CHAPTER CONTENTS -

Sucralose
A large variety of organohalides are known. The halogen might be bonded to an alkynyl group ( $\mathrm{C} \equiv \mathrm{C}-\mathrm{X}$ ), a vinylic group $(C=C-X)$, an aromatic ring ( $\mathrm{Ar}-\mathrm{X}$ ), or an alkyl group. In this chapter, however, we'll be primarily concerned with alkyl halides, compounds with a halogen atom bonded to a saturated, $s p^{3}$-hybridized carbon atom.


CHAPTER CONTENTS - 10.1 Names and Structures of Alkyl Halides

Although commonly called alkyl halides, halogen-substituted alkanes are named systematically as haloalkanes (Section 3.4), treating the halogen as a substituent on a parent alkane chain. There are three steps:


STEP 1
Find the longest chain, and name it as the parent. If a double or triple bond is present, the parent chain must contain it.


STEP 2
Number the carbons of the parent chain beginning at the end nearer the first substituent, whether alkyl or halo. Assign each substituent a number according to its position on the chain.
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5-Bromo-2,4-dimethylheptane
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1-Bromo-3-chloro-4-methylpentane
STEP 3
If the parent chain can be properly numbered from either end by step 2 , begin at the end nearer the


substituent that has alphabetical precedence. -


2-Bromo-5-methylhexane
(Not 5-bromo-2-methylhexane)


In addition to their systematic names, many simple alkyl halides are also named by identifying first the alkyl group and then the halogen. For example, $\mathrm{CH}_{3} \mathrm{I}$ can be called either iodomethane or methyl iodide. Such names are well entrenched in the chemical literature and in daily usage, but they won't be used in this book.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0308.jpg?height=247&width=1107&top_left_y=630&top_left_x=506)


Halogens increase in size going down the periodic table, so the lengths of the corresponding carbon-halogen bonds increase accordingly (TABLE 10.1). In addition, $C-X$ bond strengths decrease going down the periodic table. As we've been doing thus far, we'll continue using an X to represent any of the halogens $\mathrm{F}, \mathrm{Cl}, \mathrm{Br}$, or I .


| Halomethane | Bond length (pm) | Bond strength |  | Dipole moment (D) |
| :---: | :---: | :---: | :---: | :---: |
|  |  | ( $\mathrm{kJ} / \mathrm{mol}$ ) | ( $\mathrm{kcal} / \mathrm{mol}$ ) |  |
| $\mathrm{CH}_{3} \mathrm{~F}$ | 139 | 460 | 110 | 1.85 |
| $\mathrm{CH}_{3} \mathrm{Cl}$ | 178 | 350 | 84 | 1.87 |
| $\mathrm{CH}_{3} \mathrm{Br}$ | 193 | 294 | 70 | 1.81 |
| $\mathrm{CH}_{3} \mathrm{I}$ | 214 | 239 | 57 | 1.62 |


In our discussion of bond polarity in functional groups in Section 6.3, we noted that halogens are more electronegative than carbon. The $\mathrm{C}-\mathrm{X}$ bond is therefore polar, with the carbon atom bearing a slight positive charge ( $\delta+$ ) and the halogen a slight negative charge ( $\delta-$ ). This polarity results in a dipole moment for all the halomethanes (TABLE 10.1) and implies that the alkyl halide $C-X$ carbon atom should behave as an electrophile in polar reactions. We'll soon see that this is indeed the case.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0308.jpg?height=408&width=318&top_left_y=1872&top_left_x=703)


PROBLEM Draw structures corresponding to the following IUPAC names:
10-2 (a) 2-Chloro-3,3-dimethylhexane (b) 3,3-Dichloro-2-methylhexane
(c) 3-Bromo-3-ethylpentane (d) 1,1-Dibromo-4-isopropylcyclohexane
(e) 4-sec-Butyl-2-chlorononane (f) 1,1-Dibromo-4-tert-butylcyclohexane


substituent that has alphabetical precedence. - 10.2 Preparing Alkyl Halides from Alkanes: Radical Halogenation

As we saw briefly in Section 6.6, simple alkyl halides can sometimes be prepared by the radical reaction of an alkane with $\mathrm{Cl}_{2}$ or $\mathrm{Br}_{2}$ in the presence of ultraviolet light. The detailed mechanism is shown in FIGURE 10.2 for chlorination.
Initiation step
$\begin{aligned} & \text { Propagation steps } \\ & \text { (a repeating cycle) }\end{aligned}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0309.jpg?height=69&width=351&top_left_y=757&top_left_x=979)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0309.jpg?height=464&width=993&top_left_y=1053&top_left_x=563)

FIGURE 10.2 Mechanism of the radical chlorination of methane. Three kinds of steps are required in radical substitution reactions: initiation, propagation, and termination. The propagation steps are a repeating cycle, with $\mathrm{Cl} \cdot$ a reactant in step 1 and a product in step 2 , and with $\cdot \mathrm{CH}_{3}$ a product in step 1 and a reactant in step 2 . The symbol hv shown in the initiation step is the standard way of indicating irradiation with light ( $v$ is the lowercase Greek letter nu).

Radical substitution reactions require three kinds of steps: initiation, propagation, and termination. Once an initiation step has started the process by producing radicals, the reaction continues in a self-sustaining cycle. The cycle requires two repeating propagation steps in which a radical, the halogen, and the alkane yield alkyl halide product plus more radical to carry on the chain. The chain is occasionally terminated by the combination of two radicals.


Unfortunately, alkane halogenation is a poor synthetic method for preparing alkyl halides because mixtures of products invariably result. For example, chlorination of methane does not stop cleanly at the monochlorinated stage but continues to give a mixture of dichloro, trichloro, and even tetrachloro products.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0309.jpg?height=288&width=1128&top_left_y=2073&top_left_x=496)

The situation is even worse for chlorination of alkanes that have more than one kind of hydrogen. Chlorination of butane, for instance, gives two monochlorinated products in a $30: 70$ ratio in addition to multiply chlorinated products such as dichlorobutane, trichlorobutane, and so on.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0310.jpg?height=228&width=1305&top_left_y=187&top_left_x=410)

As another example, 2-methylpropane yields 2-chloro-2-methylpropane and 1-chloro-2-methylpropane in a $35: 65$ ratio, along with more highly chlorinated products.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0310.jpg?height=319&width=1145&top_left_y=529&top_left_x=490)


From these and similar reactions, it's possible to calculate a reactivity order toward chlorination for different kinds of hydrogen atoms in a molecule. Take the butane chlorination, for instance. Butane has six equivalent primary hydrogens $\left(-\mathrm{CH}_{3}\right)$ and four equivalent secondary hydrogens $\left(-\mathrm{CH}_{2}-\right)$. The fact that butane yields $30 \%$ of 1-chlorobutane product means that each one of the six primary hydrogens is responsible for $30 \% \div 6=5 \%$ of the product. Similarly, the fact that $70 \%$ of 2 -chlorobutane is formed means that each of the four secondary hydrogens is responsible for $70 \% \div 4=17.5 \%$ of the product. Thus, a secondary hydrogen reacts $17.5 \% \div 5 \%=$ 3.5 times as often as a primary hydrogen.

A similar calculation for the chlorination of 2-methylpropane indicates that each of the nine primary hydrogens accounts for $65 \% \div 9=7.2 \%$ of the product, while the single tertiary hydrogen ( $\mathrm{R}_{3} \mathrm{CH}$ ) accounts for $35 \%$ of the product. Thus, a tertiary hydrogen is $35 \% \div 7.2 \%=5$ times as reactive as a primary hydrogen toward chlorination.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0310.jpg?height=302&width=658&top_left_y=1367&top_left_x=731)


The observed reactivity order of alkane hydrogens toward radical chlorination can be explained by looking at the bond dissociation energies given previously in TABLE 6.3. The data show that a tertiary $\mathrm{C}-\mathrm{H}$ bond ( $400 \mathrm{~kJ} /$ mol ; $96 \mathrm{kcal} / \mathrm{mol}$ ) is weaker than a secondary $\mathrm{C}-\mathrm{H}$ bond ( $410 \mathrm{~kJ} / \mathrm{mol} ; 98 \mathrm{kcal} / \mathrm{mol}$ ), which is in turn weaker than a primary C-H bond ( $421 \mathrm{~kJ} / \mathrm{mol} ; 101 \mathrm{kcal} / \mathrm{mol}$ ). Since less energy is needed to break a tertiary C-H bond than to break a primary or secondary $\mathrm{C}-\mathrm{H}$ bond, the resultant tertiary radical is more stable than a primary or secondary radical.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0310.jpg?height=334&width=685&top_left_y=1969&top_left_x=720)


PROBLEM Draw and name all monochloro products you would expect to obtain from radical chlorination of 10-3 2-methylpentane. Which, if any, are chiral?


