CHAPTER CONTENTS - 11.1 The Discovery of Nucleophilic Substitution Reactions

Discovery of the nucleophilic substitution reaction of alkyl halides dates back to work carried out by the German chemist Paul Walden in 1896. Walden found that the pure enantiomeric (+)- and ( - )-malic acids could be interconverted through a series of simple substitution reactions. When Walden treated (-)-malic acid with $\mathrm{PCl}_{5}$, he isolated (+)-chlorosuccinic acid. This, on treatment with wet $\mathrm{Ag}_{2} \mathrm{O}$, gave (+)-malic acid. Similarly, reaction of $(+)$-malic acid with $\mathrm{PCl}_{5}$ gave (-)-chlorosuccinic acid, which was converted into (-)-malic acid when treated with wet $\mathrm{Ag}_{2} \mathrm{O}$. The full cycle of reactions is shown in FIGURE 11.2.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0331.jpg?height=158&width=612&top_left_y=951&top_left_x=751)
(-)-Malic acid
$[\alpha]_{D}=-2.3$
$\uparrow \mathrm{Ag}_{2} \mathrm{O}, \mathrm{H}_{2} \mathrm{O}$
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(-)-Chlorosuccinic acid
(+)-Chlorosuccinic acid

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(+)-Malic acid
$[\alpha]_{D}=+2.3$


FIGURE 11.2 Walden's cycle of reactions interconverting (+)- and (-)-malic acids.
At the time, the results were astonishing. The eminent chemist Emil Fischer called Walden's discovery "the most remarkable observation made in the field of optical activity since the fundamental observations of Pasteur." Because (-)-malic acid was converted into (+)-malic acid, some reactions in the cycle must have occurred with a change, or inversion, of configuration at the chirality center. But which ones, and how? (Remember from Section 5.5 that the direction of light rotation and the configuration of a chirality center aren't directly related. You can't tell by looking at the sign of rotation whether a change in configuration has occurred during a reaction.)


Today, we refer to the transformations taking place in Walden's cycle as nucleophilic substitution reactions because each step involves the substitution of one nucleophile (chloride ion, $\mathrm{Cl}^{-}$, or hydroxide ion, $\mathrm{HO}^{-}$) by another. Nucleophilic substitution reactions are one of the most common and versatile reaction types in organic chemistry.


$$
\mathrm{R}-\mathrm{X}+\mathrm{Nu}:^{-} \longrightarrow \mathrm{R}-\mathrm{Nu}+\mathrm{X}:^{-}
$$


Following the work of Walden, further investigations were undertaken during the 1920s and 1930s to clarify the mechanism of nucleophilic substitution reactions and to find out how inversions of configuration occur. Among the first series studied was one that interconverted the two enantiomers of 1-phenyl-2-propanol (FIGURE 11.3). Although this particular series of reactions involves nucleophilic substitution of an alkyl para-toluenesulfonate (called a tosylate) rather than an alkyl halide, exactly the same type of reaction is involved as that studied by Walden. For all practical purposes, the entire tosylate group acts as if it were simply a halogen substituent. (In fact, when you see a tosylate substituent in a molecule, do a mental substitution and tell yourself that you're
dealing with an alkyl halide.)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0332.jpg?height=1353&width=1166&top_left_y=253&top_left_x=477)


FIGURE 11.3 A Walden cycle interconverting (+) and (-) enantiomers of 1-phenyl-2-propanol. Chirality centers are marked by asterisks, and the bonds broken in each reaction are indicated by red wavy lines. The inversion of chirality occurs in step 2, where acetate ion substitutes for tosylate ion.

