Chemistry of dinitroacetonitrile—IV

Synthetic approach to the skeleton of histrionicotoxin

“…The aqueous solution was extracted with methylene chloride (1 X 300 ml). The methylene chloride solution was dried over anhydrous magnesium sulfate, and the methylene chloride was removed at reduced pressure, to give 36.3 g of keto alcohol 9 in an 83.5% yield from acid 17: ir (neat) 2.9 (m), 5.8 (s), 6.1 (w), 8.3 (s), 8.5 (s), and 12.2 µ (w); nmr (CDCI3) 1.6 (m, 6), 2.4 (m, 4), 2.6 (m, 2), 3.2 (broad singlet, 1 ), 3.6 (m, 2), 3.7 (s, 3), 4.7 (d, 1, J = 12 Hz), and 6.1 ppm (doublet of triplets, 1, J = 8, 12 Hz); mass spectrum (M -HaO) m/e 210.…”

Synthesis and x-ray study of novel azofurazan-annulated macrocyclic lactams

“…We have successfully adapted this strategy to the synthesis of the amino acid 1. As outlined in Scheme 1, commercially available cyanoacetic ester was converted to cyano oxime (nearly quantitative yield) by nitrosation with sodium nitrite in the presence of an acid by a modified literature procedure [18]. Subsequent treatment with an excess of hydroxylamine hydrochloride and a mixture of NaOH and KOH with heating and vigorous stirring followed by acidification gave the amino acid 1 in 78% yield.…”

Michael Reaction with Nitroform and Related Syntheses

“…Analytical and spectroscopic data [10] support this formulation. The infrared spectra no longer exhibit the characteristic broad band of the trinitromethyl grouping (at 1614 cm-) and the carbonyl absorption bands fall within the region of an lX,p-unsaturated ketone.…”