PROBLEM Taking the relative reactivities of $1^{\circ}, 2^{\circ}$, and $3^{\circ}$ hydrogen atoms into account, what product(s) would 10-4 you expect to obtain from monochlorination of 2 -methylbutane? What would the approximate percentage of each product be? (Don't forget to take into account the number of each kind of


hydrogen.) -


hydrogen.) - 10.3 Preparing Alkyl Halides from Alkenes: Allylic Bromination

We've already seen several methods for preparing alkyl halides from alkenes, including the reactions of HX and $\mathrm{X}_{2}$ with alkenes in electrophilic addition reactions (Section 7.7 and Section 8.2). The hydrogen halides HCl , HBr , and HI react with alkenes by a polar mechanism to give the product of Markovnikov addition. Bromine and chlorine undergo anti addition through halonium ion intermediates to give 1,2-dihalogenated products.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0311.jpg?height=348&width=1097&top_left_y=514&top_left_x=514)


Another laboratory method for preparing alkyl halides from alkenes is by reaction with $N$-bromosuccinimide (abbreviated NBS), in the presence of ultraviolet light, to give products resulting from substitution of hydrogen by bromine at the position next to the double bond-the allylic position. Cyclohexene, for example, gives 3-bromocyclohexene.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0311.jpg?height=429&width=982&top_left_y=1046&top_left_x=566)

This allylic bromination with NBS is analogous to the alkane chlorination reaction discussed in the previous section and occurs by a radical chain-reaction pathway (FIGURE 10.3). As in alkane halogenation, a Br• radical abstracts an allylic hydrogen atom, forming an allylic radical plus HBr . The HBr then reacts with NBS to form $\mathrm{Br}_{2}$, which in turn reacts with the allylic radical to yield the brominated product and a $\mathrm{Br} \cdot$ radical that cycles back into the first step and carries on the chain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0311.jpg?height=598&width=952&top_left_y=1707&top_left_x=584)

FIGURE 10.3 Mechanism of allylic bromination of an alkene with NBS. The process is a radical chain reaction in which (1) a $\mathrm{Br} \cdot \mathrm{radical}$ abstracts an allylic hydrogen atom of the alkene and gives an allylic radical plus HBr . (2) The HBr then reacts with NBS to form $\mathrm{Br}_{2}$, which (3) reacts with the allylic radical to yield the bromoalkene product and a $\mathrm{Br} \cdot$ radical that continues the chain.


Why does bromination with NBS occur exclusively at an allylic position rather than elsewhere in the molecule? The answer, once again, is found by looking at bond dissociation energies to see the relative stabilities of various
kinds of radicals. Although a typical secondary alkyl C-H bond has a strength of about $410 \mathrm{~kJ} / \mathrm{mol}(98 \mathrm{kcal} / \mathrm{mol})$ and a typical vinylic $\mathrm{C}-\mathrm{H}$ bond has a strength of $465 \mathrm{~kJ} / \mathrm{mol}$ ( $111 \mathrm{kcal} / \mathrm{mol}$ ), an allylic $\mathrm{C}-\mathrm{H}$ bond has a strength of only about $370 \mathrm{~kJ} / \mathrm{mol}(88 \mathrm{kcal} / \mathrm{mol})$. An allylic radical is therefore more stable than a typical alkyl radical with the same substitution by about $40 \mathrm{~kJ} / \mathrm{mol}(9 \mathrm{kcal} / \mathrm{mol})$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0312.jpg?height=288&width=955&top_left_y=387&top_left_x=582)


We can thus expand the stability ordering to include vinylic and allylic radicals.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0312.jpg?height=340&width=1332&top_left_y=768&top_left_x=380)


hydrogen.) - 10.4 Stability of the Allyl Radical: Resonance Revisited

To see why an allylic radical is so stable, look at the orbital picture in FIGURE 10.4. The radical carbon atom with an unpaired electron can adopt $s p^{2}$ hybridization, placing the unpaired electron in a $p$ orbital and giving a structure that is electronically symmetrical. The $p$ orbital on the central carbon can therefore overlap equally well with a $p$ orbital on either of the two neighboring carbons.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0312.jpg?height=646&width=470&top_left_y=1372&top_left_x=513)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0312.jpg?height=175&width=573&top_left_y=1536&top_left_x=1036)

FIGURE 10.4 An orbital view of the allyl radical. The $p$ orbital on the central carbon can overlap equally well with a $p$ orbital on either neighboring carbon, giving rise to two equivalent resonance structures.

Because the allyl radical is electronically symmetrical, it has two resonance forms-one with the unpaired electron on the left and the double bond on the right and another with the unpaired electron on the right and the double bond on the left. Neither structure is correct by itself; the true structure of the allyl radical is a resonance hybrid of the two. (You might want to review Section 2.4 to Section 2.6 to brush up on resonance.) As noted in Section 2.5, the greater the number of resonance forms, the greater the stability of a compound, because bonding electrons are attracted to more nuclei. An allyl radical, with two resonance forms, is therefore more stable than a typical alkyl radical, which has only a single structure.

In molecular orbital terms, the stability of the allyl radical is due to the fact that the unpaired electron is delocalized, or spread out, over an extended $\pi$-orbital network rather than localized at only one site, as shown
by the computer-generated MO in FIGURE 10.4. This delocalization is particularly apparent in the so-called spin-density surface in FIGURE 10.5, which shows the calculated location of the unpaired electron. The two terminal carbons share the unpaired electron equally.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0313.jpg?height=461&width=749&top_left_y=363&top_left_x=683)


FIGURE 10.5 The spin density surface of the allyl radical locates the position of the unpaired electron and shows that it is equally shared between the two terminal carbons.


In addition to its effect on stability, delocalization of the unpaired electron in the allyl radical has other chemical consequences. Because the unpaired electron is delocalized over both ends of the $\pi$ orbital system, reaction with $\mathrm{Br}_{2}$ can occur at either end. As a result, allylic bromination of an unsymmetrical alkene often leads to a mixture of products. For example, bromination of 1-octene gives a mixture of 3-bromo-1-octene and 1-bromo-2-octene. The two products are not formed in equal amounts, however, because the intermediate allylic radical is not symmetrical and reaction at the two ends is not equally likely. Reaction at the less hindered, primary end is favored.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0313.jpg?height=616&width=1047&top_left_y=1248&top_left_x=539)


The products of allylic bromination reactions are useful for conversion into dienes by dehydrohalogenation with base. Cyclohexene can be converted into 1,3-cyclohexadiene, for example.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0313.jpg?height=281&width=885&top_left_y=1952&top_left_x=623)


WORKED EXAMPLE 10.1 -


Predicting the Product of an Allylic Bromination Reaction -

What products would you expect from the reaction of 4,4-dimethylcyclohexene with NBS?


Strategy -

Draw the alkene reactant, and identify the allylic positions. In this case, there are two different allylic positions; we'll label them $\mathbf{A}$ and $\mathbf{B}$. Now abstract an allylic hydrogen from each position to generate the two corresponding allylic radicals. Each of the two allylic radicals can add a Br atom at either end ( $\mathbf{A}$ or $\mathbf{A}^{\prime} ; \mathbf{B}$ or $\mathbf{B}^{\prime}$ ), to give a mixture of up to four products. Draw and name the products. In the present instance, the "two" products from reaction at position $\mathbf{B}$ are identical, so only three products are formed in this reaction.


