e2 reactions e2 = elimination, bimolecular reaction is concerted (one step) rate =...
TRANSCRIPT
E2 Reactions E2 = elimination, bimolecular Reaction is concerted (one step) Rate = k[substrate][base]
(a second order process) E2 can occur with SN2. Occurs by abstraction of H+ from a C
adjacent to the C with the LG. Products follow Zaitsev’s Rule. If the base is strong, E2 will occur
instead of E1 for 3° alkyl halides.
E2 Reaction Mechanism One-step and requires a strong base. Best transition state is anti-coplanar. Example: t-butyl bromide + methoxide Why don’t SN2, SN1, or E1 occur?
E2 Reaction Mechanism Example: t-butyl bromide + methoxide
E2 Reaction Mechanism Anti-periplanar alignment allows pi
bond to form from sp3 orbitals.
E2 Reaction Profile
rate = ?
k = ?
Factors Affecting E2 Reactions
Structure of the substrate Strength of the base Nature of the leaving group The solvent in which the reaction
is run.
Factors Affecting E2 Reactions - Structure of the Substrate
Structure of the alkyl halide: 3° > 2° >1°
This is due to the stability of the more highly substituted alkene (Zaitsev’s Rule).
Factors Affecting E2 Reactions - Structure of the Substrate
Decide whether the following substrates could react by E1 or E2 (and by SN1 or SN2).
Br
Cl
Br
I
Factors Affecting E2 Reactions - Strength of the Base
The base must be strong. Which of the following bases favor E2 and which favor E1 reactions?
OH
H2ON
CH2
Factors Affecting E2 Reactions - the Leaving Group
The LG should be good. Which of the following substrates have good LGs?
Cl
NH2
OCH3
H
O S
O
O
CH3
Factors Affecting E2 Reactions - Solvent Effects
Polarity is not so important because negative charge is spread over the transition state.
Zaitsev’s Rule
When two or more elimination products are possible, the more stable alkene will predominate. This is usually the product with the more substituted double bond.
Zaitsev’s Rule
Show the E2 elimination products that could come from:
Cl
Br
Which E2 reaction would occur more quickly?
E2 Reactions - Summary The structure of the substrate affects the
rate. Relative rates for E2: 3°>2°>1°.
The base must be strong. The LG should be good. The solvent should be polar. Coplanar (usually anti) transition state is
required. Products will follow Zaitsev’s Rule. Can occur with SN2 for 2° alkyl halides.
E2 Reactions - Summary Predict the products
RO-Br
Cl RO-
ClCH3CH2OH
E2 Competes with SN2 for 2° Alkyl Halides
E1 and E2 ReactionsE1 E2
Base weak ones work strong
Substrate 3°>2° 3°>2°>1°
Leaving group good good
Solvent polar, ionizing polar, aprotic is better
E1 and E2 ReactionsE1 E2
Rate =k[RX] =k[RX][Base]
Carbocation intermediate?
Y N
Stereochemistry Zaitsev’s rule Zaitsev’s rule
Rearrangement ~H, ~ CH3 possible
No rearrangements
How Do You Decide Which Reaction(s) Happen?
The strength and structure of the nucleophile/base is paramount. Strong ones always give a
second order reaction (SN2 or E2).
If the base is bulky, E2 will occur instead of SN2.
How Do You Decide Which Reaction(s) Happen?
Now, look at the structure of the substrate.
1° alkyl halides will undergo SN2 and perhaps E2 unless rearrangement is possible.
3° alkyl halides will NOT undergo SN2.
2° alkyl halides are the toughest to predict.
How Do You Decide Which Reaction(s) Happen?
Evaluate, in order, Nucleophile, strength and
structure -or- Base, strength and structure Structure of the alkyl halide/carbocation Leaving group Solvent
YOU MUST BE ABLE TO DRAW THE MECHANISM!
Elimination Reactions Predict the products
OCH3
CH3OH
Br Na+ -OCH2CH3
ethanol
Did this product come from the reaction of 1-chlorobutane with a) sodium acetate or b) sodium t-butoxide?
This product came from the reaction of 1-chlorobutane with sodium acetate. The C=O and C-O peaks show ester.
OC
CH3
O
Did this product come from the reaction of 1-chloropentane with a) sodium acetate or b) sodium t-butoxide?
This product came from the reaction of 1-chloropentane with sodium t-butoxide. The sp2C-H and C=C peaks show alkene.