In the three-step reaction sequence shown in FIGURE 11.3, (+)-1-phenyl-2-propanol is interconverted with its (-) enantiomer, so at least one of the three steps must involve an inversion of configuration at the chirality center. Step 1, formation of a tosylate, occurs by breaking the $\mathrm{O}-\mathrm{H}$ bond of the alcohol rather than the $\mathrm{C}-\mathrm{O}$ bond to the chiral carbon, so the configuration around the carbon is unchanged. Similarly, step 3, hydroxide-ion cleavage of the acetate, takes place without breaking the $\mathrm{C}-\mathrm{O}$ bond at the chirality center. Thus, the inversion of stereochemical configuration must take place in step 2, the nucleophilic substitution of tosylate ion by acetate ion.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0332.jpg?height=218&width=1014&top_left_y=2051&top_left_x=550)


From this and nearly a dozen other series of similar reactions, researchers concluded that the nucleophilic substitution reaction of a primary or secondary alkyl halide or tosylate always proceeds with inversion of configuration. (Tertiary alkyl halides and tosylates, as we'll see shortly, give different stereochemical results and react by a different mechanism than the primary and secondary ones.)


WORKED EXAMPLE 11.1 -


Predicting the Stereochemistry of a Nucleophilic Substitution Reaction -

What product would you expect from a nucleophilic substitution reaction of ( $R$ )-1-bromo-1-phenylethane with cyanide ion, ${ }^{-} \mathrm{C} \equiv \mathrm{N}$, as nucleophile? Show the stereochemistry of both reactant and product, assuming that inversion of configuration occurs.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0333.jpg?height=191&width=473&top_left_y=520&top_left_x=823)


Strategy -

Draw the $R$ enantiomer of the reactant, and then change the configuration of the chirality center while replacing the ${ }^{-} \mathrm{Br}$ with $\mathrm{a}^{-} \mathrm{CN}$.


Strategy -

Solution
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0333.jpg?height=201&width=716&top_left_y=935&top_left_x=707)
(R)-1-Bromo-1-phenylethane
(S)-2-PhenyIpropanenitrile


Strategy -

PROBLEM What product would you expect from a nucleophilic substitution reaction of ( $S$ )-2-bromohexane
11-1 with acetate ion, $\mathrm{CH}_{3} \mathrm{CO}_{2}^{-}$? Assume that inversion of configuration occurs, and show the stereochemistry of both the reactant and product.


Strategy - 11.2 The $\mathrm{S}_{\mathrm{N}} 2$ Reaction

In almost all chemical reactions, there is a direct relationship between the rate at which the reaction occurs and the concentrations of the reactants. When we measure this relationship, we measure the kinetics of the reaction. For example, let's look at the kinetics of a simple nucleophilic substitution-the reaction of $\mathrm{CH}_{3} \mathrm{Br}$ with $\mathrm{OH}^{-}$to yield $\mathrm{CH}_{3} \mathrm{OH}$ plus $\mathrm{Br}^{-}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0333.jpg?height=88&width=733&top_left_y=1669&top_left_x=693)

With a given temperature, solvent, and concentration of reactants, the substitution occurs at a certain rate. If we double the concentration of $\mathrm{OH}^{-}$, the frequency of encounters between reaction partners doubles and we find that the reaction rate also doubles. Similarly, if we double the concentration of $\mathrm{CH}_{3} \mathrm{Br}$, the reaction rate again doubles. We call such a reaction, in which the rate is linearly dependent on the concentrations of two species, a second-order reaction. Mathematically, we can express this second-order dependence of the nucleophilic substitution reaction by setting up a rate equation. As either [ RX ] or [ ${ }^{-} \mathrm{OH}$ ] changes, the rate of the reaction changes proportionately.


$$
\begin{aligned}
\text { Reaction rate } & =\text { Rate of disappearance of reactant } \\
& =k \times[\mathrm{RX}] \times\left[{ }^{-} \mathrm{OH}\right]
\end{aligned}
$$


where
$[\mathrm{RX}]=\mathrm{CH}_{3} \mathrm{Br}$ concentration in molarity
$[-\mathrm{OH}]=-\mathrm{OH}$ concentration in molarity
$k=$ a constant value (the rate constant)
A mechanism that accounts for both the inversion of configuration and the second-order kinetics that are observed with nucleophilic substitution reactions was suggested in 1937 by the British chemists E. D. Hughes
and Christopher Ingold, who formulated what they called the $\mathbf{S}_{\mathbf{N}} \mathbf{2}$ reaction-short for substitution, nucleophilic, bimolecular. (Bimolecular means that two molecules, nucleophile and alkyl halide, take part in the step whose kinetics are measured.)


