Stepwise Formation of 1,3-Diazolium-4-thiolates by Munchnone Cycloadditions: Promising Candidates for Nonlinear Optics

被引：9

作者：

Cantillo, David ^{[1
]}

Avalos, Martin ^{[1
]}

Babiano, Reyes ^{[1
]}

Cintas, Pedro ^{[1
]}

Jimenez, Jose L. ^{[1
]}

Light, Mark E. ^{[2
]}

Palacios, Juan C. ^{[1
]}

Porro, Rocio ^{[1
]}

机构：

[1] Univ Extremadura, Fac Ciencias, QUOREX Res Grp, Dept Quim Organ & Inorgan, E-06006 Badajoz, Spain

[2] Univ Southampton, Dept Chem, Southampton SO17 1BJ, Hants, England

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 79卷 / 09期

关键词：

1,3-DIPOLAR CYCLOADDITIONS; THIONATION; THIOISOMUNCHNONES; ISOTHIOCYANATES; MESOIONICS;

D O I：

10.1021/jo500349g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An improved preparation of mesoionic heterocycles 1,3-diazolium-4-thiolates by [3 + 2] cycloadditions of munchnones with aryl isothiocyanates is reported. The process takes place with high or complete regioselectivity, and fast and clean transformations are observed under microwave heating in DMF. DFT calculations support that this cycloaddition proceeds preferably through a stepwise mechanism. Given the pattern substitution around the mesoionic ring resulting in a push pull system, theoretical estimations predict large hyperpolarizabilities in some cases, which is typical of molecules exhibiting nonlinear optical responses.

引用

页码：4201 / 4205

页数：5

共 7 条

[1] TRANS-1-(DIMETHYLAMINO)-1,3-BUTADIENE - CONCERTED AND STEPWISE (4+2) CYCLOADDITIONS
SUSTMANN, R
ROGGE, M
NUCHTER, U
BANDMANN, H
CHEMISCHE BERICHTE-RECUEIL, 1992, 125 (07): : 1647 - 1656
[2] Push-pull 1,3-thiazolium-5-thiolates. Formation via concerted and stepwise pathways, and theoretical evaluation of NLO properties
Cantillo, David
Avalos, Martin
Babiano, Reyes
Cintas, Pedro
Jimenez, Jose L.
Light, Mark E.
Palacios, Juan C.
Rodriguez, Valentin
ORGANIC & BIOMOLECULAR CHEMISTRY, 2010, 8 (23) : 5367 - 5374
[3] REACTIONS OF 1,1-BIS(DIMETHYLAMINO)-1,3-BUTADIENE WITH OLEFINS - (4+2) CYCLOADDITIONS AND ZWITTERION FORMATION
SUSTMANN, R
ROGGE, M
NUCHTER, U
BANDMANN, H
CHEMISCHE BERICHTE-RECUEIL, 1992, 125 (07): : 1657 - 1664
[4] Nitrone Ylides: Two Possible 1,3-Dipolar Cycloadditions but Only One Stepwise Formation of all-cis-5-Aryl-2,3,5-trisubstituted N-Hydroxypyrrolidines
Merino, Pedro
Tejero, Tomas
Diez-Martinez, Alba
Gueltekin, Zeynep
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (32) : 6567 - 6573
[5] Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1,3-Dienes
Yan Chaoxian
Yang Fan
Wu Ruizhi
Zhou Dagang
Yang Xing
Zhou Panpan
ACTA PHYSICO-CHIMICA SINICA, 2018, 34 (05) : 497 - 502
[6] Formation of pyrazol-1,3,4-thiadiazoles through 1,3-dipolar cycloadditions of 3-thioxo-[1,2,4]-triazepin-5-one with nitrilimines: an experimental and computational study
Esseffar, M.
El Messaoudi, M.
Azzouzi, S.
Jalal, R.
Saez, J. A.
Domingo, L. R.
Latorre, J.
Liu-Gonzalez, M.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2009, 22 (01) : 31 - 41
[7] 1,3-DIPOLAR CYCLOADDITIONS OF N,ALPHA-DIPHENYLNITRONE TO THE 4,5-POSITIONS OF 1H-AZEPINE AND 1H-1,2-DIAZEPINE DERIVATIVES - FORMATION OF ENDO-TYPE AND EXO-TYPE CYCLOADDUCTS AND COMPUTER-ASSISTED LINE-SHAPE SIMULATION OF THE NMR-SPECTRA OF THE ADDUCTS
SAITO, K
YOSHINO, A
TAKAHASHI, K
HETEROCYCLES, 1991, 32 (01) : 1 - 6

← 1 →