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  • 1970-1974  (2)
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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXIII. On the Cleavage of the Carbene-Metal Bond during the Reaction of Methoxy(organyl)carbene Complexes of Chromium(0) with AcidsMethoxy(phenyl)carbene or methoxy(methyl)carbene complexes of chromium(0) react with hydrogen chloride in the presence of an excess of triarylphosphine to give the phosphonium salts [R′3P-CH(OCH3)R]Cl (5), which have been characterized as the corresponding hexafluorophosphates (10). We assume that the α-chloroethers ClCH(OCH3)R (14) are formed as primary products. In the reaction of the carbene complexes with acetic or benzoic acid the esters R′CO2CH(OCH3)R (13) can be isolated as the analogous insertion products.
    Notes: Methoxy(phenyl)carben- und Methoxy(methyl)carben-Komplexe des Chroms(0) reagieren mit Chlorwasserstoff in Gegenwart eines Überschusses an Triarylphosphin zu den Phosphoniumsalzen [R″3P-CH(OCH3)R]Cl (5), welche als Hexafluorophosphate (10) charakterisiert wurden. Die α-Chloräther ClCH(OCH3)R (14) entstehen dabei vermutlich als Primärprodukte. Bei der Reaktion der Carben-Komplexe mit Essigsäure oder Benzoesäure können als entsprechende Insertionsprodukte die Ester R′CO2CH(OCH3)R (13) isoliert werden.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (α-Methoxybenzylidene)triphenylphosphorane and (1-Methoxyethylidene)triphenylphosphorane(α-Methoxybenzylidene)triphenylphosphorane (2a) and (l-Methoxyethylidene)triphenylphosphorane (2b) have been prepared from the corresponding phosphonium salts. While 2a reacts with benzaldehyde to form α-methoxystilbene (3, 4) and triphenylphosphine oxide by means of the Wittig-reaction, the expected olefin could not be found in the analogous reaction of 2b. Instead of that, however, α-methoxypropiophenone (10) and triphenylphosphine are formed.  -  α,α′-Dimethoxystilbene (6a, 7a) and triphenylphosphine result from the thermal decomposition of 2a.
    Notes: (α-Methoxybenzyliden)triphenylphosphoran (2a) und (l-Methoxyäthyliden)triphenylphosphoran (2b) wurden aus den entsprechenden Phosphoniumsalzen dargestellt. Während 2a mit Benzaldehyd im Sinne der Wittig-Reaktion zu α-Methoxystilben (3, 4) und Triphenylphosphinoxid reagiert, wurde bei der gleichen Reaktion mit 2b das erwartete Olefin nicht gefunden, statt dessen jedoch α-Methoxypropiophenon (10) und Triphenylphosphin.  -  Die thermische Zersetzung von 2a führt zu α,α′-Dimethoxystilben (6a, 7a) und Triphenylphosphin.
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