CEQUINOR (UNLP-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, 1900 La Plata, Argentina.
J Org Chem. 2012 Aug 3;77(15):6456-62. doi: 10.1021/jo3009726. Epub 2012 Jul 20.
Chlorodifluoroacetyl azide, ClF(2)CC(O)N(3), was prepared and characterized by IR (gas, Ar matrix), Raman (liquid), UV-vis (gas), and (19)F, (13)C NMR spectroscopy. The vibrational spectra were analyzed in terms of a single conformer, gauche-syn, where the Cl-C and the N(α)═N(β) bonds are gauche and syn to the C═O bond, respectively. The photo and thermal decomposition reactions of the azide were studied with the aid of matrix isolation. In both cases, a new isocyanate species ClF(2)CNCO was produced and characterized by matrix IR spectroscopy. The conformational properties and the Curtius rearrangement pathways of this new carbonyl azide were theoretically explored, which suggest the preference of a concerted over stepwise decomposition for the global minimum gauche-syn conformer.
一氟二氯乙酰胺，ClF2CC(O)N3，通过红外（气体，氩基质）、拉曼（液体）、紫外-可见（气体）和（19F，13C）NMR 光谱进行了制备和表征。振动光谱根据单个构象进行了分析，即 gauche-syn，其中 Cl-C 和 N(α)═N(β)键分别与 C═O 键 gauche 和 syn。在基质隔离的帮助下，研究了叠氮化物的光解和热分解反应。在这两种情况下，都产生了一种新的异氰酸酯 ClF2CNCO，并通过基质红外光谱进行了表征。理论上探讨了这种新的羰基叠氮化物的构象性质和 Curtius 重排途径，这表明对于全局最小 gauche-syn 构象，协同分解优先于逐步分解。
