Direct observation of various reaction pathways of arylnitrenes in different crystal environments caused by acid–base complex formation

Abstract

The structures of reaction intermediates, arylnitrenes and their final products have been successfully analyzed by X-rays using acid–base complex formation. The acid–base complexes of 2-azidobenzoic acid (2a), 3-azidobenzoic acid (3a) and 4-azidobenzoic acid (4a) were made with dibenzylamine (db), N-benzyl-2-phenylethylamine (bp) and dicyclohexylamine (dc). For the complex crystals of (3a) and db (3a-db), and (4a) and db (4a-db) two forms of (I) and (II) were obtained. Eight types of complex crystals, (2a-db), (3a-db-I), (3a-db-II), (3a-dc), (4a-db-I), (4a-db-II), (4a-bp) and (4a-dc), suitable for X-ray analysis were obtained. When the crystals were irradiated with UV light at low temperatures, the reactions proceeded keeping the single-crystal form in the five crystals (2a-db), (3a-db-I), (3a-db-II), (3a-dc) and (4a-bp). Less than 25% of each azidobenzoic acids was transformed into an arylnitrene and dinitrogen. In three crystals the arylnitrenes produced gave new final products; 2,1-benzisoxazolone was observed for (2a-db) and trans-azobenzenes (i.e. dimerized nitrenes) were obtained for (3a-db-II) and (4a-bp). For (3a-db-I) and (3a-dc) the intermediate arylnitrenes were observed but did not transform to new products. All the structural changes were directly observed by X-ray analysis because the incomplete reactions occurred with retention crystallinity. The crystal environment, including the hydrogen bonding between the benzoic acid and the amine, places restrictions on the movement of the arylnitrene and influences the reaction pathway followed for conversion of the arylnitrene to its final product.