Electrophilic Addition Mechanism in Alkenes
Translated by
ScribdTranslationsElectrophilic Addition Mechanism in Alkenes
Translated by
ScribdTranslationsElectrophilic additions (EA) to alkenes,
the mechanism and stereochemistry
[Введите подзаголовок документа]
CHIȘ INĂU 2019
1
Table of contents:
1. Introducere................................................................................................................................2
2. Reaction mechanism..........................................................................................................2
3. The stages of the reaction mechanism.........................................................................................3
4. Electrophilic addition reactions...............................................................3
5. Electrophilic reagents.................................................................4
5
2
1. Introduction
In organic chemistry, electrophilic addition (AEis a type of addition chemical reaction within
to which a pi (π) bond in an organic compound is broken, forming two new bonds
sigma (σ). The substrate in electrophilic addition must have a double bond or a triple bond.
Fig.1. General reaction of electrophilic addition
2. The mechanism of the reaction
Electrophilic addition is a process in which a π bond disappears, replaced by two new ones.
sigma bonds, formed at each of the atoms participating in the initial pi bond. In general, it is a
characteristic reaction of alkenes, which is why it will be exemplified on these compounds. Not
It should be forgotten, however, that dienes or alkynes also give electrophilic addition reactions.
The electronic effects in the substrate molecule, respectively in the reactant, give an indication
clear about how each of these species participates in the process.
The electrophilic reactant is most often a proton (H+), addition reactions of
+
comes from acid) or from acid hydrolysis (H+ comes from the catalyst), or other
electrophilic species (denoted generically as E+, such as for example Cl+ on Br+ in the case of the addition of
(halogens). In the propagation stage, the electrophile attaches to that carbon atom in the double bond.
connection with increased electronic density. Indeed, under the influence of donor effects or
attractive to electrons, a shift of the π electrons of the double bond occurs towards one or
the other among the carbon atoms.
For example, in the molecule of propene under the +I electron-donating effect of the methyl group,
π electrons are pushed towards the terminal carbon atom, the electron density at this atom of
carbon increases, with the electrophilic reactant being fixed to it in the end.
In the "termination stage", the carbocation intermediate fixes the negative residue of the reactant,
with the formation of the final addition product.
3
3. The stages of the reaction mechanism
3.1. Generation of the electrophilic reagent and formation of the complex
3.2. Electrophilic attack or transformation of the complex in complex with the formation of a
carbocationic intermediate
3.3. Formation of the final additive product through the stabilization of the complex in addition
of a nucleophile;
The general mechanism of electrophilic addition reactionsЕ-reactions) (Fig. 2.):
Fig. 2. The general mechanism AE
4. Electrophilic addition chemical reactions
Example of the electrophilic addition reaction mechanism based on propene hydration
with the electrophilic reagent H+and the formation of the secondary alcohol propan-2-ol.
The short form of the hydration reaction:
4
Thus, the stages of the addition of hydrochloric acid to propene in the electrophilic addition mechanism,
it could be represented as follows:
In practice, due to the fact that in an organic solution, a hydric acid is a polar species,
however, in a non-ionized state, it will form with the alkene what is known as a charge transfer complex; inside
in this complex the H−Hal bond is strongly polarized, approaching an ionic, dissociable type.
thus allowing for the transfer of protons. Therefore, such a mechanism is written more correctly
thus
5. Electrophilic reagents
Electrophiles are reactants that exhibit an electronic deficit at the central reaction atom.
(the atom that is attacking or that is suffering the attack), thus having a certain affinity for
electron donors for electron-rich species. Similar to nucleophiles, the charge is not a
absolute requirement, however the electronic deficit (in the form of, for example, a vacant orbital) is
absolutely necessary for inducing electrophilic character.
Electrophilic reagents:
H+, CH3++NO2+, SO3, CO2AlCl3, FeBr3, R-COCl.
Conclusions:
5
Such a study of the reaction mechanism explains why hydrazine addition reactions, water
Alcohols derived from alkenes follow an empirical rule observed since 1870 by the Russian chemist.
Vladimir Vasilievich Markovnikov (known since then as 'Markovnikov's rule') -
this says that in such a process, the proton attaches to the least substituted carbon,
while the negatively charged remainder ("nucleophilic rest") attaches to the most carbon atom
substituted.
In certain situations, it is possible that a reaction may also occur during the 'propagation stage'.
isomerization of the carbocation intermediate. Indeed, if the species generated in the first phase is
a primary carbocation exists and there is a possibility that it can isomerize into a secondary one or
tertiary, the isomerization process will occur before the fixation of the nucleophilic remainder, resulting in a
reaction product with a different structure than that of the raw material.
Markovnikov's rule: electrophilic addition of reactants HX to the double bond in alkenes
it follows that, in the first stage, the most stable carbocation should be formed (e.g. stabilized by
electron-repelling effect + I, + E). The overall speed of the addition essentially depends on the stability
of this carbocation: the more stable it is, the faster it forms because of the effects
Electrons +I, +E stabilize the transition states through which this carbocation is formed.
Bibliography:
6
Avram, M. (1983). Organic Chemistry, vol. 1, RSR Academy Publishing House, Bucharest
2. McMurry, J., Organic Chemistry (2008). 7th ed., Thomson Brooks/Cole
3. Neni ț escu, C. D., Organic Chemistry, vol I, Educational and Pedagogical Publishing House, Bucharest, 1980