Strategy -

Solution
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0314.jpg?height=676&width=1556&top_left_y=551&top_left_x=298)


Strategy -


Strategy -

PROBLEM The major product of the reaction of methylenecyclohexane with $N$-bromosuccinimide is 10-6 1-(bromomethyl)cyclohexene. Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0314.jpg?height=221&width=652&top_left_y=1578&top_left_x=395)


Strategy - 10.5 Preparing Alkyl Halides from Alcohols

The most generally useful method for preparing alkyl halides is to make them from alcohols, which themselves can be obtained from carbonyl compounds as we'll see in Sections $\mathbf{1 7 . 4}$ and 17.5. Because of the importance of this process, many different methods have been developed to transform alcohols into alkyl halides. The simplest method is to treat the alcohol with $\mathrm{HCl}, \mathrm{HBr}$, or HI . For reasons that will be discussed in Section 11.5, this reaction works best with tertiary alcohols, $\mathrm{R}_{3} \mathrm{COH}$. Primary and secondary alcohols react much more slowly and at higher temperatures.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0315.jpg?height=432&width=868&top_left_y=180&top_left_x=626)


The reaction of HX with a tertiary alcohol is so rapid that it's often carried out simply by bubbling pure HCl or HBr gas into a cold ether solution of the alcohol. 1-Methylcyclohexanol, for example, is converted into 1-chloro-1-methylcyclohexane by treatment with HCl .
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0315.jpg?height=202&width=836&top_left_y=758&top_left_x=680)


1-Methylcyclohexanol 1-Chloro-1-methylcyclohexane -

(90\%)
Primary and secondary alcohols are best converted into alkyl halides by treatment with either thionyl chloride $\left(\mathrm{SOCl}_{2}\right)$ or phosphorus tribromide $\left(\mathrm{PBr}_{3}\right)$. These reactions, which normally take place readily under mild conditions, are less acidic and less likely to cause acid-catalyzed rearrangements than the HX method.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0315.jpg?height=289&width=1207&top_left_y=1208&top_left_x=454)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0315.jpg?height=204&width=885&top_left_y=1535&top_left_x=471)


As the preceding examples indicate, the yields of these $\mathrm{SOCl}_{2}$ and $\mathrm{PBr}_{3}$ reactions are generally high and other functional groups such as ethers, carbonyls, and aromatic rings don't usually interfere. We'll look at the mechanisms of these and other related substitution reactions in Section 11.3.


Alkyl fluorides can also be prepared from alcohols. Numerous alternative reagents are used for such reactions, including diethylaminosulfur trifluoride $\left[\left(\mathrm{CH}_{3} \mathrm{CH}_{2}\right)_{2} \mathrm{NSF}_{3}\right]$ and HF in pyridine solvent.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0315.jpg?height=156&width=543&top_left_y=1993&top_left_x=796)


Cyclohexanol


Fluorocyclohexane -


Fluorocyclohexane - 10.6 Reactions of Alkyl Halides: Grignard Reagents

Alkyl halides, RX, react with magnesium metal in ether or tetrahydrofuran (THF) solvent to yield alkylmagnesium halides, RMgX . The products, called Grignard reagents (RMgX) after their discoverer, Francois Auguste Victor Grignard, who received the 1912 Nobel Prize in Chemistry, are examples of organometallic compounds because they contain a carbon-metal bond. In addition to alkyl halides, Grignard reagents can also be made from alkenyl (vinylic) and aryl (aromatic) halides. The halogen can be Cl, Br, or I, although chlorides are less reactive than bromides and iodides. Organofluorides rarely react with magnesium.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0316.jpg?height=334&width=530&top_left_y=538&top_left_x=792)


As you might expect from the discussion of electronegativity and bond polarity in Section 6.3, the carbon-magnesium bond is polarized, making the carbon atom of Grignard reagents both nucleophilic and basic. An electrostatic potential map of methylmagnesium iodide, for instance, indicates the electron-rich (red) character of the carbon bonded to magnesium.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0316.jpg?height=414&width=1073&top_left_y=1075&top_left_x=518)


A Grignard reagent is formally the magnesium salt, $\mathrm{R}_{3} \mathrm{C}^{-+} \mathrm{MgX}$, of a carbon acid, $\mathrm{R}_{3} \mathrm{C}-\mathrm{H}$, and is thus a carbon anion, or carbanion. But because hydrocarbons are such weak acids, with $\mathbf{p} \mathbf{K}_{\mathbf{a}}$ 's in the range 44 to 60 (Section 9.7), carbon anions are very strong bases. Grignard reagents must therefore be protected from atmospheric moisture to prevent their being protonated and destroyed in acid-base reactions: $\mathrm{R}-\mathrm{Mg}-\mathrm{X}+\mathrm{H}_{2} \mathrm{O} \rightarrow \mathrm{R}-\mathrm{H}+$ HO-Mg-X.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0316.jpg?height=128&width=1383&top_left_y=1733&top_left_x=368)


Grignard reagents themselves don't occur in living organisms, but they serve as useful carbon-based nucleophiles in several important laboratory reactions, which we'll look at in detail in Section 17.5. In addition, they act as a simple model for other, more complex carbon-based nucleophiles that are important in biological chemistry. We'll see many examples of these in Chapter 29.


PROBLEM How strong a base would you expect a Grignard reagent to be? Look at Table 9.1 and predict $\mathbf{1 0 - 9}$ whether the following reactions will occur as written. (The $\mathrm{p} K_{\mathrm{a}}$ of $\mathrm{NH}_{3}$ is 35.)
(a) $\mathrm{CH}_{3} \mathrm{MgBr}+\mathrm{H}-\mathrm{C} \equiv \mathrm{C}-\mathrm{H} \longrightarrow \mathrm{CH}_{4}+\mathrm{H}-\mathrm{C} \equiv \mathrm{C}-\mathrm{MgBr}$
(b) $\mathrm{CH}_{3} \mathrm{MgBr}+\mathrm{NH}_{3} \longrightarrow \mathrm{CH}_{4}+\mathrm{H}_{2} \mathrm{~N}-\mathrm{MgBr}$


PROBLEM How might you replace a halogen substituent by a deuterium atom if you wanted to prepare a 10-10 deuterated compound?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0316.jpg?height=112&width=556&top_left_y=2356&top_left_x=416)


Fluorocyclohexane - 10.7 Organometallic Coupling Reactions

Many other kinds of organometallic compounds can be prepared in a manner similar to that of Grignard reagents. For instance, alkyllithium reagents, RLi, can be prepared by the reaction of an alkyl halide with lithium metal. Alkyllithiums are both nucleophiles and strong bases, and their chemistry is similar in many respects to that of alkylmagnesium halides.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0317.jpg?height=391&width=1373&top_left_y=452&top_left_x=368)


One particularly valuable reaction of alkyllithiums occurs when making lithium diorganocopper compounds, $\mathrm{R}_{2} \mathrm{CuLi}$, by reaction with copper(I) iodide in diethyl ether as solvent. Often called Gilman reagents ( $\mathbf{L i R}_{\mathbf{2}} \mathbf{C u}$ ), lithium diorganocopper compounds are useful because they undergo a coupling reaction with organochlorides, bromides, and iodides (but not fluorides). One of the alkyl groups from the lithium diorganocopper reagent replaces the halogen of the organohalide, forming a new carbon-carbon bond and yielding a hydrocarbon product. Lithium dimethylcopper, for instance, reacts with 1-iododecane to give undecane in a $90 \%$ yield.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0317.jpg?height=310&width=1207&top_left_y=1132&top_left_x=456)


This organometallic coupling reaction is useful in organic synthesis because it forms carbon-carbon bonds, thereby allowing the preparation of larger molecules from smaller ones. As the following examples indicate, the coupling reaction can be carried out on aryl and vinylic halides as well as on alkyl halides.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0317.jpg?height=147&width=1231&top_left_y=1591&top_left_x=474)
trans-1-Iodo-1-nonene
trans-5-Tridecene (71\%)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0317.jpg?height=153&width=1049&top_left_y=1870&top_left_x=538)


