Über einige neue Reaktionen aliphatischer Nitrile

Abstract

I.Unserer ersten Absicht folgend, verwandten wir als Versuchsobjekte zu Beginn unserer Arbeit ausschliefilich die Nitrile der Isobutter-und Diathylessig-saure. Wir versuchten, in Anlehnung an die van B o d r o u x und T a b o u r y z ) l) Diathyl-allyl-acetamid wird linter dem Namen ,,NooonaZ" als Hypnotiium vertrieben.C. r. 160, 531, 1211 (1910).

Transition-metal dialkylamides and disilylamides

“…At room temperature and above a single resonance is observed, but below -30°t wo resonances appear in the integral ratio 1:1 separated by 2 ppm. This clearly indicates the temperature-dependent rate of proximal and distal methyl exchange and the large diamagnetic anisotropy associated with the M-M triple bond.62 1.884 (8), 1.882 (9) Á; N-C, 1.516 (12). 1.484 (11), 1.491 (13), 1.468 (11), 1.473 (11), 1.465 (10) A; N-Cr-N angles, 120.7 (4), 118.6 (4), 120.7 (4)°; Cr-N-C angles, 115.9 (4), 129.4 (5), 122.3 (4), 123.2 (5), 128.0 (4), 115.9…”

A STUDY OF THE ALKYLATION OF HYDRATROPONITRILE WITH BUTYL HALIDES1

“…Preparation of a-phenyl-a-methylcapronitrile. The procedure used was similar to that of Ziegler and Ohlinger (4). In a 1-1. three-necked flask equipped with a stirrer, reflux condenser, and dropping-funnel was placed a mixture of 34 g. (0.26 mole) of hydratroponitrile, 28 g. (0.3 mole) of n-butyl chloride and an equal volume of dry toluene.…”

“…The yields of alkylated nitrile, in many cases in excess of 90%, appear in general to be dependent upon three factors: (a) the alkyl halide, (b) the nitrile (3,4), and (c) the temperature and manner in which the alkylation is carried out. Both a low-temperature method (5) and a high-temperature method (80 to 100°) due to Ziegler and Ohlinger (4) have been reported.…”

“…The yields of alkylated nitrile, in many cases in excess of 90%, appear in general to be dependent upon three factors: (a) the alkyl halide, (b) the nitrile (3,4), and (c) the temperature and manner in which the alkylation is carried out. Both a low-temperature method (5) and a high-temperature method (80 to 100°) due to Ziegler and Ohlinger (4) have been reported. Tilford, et al (6) have shown that cyclohexyl cyanide was alkylated in best yields by normal alkyl bromides and in poorer yields by secondary and branched chain bromides, whereas tertiary butyl bromide gave no product whatever.…”

Funcionalização regiosseletiva de cloroquinolinas visando a síntese de compostos de interesse medicinal

“…Contudo, a partir de 1932, Ziegler foi o primeiro a introduzir dialquilamidetos de lítio como bases, as quais primeiro foram aplicadas na enolização de compostos carbonílicos e as contribuições mais efetivas em reações de DoM surgiram a partir dos trabalhos de Beak, Meyers e Snieckus. (BEAK;SNIECKUS, 1982;HAMELL;LEVINE, 1950;MULVEY, 2009;QUEGUINER et al, 1991;WHISLER et al, 2004;ZIEGLER, K.;OHLINGER, 1932) Amidetos de lítio como LDA, LiHMDS e LiTMP, embora apresentem um átomo de nitrogênio com características nucleofílicas, apresentam impedimento estérico suficiente para serem nucleófilos pobres, fato que as torna excelentes bases para abstração de hidrogênios (SMITH, 2010). Tais reagentes de lítio, mostram-se eficientes na abstração de hidrogênio de sistemas heteroaromáticos do tipo π deficientes, como por exemplo as piridinas, as quais são metaladas na posição orto ao grupo dirigente, uma vez que essa regiosseletividade pode ser explicada em função da acidez da ligação C-H que pode ser prevista por cálculos de termoquímica computacional, como por exemplo, DFT (A. EL-HITI; SMITH; S. HEGAZY, KADIYALA et al, 2013;SNÉGAROFF et al, 2011).…”