Vlasenko Marina P, Pozharskii Alexander F, Ozeryanskii Valery A, Kletskii Mikhail E, Lisovin Anton V, Demidov Oleg P, Tkachuk Anna V
Department of Chemistry, Southern Federal University, Zorge Street 7, 344090 Rostov-on-Don, Russian Federation.
Institute of Physical and Organic Chemistry, Southern Federal University, Stachki Avenue 194/2, 344090 Rostov-on-Don, Russian Federation.
J Org Chem. 2024 Jul 5;89(13):9210-9222. doi: 10.1021/acs.joc.3c02964. Epub 2024 Jun 14.
Six previously unknown zwitterions with positively and negatively charged [NHN] hydrogen bonds were synthesized by acylation of 4,5-bis(dimethylamino)-1-tosylamino-8-aminonaphthalene with subsequent alkaline treatment of the resulting 8-acylamino derivatives. Using NMR and XRD measurements in conjunction with quantum chemical DFT/PBE1PBE/6-311++G(d,p) calculations, it was shown that the negatively charged [NHN] bond in such compounds commonly differs from the [NHN] bond by significantly lower linearity, higher asymmetry, and moderate to strong paramagnetic shift of the chelated NH proton signal. Among other remarkable findings, the most important are (1) unusually high polarity (μ = 21-26 D) of the obtained zwitterions, (2) sharp difference in structures of the solid 1,8-bis(tosylated) zwitterion (BTZ) grown from MeCN or DMF, and (3) registration for one of the stereoisomers of BTZ with the record short [NHN] hydrogen bridge (N···N = 2.510 Å) almost reaching the theoretical limit (2.50 Å) for the [NHN] hydrogen bond.
通过4,5-双（二甲基氨基）-1-对甲苯磺酰氨基-8-氨基萘的酰化反应，随后对所得的8-酰基氨基衍生物进行碱性处理，合成了六种先前未知的带有正负电荷[NHN]氢键的两性离子。结合量子化学DFT/PBE1PBE/6-311++G(d,p)计算使用NMR和XRD测量表明，此类化合物中带负电荷的[NHN]键通常与[NHN]键不同，其线性度明显较低、不对称性较高，且螯合NH质子信号有中等至强烈的顺磁位移。在其他显著发现中，最重要的是：（1）所得两性离子具有异常高的极性（μ = 21 - 26 D）；（2）从MeCN或DMF中生长的固体1,8-双（对甲苯磺酰化）两性离子（BTZ）的结构存在明显差异；（3）记录了BTZ的一种立体异构体具有创纪录的短[NHN]氢键（N···N = 2.510 Å），几乎达到了[NHN]氢键的理论极限（2.50 Å）。