Iodobenzene
Toluene (91\%)
An organocopper coupling reaction is carried out commercially to synthesize muscalure, (9Z)-tricosene, the sex attractant secreted by the common housefly. Minute amounts of muscalure greatly increase the lure of insecticide-treated fly bait and provide an effective and species-specific means of insect control.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0317.jpg?height=242&width=1075&top_left_y=2232&top_left_x=525)


The mechanism of the coupling reaction involves initial formation of a triorganocopper intermediate, followed
by coupling and loss of a mono-organocopper, RCu. The coupling is not a typical polar nucleophilic substitution reaction of the sort considered in the next chapter.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0318.jpg?height=123&width=1169&top_left_y=296&top_left_x=478)


In addition to the coupling reaction of diorganocopper reagents with organohalides, related processes also occur with other organometallic reagents, particularly organopalladium compounds. One of the most commonly used procedures is the coupling reaction of an aromatic or vinyl substituted boronic acid $\left[\mathrm{R}-\mathrm{B}(\mathrm{OH})_{2}\right]$ with an aromatic or vinyl substituted organohalide in the presence of a base and a palladium catalyst. This reaction is less general than the diorganocopper reaction because it doesn't work with alkyl substrates, but it is preferred when possible because it uses only a catalytic amount of metal rather than a full equivalent and because palladium compounds are less toxic than copper compounds. For example:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0318.jpg?height=388&width=1166&top_left_y=733&top_left_x=477)


Called the Suzuki-Miyaura reaction, this process is particularly useful for preparing so-called biaryl compounds, which have two linked aromatic rings. A large number of commonly used drugs fit this description, so the Suzuki-Miyaura reaction is much-used in the pharmaceutical industry. As an example, valsartan, marketed as Diovan, is widely prescribed to treat high blood pressure, heart failure, and diabetic kidney disease. Its synthesis begins with a Suzuki-Miyaura coupling of ortho-chlorobenzonitrile with para-methylbenzeneboronic acid.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0318.jpg?height=613&width=1633&top_left_y=1382&top_left_x=243)


Shown in a simplified form in FIGURE 10.6, the mechanism of the Suzuki-Miyaura reaction involves initial reaction of the aromatic halide with the palladium catalyst to form an organopalladium intermediate, followed by reaction of that intermediate with the aromatic boronic acid. The resultant diorganopalladium complex then decomposes to the coupled biaryl product plus regenerated catalyst.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0319.jpg?height=445&width=955&top_left_y=192&top_left_x=582)

FIGURE 10.6 Mechanism of the Suzuki-Miyaura coupling reaction of an aromatic boronic acid with an aromatic halide to give a biaryl. The reaction takes place by (1) reaction of the aromatic halide, ArX, with the catalyst to form an organopalladium intermediate, followed by (2) reaction with the aromatic boronic acid. (3) Subsequent decomposition of the diarylpalladium intermediate gives the biaryl product.


PROBLEM How would you carry out the following transformations using an organocopper coupling reaction? 10-11 More than one step is required in each case.
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0319.jpg?height=150&width=454&top_left_y=852&top_left_x=478)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0319.jpg?height=87&width=822&top_left_y=859&top_left_x=1015)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0319.jpg?height=112&width=484&top_left_y=1012&top_left_x=414)


Fluorocyclohexane - 10.8 Oxidation and Reduction in Organic Chemistry

We've pointed out on several occasions that some of the reactions discussed in this and earlier chapters are either oxidations or reductions. As noted in Section 8.7, an organic oxidation results in a loss of electron density by carbon, caused either by bond formation between carbon and a more electronegative atom (usually $\mathrm{O}, \mathrm{N}$, or a halogen) or by bond-breaking between carbon and a less electronegative atom (usually H). Conversely, an organic reduction results in a gain of electron density by carbon, caused either by bond formation between carbon and a less electronegative atom or by bond-breaking between carbon and a more electronegative atom (Section 8.6).


Oxidation $\quad$| Decreases electron density on carbon by: |  |  |
| :--- | :--- | :--- |
|  | - forming one of these: $\mathrm{C}-\mathrm{O} \quad \mathrm{C}-\mathrm{N}$ | $\mathrm{C}-\mathrm{X}$ |
|  | $\quad$ or breaking this: $\mathrm{C}-\mathrm{H}$ |  |


Based on these definitions, the chlorination reaction of methane to yield chloromethane is an oxidation because a $\mathrm{C}-\mathrm{H}$ bond is broken and a $\mathrm{C}-\mathrm{Cl}$ bond is formed. The conversion of an alkyl chloride to an alkane via a Grignard reagent followed by protonation is a reduction, however, because a $\mathrm{C}-\mathrm{Cl}$ bond is broken and a $\mathrm{C}-\mathrm{H}$ bond is formed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0319.jpg?height=215&width=1114&top_left_y=2050&top_left_x=519)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0319.jpg?height=169&width=500&top_left_y=2279&top_left_x=520)


Reduction: $\mathrm{C}-\mathrm{Cl}$ bond broken and $\mathrm{C}-\mathrm{H}$ bond formed


Methane


As other examples, the reaction of an alkene with $\mathrm{Br}_{2}$ to yield a 1,2-dibromide is an oxidation because two $\mathrm{C}-\mathrm{Br}$ bonds are formed, but the reaction of an alkene with HBr to yield an alkyl bromide is neither an oxidation nor a reduction because both a $\mathrm{C}-\mathrm{H}$ and a $\mathrm{C}-\mathrm{Br}$ bond are formed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0320.jpg?height=207&width=641&top_left_y=341&top_left_x=487)


Oxidation: Two new bonds formed between carbon and a more electronegative element
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0320.jpg?height=141&width=629&top_left_y=599&top_left_x=485)


> Neither oxidation nor reduction:
> One new $\mathrm{C}-\mathrm{H}$ bond and one new $\mathrm{C}-\mathrm{Br}$ bond formed


Ethylene


Bromoethane -

A list of compounds of increasing oxidation level is shown in FIGURE 10.7. Alkanes are at the lowest oxidation level because they have the maximum possible number of $\mathrm{C}-\mathrm{H}$ bonds per carbon, and $\mathrm{CO}_{2}$ is at the highest level because it has the maximum possible number of $\mathrm{C}-\mathrm{O}$ bonds per carbon. Any reaction that converts a compound from a lower level to a higher level is an oxidation, any reaction that converts a compound from a higher level to a lower level is a reduction, and any reaction that doesn't change the level is neither an oxidation nor a reduction.


Bromoethane -

| $\mathrm{CH}_{3} \mathrm{CH}_{3}$ | $\mathrm{H}_{2} \mathrm{C}=\mathrm{CH}_{2}$ | $\mathrm{HC} \equiv \mathrm{CH}$ |  |  |
| :---: | :---: | :---: | :---: | :---: |
|  | $\mathrm{CH}_{3} \mathrm{OH}$ | $\mathrm{H}_{2} \mathrm{C}=\mathrm{O}$ | $\mathrm{HCO}_{2} \mathrm{H}$ | $\mathrm{CO}_{2}$ |
|  | $\mathrm{CH}_{3} \mathrm{Cl}$ | $\mathrm{CH}_{2} \mathrm{Cl}_{2}$ | $\mathrm{CHCl}_{3}$ | $\mathrm{CCl}_{4}$ |
|  | $\mathrm{CH}_{3} \mathrm{NH}_{2}$ | $\mathrm{H}_{2} \mathrm{C}=\mathrm{NH}$ | $\mathrm{HC} \equiv \mathrm{N}$ |  |
| Low oxidation level |  |  |  | High oxidation level |


Bromoethane -

Worked Example 10.2 shows how to compare the oxidation levels of different compounds with the same number of carbon atoms.


