The electron ionization (EI) and collision-induced dissociation (CID) spectra of substituted N-(ortho-cyclopropylphenyl)benzamides 1-7 and N-[ortho-(1-methylcyclopropyl)phenyl]benzamides 8-12 were recorded. In addition to routine bond cleavages, the molecular ions (M+) of 1-12 undergo cyclization into the corresponding 3-aryl-1-alkyl-1-ethyl-1H-benzoxazines and isomeric 5-ethyl-2-oxodibenzoazepines. The presence of a methyl group in the cyclopropyl ring (compounds 8-12) makes the formation of 5-ethyl-2-oxodibenzoazepine less favorable. In accord with mass spectrometric predictions, compound 13 (3-p-tolyl-1-ethyl-1H-benzoxazine) was obtained as a major product of the reaction of N-(ortho-cyclopropylphenyl)-4-methylbenzamide 1 with sulfuric acid. Traces of 5-ethyl-2-oxodibenzoazepine were also detected in gas chromatography-mass spectrometry (GC-MS) analysis of the reaction mixture although the yield was too low to allow its isolation.

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Esters of 2-arylcyclopropanecarboxylic acids react with nitrous acid generated in situ with regioselective insertion of the nitrosyl cation into the cyclopropane ring. Depending on the substrate/nitrosylating agent ratio, the reaction proceeds with the formation of either aryl-substituted 3-ethoxycarbonyl-4,5-dihydroisoxazoles or the corresponding isoxazoles. The nature and position of the substituents in the aromatic ring of the starting 2-arylcyclopropanecarboxylic acid esters affect the reaction rate but have no effect on the regioselectivity of the attack by the nitrosyl cation on the three-membered ring. A dependence of the reactivity of isomeric substrates on their stereochemistry and position of the nitro group in the aromatic ring is noted for 2-and 4-nitrophenyl derivatives of esters of cis-and trans-2-arylcyclopropanecarboxylic acids.Keywords: 5-aryl-3-ethoxycarbonyl-4,5-dihydroisoxazoles, 5-aryl-3-ethoxycarbonylisoxazoles, ethyl esters of 2-arylcyclopropanecarboxylic acids, insertion of the nitrosyl cation into the cyclopropane ring.The reaction of arylcyclopropanes with nitrosylating agents, which proceeds through insertion of the nitrosyl cation or nitrosyl radical into the cyclopropane ring, may be seen as one of the most efficient methods for the synthesis of aryl-substituted 4,5-dihydroisoxazoles and isoxazoles, which are potential pharmaceutical agents and important precursors for the preparation of biologically-active compounds, including natural products [1][2][3][4][5][6].