Lecture28 NucleophilicSubstitutionvs.

Elimination Chem 210

ReadingAssignmentforToday: chapters7.3,7.4,7.5,7.6

textbookproblems:7.31,7.32
practiceproblemslistedoncanvasforLecture28
FilesSupplementalIntermediateProblemSets

ReadingAssignmentforMonday: chapter7
Lecture28 Review:EnergyDiagramsSN1,SN2,E1andE2 Chem 210

SN1: unimolecular nucleophilic substitution SN2: bimolecular nucleophilic substitution

E E Nu C LG transition state
rate-determining step
Nu
X
X

C
carbocation

Nu

starting RACEMIC starting INVERSION

materials products MIXTURE materials products

reaction progress reaction progress

rate = k [electrophile] rate = k [electrophile] [nucleophile]

E1: unimolecular elimination E2: bimolecular elimination

-hydrogen
atom H
Base
E rate-determining step C C E
transition state
X
X -hydrogen
rotation atom H
around C-C
anti
carbocation bond
LG

C C
H Higher substituted product
is favored UNLESS base
starting Mixture of products: starting is sterically hindered!
materials products E and Z materials products

reaction progress reaction progress

rate = k [electrophile] rate = k [electrophile] [Base]
CompetitionbetweenSN1,SN2,E1andE2 Chem 210
Competition between SN1, SN2, E1 and E2

nucleophile only Nucleophile/Lewis Base Electrophile Product Explanation

unhindered anion with pKa

of conj. acids <15
uncharged sp3 (N,P,S) 1 SN2 Reagent functions as a nucleophile only:
examples: reagent is a
When the reagent functions exclusively as a nucleophile (and not as a base), only
substitution reactions occur for 1 and 2 electrophiles. 3 electrophiles are
Cl Br I N3 CN nucleophile only 2 SN2
sterically more hindered and will result in mixtures of SN1 products and E1
O
products (if -hydrogen atom is present) if the reaction is conducted in a polar
HS RS -H necessary for elimination
R O reaction solvent that stabilizes intermediate carbocations.
3 SN1 E1
R3P R3N RSH H2S polar medium necessary

strong nucleophile
& strong base Reagent is a strong nucleophile and strong base:
unhindered anion with pKa 1 SN2 For 1 electrophiles, the SN2 product is favored. 2 and 3 electrophiles are sterically
of conj. acids 15-30 reagent is a more hindered and the E2 reaction mechanism is preferred.
examples:
strong nucleophile
& strong base 2 E2 important: acetylides will undergo SN2
HO H3CO
nBuLi H3C I
-H necessary for elimination H3C H H3C Li H3C
H3CH2CO
3 E2 pKa = 26
nucleophile SN2 CH3

weak nucleophile
& weak base 1 no reaction
Reagent is a weak nucleophile and a weak base:
examples: reagent is a
Under these conditions, unimolecular reactions (SN1 and E1) are favored for 3
H2O weak nucleophile
2 no reaction electrophiles. No reaction occurs for 1 and 2 electrophiles. A polar solvent is
& weak base
R-OH needed - either polar protic solvent (H2O or ROH) or polar aprotic solvent
-H necessary for elimination (DMF, DMSO or HMPA) to stabilize the intermediate carbocation.
RCO2H
3 SN1 E1
or resonance-stabilized polar medium necessary
carbocation
base only if unhindered
and no -H
strong bases with pKa of Reagent functions as a strong base only:
conj. acids > 30 1 E2 or SN2
reagent is a with unhindered When the reagent functions exclusively as a base (and not as a nucleophile), only
hindered bases with pKa
base elimination reactions occur. Such reagents are generally strong bases, resulting in
of conj. acids > 10
base only 2 E2 an E2 process. This mechanism is not sensitive to steric hindrance of the
examples:
electrophile and can occur for primary, secondary, and tertiary substrates. For 1
H
N -H necessary for elimination electrophiles without a -hydrogen atom, SN2 products are observed.

N O 3 E2
DBU

polar medium: polar protic solvent (H2O or ROH) or polar aprotic solvent (DMF, DMSO or HMPA) to stabilize the carbocation.