Substitution Mechanisms

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Organic Chemistry › Substitution Mechanisms

Questions 1 - 10
1

Which of the following substrates would have the fastest reaction rate for an SN1 mechanism?

Explanation

The SN1 mechanism involves the formation of a carbocation intermediate in the rate-determining step. The most stable carbocation will produce the fastest reaction. We can immediately eliminate any answer choices that will produce primary or secondary carbocations, since a tertiary carbocation will be much more stable. When comparing tertiary carbocations, larger and more electronegative substituents will allow for more charge stabilization.

Since the tertiary carbocation formed by the dissociation of iodide from will the be most stable, this substrate will react the fastest.

2

Which of the following substrates would have the fastest reaction rate for an SN1 mechanism?

Explanation

The SN1 mechanism involves the formation of a carbocation intermediate in the rate-determining step. The most stable carbocation will produce the fastest reaction. We can immediately eliminate any answer choices that will produce primary or secondary carbocations, since a tertiary carbocation will be much more stable. When comparing tertiary carbocations, larger and more electronegative substituents will allow for more charge stabilization.

Since the tertiary carbocation formed by the dissociation of iodide from will the be most stable, this substrate will react the fastest.

3

Which SN2 reaction would proceed the fastest?

1-bromopentane and sodium iodide

1-bromo-2-methylpentane and sodium iodide

1-chloropentane and sodium iodide

sec-butyl bromide and sodium iodide

tert-butyl bromide and sodium iodide

Explanation

SN2 reactions involve a backside nucleophilic attack on an electrophilic carbon. As a result, less steric congestion for this backside attack results in a faster reaction, meaning that SN2 reactions proceed fastest for primary carbons. In addition, beta-branching next to a primary carbon results in a slower reaction, as does a poorer leaving group (i.e. chloride instead of bromide).

1-bromopentane has a good leaving group (bromine) attached to a primary carbon with no beta-branching, meaning it will proceed the fastest.

4

Which SN2 reaction would proceed the fastest?

1-bromopentane and sodium iodide

1-bromo-2-methylpentane and sodium iodide

1-chloropentane and sodium iodide

sec-butyl bromide and sodium iodide

tert-butyl bromide and sodium iodide

Explanation

SN2 reactions involve a backside nucleophilic attack on an electrophilic carbon. As a result, less steric congestion for this backside attack results in a faster reaction, meaning that SN2 reactions proceed fastest for primary carbons. In addition, beta-branching next to a primary carbon results in a slower reaction, as does a poorer leaving group (i.e. chloride instead of bromide).

1-bromopentane has a good leaving group (bromine) attached to a primary carbon with no beta-branching, meaning it will proceed the fastest.

5

In reactions involving the alkylation of acetylide ions, it is preferred that the alkyl halide be primary. What is the reason for this?

The mechanism for these reactions is SN2

The reactions generally occur in two steps

The reaction involves a carbocation as intermediate

The mechanism for these reactions is SN1

An answer cannot be determined without more information about the reaction conditions

Explanation

The reason that the alkyl halide is preferred to be primary is because the mechanism for these reactions is SN2. SN2 indicates a substitution reaction that takes place in one step. A primary alcohol is preferred to prevent steric congestion caused by the simultaneous binding of the nucleophile and release of the leaving group. This reaction mechanism is faster because it omits the formation of a carbocation intermediate.

In contrast, SN1 reactions take place in two steps and involve the formation of a carbocation intermediate.

6

In reactions involving the alkylation of acetylide ions, it is preferred that the alkyl halide be primary. What is the reason for this?

The mechanism for these reactions is SN2

The reactions generally occur in two steps

The reaction involves a carbocation as intermediate

The mechanism for these reactions is SN1

An answer cannot be determined without more information about the reaction conditions

Explanation

The reason that the alkyl halide is preferred to be primary is because the mechanism for these reactions is SN2. SN2 indicates a substitution reaction that takes place in one step. A primary alcohol is preferred to prevent steric congestion caused by the simultaneous binding of the nucleophile and release of the leaving group. This reaction mechanism is faster because it omits the formation of a carbocation intermediate.

In contrast, SN1 reactions take place in two steps and involve the formation of a carbocation intermediate.

7

Which of the following determines the general rate of an reaction?

Rate=k\[substrate\]

Rate=k\[substrate\]\[nucleophile\]

Rate=k\[nucleophile\]

Rate=k\[substrate\]\[base\]

Explanation

The rate of an reaction is determined only by the concentration of the substrate. Unlike an reaction, where the addition occurs in one step and requires the activity of the substrate and the nucleophile, an reaction occurs in two steps and is only limited by the activity (i.e. leaving ability) of the substrate. Once the leaving group leaves the substrate, the nucleophile does not hesitate to attack the exposed carbocation.

8

Which of the following determines the general rate of an reaction?

Rate=k\[substrate\]

Rate=k\[substrate\]\[nucleophile\]

Rate=k\[nucleophile\]

Rate=k\[substrate\]\[base\]

Explanation

The rate of an reaction is determined only by the concentration of the substrate. Unlike an reaction, where the addition occurs in one step and requires the activity of the substrate and the nucleophile, an reaction occurs in two steps and is only limited by the activity (i.e. leaving ability) of the substrate. Once the leaving group leaves the substrate, the nucleophile does not hesitate to attack the exposed carbocation.

9

Which of the following molecules would most readily undergo an SN2 mechanism?

Screen shot 2015 09 21 at 5.21.16 pm

IV

I

II

III

V

Explanation

is a better leaving group than because it is a larger molecule and can distribute the negative charge over a larger area. SN2 works better with better leaving group and with less-substituted carbons (methyl > primary > secondary > tertiary)

10

Which of the following molecules would most readily undergo an SN2 mechanism?

Screen shot 2015 09 21 at 5.21.16 pm

IV

I

II

III

V

Explanation

is a better leaving group than because it is a larger molecule and can distribute the negative charge over a larger area. SN2 works better with better leaving group and with less-substituted carbons (methyl > primary > secondary > tertiary)

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