Formation of 6,6'-(Butane-1,4-diyl)bis(1,2,3,4-tetrahydronaphthalene) in the reaction of tetralin with aluminium chloride

1984 ◽  
Vol 37 (11) ◽  
pp. 2379 ◽  
Author(s):  
MA Wilson ◽  
H Rottendorf ◽  
PJ Collin ◽  
AM Vassallo
Keyword(s):  
Ion Pairs ◽  
Aluminium Chloride ◽  
Substitution Reactions ◽  
Electrophilic Attack ◽  
Intramolecular Substitution ◽  
Proton Loss

It has been shown that the reaction of aluminium chloride with tetralin yields 6,6'-(butane-1,4-diy1)-bis(1,2,3,4-tetrahydronaphthalene) as well as a number of other products. It is suggested that this compound is formed by protonation of tetralin, fragmentation of the alicyclic ring and then electrophilic attack of a further tetralin molecule. The positions of substitution in the product suggests that ion pairs are involved in the reaction. It is clear that intermediates have sufficient lifetime to undergo intermolecular substitution reactions in addition to intramolecular substitution or proton loss.

Intramolecular substitution reactions involving π-nucleophiles and N-acyliminium cations generated from azetidin-2-ones

Tetrahedron ◽  
2010 ◽  
Vol 66 (22) ◽  
pp. 3904-3911 ◽  
Author(s):  
Barbara Grzeszczyk ◽  
Barbara Szechner ◽  
Bartłomiej Furman ◽  
Marek Chmielewski
Keyword(s):  
Substitution Reactions ◽  
Intramolecular Substitution

Electrophilic aromatic substitution reactions of compounds with Craig-Möbius aromaticity

2021 ◽  
Vol 118 (39) ◽  
pp. e2102310118
Author(s):  
Yuanting Cai ◽  
Yuhui Hua ◽  
Zhengyu Lu ◽  
Qing Lan ◽  
Zuzhang Lin ◽  
...  
Keyword(s):  
Density Functional ◽  
Electronic Effect ◽  
Density Functional Theory Calculations ◽  
Electrophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
Electrophilic Attack ◽  
Functional Theory ◽  
Aromatic Species ◽  
Selective Formation

Electrophilic aromatic substitution (EAS) reactions are widely regarded as characteristic reactions of aromatic species, but no comparable reaction has been reported for molecules with Craig-Möbius aromaticity. Here, we demonstrate successful EAS reactions of Craig-Möbius aromatics, osmapentalenes, and fused osmapentalenes. The highly reactive nature of osmapentalene makes it susceptible to electrophilic attack by halogens, thus osmapentalene, osmafuran-fused osmapentalene, and osmabenzene-fused osmapentalene can undergo typical EAS reactions. In addition, the selective formation of a series of halogen substituted metalla-aromatics via EAS reactions has revealed an unprecedented approach to otherwise elusive compounds such as the unsaturated cyclic chlorirenium ions. Density functional theory calculations were conducted to study the electronic effect on the regioselectivity of the EAS reactions.

Kinetics and mechanism of substitution reactions of (dimethylsulfoxide)pentaamminecobalt(III) ion in dimethylsulfoxide solvent: complications due to redox and conjugate base processes

1976 ◽  
Vol 54 (23) ◽  
pp. 3685-3692 ◽  
Author(s):  
S. T. Danny Lo ◽  
Evelyn M. Oudeman ◽  
Jean C. Hansen ◽  
Thomas W. Swaddle
Keyword(s):  
Ion Pairs ◽  
Activation Parameters ◽  
Rate Coefficients ◽  
Solvent Exchange ◽  
Exchange Reactions ◽  
Substitution Reactions ◽  
Enthalpy Of Activation ◽  
A Minor ◽  
Conjugate Base ◽  
Anation Rate

Simple anation and solvent exchange reactions of Co(NH3)5DMSO3+ in DMSO are accompanied by reactions in which the conjugate base of this complex undergoes either internal redox to cobalt(II) or relatively rapid substitution. These conjugate base reactions are eliminated by addition of H+, although a minor redox pathway persists within ion pairs of Co(NH3)5DMSO3+ with chloride or bromide. The latter pathway is evidently not mechanistically related to the solvent exchange or anation reactions, which proceed by dissociative interchange (Id) according to the activation parameters (volume of activation = +10 cm3 mol−1 for DMSO exchange; enthalpy of activation = 123, 121, and ∼126 kJ mol−1 for DMSO exchange and bromide and chloride anation respectively). Enthalpies of activation for solvent exchange and for the limiting anation rate are shown to be better criteria of mechanism than the corresponding rate coefficients.

ELECTROPHILIC REACTIONS OF STEROIDAL AND OTHER α-PHENYL DIENES

1966 ◽  
Vol 44 (19) ◽  
pp. 2233-2239
Author(s):  
Maurice Douek ◽  
George Just
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Perchloric Acid ◽  
Electrophilic Substitution ◽  
Aluminium Chloride ◽  
Substitution Reactions ◽  
Electrophilic Reactions ◽  
Electrophilic Substitution Reactions

3-Phenylcholesta-3,5-diene (I) is shown to undergo electrophilic substitution reactions exclusively at the 6 position with formaldehyde – perchloric acid, acetic anhydride – aluminium chloride, and the Vilsmeier reagent.In the case of formaldehyde, the final product is "dimmer" II. The reaction is specific for formaldehyde and can be used to detect trace amounts of formaldehyde in, for example, commercial acetic acid and acetic anhydride.

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