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 organic chemistry: SN2, E2, SN1, E1

SN 2 SN1/E1

E2

SN1 and E1 have identical rate determining steps, so they

generally occur simultaneously and have the same properties.

SN2 and E2 SN1/E1

mechanism one step—this single step is the rate-determining step (RDS)
big SN2: steric hindrance blocking Nu (Nu is in RDS)
obstacle E2: blocking B isn’t a big obstacle (B doesn’t join substrate)
stereo- SN2: inversion (backside attack, since LG blocks frontside)
chemistry E2: cis vs. trans determined by anti-periplanar transition-state
regio- E2: possible products from deprotonation of any β-carbon
chemistry major product w/ bulky base: less substituted (steric hindrance)
major product with non-bulky base: more substituted
rate Rate = k [substrate] [Nu- or B-], so [Nu-/B-] ↑ → rate ↑
expression (substrate and Nu-/B- are in RDS)
Nu quality requires good Nu/strong B (Nu/B is in RDS)
bulky Nu/B favors E2 vs. SN2 (blocking B isn’t a big obstacle)
LG quality requires good leaving group (because leaving group is in RDS)
preferred polar aprotic (no O-H or N-H bonds)
solvent? (for SN2, hydrogen-bonds to solvent would block Nu)
(for E2, protic solvent would protonate the base)
substrate SN2: methyl>1º>2º; 3° gives no SN2 (substitutents block Nu)
E2: 1º, 2º, or 3° (blocking B is not a big obstacle)
two steps—RDS is formation of carbocation
stabilizing carbocation
(Nu/B isn’t in RDS, so blocking it isn’t an obstacle)
SN1: racemization (planar carbocation intermediate)
E1: both cis and trans isomers will be produced
E1: possible products from deprotonation of any β-C
major product: more substituted alkene
(e--donating alkyl substituents stabilize alkenes)
Rate = k [substrate], so [Nu-/B-]↑ → rate unchanged
(only the substrate is in RDS)
can work with a poor Nu/weak B
(Nu/B isn’t in RDS)
requires good leaving group (because LG is in RDS)
polar protic (at least one O-H or N-H bond)
(hydrogen-bonds to solvent stabilize carbocation)
3º > 2º; methyl and 1° give no SN1/E1
(alkyl substituents stabilize the carbocation)

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 organic chemistry: SN2, E2, SN1, E1

comparing the same element

charge resonance
nucleophilicity negative charge à better Nu resonance à worse Nu
(charge is stabilized)
basicity negative charge à stronger base resonance à weaker base
(charge is stabilized)
leaving-group ability positive charge à better LG resonance à better LG
(more willing to accept electrons) (charge will be stabilized)

comparing different elements

same row
big difference electronegativity
nucleophilicity less electronegative à better Nu
(willing to donate electrons)
basicity less electronegative à stronger base
(willing to donate electrons)
leaving-group ability more electronegative à better LG
(willing to accept electrons)
same column
size
bigger à better Nu (usually)
(big Nu’s are less hindered by solvent, more polarizable)
bigger à weaker base
(large base can spread out and stabilize electron density)
bigger à better leaving group
(big LG’s can spread out and stabilize electron density)

nucleophiles, leaving groups, bases

nucleophiles leaving groups
- - -
N O F N O F good Nu (SN2 or SN1) N O F N+ O+ good LG
P S Cl P- S- Cl- poor Nu (SN1 only) P S Cl P+ S+ not a LG
- -
Se Br Se Br not a Nu Br
I I- I
The α carbon is attached to
-
cyanide NC (charge on the C) azide N3 - the oxygen, not to the sulfur.
bases Nucleophiles and bases shown with charges before attacking.
N O F N- O- strong base (E2) Leaving groups shown with charges before leaving.
- - -
P S Cl P S Cl weak base (E1) The tables for individual atoms assume no resonance. Resonance
Br Br- not a base makes atoms into worse nucleophiles and bases and into better leaving
-
I I groups.

