Elimination Reactions
Elimination reaction: A reaction in which a molecule loses atoms or groups of atoms,
usually from adjacent atoms, often resulting in a new pi bond.
β α
β-hydrogen H C C LG C C
• Called β-elimination (most common elimination reaction)
• Useful reaction to synthesize alkenes, alkynes, other pi bond functional groups
The E2 Mechanism
Methoxide ion
An alkoxide ion (RO-) and a strong base
H
Example: Na OCH3
+ CH3OH + Na Cl
CH3OH
Cl
H OCH3
Mechanism: + CH3OH + Cl
Cl
Kinetics: rate = k [R–Cl] [CH3O-] Elimination Bimolecular → E2
What if more than one alkene product is possible?
Hb Ha
KOH, CHOH 1-butene
Remove Ha terminal alkene
Br
trans-2-butene
}
Hb Ha
(E)-2-butene
KOH, CHOH + internal alkenes
Remove Hb cis-2-butene
Br (Z)-2-butene
Alkene stereochemistry nomenclature
Cis and trans: carbon chain position E and Z: Cahn-Ingold-Prelog priorities
C C C High High High Low
C C C C C C C C
C Low Low Low High
cis trans Z E
(zusammen = together) (entgagen = against)
May be ambiguous Never ambiguous
Lecture Supplement: Elimination Reactions 13
Which alkene product is major (produced in greatest amount)?
Example: Reactants A + B When Eact (A) < Eact (B) → Rate A > rate B
→ A is major product
→ Faster product is major
Transition state energy: torsional strain considerations
Useful vocabulary:
• Dihedral angle: angle formed between two planes (three atoms = one plane)
• Periplanar: coplanar = lying in the same plane
• Anti: dihedral angle is 180o Syn: dihedral angle is 0o
δ- OH
δ-
HO H OH H
CH3CH2 H
or CH3CH2 H
H H
Br Br H H H
δ-
δ-Br
δ− δ−OH
HO H
H3C H H
H H3C H
HO H
Br H3C CH3 or
H CH3 H Br H CH3
δ− δ−Br
δ-OH
δ-
HO H
H3C H
H H
HO H H3C H
Br H CH3 or
H3C H H3C Br H3C H
δ-
δ- Br
• Anti-periplanar arrangement of H–C, C–Br bonds: If H–C and C–Br bonds cannot be
periplanar E2 cannot occur from this conformation. Syn-periplanar possible, but rare.
• Transition state stability: Torsional strain influences Eact
Prediction based on transition state torsional strain:
1-butene (greatest amount formed) > (E)-2-butene > (Z)-2-butene (least amount)
14 Lecture Supplement: Elimination Reactions
Transition state energy also influenced by product stability...
Product stability: alkene steric strain
• Atoms/groups attached to alkene sp2 carbons lie in same plane → eclipsed!
• Prediction: Increasing steric strain decreases alkene stability
Alkene Structure Space Filling Model Strain
H H
cis-2-butene More steric strain
H3 C CH3
H CH3
trans-2-butene Less steric strain
H3 C H
Conclusion: Trans alkene more stable than cis alkene
Warning!!! E not always more stable than Z
Alkene stability: internal versus terminal
An internal alkene A terminal alkene
General rule: Internal alkene more stable than terminal alkene
Lecture Supplement: Elimination Reactions 15
Alkene stability: number of Csp2–Csp3 bonds
• Fact: Bonds to sp2 carbon and stronger (more stable) than bonds to sp3 carbon.
BDE = Bond dissociation energy. ↑ BDE = stronger bond
Relevant BDE (kcal mol-1): Csp3–Csp3 89 Csp2–Csp3 102
Csp3–H 98 Csp2–H 109 ← sp2 bonds stronger
• Conclusion: Alkene isomer with more bonds to C=C is more stable.
Example: 1-butene versus E-2-butene
Csp2–Csp3 2 x 102 = 204 1 x 102 = 102
Csp3–Csp3 0 x 89 = 0 1 x 89 = 89
Csp2–H 2 x 109 = 218 3 x 109 = 327
Csp3–H 6 x 98 = 588 5 x 98 = 490
Total (kcal mol-1) = 1010 more stable = 1008 less stable
General alkene stability trend
H2C=CH2 < RCH=CH2 < R2C=CH2 < RCH=CHR < R2C=CHR < R2C=CR2
Caveat: Steric strain can become quite severe!
