The SN1 reaction is a substitution reaction in organic chemistry.

"SN" stands for

nucleophilic substitution and the "1" represents the fact that the rate-determining step is
unimolecular.[1][2] The reaction involves a carbocation intermediate and is commonly seen
in reactions of secondary or tertiary alkyl halides or, under strongly acidic conditions,
with secondary or tertiary alcohols. With primary alkyl halides, the alternative SN2
reaction occurs. Among inorganic chemists, the SN1 reaction is often known as the
dissociative mechanism. A reaction mechanism was first proposed by Christopher Ingold
et al. in 1940.[3]

Contents
[hide]

• 1 Mechanism
• 2 Kinetics
• 3 Scope of the reaction
• 4 Stereochemistry
• 5 Side reactions
• 6 Solvent effects
• 7 See also
• 8 References
• 9 Further reading

• 10 External links

[edit] Mechanism
An example of a reaction taking place with an SN1 reaction mechanism is the hydrolysis
of tert-butyl bromide with water forming tert-butyl alcohol:

This SN1 reaction takes place in three steps:

• Formation of a tert-butyl carbocation by separation of a leaving group (a bromide

anion) from the carbon atom: this step is slow and reversible.[4]
 • Nucleophilic attack: the carbocation reacts with the nucleophile. If the
nucleophile is a neutral molecule (i.e. a solvent) a third step is required to
complete the reaction. When the solvent is water, the intermediate is an oxonium
ion. This reaction step is fast.

• Deprotonation: Removal of a proton on the protonated nucleophile by water

acting as a base forming the alcohol and a hydronium ion. This reaction step is
fast.

[edit] Kinetics
In contrast to SN2, SN1 reactions take place in two steps (excluding any protonation or
deprotonation). The rate determining step is the first step, so the rate of the overall
reaction is essentially equal to that of carbocation formation and does not involve the
attacking nucleophile. Thus nucleophilicity is irrelevant and the overall reaction rate
depends on the concentration of the reactant only.

rate = k[reactant]

In 1954 it was found that addition of a small amount of lithium perchlorate to certain
acetolysis reactions (for example that of the tosylate of cholesterol) led to a remarkable
reaction rate increase.[5] Based on this special salt effect the general mechanism was
refined to include a contact ion pair (CIP) with cation and anion together in a solvent
cage which then dissociates to a so-called solvent-separated ion pair (SSIP) and then on
to free ions (FI). All the interconversions are reversible and the added salt prevents the
reformation of CIP from SSIP.
In some cases the SN1 reaction will occur at an abnormally high rate due to neighbouring
group participation (NGP). NGP often lowers the energy barrier required for the
formation of the carbocation intermediate.

[edit] Scope of the reaction

The SN1 mechanism tends to dominate when the central carbon atom is surrounded by
bulky groups because such groups sterically hinder the SN2 reaction. Additionally, bulky
substituents on the central carbon increase the rate of carbocation formation because of
the relief of steric strain that occurs. The resultant carbocation is also stabilized by both
inductive stabilization and hyperconjugation from attached alkyl groups. The Hammond-
Leffler postulate suggests that this too will increase the rate of carbocation formation.
The SN1 mechanism therefore dominates in reactions at tertiary alkyl centers and is
further observed at secondary alkyl centers in the presence of weak nucleophiles.

An example of a reaction proceeding in a SN1 fashion is the synthesis of 2,5-dichloro-

2,5-dimethylhexane from the corresponding diol with concentrated hydrochloric acid [6]:

[edit] Stereochemistry
Because the intermediate carbocation is planar, the central carbon is not a stereocenter.
Even if it were a stereocenter prior to becoming a carbocation, the original configuration
at that atom is lost. Rather, the central carbon can be prochiral. Nucleophilic attack can
occur from either side of the plane, so the product might consist of a mixture of two
stereoisomers. In fact, if the central carbon is the only stereocenter in the reaction,
racemization may occur. This stands in contrast to the SN2 mechanism, where the chiral
configuration of the substrate is inverted. However, an excess of inversion is usually
observed, as the leaving group can remain in proximity to the carbocation intermediate
for a short time and block nucleophilic attack. For example, in the reaction of S-3-chloro-
3-methylhexane with iodide ion, if the carbocation intermediate is free of the leaving
group then it is achiral and stands an equal chance of attack on either side. This leads to a
mixture of R-3-iodo-3-methylhexane and S-3-iodo-3-methylhexane:
[edit] Side reactions
Two common side reactions are elimination reactions and carbocation rearrangement. If
the reaction is performed under warm or hot conditions (which favor an increase in
entropy), E1 elimination is likely to predominate, leading to formation of an alkene. Even
if the reaction is performed cold, some alkene may be formed. If an attempt is made to
perform an SN1 reaction using a strongly basic nucleophile such as hydroxide or
methoxide ion, the alkene will again be formed, this time via an E2 elimination. This will
be especially true if the reaction is heated. Finally, if the carbocation intermediate can
rearrange to a more stable carbocation, it will give a product derived from the more stable
carbocation rather than the simple substitution product.

[edit] Solvent effects

Since the SN1 reaction involves formation of an unstable carbocation intermediate in the
rate-determining step, anything that can facilitate this will speed up the reaction. The
normal solvents of choice are both polar (to stabilize ionic intermediates in general) and
protic (to solvate the leaving group in particular). Typical polar protic solvents include
water and alcohols, which will also act as nucleophiles.

The Y scale correlates solvolysis reaction rates of any solvent (k) with that of a standard
solvent (80% v/v ethanol/water) (k0) through

with m a reactant constant (m = 1 for tert-butyl chloride) and Y a solvent parameter.[7]

For example 100% ethanol gives Y = −2.3, 50% ethanol in water Y = +1.65 and 15%
concentration Y = +3.2.[8]
 Chapter 8: Nucleophilic Substitution

SN1 mechanism
SN1 indicates a substitution, nucleophilic, unimolecular reaction, described by the
expression rate = k [R-LG].
This implies that the rate determining step of the mechanism depends on the
decomposition of a single molecular species.

This pathway is a multi-step process with the following characteristics:

step 1: slow loss of the leaving

group, LG, to generate a
carbocation intermediate, then

step 2 : rapid attack of a

nucleophile on the
electrophilic carbocation to
form a new σ bond

Multi-step
reactions have
intermediates
and a several
transition states
(TS).

In an SN1 there
is loss of the
leaving group
generates an
intermediate
carbocation
which is then
undergoes a
rapid reaction
with the
nucleophile..

General case SN1 reaction

Lets look at how the various components of the reaction influence the reaction pathway:

R-
Reactivity order : (CH3)3C- > (CH3)2CH- > CH3CH2- > CH3-

In an SN1 reaction, the rate determining step is the loss of the leaving group to form the
intermediate carbocation. The more stable the carbocation is, the easier it is to form, and
the faster the SN1 reaction will be. Some students fall into the trap of thinking that the
system with the less stable carbocation will react fastest, but they are forgetting that it is
the generation of the carbocation that is rate determining.

The following images show a selection of alkyl bromides and their relative rates of
reaction in an SN1 hydrolysis.
Try to correlate the structure of the alkyl bromide with the type of carbocation that will
be formed.
If you need help, click the L button to show you where the carbocation will be formed.

Relative rate of hydrolysis 1 2 43 100,000,000

L button highlights C+ center, R button resets
You should have found that the carbocations get more stable as you go left to right in the
table. As the carbocation gets easier to form, so the rate of reaction increases.

-LG
The only event in the rate determining step of the SN1 is breaking the C-LG bond.
Therefore, there is a very strong dependence on the nature of the leaving group, the better
the leaving, the faster the SN1 reaction will be.

Nu
Since the nucleophile is not involved in the rate determining step, the nature of the
nucleophile is unimportant in an SN1 reaction. However, the more reactive the
nucleophile, the more likely an SN2 reaction becomes.

Stereochemistry
 In an SN1, the nucleophile attacks the planar carbocation. Since
there is an equally probability of attack on each face there will be
a loss of stereochemistry at the reactive center as both products
will be observed.

Solvent
Polar solvents which can stabilise carbocations which can favour the SN1 reaction (e.g.
H2O, ROH)

Since a carbocation intermediate is formed, there is the possibility of rearrangements

(e.g. 1,2-hydride or 1,2-alkyl shifts) to generate a more stable carbocation. This is usually
indicated by a change in the position of the alkene or a change in the carbon skeleton of
the product when compared to the starting material.

