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3. o-Cyanophenol from the Sodium Salt of syn-o-Nitrobenzaldoxime. A reaction mixture similar to IC employing the sodium salt of syn-o-nitrobenzaldoxime8 (1.13 g, 6 mmol), o-nitrobenzonitrile (20 mg, 0.14 mmol), freshly ground potassium hydroxide (338 mg, 6 mmol), and MezSO (20 ml) stirred at room temperature for 8 hr and worked up as in IC gave 500 mg (66%) of o-cyanophenol, mp 94-95O (lit.Io mp 98O). Piperonylonitrile. A. From Isolated Piperonaldoxime.The oxime employed, prepared quantitatively in aqueous ethanol, melted at 107-110' (lit." syn isomer 112O, anti isomer 146O); NMR [(CD&SO] 6 8.07 (s, 1, HC=N), 11.01 (s, 1, NOH). A mixture of the oxime (1 g, 6 mmol), p-nitrobenzonitrile (900 mg, 6.1 mmol), freshly ground potassium hydroxide (676 mg, 12 mmol), and 20 ml of MezSO was stirred at room temperature for 3-4 hr. The mixture was poured into ice water (150 ml) and the solution was acidified and extracted with ether. The ethereal extract was successively washed with cold 5% aqueous sodium hydroxide and water. After drying (MgS04) and removal of the solvent in vacuo, 807 mg (92%) of the nitrile was obtained. Recrystallization from ethanol-water gave analytically pure material (645 mg, 73%), mp 87-89' (lit.4 mp 91-93O). Anal. Calcd for C&N02: C, 65.31; H, 3.43; N, 9.52. Found C, 65.16; H, 3.46; N, 9.66.B. From Piperonaldoxime Prepared in Situ. A mixture of hydroxylamine hydrochloride (462 mg, 6.5 mmol), sodium methoxide (350 mg, 6.5 mmol), and 20 ml of MezSO was stirred at room temperature for 15 min. Piperonal (1 g, 6.5 mmol) was added and the mixture was heated at 70' for 2 hr. Heating was then discontinued, p-nitrobenzonitrile (980 mg, 6.5 mmol) and freshly ground potassium hydroxide (758 mg, 13 mmol) were added, and the mixture was stirred at room temperature for 3-4 hr. Work-up as in part A and recrystallization from ethanol-water afforded 742 mg (78%) of piperonylonitrile, mp 87-891° (lit.4 mp 92-93').Yavari, Esfandiari, Mostashari, and Hunter Chem.When benzofurazan is irradiated by ultraviolet light (3000 A), a reactive nitrile oxide intermediate is produced.In order to trap this intermediate, benzofurazan has been irradiated in dimethyl acetylenedicarboxylate (DAD).The nitrile oxide reacts with DAD to produce various geometrical isomers of dimethyl 3-(4-cyanobuta-l,3-dienyl)isoxazole-4,5-dicarboxylate (8). The isoxazoles have been characterized by their NMR spectra. All the isomers have been degraded to the same dimethyl 3-carboxaldehydeisoxazole-4,5-dicarboxylate (9) by ozonolysis. Cis,cis, trans,cis, and trans,trans isomers of 8 have been identified.

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The preparation and characterisation of some nickel(ii) and copper(i1) complexes with methyl-substituted tetrahydro-1.5-benzodiazepines are reported. Some magnetic properties and electronic and vibrational spectroscopic data are discussed. The nickel perchlorate complexes appear to be square-planar with two diazepine ligands assuming a trans-arrangement. The copper perchlorate complex of the trimethylbenzodiazepine is also squareplanar but a decrease in the methyl-substitution of the diazepine ligand apparently allows the approach of further co-ordinating species and the formation of five-co-ordinate complexes. Five-co-ordination is also present in the nickel chloride complexes whereas the corresponding bromide and iodide complexes are square-planar. COMPLEXES of cyclic diamines have been extensivelystudied in recent y e a r ~. l -~ Very often such complexes exist in uncommon geometries due to the steric hindrance of the cyclic ligands6 Although 1,5-benzodiazepines have found extensive application in the pharmaceutical industry and in some cases have carcinostatic activity,8 (1) R1 = Me,% R = R3 = H, abbreviation used in this paper: meaz; R1 = Rs = Me, R2 = H, dmaz; R1 = R3 = R3 = Me, tmaz. relatively little work has been published on their behaviour towards metal ions. Recently some 2,4dimethyl-lH-l,5-benzodiazepinium metal salts have been d e s ~r i b e d . ~~ lo We now report the preparation and

Freezing water and nitrogen at low atmospheric pressure.