- Catalytic Cleavage of Unactivated C(aryl)-P Bonds by Chromium
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We describe here the coupling to transform aryl phosphine derivatives by the cleavage of unactivated C(aryl)-P bonds with chromium catalysis, allowing us to achieve the reaction with alkyl bromides and arylmagnesium reagents under mild conditions. Mechani
- Ling, Liang,Luo, Meiming,Tang, Jinghua,Yuan, Shuqing,Zeng, Xiaoming
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p. 1581 - 1586
(2022/03/14)
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- Method for preparing aryl ketone derivatives
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The present invention discloses a method for preparing aryl ketone derivatives. The method provided by the invention adopts 1-(hetero)arylcycloalcohol as a starting material, and raw materials are easy to obtain and have a plurality of kinds; the products obtained by utilizing the method have various types and wide applications, and the obtained products can be conveniently converted and derivatized to obtain important phosphorus ligands and catalysts; and in addition, the method disclosed in the invention has the advantages of mild reaction conditions, a high yield of the target products, lowpollution and a simple reaction operation and post-treatment process, and is suitable for industrial production.
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Paragraph 0019
(2019/10/01)
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- Bisphosphine catalyzed sequential [3 + 2] cycloaddition and Michael addition of ynones with benzylidenepyrazolones: Via dual α′,α′-C(sp3)-H bifunctionalization to construct cyclopentanone-fused spiro-pyrazolones
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A bisphosphine-catalyzed sequential [3 + 2] cycloaddition and Michael addition reaction of ynones with benzylidenepyrazolones has been developed. Under the catalysis of DPPB [1,4-bis(diphenylphosphino)butane], the reaction proceeded smoothly to give spiro-[cyclopentanone] pyrazolone derivatives in moderate to good yields with good diastereoselectivities via sequential dual α′,α′-C(sp3)-H bifunctionalization annulation. This strategy provides a novel route toward the synthesis of spiro-[cyclopentanone] pyrazolones containing three contiguous stereocenters which possess potential pharmaceutical activities.
- Zhang, Jiayong,Miao, Zhiwei
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supporting information
p. 9461 - 9471
(2019/01/03)
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- Synthesis of pincer ruthenium RuCl(CNN)(PP) catalysts from [RuCl(μ-Cl)(η6-p-cymene)]2
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The cationic [RuCl(η6-p-cymene)(HCNNa)]Cl (1a) (HCNNa = 1-(6-arylpyridin-2-yl)methanamine) and the neutral RuCl 2(η6-p-cymene)(HCNNb) (1b) (HCNN b = 2-aminomethylbenzo[h]quinoline) complexes have been obtained by reaction of the precursor [RuCl(μ-Cl)(η6-p-cymene)] 2 with the corresponding nitrogen ligand (HCNNa and HCNNb) in THF. Complex 1a reacts cleanly with monodentate (P = PPh3) and bidentate phosphines (PP = dppb, dppf) in ethanol in the presence of NEt3, affording the pincer catalysts RuCl(CNN a)(PPh3)2 (2) and RuCl(CNNa)(PP) (PP = dppb 3, dppf 4). Similarly, the benzo[h]quinoline pincer derivative RuCl(CNNb)(dppb) (5) is obtained from 1b and dppb. Complex 3 has also been prepared in a one-pot reaction from [RuCl(μ-Cl)(η6-p- cymene)]2, HCNNa, and dppb in ethanol. Similarly, the chiral complex RuCl(CNNa)((R,S)-Josiphos) was isolated as a single stereoisomer by treatment of [RuCl(μ-Cl)(η6-p-cymene)] 2 with HCNNa and (R,S)-Josiphos in 1-butanol. Reaction of 1a and 1b with dppb affords cymene diphosphine species by displacement of the HCCN ligand.
- Zhang, Shuanming,Baratta, Walter
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supporting information
p. 3339 - 3342
(2013/07/19)
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- A catalytic method for the reduction of secondary and tertiary phosphine oxides
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TMDS has been found to be an efficient hydride source for the reduction of tertiary and secondary phosphine oxides using a catalytic amount of Ti(Oi-Pr)4. All classes of tertiary phosphine oxides, such as triaryl, trialkyl, and diphosphine, were effectively reduced. Georg Thieme Verlag Stuttgart.
