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)

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 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

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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.

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 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

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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.

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 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

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