通过重氮中间体的简便分子内[2 + 3]环加成反应形成意外的3,3-二苯基-3-吲唑。

Formation of an unexpected 3,3-diphenyl-3-indazole through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate.

作者信息

King Andrew T, Hiscocks Hugh G, Matesic Lidia, Bhadbhade Mohan, Bishop Roger, Ung Alison Thavary

机构信息

School of Mathematical and Physical Sciences, University of Technology Sydney, PO Box 123, Broadway, NSW, 2007, Australia.

Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW, 2232, Australia.

出版信息

Beilstein J Org Chem. 2019 Jun 19;15:1347-1354. doi: 10.3762/bjoc.15.134. eCollection 2019.

The one-pot reaction of 2,6-bis(diphenylmethyl)-4-methoxyaniline with -butylnitrite, BTEAC and DABSO in the presence of CuCl provided an unexpected 3-indazole product . The structure of the compound was determined by HRMS, IR, NMR and further confirmed by single crystal X-ray crystallography. The compound crystallises in the triclinic -1 space group, with unit cell parameters = 9.2107 (4), = 10.0413 (5), = 14.4363 (6) Å, α = 78.183 (2), β = 87.625 (2), γ = 71.975 (2)°. The formation of proceeded through a facile intramolecular [2 + 3] cycloaddition of the diazo intermediate . The molecules of are organised by edge-face Ar-H···π, face-face π···π, and bifurcated OCH-H···N interactions. In addition to these, there are Ar-H···H-Ar close contacts, (edge-edge and surrounding inversion centres) arranged as infinite tapes along the direction.

2,6-双（二苯基甲基）-4-甲氧基苯胺与亚硝酸丁酯、四丁基氯化铵（BTEAC）和1,4-二氮杂双环[2.2.2]辛烷（DABSO）在氯化铜存在下的一锅反应得到了一种意想不到的3-吲唑产物。该化合物的结构通过高分辨质谱（HRMS）、红外光谱（IR）、核磁共振（NMR）确定，并通过单晶X射线晶体学进一步证实。该化合物结晶于三斜晶系的P-1空间群，晶胞参数a = 9.2107 (4)、b = 10.0413 (5)、c = 14.4363 (6) Å，α = 78.183 (2)、β = 87.625 (2)、γ = 71.975 (2)°。产物的形成是通过重氮中间体的分子内[2 + 3]环加成反应进行的。产物分子通过边-面Ar-H···π、面-面π···π和分叉的OCH-H···N相互作用排列。除此之外，还存在Ar-H···H-Ar紧密接触（边-边和周围的反演中心），沿b方向排列成无限长的带。