- Berthod, Mika?l,Favre-Réguillon, Alain,Mohamad, Jahjah,Mignani, Gérard,Docherty, Gordon,Lemaire, Marc
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p. 1545 - 1548
(2008/02/05)
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- A mild and efficient CsOH-promoted synthesis of ditertiary phosphines
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A mild and efficient method for the synthesis of ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves, and DMF, various dihalides were coupled with diphenylphosphine at room temperature, and the results have demonstrated that this methodology offers a general synthetic procedure producing a variety of ditertiary phosphines in high yields.
- Honaker, Matthew T.,Salvatore, Ralph Nicholas
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p. 277 - 283
(2007/10/03)
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- CsOH-promoted P-alkylation: A convenient and highly efficient synthesis of tertiary phosphines
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A mild and efficient method for the synthesis of tertiary phosphines and ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves and DMF at room temperature, various secondary phosphines and alkyl bromides were examined, and the results have demonstrated that this methodology offers a general synthetic procedure to produce tertiary phosphines in moderate to high yields. Optically active tertiary phosphine synthesis is also described.
- Honaker, Matthew T.,Sandefur, Benjamin J.,Hargett, James L.,McDaniel, Alicia L.,Salvatore, Ralph Nicholas
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p. 8373 - 7377
(2007/10/03)
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- Preparation of organohalosilanes
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When oganohalosilanes are prepared by charging a reactor with a contact mass containing a metallic silicon powder and a copper catalyst, and introducing an organohalide-containing gas into the reactor to effect the direct reaction, a poly(organo)phosphino compound is added to the contact mass. The invention is successful in producing organohalosilanes at a significantly improved production rate without reducing the selectivity of useful silane.
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- Method for producing benzoic acid derivatives
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The invention relates to a method for producing a benzoic acid derivative represented by the general formula (1). The method includes the step of reacting an aromatic compound represented by the general formula (2), with carbon monoxide and a hydroxy compound (i.e., water or an alcohol), in the presence of (a) a metal compound containing a metal of 8, 9 and 10 groups of periodic table, (b) a first phosphine derivative represented by the general formula (R1)2P—Q—P(R1)2, and (c) a base, It is possible to easily and efficiently produce the benzoic acid derivative by the method.
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- Process for the hydrogenation of imines
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A process for the hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium catalysts containing diphosphine ligands, with or without an inert solvent, the reaction mixture containing a soluble ammonium chloride, bromide or iodide or a soluble metal chloride, bromide, or iodide, wherein the reaction mixture additionally contains at least one solid acid with the exception of ion exchangers. Improved optical yields and high chemical conversion rates are achieved while the catalyst is easily separable.
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- Iridium-diphospine complexes and process for the hydrogenation of imines
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Compounds of formulae I: (DIP)IrXq Yr (Z), Ia: (DIP)IrXs Yt (Z)2 and Ib: (DIP)Ir(Z)3 or mixtures of at least two of those compounds, wherein DIP is a ditertiary diphosphine, the two phosphine groups of which are bonded to a C2 -, C3 - or C4 -carbon chain, with the result that the diphosphine forms a 5- to 7-membered ring together with the Ir atom, X is Cl, Br or I, Y is a hydrogen atom, q and r are 0, 1 or 2 and the sum of q+r is 2, s and t are 0 or 1 and the sum of s+t is 1, and Z is the anion of an organic oxy acid that contains a group C(=O), S(=O)O or P(=O)O in the anion. The compounds are excellent catalysts for the hydrogenation of imines, especially for the enantioselective hydrogenation of prochiral imines.
