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Alkynolpyridines and Their Complexes with Triphenylphosphine Oxide

机译：炔诺吡啶及其与三苯基氧化膦的配合物

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摘要

2,6-Bis(3-methyl-butyn-3-ol)pyridine (1) and 2-bromo-6-[3-methyl-butyn-3-ol]pyridine (2) form complexes with triphenylphosphine oxide, 1·2tppo and 2·tppo, respectively. Hydrogen bonding dominates the crystal packing in 1, but in the complexes phenyl embraces play a major role. Hydrogen bonding between the hydroxyl end groups of 1 link the molecules into infinite chains, and the chains are cross-linked through hydrogen bonding between one hydroxyl group and the pyridine nitrogen atom to form layers. In 1·2tppo the hydroxyl groups are terminated through O-H…O = P interactions, but the chain structure is perpetuated sextuple embraces. The loosely associated chains peak so that the pyridyl rings of one chain are inserted into cavities of the next. Replacement of one of the alkynol arms by a bromine atom in 2·2tppo results in formation of a dimer through C-H…O interactions. Phenyl embraces coupled with C-H…N and C-H…Br interactions extend the structure in two dimensions, and the resulting layers stack normal to this plane. Thermal analysis of the complexes reveals that decomposition of 1·typo occurs through simultaneous loss of both components, while the monoalkynol pyridine diffuses out of the complex first in 2·tppo.
机译：2,6-双（3-甲基-丁炔-3-醇）吡啶（1）和2-溴-6- [3-甲基-丁炔-3-醇]吡啶（2）与三苯基氧化膦形成配合物，1· 2tppo和2·tppo。氢键在1中的晶体堆积中占主导地位，但在配合物中，苯基环抱起主要作用。 1的羟基端基之间的氢键将分子连接成无限链，并且该链通过一个羟基和吡啶氮原子之间的氢键交联以形成层。在1·2tppo中，羟基通过O-H…O = P相互作用而终止，但链结构是永久性的六元组。松散缔合的链达到峰值，因此一条链的吡啶环插入另一条链的腔中。在2·2tppo中，一个溴原子取代炔醇臂之一，导致通过C-H…O相互作用形成二聚体。苯基结合物与C-H…N和C-H…Br相互作用耦合，从而在二维上扩展了结构，并且最终的层垂直于该平面堆叠。对配合物的热分析表明，通过同时损失两个组分，发生了1·typo的分解，而一炔炔吡啶则首先以2·tppo的形式从配合物中扩散出来。

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