Reaktionen mit Nitro‐acetonitril

Abstract

R i e d und K o h l e r 145 3,4-Seeo-koprostan-3,4-diol (XIII) 200 mg der 3,4-Seco-koprostan-3,4-disLure(XII) wurden mit Diazomethan in den Dimethylester verwandelt (Schmp. el0), der in abs. Ather mit LiAlH, bei 20° zum Dialkohol umgesetzt wurde. Ausbeute nach Chromatographie an A1,0, (Elution mit Methanol) 150 mg Reinsubstanz. Schmp. 146O. ~,,H,,O, (40697) Ber. C 79,74 H 12,39 Gef. )) 80,16 )) 12,38 3,4-Seeo-ko~ostan-3,4-d~a~ure-di.meth ylamid 400 mg der 3,4-Seoo-koprostan-3,4-diskiure wurden, analog wie oben beschrieben, zum Di-skiuredimethylcynid umgesetzt. Ausbeute praktisoh quantitativ. Die Substanz lie13 sioh aus ebs. Ather umkristallisieren. Lange Prismen, die sioh zu Rosetten zusammensohlossen, vom Schmp. 156-157 O. CsiH,,O,N, (48898) Ber. C 76,17 H 11,55 N5,73 Gef. )r76,47)) 11,60 )) 5,68 3,4-Seco-ko?~.ostan-3,4-di-dimethyEamin-dih ydrochlorid (XIV)200 mg des Di-dimethylamids wurden, wie zuvor besohrieben, mit LiAIH, in Ather zum entsprechenden Di-dimethylamin reduziert. Das Dihydrochlorid wurde aus Aoeton umkristallisiert. Ausbeute praktisch quantitativ. Bei 256" beginnt die Substanz sich zu zersetzen.CnH,sN,C1, (53397) Ber. C 69,75 H 11,71 N 5,25Gef. D 69,60 )) 11,96 )) 5,23

Chemistry of 2-aryl-1-cyano-1-nitroethenes. Part II. Chemical transformations

“…Reactions conducted in diethyl ether at room temperature gave a mixture of regioisomeric 1-aryl-4-nitro-5-phenyl-4,5-dihydro-1H-1,2,3-triazole-4-carbonitriles (3a,b) and 1-aryl-5-nitro-4-phenyl-4,5-dihydro-1H-1,2,3-triazole-5-carbonitriles (5a,b). Finally, 1-aryl-5(4)-phenyl-1H-1,2,3-triazole-4(5)-carbonitriles (4a,b, 6a,b) (Table 1) were formed as a result of spontaneous nitrous acid extrusion from primary [2,3] cycloaddition products [7]. Piet et al [12] also deal with the [2+3] cycloaddition reactions of PCN (1) with phenylazide (2a) and methylazide (7).…”

“…The kinetic aspects of these transformations have also been recently discovered [9] In the same year, Pizzo et al [3] showed an example of intramolecular cycloaddition in 2-(2' -(3",3"-dimethyl)allyloxyphenyl)-1-cyano-1-nitroetene (46) generated in situ. This reaction led to the formation of cis-4a,10b,-dihydro- 1-cyano-4,4,dimethylbenzo[b]pyrene- [4,3-d] [1,2] oxazine-2-oxide (47) and its 4a-epimer (48) in a 16:1 ratio and with a 60% yield of (48). …”

“…ACNs have been known since the first half of the twentieth century [2]. Currently, several compounds of this group are known; nonetheless, their chemical properties are not well recognized [3][4][5][6].…”

Novel synthesis scheme and in vitro antimicrobial evaluation of a panel of (E)-2-aryl-1-cyano-1-nitroethenes

“…In 760 mL, four-neck glass equipped with a mechanic stirrer, a dropping funnel, a thermometer and a reflux condenser, 60 g of methazonic acid (prepared from nitromethane according to the procedure described previously 18 ) was dissolved in 300 mL of diethyl ether. Next, reaction mixture was heated to boiling, and dropped slowly 43 mL of tionyl chloride.…”

The Reaction of Nitroacetonitrile With Aromatic Amines

“…T h e hydrolysis of these alleged amidines t o their starting materials was attributed recently (2) to the for~nation of a resonance-stabilized c a r b o n i~~m ion, although no other anlidines are known to hydrolyze in this way.…”