The preparation and characterization of products of the chemical and photochemical rearrangements of a 19‐membered o,o′‐azoxybenzocrown are presented. In photochemical rearrangement, besides the expected product i. e. 19‐membered o‐hydroxy‐o,o′‐azobenzocrown (19‐o‐OH) obtained under defined conditions with 75 % yield, also other macrocyclic products were isolated and identified, namely: 19‐membered p‐hydroxy‐o,o′‐azobenzocrown (19‐p‐OH), 21‐membered o′‐hydroxy‐o,p′‐azobenzocrown (21‐o′‐OH) and 19‐membered macrocycle containing a 5‐membered ring bearing an aldehyde group (19‐al). The structures of two atypical products of the photochemical rearrangement – 21‐o′‐OH and 19‐al – were determined in the solid state by X‐ray analysis and in solution using NMR spectroscopy. Tautomeric equilibrium of the formed hydroxyazobenzocrowns and its change depending on acidity/basicity of the environment and alkali and alkaline earth metal cations complexation were studied using UV‐Vis spectrophotometry, spectrofluorimetry and ¹H NMR spectroscopy.

中文翻译：

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19元偶氮苯并冠的光化学重排：产品及其性能。

的一个19元的化学和光化学重排的产物的制备和表征ö，O' -azoxybenzocrown被呈现。在光化学重排中，除了预期的产品i。e。19元ö羟基ø，O' -azobenzocrown（19- ö -OH）用75％的产率限定的条件下获得的，还有其它的大环产物分离和鉴定，即：19元p羟基Ò，ö '-偶氮苯并冠（19- p -OH），21元邻' -羟基-o，p'-azobenzocrown（21- O' -OH）和19元含5元环轴承醛基（大环化合物19-AL） 。的光化学重排两种非典型产物的结构- 21- O' -OH和19人-通过X射线分析和使用NMR光谱溶液在固体状态进行了测定。使用紫外可见分光光度法，荧光分光光度法和¹ H NMR光谱研究了形成的羟基偶氮苯并冠的互变异构平衡及其随环境的酸度/碱度以及碱金属和碱土金属阳离子的络合而变化。