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- Structure of diiodine adducts of some di- and tri-tertiaryphosphines in the solid state and in solution
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A series of ditertiaryphosphine-tetraiodine adducts R2P(I2)(CH2)nP(I2)R 2 (R = Ph, n = 1-4; R = PhCH2 or o-CH3C6H4, n = 2) and two tritertiaryphosphine-hexaiodine adducts, PhP(CH2CH2PPh2)2I6 and CH3C(CH2-PPh2)3I6 have been prepared and characterised by 31P-{H} solution NMR and Raman spectroscopy. In the case of Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4), 31P-{H} NMR magic angle spinning NMR spectroscopy has been used to investigate the nature of the compounds in the solid state. In agreement with our previous extensive studies on the monophosphine derivatives, R3PI2, the tetraiododiphosphine compounds Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4) isolated from diethyl ether contain molecular four-co-ordinate phosphorus centres onto which the diiodine is bound as a linear spoke, as indicated by their 3IP-{H} NMR shifts obtained in CDCl3 solution. Again, in agreement with our previous solution studies of the monophosphine derivatives R3PI2, the diphosphine-tetraiodine adducts completely ionise in CDCl3 solution to produce the ionic compounds [R2P(I)(CH2)nP(I)R2]2I; the solution 31P-{H} NMR shifts are very similar to analogous solution shifts previously assigned to [R3PI]I. The Raman band assignable to v(P-I) has been identified for the compounds and a further band at lower frequency has been observed and assigned to v(I-I). Although the solid-state NMR spectra of the triphosphine-hexaiodine adducts were not recorded, a band assignable, to v(I-I) was observed in the Raman spectrum, suggesting the molecular four-co-ordinate spoke structure also prevails for these hexaiodotritertiaryphosphine compounds in the solid state. From solution 31P-{H} NMR shifts these adducts also appear to ionise in CDCl3 solution.
- Bricklebank, Neil,Godfrey, Stephen M.,McAuliffe, Charles A.,Deplano, Paula,Mercuri, Marie L.,Sheffield, Joanne M.
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p. 2379 - 2382
(2007/10/03)
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- Process for the preparation of substituted phenols
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A process for the preparation of substituted phenols, in particular, the condensation of phenols having one or more alkyl substituents with a butadiene derivative comprising at least six carbon atoms, in particular myrcene and/or β-springene is disclosed. The cyclization, in the form of chromans, of the products obtained during this condensation and their hydrogenation in order to prepare vitamin E is also disclosed.
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- An Unusual Acyliminium Cyclization and Other Drawbacks during an Attempted Synthesis of a Chiral Primary α-Phosphinoalkanamine
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Studies towards the synthesis of a chiral primary α-phosphinoalkanamine 1a are reported. O-Activated, N-carbamate-protected phenylalaninol 3a did not undergo 5N reaction with KPPh2: instead, after TV-deprotonalion, intramolecular substitution led to formation of the aziridine derivative 5a (Scheme 2). N-Phthalimido-protected. O-activated phenylalaninol 3b also underwent an intramolecular process on treatment with KPPh2, i.e., an unusual aryl-acyliminium cyclization furnishing the (epoxymethano)isoindolo[1,2-a]isoquinolinone 7 (Scheme 3). In a reaction with KPPh2, the N,N-dibenzyl-protected and activated phenylalaninol 3d finally yielded the intermolecular SN reaction product 2a (Scheme 4). However, debenzylation by catalytic hydrogenation turned out to be impossible.
- Christoffers, Jens
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p. 845 - 852
(2007/10/03)
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- Process for the preparation of ketones
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A process for the preparation of ketones which comprises reacting a conjugated diolefin and water in the liquid phase in the presence of a catalyst system comprising: a) a group VIII metal compound, and b) a source of protons.
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- Radical Cations of Bis(diphenylphosphino) Derivatives (Ph2P-R-PPh2): The Formation of Localized, Cyclic, and Dimeric Configurations. An ESR and Quantum Chemical Study
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A matrix ESR study on radiogenic radical cations of Ph2P-R-PPh2 derivatives with various linkers (R) is presented.The experiments show that in a frozen dichloromethane solution the radical cations can adopt localized (Ph2PR*+), cyclic , and dimeric (Ph2RP*-PRPh2+) configurations, depending on the nature of the linker.The cyclic and dimeric products are formed in the reaction of a localized cation with a second free-electron pair, resulting in an intra- or intermolecular three-electron P-P ?* bond, respectively.The formation of the cyclic structure, with a strongly bent P-P ?* bond, requires a specific proximate position of the two phosphine moieties in the precursor molecule.The mutual orientation of the two free-electron pairs of the precursors is assessed by NMR via the nJPP spin-spin coupling constant.Ab initio UHF quantum chemical calculations at the 3-21G*/SCF level support the assignments.