This pathway is most common for systems with good leaving groups, stable carbocations
and weaker nucleophiles. A typical example is the reaction of HBr with a tertiary alcohol.
 SN1 MECHANISM FOR REACTION OF
ALCOHOLS WITH HBr

Step 1:
An acid/base reaction. Protonation of the
alcoholic oxygen to make a better leaving group.
This step is very fast and reversible. The lone
pairs on the oxygen make it a Lewis base.

Step 2:
Cleavage of the C-O bond allows the loss of the
good leaving group, a neutral water molecule, to
give a carbocation intermediate. This is the rate
determining step (bond breaking is endothermic)

Step 3:
Attack of the nucleophilic bromide ion on the
electrophilic carbocation creates the alkyl
bromide.
 SN1 MECHANISM FOR REACTION OF
ALKYL HALIDES WITH H2O

Step 1:
Cleavage of the already polar C-Br bond allows
the loss of the good leaving group, a halide ion,
to give a carbocation intermediate. This is the rate
determining step (bond breaking is endothermic)

Step 2:
Attack of the nucleophile, the lone pairs on the O
atom of the water molecule, on the electrophilic
carbocation creates an oxonium species.

Step 3:
Deprotonation by a base yields the alcohol as the
product.

Note that this is the reverse of the reaction of an

alcohol with HBr.

In principle, the nucleophile here, H2O, could be

replaced with any nucleophile, in which case the
final deprotonation may not always be necessary.

Chapter 8: Nucleophilic Substitution

Carbocations
Stability:
The general stability order of simple alkyl carbocations is: (most stable) 3o > 2o > 1o >
methyl (least stable)
This is because alkyl groups are weakly electron donating due to hyperconjugation and
inductive effects. Resonance effects can further stabilise carbocations when present.

Structure:

Alkyl carbocations are sp2 hybridised, planar

systems at the cationic C centre.
The p-orbital that is not utilised in the hybrids is
empty and is often shown bearing the positive
charge since it represents the orbital available to
accept electrons.

Reactivity:

As they have an
incomplete octet,
carbocations are
excellent electrophiles
and react readily with
nucleophiles.
Alternatively, loss of H+
can generate a π bond.

The electrostatic
potential diagrams
clearly show the
cationic center in blue,
this is where the
nucleophile will attack.

Rearrangements:
Carbocations are prone to rearrangement via 1,2-hyride or 1,2-alkyl shifts if it generates a
more stable carbocation

Reactions involving carbocations:

1. Substitutions via the SN1
2. Eliminations via the E1
3. Additions to alkenes and alkynes (HX, H3O+)

Chapter 8: Nucleophilic Substitution

SN2 mechanism
SN2 indicates a substitution, nucleophilic, bimolecularreaction,described by the
expression rate = k [Nu][R-LG].
This implies that the rate determining step involves an interactionbetween these two
species, the nucleophile and the organic substrate.

This pathway is a concerted process (single step) as shown by the followingreaction

coordinate diagrams, where there is simultaneous attack of thenucleophile and
displacement of the leaving group.

The nucleophile attacks at the carbon with the partial positive chargeas a result of the
polar σ bond to the electronegativeatoms in the leaving group.
Single step
reactions have no
intermediates and a
single
transitionstate
(TS).

In an SN2 there is
simultaneous
formation of the
carbon-
nucleophilebond
and breaking of the
carbon-leaving
group bond, hence
the
reactionproceeds
via a TS in which
the central C is
partially bonded to
five groups.
General case SN2 reaction

Let's look at how the various components of the reaction influence thereaction pathway:

R-
Reactivity order : CH3- > CH3CH2- > (CH3)2CH- > (CH3)3C-
In an SN2 reaction, the transition state has 5 groups around the
centralC atom. As a consequence of the steric requirements at this
center, lesshighly substituted systems (i.e. more smaller H groups) will
favouran SN2 reaction by making it easier to achieve the transition
state.

The following two series of images show four alkyl bromides anda chloride ion as a
potential nucleophile. Relative rate of reaction datafor an SN2 reaction with iodide is also
given.
Use the lower row of space filling models (which are great for seeingsteric effects) to
rotate the molecules to look at the electrophilic Ccenter from the side opposite to the
leaving group (which is where thenucleophile attacks from) to see how much of it the
electrophilic centeryou can see.
If you need help recognising the electrophilic center, use the L buttonto highlight it.