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 organic chemistry: SN2, E2, SN1, E1

what happens in SN2, SN1, E2, and E1 mechanisms

what happens big obstacle
SN 2 One step: Nucleophile joins α carbon and leaving group leaves α carbon steric hindrance
SN 1 Step one: Leaving group leaves α carbon stabilizing the
Step two: Nucleophile joins α carbon carbocation
E2 One step: Base takes β hydrogen, π bond forms between α and β carbons, leaving group leaves α carbon. none
E1 Step one: Leaving group leaves α carbon stabilizing the
Step two: Base takes β hydrogen, π bond forms between α and β carbons carbocation

how to determine SN2 vs. E2 vs. SN1 vs. E1 for haloalkane and alkylsulfonate substrates
poor Nu / weak base good Nu / weak base good Nu / strong base
- - - - - - -
O with no formal charge Cl , Br , I , NC , N3 , S , Se , or N- , O-
-
CH3COO
or N, S, or Se with no formal charge
methyl α-carbon no reaction SN 2 1 E2 with tert-butyl-oxide (bulky base) 2
1° α-carbon Otherwise, SN2
2° α-carbon 95% SN1 SN 2 1 E2
5% E1 (usually not shown)
3° α-carbon 95% SN1 95% SN1 E2
5% E1 (usually not shown) 5% E1 (usually not shown)
For cases with “95% SN1, 5% E1”, E1 products are generally not shown unless the problem specifies “all possible products”.
1
No reaction if beta-carbon is 4°.
2
SN2 for methyl α-carbon.

The table displays the major reaction(s) for each case—in some cases there may be significant levels of other competing
reactions.
This table may not give the correct answer in all real-world situations, but it will generally be accurate for the questions that
are typical of exams.

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11.12: A Summary of Reactivity - SN1, SN2, E1, E1cB, and E2
Objectives
After completing this section, you should be able to
1. determine whether a specified substrate is most likely to undergo an E1, E2, SN1 or SN2 reaction under a given set of
conditions.
2. describe the conditions under which a given substrate is most likely to react by a specified mechanism (E1, E2, SN1 or
SN2).

 Study Notes
This section summarizes much of what has been discussed in the chapter. It focuses on how a given substrate will behave under
certain conditions, but does not deal with the stereochemistry of the products.

Having discussed the many factors that influence nucleophilic substitution and elimination reactions of alkyl halides, we must now
consider the practical problem of predicting the most likely outcome when a given alkyl halide is reacted with a given nucleophile.
As we noted earlier, there are multiple variables to be considered, the most important being the substitution of the alkyl
halide. SN2 reactions favor alkyl halides with little steric hindrance such as methyl halides and primary halides. In general, in order
for an SN1 or E1 reaction to occur, the relevant carbocation intermediate must be relatively stable such as with tertiary halides,
secondary allylic halides, and secondary benzylic halides.
The next most import variable for predicting the outcome of a reaction is the nature of the nucleophilic reactant. Strong
nucleophiles favor SN2 substitution, and strong bases, especially strong hindered bases (such as tert-butoxide) favor E2
elimination. Weak nucleophiles that are also weak bases tend to favor SN1 and E1 reactions.
Good Nucleophiles Which are Weak Bases: I–, Br–, SCN–, N3–, CH3CO2– , RS–, CN–, Amines, etc.
Good Nucleophiles Which are Strong Bases: HO–, RO–.
Poor Nucleophiles which are Weak Bases: H2O, ROH, RSH.

General Rules For Predicting a Reaction

Consider these in the order listed.
Methyl Alkyl Halides
An SN2 substitution occurs regardless if a good or poor nucleophile is used.
Primary Alkyl Halides

An E2 elimination occurs if a strong, sterically hindered base is used.

An E1cB elimination occurs if a strong base is used and the leaving group is two carbons away from a carbonyl group.
An SN2 substitution occurs if a good nucleophile is used.

Secondary Alkyl Halides

An E1cB elimination occurs if a strong base is used and the leaving group is two carbons away from a carbonyl group.
An E2 elimination occurs if a strong base is used.
An SN2 reaction occurs if a good nucleophile that is a weak bases is used in a polar aprotic solvent.
An SN1 reaction along with an E1 reaction occurs if a poor nucleophile that is a weak bases is used in a protic solvent.