- Janssen, Rene A. J.,Aagaard, Olav M.,Cabbolet, Marcoen J. T. F.,Waal, Bas F. M. de
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p. 9256 - 9263
(2007/10/02)
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- Preparation of biaryl compounds
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A method for the preparation of biaryl compounds is disclosed which comprises contacting an aromatic halide in the presence of a catalyst comprising zerovalent nickel, a bidentate phosphorus-containing coordinating ligand and a reducing metal in a polar, aprotic solvent system for a time and under conditions suitable for the formation of biaryl compound.
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- Process for the preparation of lactones from higher alkenols
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Process for the preparation of lactones, having 4 or 5 carbon atoms in the ring by reacting a higher alkenol with a carbon monoxide containing gas in the presence of a catalytic system comprising (a) a palladium compound, (b) a bidentate phosphine, arsine and/or stibine, and (c) a protonic acid having a pKa 2.
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- Process for the preparation of aldehydes
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Process for the preparation of aldehydes by hydroformylation of an alkenically unsaturated compound in the presence of (a) Pd, a Pd compound, Pt and/or a Pt compound, (b) an anion of a carboxylic acid with a pKa 1 R2 -M-R-M-R3 R4, wherein M is P, As or Sb, R is a divalent organic bridging group having at least 3 carbon atoms in the bridge, and R1, R2, R3 and R4 are hydrocarbon groups.
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- Process for the coproduction of anilines and oxamides
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A process for the coproduction of anilines of the formula wherein X is a halogen atom, an alkyl-, alkoxy-, aryloxy-, cyano-, ester- or trifluoromethyl group and n is an integer from 0 to 5, and oxamides of the formula wherein each R independently is an alkyl group which comprises reacting an aromatic nitro compound of the general formula wherein X and n are as defined above with carbon monoxide and a molar excess in relation to the nitro compound of an amine HNR2 wherein R is an alkyl group, in the presence of a catalyst system comprising (a) palladium metal or a compound thereof, (b) a bidentate ligand of the formula, R1R2--M--A--M--R3R4, in which M is P, As or Sb, A is a divalent organic bridging group having at least 2 carbon atoms in the bridge, none of these carbon atoms carrying substituents that may cause steric hindrance, and R1,R2,R3 and R4 represent similar or dissimilar optionally substituted hydrocarbon groups, and (c) an acid or a transition metal salt of said acid.
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- ELECTROCHEMICAL SYNTHESIS OF TERTIARY PHOSPHINES FROM ORGANIC HALIDES AND CHLOROPHOSPHINES
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The electrochemical synthesis of a wide range of tertiary mono- and diphosphines has been achieved in very simple and mild conditions, in an undivided electrolytic cell with a sacrificial anode of magnesium.
- Folest, J. C.,Nedelec, J. Y.,Perichon, J.
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p. 1885 - 1886
(2007/10/02)
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- SYNTHESE DE NOUVEAUX SELS DE TETRAPHOSPHONIUM MACROCYCLIQUES
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A one step synthesis of tetraphosphonium salts of the saturated 5 and ethylenic 3 macrocycles containing C-C bridges has been carried out in good yield.The cleavage of the carbon bridges during basic hydrolysis is highly regioselective.
- Vincens, Maurice,Grimaldo Moron, Jose T.,Pasqualini, Roberto,Vidal, Michel
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p. 1259 - 1262
(2007/10/02)
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- Process for the carbonylation of ethylenically unsaturated compounds
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Process for the preparation of a carboxylic ester or acid by reacting an ethylenically unsaturated compound in which each of the carbon atoms of the carbon-carbon double bond is secondary or tertiary, with CO in the presence of an alkanol or water, respectively, and of a catalytic system prepared by combining:-, a) Pd and/or a Pd compound, b) a strong acid, except hydrohalogenic and carboxylic acids, and c) a bidentate ligand, using a molar ratio of acid to ligand of greater than 0.5.
