Observation of a Single-pot Aromatic Reductive Denitration

4,N,N-Trimethyl-3-nitrobenzenamine gave reductive denitration products (ca. 28%) upon treatment with n-butyl nitrite in the presence of catalytic amounts of ammonium chloride and water in an unprecedented one-reagent single-pot process. The three isomeric N,N-dimethylnitrobenzenamines showed the same behaviour to a much lesser extent; the ortho isomer was partially (7%) transformed into 1-methylbenzotriazole

Low-water-content diazomethane-d(2) and its isotopic assay

A multiple D2O-CH2N2 exchange followed by a final anhydrification with K2CO3 gave an alcohol-free low-water-content ether solution of CD2N2. Procedural improvements for the exchange are reported. The extent of deuteration with a quantitative evaluation of the actual species present in any solution of diazomethane could be determined by a GC-MS analysis and H-1 NMR spectrometry on a suitable derivative. In addition, a procedure for the quantitative determination of water in diazomethane solutions has been developed

THE PHOTOLYSIS OF 2,4,5,6-TETRACHLORO-1,3-DICYANOBENZENE

2,4,5,6-Tetrachloro-1,3-dicyanobenzene undergoes extensive transformation to many photoproducts of single and sequential excitation on UV irradiation in ethanol. Cl \u2192 H and CN \u2192 H exchange take place with the solvent, and solvent incorporation occurs followed by cyclization on the cyano groups(s) and/or further side-chain deoxygenation. Cl \u2192 Et exchange is also observed. The photoproducts were identified by gas chromatography\u2014mass spectrometry (GC\u2014MS). Some were isolated and analysed by IR and nuclear magnetic resonance (NMR) spectroscopy, which provided evidence for their structural identification. o-Cholorobenzonitrile was found to yield only the product of photoreduction of the C-Cl bond

17O NMR Studies on alpha-Diamides

17O NMR spectra of several \u3b1-diamides were obtained at natural isotopic abundance in acetonitrile solution in order to study the conformations of these compounds in solution. The 17O NMR shifts vary with the intercarbonyl dihedral angle \u3b1 in a sense opposite to that observed for \u3b1-diketones

Nucleophilic Substitution in Diphenylmethyl Derivatives. I. Formolysis of Diarylmethyl Derivatives: an alpha-Substituent Effect

The reactions of formic acid with and without addition of sodium formate with diphenylmethanol (4) and chlorodiphenylmethane (3) were compared to those with hydroxydiphenylacetic (benzilic) acid (12a) and chlorodiphenylacetic acid (14a). Formic acid did not favour any S(N)1-type reaction on 4, but a strong catalysis by iodide ion was observed. Sodium formate rapidly performed the substitution of the chlorine in 3. A similar outcome was obtained with chloro acid 14a, but the rationalization of the results is different. Chloro acid 14a and its methyl ester 14b were prompt to react, but the equilibria were shifted to alpha-formyloxy products 13 only by the addition of HCOONa. HCOOH was unable to perform any reduction on either 3 and 4 or 12a and 14a, a fact which was taken as evidence for concerted substitution mechanisms on ion pairs or betaine 15. Mechanistic implications are drawn

ADDITION OF A METHYLENE GROUP ACROSS THE ESTER CARBONYL FUNCTION

Diazomethane in ethyl ether promptly added to the carbonyl group of the phenyl trifluoroacetate to yield 2-phenoxy-2-trifluoromethyloxiran