Tertiary Alkyl Halides

An E1cB elimination occurs if a strong base is used and the leaving group is two carbons away from a carbonyl group.

11.12.1 https://chem.libretexts.org/@go/page/31517
An E2 elimination occurs if a strong base is used.
An SN1 reaction along with an E1 reaction occurs if a poor nucleophile that is a weak bases is used in a protic solvent.

Worked Example11.12.1

1) For the following, please determine what kind of reaction is occurring and predict the product(s).
a)
Br NaCN
H3 C C ?
H CH3 Acetone

b)
Br NaOCH3
H3 C C ?
H CH3 Acetone

c)
Br HOCH3
H3 C C ?
H CH3

Answer
a) The substrate is a secondary halide so the product is determined by the nature of the nucleophile used in the reaction.
Cyanide (-CN) is a good nucleophile which is a weak base. The fact that the nucleophile is a weak base means that an E2
reaction is not favored. Also, the fact that cyanide is a good nucleophile means that SN2 substitutions are favored over
SN1. When a secondary halide is reacted with a good nucleophile which is a weak base, the preferred reaction is SN2.
After SN2 substitution the product is a nitrile.
Br C N
NaCN
H 3C C H 3C C
H CH3 Acetone H CH3

b) The substrate is a secondary halide so the product is determined by the nature of the nucleophile used in the reaction.
Methoxide (-OCH3) is a strong base so it could prefer to remove a hydrogen from the substrate. This makes an E2
elimination the preferred reaction and an alkene the product.
H
Br NaOCH3 H 3C C
H 3C C
Acetone C H
H CH3
H

c) The substrate is a secondary halide so the product is determined by the nature of the nucleophile used in the reaction.
Methanol (HOCH3) is a weak nucleophile that is a weak base. Being a weak base means that methanol is not capable of
actively removing a hydrogen to cause an E2 reaction. Also, because methanol is a weak nucleophile is not capable of
attacking the substrate and causing an SN2 reaction. For the methanol nucleophile to react the substrate must first eject it
leaving group to form the highly reactive carbocation intermediate. Formation of the carbocation is the rate determine step
for both the SN1 and E1 reactions so they each form a separate product.
H
Br HOCH3 H3C C O CH3
H 3C C
C H
+ H 3C C
H CH3 H CH3
H

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Exercises 11.12.1

1. Identify the dominant reaction mechanism (SN1, SN2, E1, or E2) and predict the major product for the following reactions.

a)

b)

c)

d)

e)

2) Identify the function of the following reagents. The reagents will be a strong/weak nucleophile and/or a strong/weak
base.
a) Cl-
b) NaH
c) t-BuO-
d) OH-
e) H2O
f) HS-
g) MeOH
3) Identify which mechanism the following reactions would undergo.

4) Identify all the products of the following reactions and specify the major product.

a)

b)

c)

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 d)

e)
5) The following reaction yields five different products. Give the mechanisms for how each is formed.

6) Label the following reactions as SN1, SN2, E1, or E2.

Answer
1)

2)
a) Cl- ; strong nucleophile
b) NaH ; strong base
c) t-BuO- ; strong base

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d) OH- ; strong nucleophile ; strong base
e) H2O ; weak nucleophile ; weak base
f) HS- ; strong nucleophile
g) MeOH ; weak nucleophile ; weak base
3)
a) E2, SN1
b) SN2, E2
c) SN2
d) SN1, E1
e) E2, SN1
4)

a)

b)

c)

d)

e)
5)

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 6)
A – SN2
B – E1
C – SN1
D – E2

Contributors and Attributions

William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry
Prof. Steven Farmer (Sonoma State University)

11.12: A Summary of Reactivity - SN1, SN2, E1, E1cB, and E2 is shared under a not declared license and was authored, remixed, and/or curated
by LibreTexts.

11.12.6 https://chem.libretexts.org/@go/page/31517