Organische Verbindungen des Phosphors. I. Mitt.

Pass, F.; Schindlbauer, H.

doi:10.1007/bf00925230

Cited by 54 publications

(16 citation statements)

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“…General: For experimental details, see Part 15 of this series 1. − Phenylphosphane, diphenylphosphane,30a,30b dicyclohexylphosphane,30c and C 7 H 8 Mo(CO) 4 31 were synthesized by known methods. Methyl 1‐cyclohexenecarboxylate ( 1 ) was purchased from Aldrich GmbH .…”

Section: Methodsmentioning

confidence: 99%

Novel Electron-Rich Hydrophilic Phosphanes with Carboxylated Cyclohexyl Substituents

Brauer

Kottsieper

Nickel

et al. 2001

Eur. J. Inorg. Chem.

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Addition of diphenylphosphane or phenylphosphane to methyl 1‐cyclohexenecarboxylate (1) under base catalysis, yields the novel tertiary or secondary phosphanes 2a, 3, or 4a containing cyclohexyl backbones with the carboxylic groups in the 2‐position. The carboxylated derivative of the borane adduct of tricyclohexylphosphane 5a is accessible by a related reaction using Cy2P(BH3)Li instead of Ph2PH or PhPH2. The complete analysis of the 1H NMR spectrum of 2a using 2D NMR spectroscopy (H,H‐, C,H‐COSY NMR spectra, 13C‐INADEQUATE) reveals the bis(equatorial) position of the Ph2P and COOMe substituents. This is supported by the results of the X‐ray structural analysis of 2b (space group P21/c). On addition of Cy2P(BH3)Li to 1 and subsequent hydrolysis, 5a, the first functionalized derivative of tricyclohexylphosphane is obtained. In contrast to 2b, the COOMe substituent in 5a occupies the axial position, the bulky phosphanyl group being equatorial as indicated by the X‐ray structural analysis (space group P21). Molybdenum(0) and palladium(II) complexes of 2a and 2b have been synthesized. The influence of the carboxylated cyclohexyl substituent on the electronic and steric parameters of 2a and 2b is discussed.

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Section: Methodsmentioning

confidence: 99%

Novel Electron-Rich Hydrophilic Phosphanes with Carboxylated Cyclohexyl Substituents

Brauer

Kottsieper

Nickel

et al. 2001

Eur. J. Inorg. Chem.

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“…Phosphorus-31 nmr spectrum: resonances at +31.5 (singlet) and +126.2 ppm (triplet of apparent septets; Jj = 190 ± 3, 7sep = 7 Hz) corresponding to the single tertiary phosphorus atom and the two primary phosphorus atoms, respectively. Mass spectrum (chamber temperature 210°, sample temperature 110°); CH3P(CH2CH2-PH2)2+ ( 6), CH3P(CH2CH2PH2)(CH2CH2PH)+ ( 4), CH3-P(CH2CH2PH2)CH2CH2+ (100), CH3PCH2CH2PH2+ (24), CH3P(C2H3)CH2CH2+ ( 6), H2PCH2CH2PH2+ (8), HP-CH2CH2PH2+ (6), H2P(CH2CH2)2+ ( 9), CH3P2H3+ (34), CH3P2H2+ (32), CH3P2H+ (7), C3H,0P+ (15), C3H9P+ (10), C3H8P+ (19), C3H7P4• (8), C3H6P+ (19), C2H8P+ (7), C2H7P+ (16) If the reaction of methylphosphine with diisopropyl vinylphosphonate was carried out at 40°rather than at the boiling point of the tetrahydrofuran using otherwise identical reaction conditions, only unchanged diisopropyl vinylphosphonate was recovered.…”

Section: Methodsmentioning

confidence: 99%

1:1 Base-catalyzed addition reactions of compounds containing two or more phosphorus-hydrogen bonds to various vinylphosphorus derivatives

King¹,

Cloyd²

1975

J. Am. Chem. Soc.

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“…[1], Phenylphosphan [28], Diphenylphosphan [29] und Pd(PPh3)4 [13] Die Lösung von 57.5 mmol Ph2PK in 150 ml DME (dargestellt durch Umsetzung von 10.7 g (57.5 mmol) Ph2PH und 2.24 g Kalium) wurde mit 9.70 g (57.5 mmol) 10a versetzt und 12 h auf 80°C erhitzt. Anschließend wur de das Lösungsmittel abdestilliert und der Rückstand in 100 ml CH2C12 aufgenommen.…”

