Conformations of four-membered ring hydrazines and hydrazine radical cations

1978 ◽  
Vol 100 (9) ◽  
pp. 2806-2810 ◽  
Author(s):  
S. F. Nelsen ◽  
V. E. Peacock ◽  
G. R. Weisman ◽  
M. E. Landis ◽  
J. A. Spencer
1978 ◽  
Vol 9 (33) ◽  
Author(s):  
S. F. NELSEN ◽  
V. E. PEACOCK ◽  
G. R. WEISMAN ◽  
M. E. LANDIS ◽  
J. A. SPENCER

2014 ◽  
Vol 136 (17) ◽  
pp. 6251-6254 ◽  
Author(s):  
Yuanting Su ◽  
Xin Zheng ◽  
Xingyong Wang ◽  
Xuan Zhang ◽  
Yunxia Sui ◽  
...  

1991 ◽  
Vol 46 (3) ◽  
pp. 326-338 ◽  
Author(s):  
H. Bock ◽  
P. Dickmann ◽  
H.-F. Herrmann

The redox behaviour of aza-substituted naphtho- and anthraquinones, which offer O=C–C=N– chelate tongs for an advantageous five-membered ring metal cation complexation, is investigated by a combination of cyclovoltammetric and ESR/ENDOR spectroscopic measurements. The formation of paramagnetic contact ion pairs like [(quinoline-5,8-semiquinone)·⊖Me⨁]·, with Me⨁ = Li⨁, Na⨁, Tl⨁, or of triple ion radical cations like [(1,4-diazo-9,10-anthrasemiquinone)eMe⨁]·⨁, with Me⨁ = Li⨁, Na⨁ is corroborated both by shifts of the second reduction potential of up to 0,67 V for e.g. quinoline 5,8-quinone upon addition of Li⨁[B(C6H5)4]⊖ to its DMF solution and by the observation of ESR/ENDOR metal couplings.


2020 ◽  
Author(s):  
Veejendra Yadav

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann<i> </i>elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.


2020 ◽  
Author(s):  
Veejendra Yadav

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann<i> </i>elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.


2020 ◽  
Author(s):  
Oisin Shiels ◽  
P. D. Kelly ◽  
Cameron C. Bright ◽  
Berwyck L. J. Poad ◽  
Stephen Blanksby ◽  
...  

<div> <div> <div> <p>A key step in gas-phase polycyclic aromatic hydrocarbon (PAH) formation involves the addition of acetylene (or other alkyne) to σ-type aromatic radicals, with successive additions yielding more complex PAHs. A similar process can happen for N- containing aromatics. In cold diffuse environments, such as the interstellar medium, rates of radical addition may be enhanced when the σ-type radical is charged. This paper investigates the gas-phase ion-molecule reactions of acetylene with nine aromatic distonic σ-type radical cations derived from pyridinium (Pyr), anilinium (Anl) and benzonitrilium (Bzn) ions. Three isomers are studied in each case (radical sites at the ortho, meta and para positions). Using a room temperature ion trap, second-order rate coefficients, product branching ratios and reaction efficiencies are reported. </p> </div> </div> </div>


2020 ◽  
Author(s):  
Shunya Ohuchi ◽  
Hiroki Koyama ◽  
Hiroki Shigehisa

A catalytic synthesis of cyclic guanidines, which are found in many biologically active compounds and natu-ral products, was developed, wherein transition-metal hydrogen atom transfer and radical-polar crossover were employed. This mild and functional-group tolerant process enabled the cyclization of alkenyl guanidines bearing common protective groups, such as Cbz and Boc. This powerful method not only provided the common 5- and 6-membered rings but also an unusual 7-membered ring. The derivatization of the products afforded various heterocycles. We also investigated the se-lective cyclization of mono-protected or hetero-protected (TFA and Boc) alkenyl guanidines and their further derivatiza-tions.


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