Beruflich Dokumente
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Prof. R. B. Sunoj
IIT Bombay
Introduction
SN2 correspond to substitution Nucleophilic Bimolecular.
Figure SN2 reaction Energy required to break the bond is compensated by bond formation.
Introduction
Example 1:
Example 2:
Example 3:
Kinetics
The rate of the reaction is found to be vary linearly with non zero slope with respect to electrophile as well as nucleophile .
Rate=K [elec][Nucl]
2 in the SN2 correspond to bimolecular.
K= equilibrium constant
In presence of large excess of nucleophile kinetics is found to be first order experimentally even though mechanism is bimolecular. rate=K[elec] Nucleophile affect the rate even being in large excess but concentration does not vary significantly and rate is found to be determined alone by electrophile. Such kinetics are known as Pseudo first order reaction.
Mechanism
During SN2 reaction nucleophile first approaches to antibonding orbital of C-Y bond. Attractive interaction between orbital, develop bond between incoming group and carbon. Simultaneously the leaving group start to depart away from carbon center. Substitution may be possible either via front side or backside attack of nucleophile.
In SN2 substitution backside attack is preferred in which approach of nucleophile is 180 away from the leaving group.
Walden Inversion
Complete Inversion in stereochemistry is observed during aliphatic
nucleophilic substitution via SN2 pathway, confirming that backside attack is preferred over front side attack. Stereochemical outcome of the SN2 reaction is termed as Walden inversion in honor of his discovery.
Only backside attack of nucleophile provide the most favorable interaction between antibonding orbital of C-Y bond and orbital of incoming nucleophile.
The term Nucleophile and Nucleofuge are kinetic term, used for discussing reactivity and kinetics.
Effect of Solvent
Solvent may play a vital role in the rate of SN2 reaction as it involves either
creation or dispersion of charge. Charged species are more stabilized in the polar solvent than non-polar solvent. Difference between the solvation capacity of reactant and transition state in various solvent lead to the solvent effect in a reaction. Reactants Transition State Charge Creation/Dispersion
Charge dispersion
Nuc
R-LG
Nuc
R R
LG LG LG LG
Nuc
Nuc
R-LG
R-LG
Nuc
Nuc Nuc
Charge creation
Charge dispersion Charge dispersion
R
R
Nuc
R-LG
In case of negative nucleophile a remarkable change in rate of SN2 reaction is observed while changing the solvent from polar protic to polar non-protic solvent. In polar aprotic solvent negatively charged nucleophile are less soluble but solvent are polar enough to solubilize the nucleophile making them highly reactive.
Solvent
Methanol Water Formamide Acetonitrile Acetone
K relative
0.9 1.0 14.1 3.58 x 104 1.41 x 106
Solubility of nucleophile is a major problem in substitution reaction, particularly in less polar aprotic solvent. Crown ether is added to solvate the counter-cation which induce the solubility
Better leaving group are mostly weak bases which stabilize the negative
charges. Example: TsO , MsO , TfO
In presence of better leaving group, SN1 reaction do not require strong base, but for SN2 reaction it is required. Example: 1. XH is always a weaker base than X . Thus XH is a better leaving group which facilitate the SN2 reaction. HS > H2S, HO > H2O, I > HI, NH2 >NH3 2. Acidic medium also protonate the base making them weaker. ROH is converted to ROH + in acid medium which is a better leaving group.
R Y R 900
Nuc R R
LG
electron withdrawing nature of groups having sp2 carbon(vinyl and phenyl) make the adjacent carbon more electrophilic and hence reactivity towards nucleophile increases. Example:
The most likely neighboring group participation in three, five, six membered ring. Four membered ring neighboring group participation is higher in case of alkyl substitution on or carbon. The effect of halogen increase as going down the group ( I> Br> Cl ).
Example 3
Example 4
Some neighboring groups are COO , COOR, COAr, OCOR, OR, OH, O, NH2 , NHR , NHCOR, SH, SR, I, Br, S
SN2 Reaction
allylic rearrangement in SN2 condition is known as SN2 reaction.
SN2 Reaction
Increasing the size of nucleophile as well as stearic hindrance at - carbon increases the extent of SN2 reaction.