Tetra-tert-butylethylene
• Tetrasubstituted alkene
• Severe steric strain
• Has never been synthesized
General rule: For alkene stability, number of alkyl groups outweighs steric strain unless
steric strain is severe.
For the 2-bromobutane + KOH E2 reaction:
KOH
+ +
CH3OH
Br
Greatest amount Least amount
More stable alkene is major E2 product.
Zaitsev’s Rule: Major product of E2 reaction is more substituted alkene.
16 Lecture Supplement: Elimination Reactions
Exceptions to Zaitsev’s Rule
Hofmann orientation: Less substituted alkene is major. Favored when....
(a) Base is sterically hindered:
base
+
Br
Base = CH3CH2O- Zaitsev orientation:
(ethoxide) 79% 21% more substituted
Less hindered product is major
Hofmann orientation:
Base = (CH3)3CO-
27% 73% less substituted
(tert-butoxide)
product is major
More hindered
(b) Leaving group is NR3, SR2, or F-:
KOCH2CH3
+ +
Br LG = Br
31% 51% 18% Zaitsev
KOCH2CH3
+ +
(CH3)3N LG = N(CH3)3
98% 1% 1% Hoffmann
E2 reactions of alkyl fluorides require harsh conditions, and are thus not very practical.
Na NH2 Na NH2
Other E2 examples: H3C C C CH3
Br Br Br
-
NH2 = a nitrogen anion = a nitranion
CH3CO2-
OCl O
Work out the mechanisms!
Lecture Supplement: Elimination Reactions 17
Base
H R
E2 Requirements: How to make Eact low enough for reaction to
R R
proceed at a useful rate?
R LG
-
Strong base (usually RO ; not ROH*)
•
• Moderate or better leaving group } interdependent
• β-H and leaving group are periplanar
* Despite reduction of basicity by H-bonding, RO- in ROH is sufficiently basic for E2.
The E1 Mechanism
- H2O
Consider this elimination reaction:
OH
H Base
E2 Mechanism: + H-Base + HO
OH
This E2 mechanism is unacceptable because...
Solution:
H3O+
Modified reaction:
OH (aq. H2SO4)
H OH2
Mechanism: Carbocation fates
OH OH2
⇑
No E2 because...
H OH2 Trisubstituted, internal alkene
• More stable alkene
• Major product
Disubstituted, terminal alkene
• Less stable alkene
• Minor product
H OH2
18 Lecture Supplement: Elimination Reactions
Kinetics: rds = ionization to form carbocation (similar to SN1).
Rate = k [ROH2+] Elimination Unimolecular → E1
E1 Requirements: How to make Eact low enough for reaction to proceed δ+
R3C LG
at a useful rate?
• Moderate or better leaving group
• Stable carbocation (1o w/res or 2o or better) Same rds as SN1
Same requirements as SN1
• Polar solvent
• E1 or E2?
Another example: DMSO, heat • Write the mechanism.
I
Elimination vs. Substitution: Which Mechanism?
• Carbocation formation is energetically expensive. Consider E2 and SN2
(mechanisms without carbocations) before E1 and SN1 (mechanisms with
carbocations).
• Consider E2 before SN2. Exception: 1o alkyl halides: consider SΝ2 before E2.
Therefore the order of preference is:
E2
SN2 } Except 1o alkyl halides where SN2 is considered before E2.
E1/SN1
Borderline cases involve a hybrid or mixed mechanism.
Lecture Supplement: Elimination Reactions 19
A Final Thought Concerning SN1 and E1 Reaction Rates
CH3 CH3
CH2
CH3 CH3OH CH3
C I C OCH3 +
C
(SN1/E1)
CH3 CH3 CH3 CH3
Rate data: kArtic ~ kAntarctic >> kEquator
Why these rates? Consider transition state of rate-determining step (ionization of carbon-
iodine bond)...
CH3
CH3
C I δ-
δ+
CH3
20 Lecture Supplement: Elimination Reactions
