2,2‐Difluor‐1,3‐diaza‐2‐sila‐cyclopenten – Synthese und Reaktionen |
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Authors: | N Sievert A Fischer U Klingebiel Prof Dr A Pal M Noltemeyer |
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Institution: | 1. G?ttingen, Institut für Anorganische Chemie der Universit?t;2. G?ttingen, Institut für Anorganische Chemie der Universit?tInst. f. Anorg. Chemie der Universit?t, Tammannstr. 4, D‐37077 G?ttingen;3. Kristallstrukturanalyse |
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Abstract: | 2,2‐Difluor‐1,3‐diaza‐2‐sila‐cyclopentene – Synthesis and Reactions N,N′‐Di‐tert‐butyl‐1,4‐diaza‐1,3‐butadiene reacts with elemental lithium under reduction to give a dilithium salt, which forms with fluorosilanes the diazasilacyclopentenes 1 – 4 ; (HCNCMe3)2SiFR, R = F ( 1 ), Me ( 2 ), Me3C ( 3 ), N(CMe3)SiMe3 ( 4 ). As by‐product in the synthesis of 1 , the tert‐butyl‐amino‐methylene‐tert‐butyliminomethine substituted compound 5 was isolated, R = N(CMe3)‐CH2‐CH = NCMe3. 5 is formed in the reaction of 1 with the monolithium salt of the 1,4‐diaza‐1,3‐butadiene in an enamine‐imine‐tautomerism. 1 reacts with lithium amides to give (HCNCMe3)2SiFNHR, 6 – 12 , R = H ( 6 ), Me ( 7 ), Me2CH ( 8 ), Me3C ( 9 ), H5C6 ( 10 ), 2,6‐Me2C6H3 ( 11 ), 2,6‐(Me2CH)2C6H3 ( 12 ). The reaction of 12 with LiNH‐2.6‐(Me2CH)2C6H3 leads to the formation of (HCNCMe3)2Si(NHR)2, ( 13 ). In the presence of n‐BuLi, 12 forms a lithium salt which looses LiF in boiling toluene. Lithiated 12 adds this LiF and generates a spirocyclic tetramer with a central eight‐membered LiF‐ring ( 14 ), (HCNCMe3)2Si(FLiFLiNR)]4, R = 2,6‐(Me2CH)2C6H3. ClSiMe3 reacts with lithiated 12 to yield the substitution product (HCNCMe3)2SiFN(SiMe3) R, ( 15 ). The crystal structures of 1 , 5 , 6 , 9 , 11 , 13 , 14 are reported. |
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Keywords: | Diazasilacyclopentenes Lithium salts Enamine‐imine tautomerism |
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