The essential feature of the $\mathrm{S}_{\mathrm{N}} 2$ mechanism is that it takes place in a single step, without intermediates, when the incoming nucleophile reacts with the alkyl halide or tosylate (the substrate) from a direction opposite the group that is displaced (the leaving group). As the nucleophile comes in on one side of the substrate and bonds to the carbon, the halide or tosylate departs from the other side, thereby inverting the stereochemical configuration. The process is shown in FIGURE 11.4 for the reaction of ( $S$ ) -2-bromobutane with $\mathrm{HO}^{-}$to give ( $R$ )-2-butanol.

FIGURE 11.4 MECHANISM
The mechanism of the $\mathbf{S}_{\mathbf{N}} \mathbf{2}$ reaction. The reaction takes place in a single step when the incoming nucleophile approaches from a direction $180^{\circ}$ away from the leaving halide ion, thereby inverting the stereochemistry at carbon.
(1) The nucleophile ${ }^{-} \mathrm{OH}$ uses its lone-pair electrons to attack the alkyl halide carbon $180^{\circ}$ away from the departing halogen. This leads to a transition state with a partially formed $\mathrm{C}-\mathrm{OH}$ bond and a partially broken $\mathrm{C}-\mathrm{Br}$ bond.
(2) The stereochemistry at carbon is inverted as the $\mathrm{C}-\mathrm{OH}$ bond forms fully and the bromide ion departs with the electron pair from the former $\mathrm{C}-\mathrm{Br}$ bond.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0334.jpg?height=136&width=272&top_left_y=908&top_left_x=1170)
(S)-2-Bromobutane
-
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0334.jpg?height=172&width=273&top_left_y=1237&top_left_x=1235)


As shown in FIGURE 11.4, the $\mathrm{S}_{\mathrm{N}} 2$ reaction occurs when an electron pair on the nucleophile Nu : ${ }^{-}$forces out the group $\mathrm{X}:^{-}$, which takes with it the electron pair from the former $\mathrm{C}-\mathrm{X}$ bond. This occurs through a transition state in which the new $\mathrm{Nu}-\mathrm{C}$ bond is partially formed at the same time that the old $\mathrm{C}-\mathrm{X}$ bond is partially broken and in which the negative charge is shared by both the incoming nucleophile and the outgoing halide ion. The transition state for this inversion has the remaining three bonds to carbon in a planar arrangement (FIGURE 11.5).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0335.jpg?height=1045&width=1113&top_left_y=193&top_left_x=514)

FIGURE 11.5 The transition state of an $\mathbf{S}_{\mathbf{N}} 2$ reaction has a planar arrangement of the carbon atom and the remaining three groups. Electrostatic potential maps show that negative charge is delocalized in the transition state.


The mechanism proposed by Hughes and Ingold is fully consistent with experimental results, explaining both stereochemical and kinetic data. Thus, the requirement for a backside approach of the entering nucleophile ( $180^{\circ}$ away from the departing X group) causes the stereochemistry of the substrate to invert, much like an umbrella turning inside-out in the wind. The Hughes-Ingold mechanism also explains why second-order kinetics are observed: the $\mathrm{S}_{\mathrm{N}} 2$ reaction occurs in a single step that involves both alkyl halide and nucleophile. Two molecules are involved in the step whose rate is measured.


PROBLEM What product would you expect to obtain from $\mathrm{S}_{\mathrm{N}} 2$ reaction of $\mathrm{OH}^{-}$with $(R)$-2-bromobutane? Show
11-2 the stereochemistry of both the reactant and product.
PROBLEM Assign configuration to the following substance, and draw the structure of the product that would 11-3 result from nucleophilic substitution reaction with $\mathrm{HS}^{-}$(reddish brown $=\mathrm{Br}$ ):
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0335.jpg?height=253&width=448&top_left_y=1820&top_left_x=416)


Strategy - 11.3 Characteristics of the $\mathrm{S}_{\mathrm{N}} 2$ Reaction

Now that we know how $\mathrm{S}_{\mathrm{N}} 2$ reactions occur, we need to see how they can be used and what variables affect them. Some $\mathrm{S}_{\mathrm{N}} 2$ reactions are fast, and some are slow; some take place in high yield and others in low yield. Understanding the factors involved can be of tremendous value. Let's begin by recalling a few things about reaction rates in general.


