Photochemical Oxygenation of 2,4,6‐Tri‐tert‐butyl‐λ3‐phosphorin and 2,4,6‐Tri‐tert‐butyl‐1,1‐dimethoxy‐λ5‐phosphorin

Dimroth, Karl; Chatzidakis, Anastasios; Schaffer, Ortwin

doi:10.1002/anie.197205061

Cited by 5 publications

References 7 publications

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Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ³‐phosphorin

Hettche

Dimroth

1973

Chem. Ber.

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2,4,6-Tripheiiyl-'h~-pliosphorin (1) wird in Benzol laiigsani durch dcn darin gelosten Luftsauerstoff oxidiert. Zwei kristallisicrtc Oxidationsprodukte wurden isoliert. Die tieferschmelzende Verbindung ist 4,4'-Dioxyhis(J-hydroxy-l-oxo-2,4,6-triphenyl-As-l-phospha-2,5-cyclohcxadicn) (2). Alkylierung mit Triathyloxonium-tetrafluoroborat liefert die drei stereoisomeren Phosphinsaureester 4€,E, 4€,Z und 4Z,2, deren Spaltung mit Zink und Eisessig zwei stereoisomere Hydroxyphosphinsaurc-athylester 5 E und Z ergibt. Die sterische Zuordnung gelang mit Hilfe der IH-NMR-Spektren.Wasserstoffperoxid-Oxidation von 1 liefert I-Hydroxy-l-ox0-2,4,6-triphenyl-h~-l-phospha-2,4-cyclohexadiene (3). Mit Triathyloxonium-tetrafluoroborat entsteht das auch auf anderem Wege aus 1 zuginglkhe J,1 -Diathoxy-2,4,6-triphenyl-i.-5-phosphorin (6) neben I-Athoxy-6-athyl-1-oxo-2,4,6-triphenyl-A~-l-phospha-2,4-cyclohexadien (13). Autoxidation and Hydrogen Peroxide Oxidation of 2,4,6-Triphenyl-X3-phosphorin2,4,6-Triphenyl-A3-phosphorin (1) is slowly oxidized in benzene solution by dissolvcd oxygen. Two crystalline oxidation products "ere isolated. The structure of the lower melting substance is 4,4'-dioxybis(l-hydroxy-l-oxo-2,4,6-triphenyl-h~-l-phospha-2,5-cyclohexadiene) (2). Alkylation with triethyloxonium tetrafluoroborate leads to three stereoisomeric phosphinates 4E,E, 4E,Z, 4Z,2, which by reduction with zinc in acetic acid yield two stereoisomeric ethyl hydroxyphosphinates 5E and 2. Steric assignment was made on the basis of the 1H n. m. r. data. Hydrogen peroxide oxidation of 1 yields J-liydroxy-l-oxo-2,4,6-tr~phenyl-h~-l-phospha-2,4-cyclohexadiene (3). Treatment with triethyloxonium tetrafluoroborate yields 1,l-dicthoxy-2,4,6-triphenyl-As-phosphorin (6) which was also prepared by another synthetic route and J-ethoxy-6-ethyl-] -oxo-2,4,6-triphcnyl-)~~-1-phospha-2,4-cyclohexadiene (13). Eildung und Eigenschaften der Dioxybis(phosphinsaure) 22,4,6-Triphenyl-)&phosphorin (1) und audere arylierte As-Phosphorine werden langsam an der Luft oxidiert. LBBt man eine Losung von 1 in Benzol, das relativ vie1 Sauerstoff lost, etwa 1 Woche im Dunkeln stehen, dann scheiden sich Kristalle vom Schmp. 165" aus. Eine zweite Verbindung vom Schmp. 225" liiI3t sich beim Einengen aus der Benzol-Losung isolierenl). Wahrend die Struktur der hoherschmelzenden Verbindung mit der Summenformel C46H3603P2 noch nicht sicher ist, konnte die der tieferschmelzenden Verbindung jetzt in allen Einzelheiten aufgeklart werden. Abweichend von unserer fruheren Feststellung1) enthalt die Summenformel ein 0-Atom

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Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ³‐phosphorin

Hettche

Dimroth

1973

Chem. Ber.

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Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide

Wossidlo

Frost

Lin

et al. 2021

Chemistry A European J

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The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of 1 J P,Se = 883 Hz is in line with a PÀ Se bond of high s-character. The σ-electron donating Me 3 Sisubstituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C 5 H 5 P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I) Cl as well as i PrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination.

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Persulfuration of phosphinines: Synthesis and X‐ray crystal structure analysis of a P₂S₃ derivative

Holand

Alcaraz

Ricard

et al. 1990

Heteroatom Chemistry

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The reaction of 4,5-dimethyl-2-phenylphosphinine with sulfur in boiling benzene in the presence of Nmethylimiduzole as a catalyst first yields a P-sulfide. This monosulfide further reacts with sulfur to give a diphosphinine trisulfide and a diphosphinine tetrasulfide. The X-ray crystal structure analysis of the trisulfide has been carried out.The two head-to-tail 1,6-dihydrophosphinine rings are connected by P-S-C and P-C links, thus forming a central I ,2,4-thiadiphospholane heterocy- cle. The P-C bridge is weak [1.881(3) A] and sulfur can insert into it to give the symmetrical tetrasulfide with two P-S-C bridges.According to a preliminary study [ 11, the reaction of phosphinines with sulfur initially yields very reactive phosphinine 1-sulfides in which the . In view of the aromaticity loss that accompanies the sulfuration of phosphorus, it seemed to us that the reaction of phosphinines with sulfur deserved more attention. We therefore decided to investigate in more depth the reaction of 4,S-dimethyl-2-phenylphosphinine (1) with sulfur.In our initial report, phosphinine 1 (a3'P + 185) was allowed to react with sulfur in boiling xylene.A signal at 6 + 145.7 appeared on the 3 i P NMR spectrum of the crude reaction mixture which was assigned to the phosphinine sulfide 2 on the basis of trapping reactions with 2,3-dimethylbutadiene and dimethyl acetylenedicarboxylate (Eq. 1). Me ' s;%CO2Me S C02Mei,

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Photochemical Oxygenation of 2,4,6‐Tri‐tert‐butyl‐λ³‐phosphorin and 2,4,6‐Tri‐tert‐butyl‐1,1‐dimethoxy‐λ⁵‐phosphorin

Cited by 5 publications

References 7 publications

Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ³‐phosphorin

Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ³‐phosphorin

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide

Persulfuration of phosphinines: Synthesis and X‐ray crystal structure analysis of a P₂S₃ derivative

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Photochemical Oxygenation of 2,4,6‐Tri‐tert‐butyl‐λ3‐phosphorin and 2,4,6‐Tri‐tert‐butyl‐1,1‐dimethoxy‐λ5‐phosphorin

Cited by 5 publications

References 7 publications

Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ3‐phosphorin

Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ3‐phosphorin

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide

Persulfuration of phosphinines: Synthesis and X‐ray crystal structure analysis of a P2S3 derivative

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Photochemical Oxygenation of 2,4,6‐Tri‐tert‐butyl‐λ³‐phosphorin and 2,4,6‐Tri‐tert‐butyl‐1,1‐dimethoxy‐λ⁵‐phosphorin

Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ³‐phosphorin

Autoxidation und Wasserstoffperoxid‐Oxidation von 2,4,6‐Triphenyl‐λ³‐phosphorin

Persulfuration of phosphinines: Synthesis and X‐ray crystal structure analysis of a P₂S₃ derivative