Section: Experimenteller Teilunclassified

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains

Liek

Machnitzki

Nickel

et al. 1999

Zeitschrift Für Naturforschung B

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Nucleophilic phosphanylation of orf/zo-fluorophenylacetic acid or orf/jofluorobenzylamine with PhPH2 using KOfBu as the base affords the hydrophilic tertiary phosphanes 3 and 4a with terminal CH2-COOH and CH2-NH2 substituents. The corresponding secondary phosphane li gands 2 or 5 may be obtained by Pd-catalyzed P-C coupling of orr/20-iodophenylacetic acid with PhPH2 or selective nucleophilic phosphanylation of orf/jo-fluorophenylacetic acid. Novel phosphonatomethyl derivatives 7a, 7b of triphenylphosphane have been obtained in a two sta ge synthesis using orf/zo-iodobenzylchloride or w^ta-iodobenzylbromide as starting materials. Arbusov reaction with P(OEt)3 and Pd-catalyzed P-C coupling reactions with Ph2PH gave the esters 7a, 7b. Purification of 7a was achieved via its BH3 adduct 8a. Deprotection, hydrolysis and neutralisation with NaOH affords the water soluble sodium salts 9a,9b. a-Hydroxy and a-benzylamino derivatives 12 and 14 of orr/zo-diphenylphosphanobenzyl phosphonate (e.g. 7a) and the corresponding Me2P (0) analogs 13 and 16 are accessible in a straightforward man ner by addition of (M e0)2P(0)H or Me2P(0)H to orf/?o-phosphanobenzaldehyde 11a or its benzaldimino derivative 15, respectively. An improved synthesis for lla -llc has been develo ped. Reaction of 11a with the Wittig reagent Ph3P=C(H)COOEt and subsequent hydrolysis of the intermediate ester 17a affords o/t/?o-diphenylphosphano cinnamic acid 17. The catalytical activity of 1,9a, 9b and related ligands in Suzuki-type coupling reactions has been investigated. Derivate des Triphenylphosphans mit COOHund P (0 )(0 R )2-Gruppen (z.B. A [2], B [3]) sind als Katalysatorliganden für die Hydrofor mylierung und Oligomerisation von Olefinen [4] sowie die Carbonylierung von Benzylhalogeni den in Zweiphasensystemen [3] von Bedeutung. Durch Immobilisierung aromatischer Phosphane mit P (0 )(0 R )2-Resten (B) an anorganischen Ma terialien (Zirconium(IV)-phosphat, -phosphonat, -phosphit) wurden geträgerte Katalysatoren erhal ten, die für Hydroformylierungs-und Heck-Reaktionen in heterogenen Systemen mit Erfolg einge setzt wurden [5, 6]. Die Einschiebung einer CH(Z)-Brücke in A und B führt zu Liganden C bzw. D mit flexibler

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Organische Verbindungen des Phosphors. I. Mitt.

Cited by 54 publications

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Novel Electron-Rich Hydrophilic Phosphanes with Carboxylated Cyclohexyl Substituents

Novel Electron-Rich Hydrophilic Phosphanes with Carboxylated Cyclohexyl Substituents

1:1 Base-catalyzed addition reactions of compounds containing two or more phosphorus-hydrogen bonds to various vinylphosphorus derivatives

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains

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Organische Verbindungen des Phosphors. I. Mitt.

Cited by 54 publications

References 0 publications

Novel Electron-Rich Hydrophilic Phosphanes with Carboxylated Cyclohexyl Substituents

Novel Electron-Rich Hydrophilic Phosphanes with Carboxylated Cyclohexyl Substituents

1:1 Base-catalyzed addition reactions of compounds containing two or more phosphorus-hydrogen bonds to various vinylphosphorus derivatives

Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH2-, COOH- und P(O)(OR)2-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH2, COOH and P (O)(OR)2 Functionalized Side Chains

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Wasserlösliche Phosohane, XIV. Hydrophile Derivate des Triphenylphosphans mit NH_2-, COOH- und P(O)(OR)₂-funktionalisierten Seitenketten / Water Soluble Phosphanes, XIV. Hydrophilic Derivatives of Triphenylphosphane with NH₂, COOH and P (O)(OR)₂ Functionalized Side Chains