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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: Investigations on Diazo Compounds and Azides, 58. Dication Ethers, 5. Formamidinium-substituted Diazophosphoryl Compounds: Synthesis, Properties, and Reactions Leading to TetrazolesElectrophilic diazoalkane substitution of diazophosphoryl compounds 4a - c by bis(formamidinium) ethers 3a, b leads to formamidinium-substituted (diazomethyl)phosphoryl compounds 5. These can also be considered as alkenediazonium salts, but the contribution from this resonance structure is low according to 1H NMR and IR data. Reaction of 5a - c with another equivalent of 4a - c under slightly modified conditions yields 2-vinyl-2H-tetrazoles 6 and 7. The identity of the tetrazoles has been confirmed by X-ray structure analysis of 6c as well as by thermolysis of 6c leading to pyrazole 12 which then was hydrolyzed to give the NH-pyrazole 13.
    Notes: Die Diazophosphoryl-Verbindungen 4a - c reagieren mit den Bis(formamidinium)ethern 3a, b im Sinne einer elektrophilen Diazoalkan-Substitution zu Formamidinium-substituierten (Diazomethyl)phosphoryl-Verbindungen 5. Diese lassen sich auch als Olefindiazoniumsalze auffassen, jedoch deuten 1H-NMR- und IR-Daten nur auf einen geringen Anteil dieses Bindungszustandes hin. Unter leicht modifzierten Reaktionsbedingungen reagieren 5a - c mit einem weiteren Äquivalent von 4a - c zu den 2-Vinyl-2H-tetrazolen 6 und 7. Die Identität der Tetrazole wird durch eine Röntgenstrukturanalyse von 6c sowie die Thermolyse von 6c zum Pyrazol 12 und dessen Hydrolyse zum NH-Pyrazol 13 belegt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1980 (1980), S. 1232-1238 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Phosphorylation with N-Phosphorylpyrazoles, IV1).  -  Phosphorylations of Carboxylic AcidsReaction of 1-phosphorylpyrazole (1a) with the carboxylic acids 5a-f leads initially to the mixed anhydrides 6a-f, which then transform the 1-H-pyrazole 3, arising from phosphoryl group transfer, into the 1-acylpyrazoles 7a-f. Carboxylic acid phosphinic acid anhydrides 6b, c and g-k are also formed on reaction of the phosphinic acid chloride 9 and carboxylic acids in the presence of triethylamine; acylation of 3 with 6b, c, i and k is described.
    Notes: Bei der Umsetzung von 1-Phosphorylpyrazol 1a mit den Carbonsäuren 5a-f werden zunächst die gemischten Anhydride 6a-f gebildet, die dann das bei der Phosphorylgruppen-Übertragung entstandene 1-H-Pyrazol 3 in die 1-Acylpyrazole 7a-f umwandeln. Die Carbonsäure-phosphinsäure-anhydride 6b, c und g-k entstehen auch aus dem Phosphinsäurchlorid 9 und Carbonsäuren in Gegenwart von Triethylamin; die Acylierung von 3 mit 6b, c, i und k wird beschrieben.
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