tert-Butyldiphenylsilylhydrazin – ein Baustein für Tetrakis-silylhydrazine, Silylhydrazone und O-Silylpyrazolone

✍ Scribed by Eike Gellermann; Uwe Klingebiel; Martina Schäfer

• Book ID: 101300426
• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: German
• Weight: 162 KB
• Volume: 626
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(200005)626:5<1131::aid-zaac1131>3.0.co;2-g

✦ Synopsis

3 . Von 7 entsteht nur eines der zwei mo È glichen Isomere. Ein cis/trans Isomerengemisch (8 a, b) wird in der analogen Reaktion von 1 und Acetessigsa È ureethylester erhalten, Me 3 CSiPh 2 NH±N=CMe±CH 2 ±COOEt (8 a, b). Thermisch kondensiert 8 unter EtOH-Abspaltung zum O-Silylpyrazolon 9, Me 3 CSiPh 2 O±(C=N±NH±CMe=CH±). Die Ergebnisse der Kristallstrukturanalysen von 2, 4 und 7 werden mitgeteilt. tert-Butyldiphenylsilylhydrazine ± Precursors for Tetra(silyl)hydrazines, Silylhydrazones, and O-Silylpyrazolones Abstract. tert-Butylchlorodiphenylsilane reacts with hydrazine in presence of triethylamine to give the mono(silyl)hydrazine Me 3 CSiPh 2 NHNH 2 (1). The lithium derivative of 1 (1 a) forms the N,N'-bis(silyl)hydrazines 2 and 3 in the reaction with chlorosilanes. (2: Me 3 CSiPh 2 NHNHSiPh 2 CMe 3 ; 3: Me 3 CSiPh 2 NHNHSiMe 2 CMe 3 ). The monomeric dilithiumhydrazide 4, (Me 3 CSiPh 2 ) 2 N 2 Li 2 (THF) 3 , is obtained from 2 and the bimolar amount of C 4 H 9 Li in THF. 4 reacts with an excess of SiF 4 to give the tetra(silyl)hydrazine 5, Me 3 CSiPh 2 (SiF 3 )N±N(SiF 3 )SiPh 2 CMe 3 . 1 and ketones undergo condensation to silylhydrazones, Me 3 CSiPh 2 NHN=C(Me)R (6: R = Me; 7: R = CMe 3 ), with elimination of H 2 O. Only one of the two possible isomers of 7 is formed. Cis/trans isomers (8 a, b) are obtained in the analogous reaction of 1 and ethyl acetoacetate, Me 3 CSiPh 2 NH±N=CMe±CH 2 ±COOEt (8 a, b). 8 condenses thermally with elimination of EtOH and formation of the O-silylpyrazolone 9, Me 3 CSiPh 2 O±(C=N±NH±CMe=CH±). The results of the crystal structure analysis of the compounds 2, 4, and 7 are reported.