WORKED EXAMPLE 10.2 -


Comparing Oxidation Levels -

Rank the following compounds in order of increasing oxidation level:


Comparing Oxidation Levels -

$$
\mathrm{CH}_{3} \mathrm{CH}=\mathrm{CH}_{2}
$$


Comparing Oxidation Levels -


Comparing Oxidation Levels -

$$
\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{3}
$$


Strategy -

Compounds that have the same number of carbon atoms can be compared by adding the number of $\mathrm{C}-\mathrm{O}, \mathrm{C}-\mathrm{N}$, and $\mathrm{C}-\mathrm{X}$ bonds in each and then subtracting the number of $\mathrm{C}-\mathrm{H}$ bonds. The larger the resultant value, the higher the oxidation level.


Solution -

The first compound (propene) has six $\mathrm{C}-\mathrm{H}$ bonds, giving an oxidation level of -6 ; the second (2-propanol) has one $\mathrm{C}-\mathrm{O}$ bond and seven $\mathrm{C}-\mathrm{H}$ bonds, giving an oxidation level of -6 ; the third (acetone) has two $\mathrm{C}-\mathrm{O}$ bonds and six $\mathrm{C}-\mathrm{H}$ bonds, giving an oxidation level of -4 ; and the fourth (propane) has eight $\mathrm{C}-\mathrm{H}$ bonds, giving an oxidation level of -8 . Thus, the order of increasing oxidation level is
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0320.jpg?height=112&width=914&top_left_y=2378&top_left_x=600)


Solution -


(8) CHEMISTRY MATTERS -


Naturally Occurring Organohalides -

Just forty years ago in 1980, only about 30 naturally occurring organohalides were known. It was simply assumed that chloroform, halogenated phenols, chlorinated aromatic compounds called PCBs, and other such substances found in the environment were industrial pollutants. Now, less than half a century later, the situation is quite different. More than 5000 organohalides have been found to occur naturally, and tens of thousands more surely exist. From a simple compound like chloromethane to an extremely complex one like the antibiotic vancomycin, a remarkably diverse range of organohalides exists in plants, bacteria, and animals. Many even have valuable physiological activity. The pentahalogenated alkene halomon, for instance, has been isolated from the red alga Portieria hornemannii and found to have anticancer activity against several human tumor cell lines.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0322.jpg?height=305&width=952&top_left_y=845&top_left_x=581)


Naturally Occurring Organohalides -

Some naturally occurring organohalides are produced in massive quantities. Forest fires, volcanic eruptions, and marine kelp release up to 5 million tons of $\mathrm{CH}_{3} \mathrm{Cl}$ per year, for example, while annual industrial emissions total about 26,000 tons. Termites are thought to release as much as $10^{8} \mathrm{~kg}$ of chloroform per year. A detailed examination of the Okinawan acorn worm Ptychodera flava found that the 64 million worms living in a $1 \mathrm{~km}^{2}$ study area excreted nearly 8000 pounds per year of bromophenols and bromoindoles, compounds previously thought to be non-natural pollutants.


Naturally Occurring Organohalides -

Why do organisms produce organohalides, many of which are undoubtedly toxic? The answer seems to be that many organisms use organohalogen compounds for self-defense, either as feeding deterrents, irritants to predators, or natural pesticides. Marine sponges, coral, and sea hares, for example, release foul-tasting organohalides that deter fish, starfish, and other predators. Even humans appear to produce halogenated compounds as part of their defense against infection. The human immune system contains a peroxidase enzyme capable of carrying out halogenation reactions on fungi and bacteria, thereby killing the pathogen. And most remarkable of all, even free chlorine $-\mathrm{Cl}_{2}$-has been found to be present in humans.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0322.jpg?height=681&width=896&top_left_y=1760&top_left_x=612)


Naturally Occurring Organohalides -

FIGURE 10.8 Marine corals secrete organohalogen compounds that act as a feeding deterrent to fish. (credit: "Coral reef" by Qui Nguyen, United Nations Environment Programme/Flickr, Public Domain)


Naturally Occurring Organohalides -

Much remains to be learned-only a few hundred of the more than 500,000 known species of marine organisms have been examined-but it's clear that organohalides are an integral part of the world around us.


Key Terms -

```
- alkyl halide
- Gilman reagent (LiR2Cu)
- allylic
- Grignard reagent (RMgX)
- carbanion
- organohalide
- delocalized
- organometallic
```


Key Terms -


Summary -

Alkyl halides are not often found in terrestrial organisms, but the kinds of reactions they undergo are among the most important and well-studied reaction types in organic chemistry. In this chapter, we saw how to name and prepare alkyl halides, and we'll soon make a detailed study of their substitution and elimination reactions.


Summary -

Simple alkyl halides can be prepared by radical halogenation of alkanes, but mixtures of products usually result. The reactivity order of alkanes toward halogenation is identical to the stability order of radicals: $\mathrm{R}_{3} \mathrm{C} \cdot>\mathrm{R}_{2} \mathrm{CH} \cdot$ $>\mathrm{RCH}_{2}$. Alkyl halides can also be prepared from alkenes by reaction with $N$-bromosuccinimide (NBS) to give the product of allylic bromination. The NBS bromination of alkenes takes place through an intermediate allylic radical, which is stabilized by resonance.


Summary -

Alcohols react with HX to form alkyl halides, but the reaction works well only for tertiary alcohols, $\mathrm{R}_{3} \mathrm{COH}$. Primary and secondary alkyl halides are normally prepared from alcohols using either $\mathrm{SOCl}_{2}$, $\mathrm{PBr}_{3}$, or HF in pyridine. Alkyl halides react with magnesium in ether solution to form organomagnesium halides, called Grignard reagents (RMgX), which are both nucleophilic and strongly basic.


Summary -

Alkyl halides also react with lithium metal to form organolithium reagents, RLi. In the presence of CuI, these form diorganocoppers, or Gilman reagents ( $\mathbf{L i R}_{\mathbf{2}} \mathbf{C u}$ ). Gilman reagents react with organohalides to yield coupled hydrocarbon products.


Summary of Reactions -

No stereochemistry is implied unless specifically indicated with wedged, solid, and dashed lines.


Summary of Reactions -

1. Preparation of alkyl halides
a. From alkenes by allylic bromination (Section 10.3)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0323.jpg?height=161&width=595&top_left_y=1638&top_left_x=814)
b. From alcohols (Section 10.5)
(1) Reaction with HX
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0323.jpg?height=128&width=372&top_left_y=1909&top_left_x=925)


Summary of Reactions -

Reactivity order: $3^{\circ}>2^{\circ}>1^{\circ}$
(2) Reaction of $1^{\circ}$ and $2^{\circ}$ alcohols with $\mathrm{SOCl}_{2}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0323.jpg?height=136&width=429&top_left_y=2168&top_left_x=897)
(3) Reaction of $1^{\circ}$ and $2^{\circ}$ alcohols with $\mathrm{PBr}_{3}$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0323.jpg?height=131&width=396&top_left_y=2363&top_left_x=916)
(4) Reaction of $1^{\circ}$ and $2^{\circ}$ alcohols with HF-pyridine
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0324.jpg?height=223&width=757&top_left_y=187&top_left_x=733)
2. Reactions of alkyl halides
a. Formation of Grignard (organomagnesium) reagents (Section 10.6)


Summary of Reactions -

$$
\mathrm{R}-\mathrm{X} \underset{\text { Ether }}{\mathrm{Mg}} \mathrm{R}-\mathrm{Mg}-\mathrm{X}
$$


Summary of Reactions -

b. Formation of Gilman (diorganocopper) reagents (Section 10.7)


Summary of Reactions -

$$
\begin{gathered}
\mathrm{R}-\mathrm{X} \\
2 \mathrm{R}-\mathrm{Li}+\mathrm{CuI} \xrightarrow{\substack{\text { Pentane } \\
\text { In ether }}} \mathrm{R}-\mathrm{Li}+\mathrm{LiX} \\
{[\mathrm{R}-\mathrm{Cu}-\mathrm{R}]^{-} \mathrm{Li}^{+}+\mathrm{LiI}}
\end{gathered}
$$


Summary of Reactions -

c. Organometallic coupling (Section 10.7)
(1) Diorganocopper reaction


Summary of Reactions -

$$
\mathrm{R}_{2} \mathrm{CuLi}+\mathrm{R}^{\prime}-\mathrm{X} \xrightarrow{\text { In ether }} \mathrm{R}-\mathrm{R}^{\prime}+\mathrm{RCu}+\mathrm{LiX}
$$