The rate of a chemical reaction is determined by the activation energy $\Delta G^{\ddagger}$, the energy difference between reactant ground state and transition state. A change in reaction conditions can affect $\Delta G^{\ddagger}$ either by changing the reactant energy level or by changing the transition-state energy level. Lowering the reactant energy or raising the transition-state energy increases $\Delta G^{\ddagger}$ and decreases the reaction rate; raising the reactant energy or
decreasing the transition-state energy decreases $\Delta G^{\ddagger}$ and increases the reaction rate (FIGURE 11.6). We'll see examples of all these effects as we look at $\mathrm{S}_{\mathrm{N}} 2$ reaction variables.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0336.jpg?height=462&width=1285&top_left_y=292&top_left_x=420)

FIGURE 11.6 The effects of changes in reactant and transition-state energy levels on reaction rate. (a) A higher reactant energy level (red curve) corresponds to a faster reaction (smaller $\Delta G^{\ddagger}$ ). (b) A higher transition-state energy level (red curve) corresponds to a slower reaction (larger $\Delta G^{\ddagger}$ ).


Steric Effects in the $\mathrm{S}_{\mathrm{N}} 2$ Reaction -

The first $\mathrm{S}_{\mathrm{N}} 2$ reaction variable to look at is the structure of the substrate. Because the $\mathrm{S}_{\mathrm{N}} 2$ transition state involves partial bond formation between the incoming nucleophile and the alkyl halide carbon atom, it seems reasonable that a hindered, bulky substrate should prevent easy approach of the nucleophile, making bond formation difficult. In other words, the transition state for reaction of a sterically hindered substrate, whose carbon atom is "shielded" from the approach of the incoming nucleophile, is higher in energy and forms more slowly than the corresponding transition state for a less hindered substrate (FIGURE 11.7).
(a)
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![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0336.jpg?height=173&width=333&top_left_y=1231&top_left_x=636)
(c)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0336.jpg?height=242&width=502&top_left_y=1532&top_left_x=470)
(b)
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![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0336.jpg?height=202&width=335&top_left_y=1230&top_left_x=1269)
<img class="imgSvg" id = "m6sn3ni6idn9k0hmtd" src="data:image/svg+xml;base64,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"/>
(d)
<img class="imgSvg" id = "m6sn3ni77cl0zpz301f" 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![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0336.jpg?height=250&width=375&top_left_y=1523&top_left_x=1295)


FIGURE 11.7 Steric hindrance to the $\mathbf{S}_{\mathbf{N}} \mathbf{2}$ reaction. As the models indicate, the carbon atom in (a) bromomethane is readily accessible, resulting in a fast $\mathrm{S}_{\mathrm{N}} 2$ reaction. The carbon atoms in (b) bromoethane (primary), (c) 2-bromopropane (secondary), and (d) 2-bromo-2-methylpropane (tertiary) are successively more hindered, resulting in successively slower $\mathrm{S}_{\mathrm{N}} 2$ reactions.

As FIGURE 11.7 shows, the difficulty of nucleophile approach increases as the three substituents bonded to the halo-substituted carbon atom increase in size. Methyl halides are by far the most reactive substrates in $\mathrm{S}_{\mathrm{N}} 2$ reactions, followed by primary alkyl halides such as ethyl and propyl. Alkyl branching at the reacting center, as in isopropyl halides $\left(2^{\circ}\right)$, slows the reaction greatly, and further branching, as in tert-butyl halides $\left(3^{\circ}\right)$, effectively halts the reaction. Even branching one carbon away from the reacting center, as in 2,2-dimethylpropyl (neopentyl) halides, greatly hinders nucleophilic displacement. As a result, $\mathrm{S}_{\mathrm{N}} 2$ reactions occur only at relatively unhindered sites and are normally useful only with methyl halides, primary halides, and a few simple secondary halides. Relative reactivities for some different substrates are as follows:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0337.jpg?height=516&width=1240&top_left_y=197&top_left_x=437)


