosphacycloalkanes 7, but is not completely stereoselective.The structure and properties of these diphosphacycloalkanes are discussed.He(I) photoelectron spectra of 1,5-diphosphabicyclooctane, 1,6-diphosphabicyclononane and 1,6-diphosphabicyclodecane show little evidence of interaction between phosphorus lone pairs, unlike the corresponding hydrazines.The medium-ring diphosphacycloalkanes, 1,5-dimethyl-1,5-diphosphacyclooctane and 1,6-dimethyl-1,6-diphosphacyclodecane also show little evidence of interaction between phosphorus lone pairs.
- Alder, Roger W.,Ganter, Christian,Gil, Michelle,Gleiter, Rolf,Harris, Christopher J.,et al.
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p. 1643 - 1656
(2007/10/03)
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- Synthesis of Primary and Secondary Phosphines by Selective Alkylation of PH3 under Phase Transfer Conditions
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Primary phosphines, RPH2, may be synthesized selectively by alkylation of phosphine, PH3, with alkyl halides RX (R = Me, Et, n-Bu, 2-Bu, C16H33, CH2=CH-CH2, Ph-CH2, 2-Py-CH2-CH2; X = Cl, Br) and concentrated aqueous KOH as auxilliary base in dimethylsulfoxide as a solvent or in two phase systems employing phase transfer catalysts.Under more rigorous conditions secondary phosphines R2PH (R = Me, n-Bu, CH2=CH-CH2) are also acessible in good yields.Using 1,3-dibromo(chloro)-propane or -butane diprimary phosphines H2P-(CH2)2-CHR-PH2 (R = H, Me) are obtaines, while 1,4-dibromopentane in a high yield cyclization reaction leads to 2-methylphospholane (12) with a chiral C-atom in α-position.
- Langhans, Klaus P.,Stelzer, Othmar
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p. 203 - 211
(2007/10/02)
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