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- Process for the preparation of urea derivatives and catalyst system
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The invention relates to a process for the preparation of urea derivatives of the general formula wherein R is an alkyl group and X is a halogen atom, an alkyl-, alkoxy-, aryloxy-, cyano-, ester- or trifluoromethyl group and n is from 0 to 5,which comprises reacting an aromatic nitro compound of the general formula wherein X and n are as defined above with carbon monoxide and an amine HNR2 wherein R is an alkyl group,in the presence of a catalyst system comprising (a) a group VIII noble metal or a compound thereof, (b) a bidentate ligand and (c) an acid having a pKa of more than 2 or a transition metal salt of said acid.
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- A Simple Synthesis and Some Synthetic Applications of Substituted Phosphide and Phosphinite Anions
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Based on data for the acidity relationship of phosphines and phosphinous acids and water in dimethyl sulfoxide and water, a simple method is reported for the generation of phosphide and phosphinite anions by the action of concentrated aqueous alkali on primary and secondary phosphines as well as phosphinous acids in dimethyl sulfoxide or other dipolar aprotic solvents.Alkylation of the anion yields secondary and tertiary phosphines, polyphosphines, functionally substituted phosphines as well as similarly substituted phosphine oxides.Phosphinous acids have beenalkylated in various solvents in two-phase systems containing concentrated aqueous alkali and tetrabutylammonium iodide as phase transfer catalyst.
- Tsvetkov, E. N.,Bondarenko, N. A.,Malakhova, I. G.,Kabachnik, M. I.
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p. 198 - 208
(2007/10/02)
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- METAL DIMERS AS CATALYSTS. VIII. THE CATALYSED SYNTHESIS OF THE CARBONYL COMPLEXES 5-C5H5)Ru(CO)(L)I> AND 5-C5H5)Ru(CO)(L)2>I (L = GROUP V DONOR LIGAND)
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The reaction between 5-C5H5)Ru(CO)2I> and Group V donor ligands in the presence of 5-C5Me5)Fe(CO)2>2 or 5-C5H5)Ru(CO)2>2 as catalyst yields 5-C5H5)Ru(CO)(L)I> (L = PPh3, PMe2Ph, PMePh2, P(OPh)3, P(OM
- Coville, Neil J.,Darling, Elizabeth A.
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p. 105 - 112
(2007/10/02)
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- Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XIII. Darstellung und Kristallstrukturen neuartiger Mangana- und Rhenaphosphacycloalkane durch Substitution und reduktive Cycloeliminierung mit ω-Chlor-1-(diphenylphosphino)alkanen
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The three to six-membered mangana- and rhenaphosphacycloalkanes of the type are obtained by reductive cycloelimination of the phosphane complexes (OC)4BrMPPh2-n-Cl (3a - d, 3b' - d') with sodium amalgam . 3a - d are accessible in substituting CO by the phosphanes PPh2-n-Cl (2a - d) in BrMn(CO)5 (1), 3b' - d' by reaction of 2 (1') with 2b - d .The hitherto unknown phosphane PPh2-4-Cl (2d) is formed by action of NaPPh2 on Cl-4-Cl in THF and can easily be t ransformed with O2 into the oxide Cl-4-P(O)Ph2 (4d) .For the synthesis of 5c and 5c' the reaction of PPh2-3-MgCl with 1 and 1', respectively, is also suitable . 5b is thermally labile and reacts with PPh3 under CO insertion into the Mn - C ? bond to give the cyclic acyl derivative (6) . 5b' and 5c crystallize in the monoclinic space group P21/n and C2/c with Z = 4 and 8, respectively.
- Lindner, Ekkehard,Funk, Guido,Hoehne, Sigrud
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p. 2465 - 2478
(2007/10/02)
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- Production of primary and secondary amines by reaction of ammonia with conjugated diene in the presence of Pd/phosphine catalyst and primary or secondary aliphatic alcohol solvent medium
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Short chain, unsaturated primary and secondary amines are prepared by reaction of ammonia and conjugated dienes in a primary or secondary aliphatic alcohol solvent medium and in the presence of a catalyst system comprising a palladium compound co-catalyzed with a phosphine ligand containing 2 to 4 phosphorus atoms.
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