Vinylic halides $\left(\mathrm{R}_{2} \mathrm{C}=\mathrm{CRX}\right)$ and aryl halides are not shown on this reactivity list because they are unreactive toward $\mathrm{S}_{\mathrm{N}} 2$ displacement. This lack of reactivity is due to steric factors: the incoming nucleophile would have to approach in the plane of the carbon-carbon double bond and burrow through part of the molecule to carry out a backside displacement.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0337.jpg?height=183&width=1132&top_left_y=917&top_left_x=491)


Vinylic halide


The Nucleophile -

Another variable that has a major effect on the $S_{N} 2$ reaction is the nature of the nucleophile. Any species, either neutral or negatively charged, can act as a nucleophile as long as it has an unshared pair of electrons; that is, as long as it is a Lewis base. If the nucleophile is negatively charged, the product is neutral; if the nucleophile is neutral, the product is positively charged.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0337.jpg?height=409&width=905&top_left_y=1446&top_left_x=610)


The Nucleophile -

A wide array of substances can be prepared using nucleophilic substitution reactions. In fact, we've already seen examples in previous chapters. For instance, the reaction of an acetylide anion with an alkyl halide, discussed in Section 9.8, is an $\mathrm{S}_{\mathrm{N}} 2$ reaction in which the acetylide nucleophile displaces a halide leaving group.


The Nucleophile -

$$
\mathrm{R}-\mathrm{C} \equiv \mathrm{C}:^{-}+\mathrm{CH}_{3} \mathrm{Br} \xrightarrow[\text { reaction }]{\mathrm{S}_{\mathrm{N}^{2}}} \mathrm{R}-\mathrm{C} \equiv \mathrm{C}-\mathrm{CH}_{3}+\mathrm{Br}^{-}
$$


An acetylide anion -

TABLE 11.1 lists some nucleophiles in the order of their reactivity, shows the products of their reactions with bromomethane, and gives the relative rates of their reactions. There are large differences in the rates at which various nucleophiles react.


An acetylide anion -

TABLE 11.1 Some $S_{N} 2$ Reactions with Bromomethane


An acetylide anion -

| $\mathrm{Nu}:^{-}+\mathrm{CH}_{3} \mathrm{Br} \rightarrow \mathrm{CH}_{3} \mathrm{Nu}+\mathrm{Br}^{-}$ |  |  |  |  |
| :---: | :---: | :---: | :---: | :---: |
| Nucleophile |  | Product |  | Relative rate of reaction |
| Formula | Name | Formula | Name |  |
| $\mathrm{H}_{2} \mathrm{O}$ | Water | $\mathrm{CH}_{3} \mathrm{OH}_{2}{ }^{+}$ | Methylhydronium ion | 1 |
| $\mathrm{CH}_{3} \mathrm{CO}_{2}{ }^{-}$ | Acetate | $\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{CH}_{3}$ | Methyl acetate | 500 |
| $\mathrm{NH}_{3}$ | Ammonia | $\mathrm{CH}_{3} \mathrm{NH}_{3}{ }^{+}$ | Methylammonium ion | 700 |
| $\mathrm{Cl}^{-}$ | Chloride | $\mathrm{CH}_{3} \mathrm{Cl}$ | Chloromethane | 1,000 |
| $\mathrm{HO}^{-}$ | Hydroxide | $\mathrm{CH}_{3} \mathrm{OH}$ | Methanol | 10,000 |
| $\mathrm{CH}_{3} \mathrm{O}^{-}$ | Methoxide | $\mathrm{CH}_{3} \mathrm{OCH}_{3}$ | Dimethyl ether | 25,000 |
| $\mathrm{I}^{-}$ | Iodide | $\mathrm{CH}_{3} \mathrm{I}$ | Iodomethane | 100,000 |
| ${ }^{-} \mathrm{CN}$ | Cyanide | $\mathrm{CH}_{3} \mathrm{CN}$ | Acetonitrile | 125,000 |
| HS ${ }^{-}$ | Hydrosulfide | $\mathrm{CH}_{3} \mathrm{SH}$ | Methanethiol | 125,000 |