Relative rate of reaction with I- 221,000 1,350 1 ≈0

L button highlights E+ center, R button resets

Notice how as the steric crowding increases around the electrophilic center, the rate of
reaction with iodide decreases.

-LG
The C-LG bond is brokenduring the rate determining step so the rate does depend on the
natureof the leaving group. However, if a leaving group is too good, then anSN1 reaction
may result.

Nu
Since the nucleophile is involved in the rate determining step, thenature of the
nucleophile is very important in an SN2 reaction. The morereactive the nucleophile, the
more likely the reaction will be SN2 ratherthan SN1.

Stereochemistry
When the nucleophile attacks in an SN2 it is on the oppositeside to the position of the
leaving group. As a result, the reaction willproceed with an inversion of configuration.
Solvent
Polar aprotic solvents can be used to enhance the reactivity of thenucleophile and help
promote an SN2 reaction.

Summary
This pathway is most common for systems with poorer leaving groups,1o or 2o substrates
and stronger nucleophiles.
A typical example is the reaction of NaI with primary alkyl halidesor tosylates.

Chapter 8: Nucleophilic Substitution

Nucleophiles
Nucleophile means "nucleus loving" which describes the tendency of an electron rich
species to be attracted to the positive nuclear charge of an electron poor species, the
electrophile .

The nucleophilicity expresses the ability of the nucleophile to react in this fashion.

In general terms this can be appreciated by considering the availability of the electrons in
the nucleophile. The more available the electrons, the more nucleophilic the system.
Hence the first step should be to locate the nucleophilic center. At this point we will be
considering Nu that contain lone pairs and may be anionic, however the high electron
density of a C=C is also a nucleophile.

A collection of
important
nucleophiles
are shown to
the left.

Nucleophilicity trends (compared with basicity)

 1. Across a row in the periodic table nucleophilicity (lone pair donation) C- > N- > O-
> F- since increasing electronegativity decreases the lone pair availability. This is
the same order as for basicity.
2. If one is comparing the same central atom, higher electron density will increase
the nucleophilicity,

e.g. an anion will be a better Nu (lone pair donor) than a neutral atom such as HO-
> H2O. This is the same order as for basicity.

3. Within a group in the periodic table, increasing polarisation of the nucleophile as

you go down a group enhances the ability to form the new C-X bond and
increases the nucleophilicity, so I- > Br- > Cl- > F-. The electron density of larger
atoms is more readily distorted i.e. polarised, since the electrons are further from
the nucleus.

Note that is the opposite order to basicity (acidity increases down a group) where
polarisability is much less important for bond formation to the very small proton.
Here is a table of relative nucleophilicities as measured in methanol (CH3OH):

Very Good I-, HS-, RS-

Good Br-, HO-, RO-, NC-, N3-
Fair NH3, Cl-, F-, RCO2-
Weak H2O, ROH
Very Weak RCO2H

Chapter 8: Nucleophilic Substitution

Nucleophilicity versus Basicity

Nucleophilicity and basicity are very similar properties in that species that are
nucleophiles are usually also bases (e.g. HO- , RO-).

This is not too surprising since in the LEWIS sense, they are functioning as LONE PAIR
donors (i.e. both are LEWIS BASES), compare the two pairs of reactions mechanisms
shown below to convince yourself.

However, it can avoid confusion by keeping these two types of reactivity separated
because there are important differences....

1. Nucleophilicity:
 Both these reactions depict
a nucleophile reacting with
an electrophilic C atom

Kinetically controlled reactions of lone pair donor with an electrophilic carbon (usually)
atom resulting in the formation a new C-X bond.

2. Basicity:

Both these reactions depict a

base reacting with an
electrophilic H atom, a proton

Equilibrium (thermodynamic) reaction of the lone pair donor with a proton, forming a
new H-X bond

The following general reaction mechanisms show you why it is important to appreciate
the differences, since an anion that is reacting as a nucleophile will result in a
substitution, but if it reacts as a base, then elimination will result, be it on a carbocation
(SN1 vs E1) or with the loss of a leaving group (SN2 vs E2).

SN1
Substitution
s
SN2

E1

Eliminations

E2