Summary of Reactions -

(2) Palladium-catalyzed Suzuki-Miyaura reaction
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0324.jpg?height=137&width=988&top_left_y=1059&top_left_x=620)


Additional Problems -


Visualizing Chemistry -

PROBLEM Give IUPAC names for the following alkyl halides (green $=\mathrm{Cl}$ ):


10-14 (a) -


10-14 (a) -

PROBLEM Show the product(s) of reaction of the following alkenes with NBS:


10-15 (a) -


10-15 (a) -

PROBLEM The following alkyl bromide can be prepared by reaction of the alcohol ( $S$ )-2-pentanol with $\mathrm{PBr}_{3}$.
10-16 Name the compound, assign $(R)$ or $(S)$ stereochemistry, and tell whether the reaction of the alcohol results in the same stereochemistry or a change in stereochemistry (reddish brown $=\mathrm{Br}$ ).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0325.jpg?height=277&width=434&top_left_y=192&top_left_x=428)


Mechanism Problems -

PROBLEM In light of the fact that tertiary alkyl halides undergo spontaneous dissociation to yield a
10-17 carbocation plus halide ion (see Problem 10-41), propose a mechanism for the following reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0325.jpg?height=155&width=668&top_left_y=665&top_left_x=417)


Naming Alkyl Halides -

PROBLEM Name the following alkyl halides:


Naming Alkyl Halides -


Naming Alkyl Halides -

PROBLEM Draw structures corresponding to the following IUPAC names:
10-19 (a) 2,3-Dichloro-4-methylhexane (b) 4-Bromo-4-ethyl-2-methylhexane
(c) 3-Iodo-2,2,4,4-tetramethylpentane (d) cis-1-Bromo-2-ethylcyclopentane


Naming Alkyl Halides -

PROBLEM Draw and name all the monochlorination products you might obtain from radical chlorination of
10-20 the following compounds. Which of the products are chiral? Are any of the products optically active?
(a) 2-methylbutane
(b) methylcyclopropane
(c) 2,2-dimethylpentane


Synthesizing Alkyl Halides -

PROBLEM How would you prepare the following compounds, starting with cyclopentene and any other
10-21 reagents needed?
(a) Chlorocyclopentane
(b) Methylcyclopentane
(c) 3-Bromocyclopentene
(d) Cyclopentanol
(e) Cyclopentylcyclopentane
(f) 1,3-Cyclopentadiene


Synthesizing Alkyl Halides -

PROBLEM Predict the product(s) of the following reactions:


Synthesizing Alkyl Halides -


Synthesizing Alkyl Halides -

PROBLEM A chemist requires a large amount of 1-bromo-2-pentene as starting material for a synthesis and
10-23 decides to carry out an NBS allylic bromination reaction. What is wrong with the following synthesis plan? What side products would form in addition to the desired product?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0326.jpg?height=91&width=776&top_left_y=345&top_left_x=417)


Synthesizing Alkyl Halides -

PROBLEM What product(s) would you expect from the reaction of 1-methylcyclohexene with NBS? Would you
10-24 use this reaction as part of a synthesis?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0326.jpg?height=142&width=435&top_left_y=561&top_left_x=411)


Synthesizing Alkyl Halides -

PROBLEM What product(s) would you expect from the reaction of 1,4-hexadiene with NBS? What is the
10-25 structure of the most stable radical intermediate?
PROBLEM What product would you expect from the reaction of 1-phenyl-2-butene with NBS? Explain.
10-26
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General Problems -

PROBLEM Arrange the following radicals from most stable to least stable.


General Problems -


General Problems -

PROBLEM Alkylbenzenes such as toluene (methylbenzene) react with NBS to give products in which bromine 10-31
substitution has occurred at the position next to the aromatic ring (the benzylic position). Explain, based on the bond dissociation energies in Table 6.3.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0327.jpg?height=134&width=621&top_left_y=302&top_left_x=416)