An acetylide anion -

What are the reasons for the reactivity differences observed in TABLE 11.1? Why do some reactants appear to be much more "nucleophilic" than others? The answers to these questions aren't straightforward. Part of the problem is that the term nucleophilicity is imprecise. The term is usually taken to be a measure of the affinity of a nucleophile for a carbon atom in the $\mathrm{S}_{\mathrm{N}} 2$ reaction, but the reactivity of a given nucleophile can change from one reaction to the next. The exact nucleophilicity of a species in a given reaction depends on the substrate, the solvent, and even the reactant concentrations. Detailed explanations for the observed nucleophilicities aren't always simple, but some trends can be detected from the data of TABLE 11.1.

- Nucleophilicity roughly parallels basicity when comparing nucleophiles that have the same reacting atom. Thus, $\mathrm{OH}^{-}$is both more basic and more nucleophilic than acetate ion, $\mathrm{CH}_{3} \mathrm{CO}_{2}{ }^{-}$, which in turn is more basic and more nucleophilic than $\mathrm{H}_{2} \mathrm{O}$. Since "nucleophilicity" is usually taken as the affinity of a Lewis base for a carbon atom in the $\mathrm{S}_{\mathrm{N}} 2$ reaction and "basicity" is the affinity of a base for a proton, it's easy to see why there might be a correlation between the two kinds of behavior.
- Nucleophilicity usually increases going down a column of the periodic table. Thus, $\mathrm{HS}^{-}$is more nucleophilic than $\mathrm{HO}^{-}$, and the halide reactivity order is $\mathrm{I}^{-}>\mathrm{Br}^{-}>\mathrm{Cl}^{-}$. Going down the periodic table, elements have their valence electrons in successively larger shells where they are successively farther from the nucleus, less tightly held, and consequently more reactive. This matter is complex, though, and the nucleophilicity order can change depending on the solvent.
- Negatively charged nucleophiles are usually more reactive than neutral ones. As a result, $\mathrm{S}_{\mathrm{N}} 2$ reactions are often carried out under basic conditions rather than neutral or acidic conditions.


An acetylide anion -

PROBLEM What product would you expect from $\mathrm{S}_{\mathrm{N}} 2$ reaction of 1-bromobutane with each of the following?
11-4 (a) NaI
(b) KOH
(c) $\mathrm{H}-\mathrm{C} \equiv \mathrm{C}-\mathrm{Li}$
(d) $\mathrm{NH}_{3}$


An acetylide anion -

PROBLEM Which substance in each of the following pairs is more reactive as a nucleophile? Explain.
11-5 (a) $\left(\mathrm{CH}_{3}\right)_{2} \mathrm{~N}^{-}$or $\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}$
(b) $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{~B}$ or $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{~N}$
(c) $\mathrm{H}_{2} \mathrm{O}$ or $\mathrm{H}_{2} \mathrm{~S}$


The Leaving Group -

Still another variable that can affect the $S_{N} 2$ reaction is the nature of the group displaced by the incoming
nucleophile, the leaving group. Because the leaving group is expelled with a negative charge in most $\mathrm{S}_{\mathrm{N}} 2$ reactions, the best leaving groups are those that best stabilize the negative charge in the transition state. The greater the extent of charge stabilization by the leaving group, the lower the energy of the transition state and the more rapid the reaction. But as we saw in Section 2.8 , the groups that best stabilize a negative charge are also the weakest bases. Thus, weak bases such as $\mathrm{Cl}^{-}, \mathrm{Br}^{-}$, and tosylate ion make good leaving groups, while strong bases such as $\mathrm{OH}^{-}$and $\mathrm{NH}_{2}{ }^{-}$make poor leaving groups.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0339.jpg?height=216&width=1218&top_left_y=480&top_left_x=448)

