The Reaction of 2-Cyano-2-Propyl Free Radicals With Oxygen: 2-Cyano-2-Propyl Hydroperoxide

Abstract

The reaction with oxygen of cyanisopropyl free radicals generated by the polymerization catalyst 2,2′-azobisisobutyronitrile has been investigated. In xylene, or benzene, as solvent at 55° the products identified are: (1) a new compound, 2-cyano-2-propyl hydroperoxide; (2) acetone cyanohydrin; (3) hydrogen cyanide; (4) cyanogen; (5) acetone; (6) p-methyl benzaldehyde (in xylene only); and (7) tetramethylsuccinodinitrile. The hydroperoxide is surprisingly stable; its physical constants are: b.p. 37 °C at 1 mm Hg; m.p. −9 to −8°; [Formula: see text] 1.4138; d20 1.013 g/ml. In benzene under the same experimental conditions, only a very small amount of the hydroperoxide is obtained, the principal product being acetone cyanohydrin. A free-radical mechanism is proposed. The induced decomposition of the hydroperoxide, which is important in benzene, is almost completely inhibited in the presence of xylene. The new hydroperoxide can be used as a polymerization catalyst at moderately elevated temperatures.

Artifacts Generated During Azoalkane Peroxy Radical Oxidative Stress Testing of Pharmaceuticals Containing Primary and Secondary Amines

“…The drug amine group reacts with formaldehyde to form the imine intermediate, which further reacts with cyanide (Scheme 5), explaining the incorporation of the nitrile and methylene groups observed during the labeling experiments. Previous reports showing formation of cyanide and acetone cyanohydrin during AIBN-initiated oxidation of benzene, 22 as well as formation of formaldehyde during the oxidative stress test carried out in the presence of methanol, 8 support the proposed mechanism. Table 2 shows our own measurements of cyanide levels generated during the thermal stress of AIBN in the absence of the test drug.…”

A Novel Inhibitor for Fe-type Nitrile Hydratase: 2-Cyano-2-propyl Hydroperoxide

“…Cpx was first synthesized in 1960 as a quite stable hydroperoxide under aerobic conditions. 50 Indeed, pure Cpx is stable above 120 °C. We confirmed the contamination by Cpx of the commercially available iso-BN reagents purchased from five different companies, although the amount of Cpx varied in each reagent.…”

cis-trans Isomerism of Exocyclic α,β-Unsaturated Indanones and Tetralones

“…Table I Properties of cis and trans Isomers of Exocyclic «j/S-Unsaturated Tetralones and Indanones The cis isomers were of lower melting point, consistent with a trans to cis conversion. 4 It can be seen from Table II that the ultraviolet spectral data, frequently found useful for assigning cis and trans isomers,4 are of little assistance in assigning the isomers of these exocyclic ,/3-unsaturated ketones. The infrared spectral data also present a confusing picture, but it is noteworthy that a peak assigned as due to C=C in the spectra of the trans isomers is absent in the spectra of the cis isomers.…”

“…For an excellent discussion of the physical properties of geometrical isomers of olefins, see E. L. Eliel, "Stereochemistry of Carbon Compounds," McGraw-Hill Book Co., Inc., New York, N. Y., 1962, Chapter 12, Section 12-3. (5) See ref 4,. p. 344, for a discussion of the mechanism of these acid and secondary amine promoted interconversi ons.…”