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E1 vs E2: elimination mechanisms

The differences between E1 and E2 elimination — kinetics, stereochemistry, regiochemistry, and which conditions favor each.

Quick answer E2 is one concerted step (strong base, anti-periplanar H/LG, second-order); E1 ionizes to a carbocation first (weak base, tertiary, can rearrange). Both default to Zaitsev; a bulky base gives Hofmann.
Mechanism · The E2 Mechanism1 step
One step — base, β-H, and leaving group move together.
CH3CH3HBranti · 180°Bone stepCH3CH3alkene + Br(-)
The base removes the β-hydrogen while the C–H electrons form the new π bond and the leaving group departs — all in one concerted step. It requires the β-H and the leaving group to be antiperiplanar (~180°). (E1, by contrast, loses the leaving group first to a carbocation.)

Like SN1 vs SN2, elimination is either stepwise through a carbocation (E1) or concerted (E2) — here 2-bromopropane loses HBr to propene.

Base takes a β-H, C–Br breaks, a C=C forms.

1. Both E1 and E2 Form an Alkene by Losing a β-Hydrogen and a Leaving Group

Both lose a leaving group from the α-carbon and an H from a β-carbon to form C=C; only the timing differs.

2-Bromopropane (substrate)
Propene (alkene product)

2. E2 Is One Concerted Step; E1 Goes Through a Carbocation in Two Steps

E2 pulls the β-H as C–LG breaks (one step); E1 loses the leaving group first, then a base takes a β-H.

Step 1 (slow): the C–Br bond ionizes on its own — rate-determining.
A planar, sp² carbocation forms and sits in an energy well.
Step 2 (fast): a weak base plucks a β-hydrogen → isobutylene.

3. Their Rate Laws Differ: E2 Is Second-Order, E1 Is First-Order

E2 is rate = k[substrate][base]; E1 is rate = k[substrate] — so adding base speeds E2 but not E1.

Hydroxide — a strong E2 base
Ethoxide — strong E2 base

4. E2 Demands an Anti-Periplanar β-Hydrogen and Leaving Group

E2 needs the β-H and leaving group 180° apart (both axial on a ring), so it is stereospecific; E1's planar cation is not.

2-Bromobutane
2-Butene (anti-periplanar E2 product)

5. Strong or Bulky Bases and Heat Favor E2; Weak Bases and Polar Protic Solvents Favor E1

E2 wins with a strong base and heat; E1 wins with a weak base, polar protic solvent, and a tertiary substrate.

Strong base on a tertiary halide → E2 to isobutylene.

6. Regiochemistry: Zaitsev Usually Wins, but a Bulky Base Gives the Hofmann Alkene

Usually the more-substituted Zaitsev alkene wins, but a bulky base (KOtBu) can't reach the internal H and gives the less-substituted Hofmann alkene.

2-Butene — Zaitsev (more substituted)
1-Butene — Hofmann (bulky base)

7. E1 Can Rearrange Because It Has a Carbocation; E2 Cannot

An E1 cation can undergo a 1,2-hydride or alkyl shift to a more stable cation, so a scrambled skeleton signals E1; concerted E2 never rearranges.

Tertiary carbocation (E1 intermediate)
Isobutylene from that cation

8. Summary

E2: concerted · strong base · anti-periplanar · second-order · stereospecific · no rearrangement  |  E1: stepwise cation · weak base + polar protic · first-order · tertiary · can rearrange (with SN1)  |  both Zaitsev except bulky base → Hofmann.

Worked example

Problem. Predict the major product and mechanism when 2-bromobutane is heated with sodium ethoxide (NaOEt).
  1. Ethoxide is a strong base and a poor bulky-ish nucleophile; with a 2° substrate this favours E2 (concerted, second-order).
  2. E2 needs a β-hydrogen antiperiplanar to the C–Br bond; the base removes it as bromide leaves — one step.
  3. Two β-carbons are available. Zaitsev's rule: the more-substituted (more stable) alkene dominates, so eliminate toward the internal carbon.

Answer. (E)-but-2-ene as the major product, by an E2 mechanism (Zaitsev, more-substituted alkene).

Quiz yourself

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E2. Its rate law is rate = k[substrate][base], so the base concentration appears in the rate. E1's slow step is just ionization of the substrate (rate = k[substrate]), so adding more base would not change its rate.

E2 needs the β-hydrogen and the leaving group to be anti-periplanar — on a ring, both must be axial. If the leaving group is locked equatorial (no adjacent axial H), there is no anti-periplanar geometry available and the concerted E2 cannot proceed.

1-Butene, the less-substituted alkene — the Hofmann product. The bulky tert-butoxide can't reach the crowded internal β-hydrogen, so it removes a terminal one. A small base would instead give the Zaitsev product, 2-butene.

A carbocation was involved, so it was E1 (with SN1 competing). Only the stepwise pathway forms a cation that can undergo a 1,2-hydride or alkyl shift before losing a proton. Concerted E2 has no intermediate and never rearranges.

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