General Problems -

PROBLEM Draw resonance structures for the benzyl radical, $\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \cdot$, the intermediate produced in the NBS
10-32 bromination reaction of toluene (Problem 10-31).
PROBLEM Draw resonance structures for the following species:
10-33 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0327.jpg?height=85&width=446&top_left_y=624&top_left_x=476)
(b)
<img class="imgSvg" id = "m6sn3ngtylqxj2i8w0p" src="data:image/svg+xml;base64,PHN2ZyBpZD0ic21pbGVzLW02c24zbmd0eWxxeGoyaTh3MHAiIHhtbG5zPSJodHRwOi8vd3d3LnczLm9yZy8yMDAwL3N2ZyIgdmlld0JveD0iMCAwIDEzNCA5Mi42ODg4NTg2MzUxNTkyNSIgc3R5bGU9IndpZHRoOiAxMzMuODU0MzAzMTQ5ODkzMzhweDsgaGVpZ2h0OiA5Mi42ODg4NTg2MzUxNTkyNXB4OyBvdmVyZmxvdzogdmlzaWJsZTsiPjxkZWZzPjxsaW5lYXJHcmFkaWVudCBpZD0ibGluZS1tNnNuM25ndHlscXhqMmk4dzBwLTEiIGdyYWRpZW50VW5pdHM9InVzZXJTcGFjZU9uVXNlIiB4MT0iODMuMjUxOTYzNDg3Njk4OTYiIHkxPSI2MS40MTQyMzcxODUzMjQxNiIgeDI9Ijg1Ljg4NjA5NzYzMzg3NzA2IiB5Mj0iMzYuMzUyMjg3MTk1MzUwNTU2Ij48c3RvcCBzdG9wLWNvbG9yPSJjdXJyZW50Q29sb3IiIG9mZnNldD0iMjAlIj48L3N0b3A+PHN0b3Agc3RvcC1jb2xvcj0iY3VycmVudENvbG9yIiBvZmZzZXQ9IjEwMCUiPjwvc3RvcD48L2xpbmVhckdyYWRpZW50PjxsaW5lYXJHcmFkaWVudCBpZD0ibGluZS1tNnNuM25ndHlscXhqMmk4dzBwLTMiIGdyYWRpZW50VW5pdHM9InVzZXJTcGFjZU9uVXNlIiB4MT0iODguNTYxNjM1NDY3MTcwNzYiIHkxPSI2NS4xMzk2NjExMTY5NjA5NSIgeDI9IjkxLjg1NDMwMzE0OTg5MzM4IiB5Mj0iMzMuODEyMjIzNjI5NDkzOTM2Ij48c3RvcCBzdG9wLWNvbG9yPSJjdXJyZW50Q29sb3IiIG9mZnNldD0iMjAlIj48L3N0b3A+PHN0b3Agc3RvcC1jb2xvcj0iY3VycmVudENvbG9yIiBvZmZzZXQ9IjEwMCUiPjwvc3RvcD48L2xpbmVhckdyYWRpZW50PjxsaW5lYXJHcmFkaWVudCBpZD0ibGluZS1tNnNuM25ndHlscXhqMmk4dzBwLTUiIGdyYWRpZW50VW5pdHM9InVzZXJTcGFjZU9uVXNlIiB4MT0iNjMuMDc3NjI5ODU5Mzk5MjYiIHkxPSIyMSIgeDI9IjkxLjg1NDMwMzE0OTg5MzM4IiB5Mj0iMzMuODEyMjIzNjI5NDkzOTM2Ij48c3RvcCBzdG9wLWNvbG9yPSJjdXJyZW50Q29sb3IiIG9mZnNldD0iMjAlIj48L3N0b3A+PHN0b3Agc3RvcC1jb2xvcj0iY3VycmVudENvbG9yIiBvZmZzZXQ9IjEwMCUiPjwvc3RvcD48L2xpbmVhckdyYWRpZW50PjxsaW5lYXJHcmFkaWVudCBpZD0ibGluZS1tNnNuM25ndHlscXhqMmk4dzBwLTciIGdyYWRpZW50VW5pdHM9InVzZXJTcGFjZU9uVXNlIiB4MT0iNTcuNzQ5OTgxNjM1MDk1NzEiIHkxPSI3MS42ODg4NTg2MzUxNTkyNSIgeDI9Ijg4LjU2MTYzNTQ2NzE3MDc2IiB5Mj0iNjUuMTM5NjYxMTE2OTYwOTUiPjxzdG9wIHN0b3AtY29sb3I9ImN1cnJlbnRDb2xvciIgb2Zmc2V0PSIyMCUiPjwvc3RvcD48c3RvcCBzdG9wLWNvbG9yPSJjdXJyZW50Q29sb3IiIG9mZnNldD0iMTAwJSI+PC9zdG9wPjwvbGluZWFyR3JhZGllbnQ+PGxpbmVhckdyYWRpZW50IGlkPSJsaW5lLW02c24zbmd0eWxxeGoyaTh3MHAtOSIgZ3JhZGllbnRVbml0cz0idXNlclNwYWNlT25Vc2UiIHgxPSI0MiIgeTE9IjQ0LjQwOTA0NzgxMjk3NTI0IiB4Mj0iNjMuMDc3NjI5ODU5Mzk5MjYiIHkyPSIyMSI+PHN0b3Agc3RvcC1jb2xvcj0iY3VycmVudENvbG9yIiBvZmZzZXQ9IjIwJSI+PC9zdG9wPjxzdG9wIHN0b3AtY29sb3I9ImN1cnJlbnRDb2xvciIgb2Zmc2V0PSIxMDAlIj48L3N0b3A+PC9saW5lYXJHcmFkaWVudD48bGluZWFyR3JhZGllbnQgaWQ9ImxpbmUtbTZzbjNuZ3R5bHF4ajJpOHcwcC0xMSIgZ3JhZGllbnRVbml0cz0idXNlclNwYWNlT25Vc2UiIHgxPSI0MiIgeTE9IjQ0LjQwOTA0NzgxMjk3NTI0IiB4Mj0iNTcuNzQ5OTgxNjM1MDk1NzEiIHkyPSI3MS42ODg4NTg2MzUxNTkyNSI+PHN0b3Agc3RvcC1jb2xvcj0iY3VycmVudENvbG9yIiBvZmZzZXQ9IjIwJSI+PC9zdG9wPjxzdG9wIHN0b3AtY29sb3I9ImN1cnJlbnRDb2xvciIgb2Zmc2V0PSIxMDAlIj48L3N0b3A+PC9saW5lYXJHcmFkaWVudD48L2RlZnM+PG1hc2sgaWQ9InRleHQtbWFzay1tNnNuM25ndHlscXhqMmk4dzBwIj48cmVjdCB4PSIwIiB5PSIwIiB3aWR0aD0iMTAwJSIgaGVpZ2h0PSIxMDAlIiBmaWxsPSJ3aGl0ZSI+PC9yZWN0PjwvbWFzaz48c3R5bGU+CiAgICAgICAgICAgICAgICAuZWxlbWVudC1tNnNuM25ndHlscXhqMmk4dzBwIHsKICAgICAgICAgICAgICAgICAgICBmb250OiAxNHB4IEhlbHZldGljYSwgQXJpYWwsIHNhbnMtc2VyaWY7CiAgICAgICAgICAgICAgICAgICAgYWxpZ25tZW50LWJhc2VsaW5lOiAnbWlkZGxlJzsKICAgICAgICAgICAgICAgIH0KICAgICAgICAgICAgICAgIC5zdWItbTZzbjNuZ3R5bHF4ajJpOHcwcCB7CiAgICAgICAgICAgICAgICAgICAgZm9udDogOC40cHggSGVsdmV0aWNhLCBBcmlhbCwgc2Fucy1zZXJpZjsKICAgICAgICAgICAgICAgIH0KICAgICAgICAgICAgPC9zdHlsZT48ZyBtYXNrPSJ1cmwoI3RleHQtbWFzay1tNnNuM25ndHlscXhqMmk4dzBwKSI+PGxpbmUgeDE9IjgzLjI1MTk2MzQ4NzY5ODk2IiB5MT0iNjEuNDE0MjM3MTg1MzI0MTYiIHgyPSI4NS44ODYwOTc2MzM4NzcwNiIgeTI9IjM2LjM1MjI4NzE5NTM1MDU1NiIgc3R5bGU9InN0cm9rZS1saW5lY2FwOnJvdW5kO3N0cm9rZS1kYXNoYXJyYXk6bm9uZTtzdHJva2Utd2lkdGg6MS4yNiIgc3Ryb2tlPSJ1cmwoJyNsaW5lLW02c24zbmd0eWxxeGoyaTh3MHAtMScpIj48L2xpbmU+PGxpbmUgeDE9Ijg4LjU2MTYzNTQ2NzE3MDc2IiB5MT0iNjUuMTM5NjYxMTE2OTYwOTUiIHgyPSI5MS44NTQzMDMxNDk4OTMzOCIgeTI9IjMzLjgxMjIyMzYyOTQ5MzkzNiIgc3R5bGU9InN0cm9rZS1saW5lY2FwOnJvdW5kO3N0cm9rZS1kYXNoYXJyYXk6bm9uZTtzdHJva2Utd2lkdGg6MS4yNiIgc3Ryb2tlPSJ1cmwoJyNsaW5lLW02c24zbmd0eWxxeGoyaTh3MHAtMycpIj48L2xpbmU+PGxpbmUgeDE9IjYzLjA3NzYyOTg1OTM5OTI2IiB5MT0iMjEiIHgyPSI5MS44NTQzMDMxNDk4OTMzOCIgeTI9IjMzLjgxMjIyMzYyOTQ5MzkzNiIgc3R5bGU9InN0cm9rZS1saW5lY2FwOnJvdW5kO3N0cm9rZS1kYXNoYXJyYXk6bm9uZTtzdHJva2Utd2lkdGg6MS4yNiIgc3Ryb2tlPSJ1cmwoJyNsaW5lLW02c24zbmd0eWxxeGoyaTh3MHAtNScpIj48L2xpbmU+PGxpbmUgeDE9IjU3Ljc0OTk4MTYzNTA5NTcxIiB5MT0iNzEuNjg4ODU4NjM1MTU5MjUiIHgyPSI4OC41NjE2MzU0NjcxNzA3NiIgeTI9IjY1LjEzOTY2MTExNjk2MDk1IiBzdHlsZT0ic3Ryb2tlLWxpbmVjYXA6cm91bmQ7c3Ryb2tlLWRhc2hhcnJheTpub25lO3N0cm9rZS13aWR0aDoxLjI2IiBzdHJva2U9InVybCgnI2xpbmUtbTZzbjNuZ3R5bHF4ajJpOHcwcC03JykiPjwvbGluZT48bGluZSB4MT0iNDIiIHkxPSI0NC40MDkwNDc4MTI5NzUyNCIgeDI9IjYzLjA3NzYyOTg1OTM5OTI2IiB5Mj0iMjEiIHN0eWxlPSJzdHJva2UtbGluZWNhcDpyb3VuZDtzdHJva2UtZGFzaGFycmF5Om5vbmU7c3Ryb2tlLXdpZHRoOjEuMjYiIHN0cm9rZT0idXJsKCcjbGluZS1tNnNuM25ndHlscXhqMmk4dzBwLTknKSI+PC9saW5lPjxsaW5lIHgxPSI0MiIgeTE9IjQ0LjQwOTA0NzgxMjk3NTI0IiB4Mj0iNTcuNzQ5OTgxNjM1MDk1NzEiIHkyPSI3MS42ODg4NTg2MzUxNTkyNSIgc3R5bGU9InN0cm9rZS1saW5lY2FwOnJvdW5kO3N0cm9rZS1kYXNoYXJyYXk6bm9uZTtzdHJva2Utd2lkdGg6MS4yNiIgc3Ryb2tlPSJ1cmwoJyNsaW5lLW02c24zbmd0eWxxeGoyaTh3MHAtMTEnKSI+PC9saW5lPjwvZz48Zz48dGV4dCB4PSI5MS44NTQzMDMxNDk4OTMzOCIgeT0iMzMuODEyMjIzNjI5NDkzOTM2IiBjbGFzcz0iZGVidWciIGZpbGw9IiNmZjAwMDAiIHN0eWxlPSIKICAgICAgICAgICAgICAgIGZvbnQ6IDVweCBEcm9pZCBTYW5zLCBzYW5zLXNlcmlmOwogICAgICAgICAgICAiPjwvdGV4dD48dGV4dCB4PSI4OC41NjE2MzU0NjcxNzA3NiIgeT0iNjUuMTM5NjYxMTE2OTYwOTUiIGNsYXNzPSJkZWJ1ZyIgZmlsbD0iI2ZmMDAwMCIgc3R5bGU9IgogICAgICAgICAgICAgICAgZm9udDogNXB4IERyb2lkIFNhbnMsIHNhbnMtc2VyaWY7CiAgICAgICAgICAgICI+PC90ZXh0Pjx0ZXh0IHg9IjU3Ljc0OTk4MTYzNTA5NTcxIiB5PSI3MS42ODg4NTg2MzUxNTkyNSIgY2xhc3M9ImRlYnVnIiBmaWxsPSIjZmYwMDAwIiBzdHlsZT0iCiAgICAgICAgICAgICAgICBmb250OiA1cHggRHJvaWQgU2Fucywgc2Fucy1zZXJpZjsKICAgICAgICAgICAgIj48L3RleHQ+PHRleHQgeD0iNDIiIHk9IjQ0LjQwOTA0NzgxMjk3NTI0IiBjbGFzcz0iZGVidWciIGZpbGw9IiNmZjAwMDAiIHN0eWxlPSIKICAgICAgICAgICAgICAgIGZvbnQ6IDVweCBEcm9pZCBTYW5zLCBzYW5zLXNlcmlmOwogICAgICAgICAgICAiPjwvdGV4dD48dGV4dCB4PSI2My4wNzc2Mjk4NTkzOTkyNiIgeT0iMjEiIGNsYXNzPSJkZWJ1ZyIgZmlsbD0iI2ZmMDAwMCIgc3R5bGU9IgogICAgICAgICAgICAgICAgZm9udDogNXB4IERyb2lkIFNhbnMsIHNhbnMtc2VyaWY7CiAgICAgICAgICAgICI+PC90ZXh0PjwvZz48L3N2Zz4="/>
(c)
<img class="imgSvg" id = "m6sn3ngurbsnzaie4tp" 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General Problems -

