Hydrolysis of esters
Mechanism of the base catalyzed hydrolysis of esters:
In first step hydroxide nucleophiles attacks at the electrophilic C of the ester C=O,
breaking the π bond and creating the tetrahedral intermediate. In second step the
intermediate collapses, reforming the C=O results in the loss of the leaving group
the alkoxides, RO–, leading to the carboxylic acid. In third step an acid / base
reaction occurring with very rapid equilibrium where the alkoxides RO – functions
as a base deprotonating the carboxylic acid, RCO2H, (an acidic work up would
allow the carboxylic acid to be obtained from the reaction).
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Mechanism of the acid catalyzed hydrolysis of esters:
In first step activation of the ester occurs. Protonation of the ester carbonyl makes
it more electrophilic. In second step the water O functions as the nucleophile
attacking the electrophilic C in the C=O, with the electrons moving towards the
oxonium ion, creating the tetrahedral intermediate. In third step, acid/base reaction
occurring, that deprotonate oxygen that has come from the water molecule to
neutralizes the charge. In fourth step the acid/base reaction needs to make the -
OCH3 leave, but need to convert it into a good leaving group first by protonation.
In fifth step the electrons of an adjacent oxygen help “push out” the leaving group,
a neutral methanol molecule. In sixth step, acid/base reaction occurring.
Deprotonating of the oxonium ion reveals the carbonyl C=O in the carboxylic acid
product and regenerates the acid catalyst.
Electrophilic Reactions Electrophiles participate in chemical reactions with other
compounds. The mechanism of these reactions is such that, first, the electrophile is
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generated. Then, it attacks a site rich in electrons (e.g., double bond, carbanion).
These reactions are known as electrophilic addition and electrophilic substitution
reactions.
Electrophiles are species that can accept electron pairs from nucleophiles.
Examples of electrophiles include:
Cations that can accept electron pairs, such as H+, Mg2+, Fe3+, NH4+, CH3+,
and H3O+
Molecules with an incomplete octet of electrons, such as BF3 and AlCl3
Molecules where the central atom can have more than 8 electrons in its valence
shell, such as SiCl4 and SiF4
Carbocation, which are organic molecules with a positive charge on a carbon
atom
Acyl halides, which are compounds like RCOCl and RCOBr that are highly
reactive
Alkyl halides, which are organic molecules that contain halogen atoms
Nucleophilic substitution is a substitution reaction in which an electron-rich
nucleophile displaces the halogen atom bonded to the central carbon of an
alkyl halide molecule. The halide ion that is displaced from the carbon atom is
called the leaving group. Nucleophilicity is defined as the ability of the
nucleophiles to denote their lone pairs to a positive center. It is a kinetic term
which relates to the rate at which the nucleophile attacks the substrates.
A nucleophilic addition (AN) reaction is an addition reaction where a chemical
compound with an electrophilic double or triple bond reacts with a nucleophile,
such that the double or triple bond is broken. Nucleophilic additions differ
from electrophilic additions in that the former reactions involve the group to which
atoms are added accepting electron pairs, whereas the latter reactions involve
the group donating electron pairs.
Any ion or molecule with a free electron pair or at least one pi bond is a
nucleophile. OH- is a nucleophile. It can donate a pair of electrons to the Lewis
acid H+ to form H2O. The halogens, while not nucleophilic in diatomic form (e.g.,
I2), are nucleophiles as anions (e.g., I-). Water, hydrogen sulfide, and ammonia are
all nucleophiles.
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