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- W2167945359 abstract "Aus Quecksilber-bis-diazoessigsäthylester 3) und Bis-trimethylsilyl-sulfid (4) wurde Trimethylsily-diazoessigsäureäthylester (5) bereitet. 5 ist thermisch ungewöhnlich stabil und addiert sich an Fumarsäurediäthylester (6) langsamer als Diazoessigsäureäthylester, was auf eine Stabilisierung des Grundzustandes durch die Trimethylsilyl-Gruppe hinweist. – 5 ist photolytisch zu Stickstoff und Trimethylsilyl-äthoxycarbonylcarben (2) spaltbar. 2 schiebt sich in die CH-Bindung ein (Konkurrenzkonstanten: 2°:1RR = 3.5; 3°:1° = 1.5) und liefert mit Olefinen (neben den Produkten der C H-Insertion) in zu ca. 95% cis-stereospezifischer Reaktion 1-Trimethylsilyl-1-äthoxycarbonyl-cyclopropane (23). – Aus 2-Diazo-3.3-dimethyl-butansäureäthylester (15) wurde photolytisch Äthoxycarbonyl-tert.-butylcarben (16) erzeugt. Im Unterschied zu 2 stabilisiert sich 16 (in Cyclopentan oder Isobuten) nahezu ausschließlich intramolekular zu 2.2-Dimethyl-cyclopropancarbonsäureäthylester (17) und Trimethylacrylsäthylester (18). Metal Substituted Carbenes and C-Metallated Diazoalkones, III1). Trimethylsilyldiazoethyl Acetate and its Photolysis to Trimethylsilylethoxycarbonylcarbene Starting from mercurybis(diazoethylacetate) (3) and bis(trimethylsilyl)sulfide (4) trimethylsilyldiazoethyl acetate (5) has been prepared. 5 shows unusual thermostability and adds to ethyl fumarate (6) slower than ethyl diazoacetate. This points to a stabilization of the diazo ground state by the trimethylsilyl group. — Photochemical decomposition of 5 yields trimethylsilylethoxycarbonylcarbene (2). 2 inserts readily into CH-bonds (competition factors; 2°:1° = 3.5; 3°;1° = 1.5) and yields with olefines (besides insertion products in a ca. 95 percent cis-stereospecific reaction 1-trimethylsilyl-1-ethoxycarbonyl-cyclopropanes (23). Ethoxycarbonyl-tert.-butylcarbene (16) has been generated by photolysis from ethyl 2-diazo-3.3-dimethylbutantate (15). 16 stabilizes itself almost exclusively (in cyclopentane or isobutene) by intramolecular paths yielding ethyl 2,2-dimethylcyclopropanecarboxylate (17) and ethyl trimethylacrylate (18)." @default.
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- W2167945359 title "Metallsubstituierte Carbene und C-metallierte Diazoalkane, III1)Trimethylsilyl-diazoessigsäureäthylester und seine Photolyse zum Trimethylsilyl-äthoxycarbonylcarben" @default.
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- W2167945359 doi "https://doi.org/10.1002/jlac.19697300102" @default.
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