An endoscopy of the little known peri‐fused N,N and N,O‐heterocycles is described herein using the density functional theory (DFT/B3LYP), the 2^nd order Møller–Plesset perturbation theory (MP2) and the 6–311++G(d,p) basis set. Their salient structure features, their reflection onto aromaticity, depicted by means of certain aromaticity indicators (HOMA, I_A, ABO, PDI, FLU, NICS) and their reactivity profiles are the theme of this investigation. N and O atom(s) and their relative arrangement in the ring perturb the σ and π frames of the structures and ultimately introduce peri strain. The incorporation of N and O atoms in the annelated ring causes a limited π‐delocalization over the whole structure, a relatively low aromatic character and a weakly polarized double bond of the heteroring. Bond length variation, in the range of 0.01‐0.05 Å, dihedral angles deviating from planarity by 1.2‐4.1 Å and compressed fusion bonds, particularly peri ones, indicate a σ frame–triggered ring distortion of 0.6‐2.6° as an “outward” stretching of the lower part of a still planar structure except one. The heteroring, as a masked enamine, hydrazone, imine, vinyl ether, oxime or imino ether, clamped onto naphthalene scaffold, appears to be the best description of this type of structures. The nature of the heteroring dictates their reactivity profile. Those housing the masked hydrazine and oxime entities exhibit a “ring α‐effect”‐guided reactivity, consistent with preliminary experimental findings.

中文翻译：

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萘周围的N，N-和N，O-杂环退火：杂原子引导的Peri-Fus对其结构和反应谱的影响-理论内窥镜

小已知的内窥镜围-融合N，N和N，O-杂环描述本文使用密度泛函理论（DFT / B3LYP），则2^次顺序多体微扰理论（MP2）和6-311 + + G（d，p）基集。其显着的结构特点，它们的反射在芳香性，通过的某些芳香指标（HOMA，我手段描绘_甲，ABO，PDI，FLU，NIC）和它们的反应性轮廓是该研究的主题。N和O的原子（S），并在环扰动结构的σ和π帧它们的相对排列，并最终引入围拉紧。N和O原子在退火环中的结合会在整个结构中造成有限的π-离域化，较低的芳香性和杂环的弱极化双键。键长变体中，在0.01〜0.05埃的范围内，二面角由1.2-4.1从平面偏离的和压缩的熔融粘合，特别是围其中一个表示σ框架触发的环变形为0.6-2.6°，这是除了一个平面结构的下部的“向外”拉伸。夹在萘基支架上的杂环（作为掩蔽的烯胺，，亚胺，乙烯基醚，肟或亚氨基醚）似乎是此类结构的最佳描述。杂环的性质决定了它们的反应性。那些带有掩蔽的肼和肟实体的化合物表现出“环α效应”指导的反应性，与初步的实验结果一致。