It's just as important to know which are poor leaving groups as to know which are good, and the preceding data clearly indicate that $\mathrm{F}^{-}, \mathrm{HO}^{-}, \mathrm{RO}^{-}$, and $\mathrm{H}_{2} \mathrm{~N}^{-}$are not displaced by nucleophiles. In other words, alkyl fluorides, alcohols, ethers, and amines do not typically undergo $\mathrm{S}_{\mathrm{N}} 2$ reactions. To carry out an $\mathrm{S}_{\mathrm{N}} 2$ reaction with an alcohol, it's necessary to convert the ${ }^{-}$OH into a better leaving group. This, in fact, is just what happens when a primary or secondary alcohol is converted into either an alkyl chloride by reaction with $\mathrm{SOCl}_{2}$ or an alkyl bromide by reaction with $\mathrm{PBr}_{3}$ (Section 10.5).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0339.jpg?height=486&width=1004&top_left_y=977&top_left_x=558)


The Leaving Group -

Alternatively, an alcohol can be made more reactive toward nucleophilic substitution by treating it with para-toluenesulfonyl chloride to form a tosylate. As noted previously, tosylates are even more reactive than halides in nucleophilic substitutions. Note that tosylate formation does not change the configuration of the oxygen-bearing carbon because the $\mathrm{C}-\mathrm{O}$ bond is not broken.
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A $1^{\circ}$ or $2^{\circ}$ alcohol
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The Leaving Group -

A tosylate


The Leaving Group -

The one general exception to the rule that ethers don't typically undergo $\mathrm{S}_{\mathrm{N}} 2$ reactions pertains to epoxides, the three-membered cyclic ethers that we saw in Section 8.7. Because of the angle strain in their three-membered ring, epoxides are much more reactive than other ethers. They react with aqueous acid to give 1,2-diols, as we saw in Section 8.7, and they react readily with many other nucleophiles as well. Propene oxide, for instance, reacts with HCl to give 1-chloro-2-propanol by an $\mathrm{S}_{\mathrm{N}} 2$ backside attack on the less hindered primary carbon atom. We'll look at the process in more detail in Section 18.5.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0339.jpg?height=280&width=955&top_left_y=2234&top_left_x=585)


The Leaving Group -

PROBLEM Rank the following compounds in order of their expected reactivity toward $\mathrm{S}_{\mathrm{N}} 2$ reaction:
11-6
$\mathrm{CH}_{3} \mathrm{Br}, \mathrm{CH}_{3} \mathrm{OTos}$, $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CCl}$, $\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHCl}$


The Solvent -

The rates of $\mathrm{S}_{\mathrm{N}} 2$ reactions are strongly affected by the solvent. Protic solvents-those that contain an -OH or -NH group-are generally the worst for $\mathrm{S}_{\mathrm{N}} 2$ reactions, while polar aprotic solvents, which are polar but don't have an - OH or -NH group, are the best.

Protic solvents, such as methanol and ethanol, slow down $\mathrm{S}_{\mathrm{N}} 2$ reactions by solvation of the reactant nucleophile. The solvent molecules hydrogen-bond to the nucleophile and form a cage around it, thereby lowering its energy and reactivity.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0340.jpg?height=269&width=304&top_left_y=695&top_left_x=661)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0340.jpg?height=112&width=432&top_left_y=773&top_left_x=1015)
enhanced ground-state stability)

In contrast with protic solvents-which decrease the rates of $S_{N} 2$ reactions by lowering the ground-state energy of the nucleophile-polar aprotic solvents increase the rates of $\mathrm{S}_{\mathrm{N}} 2$ reactions by raising the ground-state energy of the nucleophile. Acetonitrile $\left(\mathrm{CH}_{3} \mathrm{CN}\right)$, dimethylformamide [ $\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NCHO}$, abbreviated DMF], and dimethyl sulfoxide $\left[\left(\mathrm{CH}_{3}\right)_{2} \mathrm{SO}\right.$, abbreviated DMSO] are particularly useful. A solvent known as hexamethylphosphoramide $\left\{\left[\left(\mathrm{CH}_{3}\right)_{2} \mathrm{~N}\right]_{3} \mathrm{PO}\right.$, abbreviated HMPA $\}$ can also be useful but it should only be handled with great care and not be allowed to touch the eyes or skin. These solvents can dissolve many salts because of their high polarity, but they tend to solvate metal cations rather than nucleophilic anions. As a result, the bare, unsolvated anions have a greater nucleophilicity and $\mathrm{S}_{\mathrm{N}} 2$ reactions take place at correspondingly increased rates. For instance, a rate increase of 200,000 has been observed on changing from methanol to HMPA for the reaction of azide ion with 1-bromobutane.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0340.jpg?height=301&width=1171&top_left_y=1427&top_left_x=477)


The Solvent -

PROBLEM Organic solvents like benzene, ether, and chloroform are neither protic nor strongly polar. What 11-7 effect would you expect these solvents to have on the reactivity of a nucleophile in $\mathrm{S}_{\mathrm{N}} 2$ reactions?


