Synthesis and solid state structures of 1,3-dihalo-1,3-bis(dialkylamino)propenium salts and related compounds

IF 1.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Michael A. Land, Katrina D. Turrie, K. Robertson, J. Clyburne
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引用次数: 0

Abstract

1,3-dicholoro-1,3-bis(dialkylamino)propenium salts are prepared by condensing N,N,-dialkylamides with dichloromethylene dimethyliminium chloride ("Viehe’s Salt"). The products are versatile synthons and can be used to make a variety of ligand types. Here we report the syntheses of a number of new propenium salts and provide comprehensive characterization data for some which have already been described. Additionally, we have prepared a series of related 1,3-dihalo-1,3-bis(dimethylamino)propenium salts via halogen exchange reactions (F through I). Finally, all of the compounds described, including Viehe’s Salt and several hydrolysis products, have been characterized in the solid state using single-crystal X-ray diffraction. The symmetrical cations, [Me2NC(X)CHC(X)NMe2], were found to take one of two general structural forms. The first (X = H or F) is planar, presumably maximizing the delocalization within the backbone of the cation, while the second form is markedly twisted (X = Cl, Br or I). Calculations indicate that the latter develop increasingly positive regions of the electrostatic potential on the halide substituents, allowing cation/anion interactions via halogen bonding to dominate in the extended solids. The results of these studies illustrate the importance of the differing interionic interactions in a homologous series of small organic salts.
1,3-二卤-1,3-双(二烷基氨基)丙烯盐及相关化合物的合成和固态结构
1,3-二氯-1,3-双(二烷基胺)丙烯盐是由N,N,-二烷基酰胺与二氯甲基二甲基铵(Viehe 's Salt)缩合而成的。该产品是多功能合成子,可用于制造各种配体类型。在这里,我们报道了一些新的丙烯盐的合成,并提供了一些已经描述的综合表征数据。此外,我们通过卤素交换反应(F到I)制备了一系列相关的1,3-二卤-1,3-二(二甲氨基)丙烯盐。最后,所有描述的化合物,包括Viehe 's Salt和几种水解产物,都用单晶x射线衍射在固态下进行了表征。发现对称阳离子[Me2NC(X)CHC(X)NMe2]具有两种一般结构形式之一。第一种形式(X = H或F)是平面的,可能最大化了阳离子主干内的离域,而第二种形式是明显扭曲的(X = Cl, Br或I)。计算表明,后者在卤化物取代基上发展出越来越多的正静电电位区域,允许通过卤素键的阳离子/阴离子相互作用在扩展固体中占主导地位。这些研究结果说明了在同源系列小有机盐中不同离子间相互作用的重要性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Canadian Journal of Chemistry
Canadian Journal of Chemistry 化学-化学综合
CiteScore
1.90
自引率
9.10%
发文量
99
审稿时长
1 months
期刊介绍: Published since 1929, the Canadian Journal of Chemistry reports current research findings in all branches of chemistry. It includes the traditional areas of analytical, inorganic, organic, and physical-theoretical chemistry and newer interdisciplinary areas such as materials science, spectroscopy, chemical physics, and biological, medicinal and environmental chemistry. Articles describing original research are welcomed.
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