A Summary of $\mathrm{S}_{\mathrm{N}} 2$ Reaction Characteristics -

The effects on $\mathrm{S}_{\mathrm{N}} 2$ reactions of the four variables-substrate structure, nucleophile, leaving group, and solvent-are summarized in the following statements and in the energy diagrams of FIGURE 11.8:


Substrate $\quad$ Steric hindrance raises the energy of the $S_{N} 2$ transition state, increasing $\Delta G^{\ddagger}$ and decreasing the reaction rate (FIGURE 11.8a). As a result, $\mathrm{S}_{\mathrm{N}} 2$ reactions are best for methyl and primary substrates. Secondary substrates react slowly, and tertiary substrates do not react by an $\mathrm{S}_{\mathrm{N}} 2$ mechanism.
Nucleophile Basic, negatively charged nucleophiles are less stable and have a higher ground-state energy than neutral ones, decreasing $\Delta G^{\ddagger}$ and increasing the $\mathrm{S}_{\mathrm{N}} 2$ reaction rate (FIGURE 11.8b).

Leaving Good leaving groups (more stable anions) lower the energy of the transition state,
group
Solvent decreasing $\Delta G^{\ddagger}$ and increasing the $S_{N} 2$ reaction rate (FIGURE 11.8c). Protic solvents solvate the nucleophile, thereby lowering its ground-state energy, increasing $\Delta G^{\ddagger}$, and decreasing the $S_{N} 2$ reaction rate. Polar aprotic solvents surround the accompanying cation but not the nucleophilic anion, thereby raising the ground-state energy of the nucleophile, decreasing $\Delta G^{\ddagger}$, and increasing the reaction rate (FIGURE 11.8d).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0341.jpg?height=912&width=1449&top_left_y=517&top_left_x=338)

FIGURE 11.8 Energy diagrams showing the effects of (a) substrate, (b) nucleophile, (c) leaving group, and (d) solvent on $\mathbf{S}_{\mathbf{N}} \mathbf{2}$ reaction rates. Substrate and leaving group effects are felt primarily in the transition state. Nucleophile and solvent effects are felt primarily in the reactant ground state.


A Summary of $\mathrm{S}_{\mathrm{N}} 2$ Reaction Characteristics - 11.4 The $\mathrm{S}_{\mathrm{N}} 1$ Reaction

Most nucleophilic substitutions take place by the $S_{N} 2$ pathway just discussed. The reaction is favored when carried out with an unhindered substrate and a negatively charged nucleophile in a polar aprotic solvent, but is disfavored when carried out with a hindered substrate and a neutral nucleophile in a protic solvent. You might therefore expect the reaction of a tertiary substrate (hindered) with water (neutral, protic) to be among the slowest of substitution reactions. Remarkably, however, the opposite is true. The reaction of the tertiary halide 2-bromo-2-methylpropane $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CBr}$ with $\mathrm{H}_{2} \mathrm{O}$ to give the alcohol 2-methyl-2-propanol is more than 1 million times faster than the corresponding reaction of $\mathrm{CH}_{3} \mathrm{Br}$ to give methanol.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0341.jpg?height=483&width=1026&top_left_y=1927&top_left_x=544)


What's going on here? A nucleophilic substitution reaction is occurring-a hydroxyl group is replacing a halogen-yet the reactivity order seems backward. These reactions can't be taking place by the $S_{N} 2$ mechanism we've been discussing, so we must therefore conclude that they are occurring by an alternative substitution
mechanism. This alternative mechanism is called the $\mathbf{S}_{\mathbf{N}} \mathbf{1}$ reaction, for substitution, nucleophilic, unimolecular.