PROBLEM (S)-3-Methylhexane undergoes radical bromination to yield optically inactive 10-34 3-bromo-3-methylhexane as the major product. Is the product chiral? What conclusions can you draw about the radical intermediate?


General Problems -

PROBLEM Assume that you have carried out a radical chlorination reaction on ( $R$ )-2-chloropentane and have
10-35 isolated (in low yield) 2,4-dichloropentane. How many stereoisomers of the product are formed, and in what ratio? Are any of the isomers optically active? (See Problem 10-34.)


General Problems -

PROBLEM Why do you suppose it's not possible to prepare a Grignard reagent from a bromo alcohol such
$\mathbf{1 0 - 3 8}$ as 4-bromo-1-pentanol? Give another example of a molecule that is unlikely to form a Grignard reagent.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0327.jpg?height=110&width=747&top_left_y=2024&top_left_x=418)


General Problems -

PROBLEM Addition of HBr to a double bond with an ether (-OR) substituent occurs regiospecifically to give
10-39 a product in which the -Br and -OR are bonded to the same carbon. Draw the two possible carbocation intermediates in this electrophilic addition reaction, and explain using resonance why the observed product is formed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0327.jpg?height=136&width=235&top_left_y=2374&top_left_x=411)


General Problems -

PROBLEM Identify the reagents $\mathbf{a}-\mathbf{c}$ in the following scheme:
10-40
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0328.jpg?height=215&width=1400&top_left_y=245&top_left_x=403)


General Problems -

PROBLEM Tertiary alkyl halides, $\mathrm{R}_{3} \mathrm{CX}$, undergo spontaneous dissociation to yield a carbocation, $\mathrm{R}_{3} \mathrm{C}^{+}$, plus
10-41 halide ion. Which do you think reacts faster, $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CBr}$ or $\mathrm{H}_{2} \mathrm{C}=\mathrm{CHC}\left(\mathrm{CH}_{3}\right)_{2} \mathrm{Br}$ ? Explain.
PROBLEM Carboxylic acids $\left(\mathrm{RCO}_{2} \mathrm{H} ; \mathrm{p} K_{\mathrm{a}} \approx 5\right)$ are approximately $10^{11}$ times more acidic than alcohols (ROH;
10-42 $\mathrm{p} K_{\mathrm{a}} \approx 16$ ). In other words, a carboxylate ion $\left(\mathrm{RCO}_{2}^{-}\right)$is more stable than an alkoxide ion ( $\mathrm{RO}^{-}$). Explain, using resonance.


General Problems -

PROBLEM The relative rate of radical bromination is $1: 82: 1640$ for $1^{\circ}: 2^{\circ}: 3^{\circ}$ hydrogens, respectively. Draw
10-44 all of the monobrominated products that you might obtain from the radical bromination of the compounds below. Calculate the relative percentage of each.
(a) methylcyclobutane
(b) 3,3-dimethylpentane
(c) 3-methylpentane


General Problems -

PROBLEM Predict the product and provide the entire catalytic cycle for the following Suzuki-Miyaura 10-46 reactions.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0328.jpg?height=185&width=855&top_left_y=2176&top_left_x=407)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0329.jpg?height=232&width=778&top_left_y=193&top_left_x=416)


CHAPTER 11 -

Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0330.jpg?height=831&width=1885&top_left_y=449&top_left_x=239)


CHAPTER 11 -

FIGURE 11.1 Competition occurs throughout nature. In chemistry, competition often occurs between alternative reaction pathways, such as in the substitution and elimination reactions of alkyl halides. (credit: modification of work "Bull moose fight" by Grand Teton, National Parks Service/Flickr, Public Domain)


CHAPTER CONTENTS -

11.1 The Discovery of Nucleophilic Substitution Reactions
11.2 The $\mathbf{S}_{\mathrm{N}} 2$ Reaction
11.3 Characteristics of the $\mathbf{S}_{\mathrm{N}} \mathbf{2}$ Reaction
11.4 The $\mathrm{S}_{\mathrm{N}} 1$ Reaction
11.5 Characteristics of the $\mathrm{S}_{\mathrm{N}} 1$ Reaction
11.6 Biological Substitution Reactions
11.7 Elimination Reactions: Zaitsev's Rule
11.8 The E2 Reaction and the Deuterium Isotope Effect
11.9 The E2 Reaction and Cyclohexane Conformation
11.10 The E1 and E1cB Reactions
11.11 Biological Elimination Reactions
11.12 A Summary of Reactivity: $\mathrm{S}_{\mathrm{N}} 1, \mathrm{~S}_{\mathrm{N}} 2, \mathrm{E} 1, \mathrm{E} 1 \mathrm{CB}$, and E 2


CHAPTER CONTENTS -

WHY THIS CHAPTER? Nucleophilic substitution and base-induced elimination are two of the most widely occurring and versatile reactions in organic chemistry, both in the laboratory and in biological pathways. We'll look at them closely in this chapter to see how they occur, what their characteristics are, and how they can be used. We'll begin with substitution reactions.


CHAPTER CONTENTS -

We saw in the preceding chapter that the carbon-halogen bond in an alkyl halide is polar and that the carbon atom is electron-poor. Thus, alkyl halides are electrophiles, and much of their chemistry involves polar reactions with nucleophiles and bases. Alkyl halides do one of two things when they react with a nucleophile/ base such as hydroxide ion: they either undergo substitution of the X group by the nucleophile, or they undergo
elimination of HX to yield an alkene.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0331.jpg?height=152&width=990&top_left_y=260&top_left_x=516)


CHAPTER CONTENTS -

Elimination
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0331.jpg?height=145&width=877&top_left_y=459&top_left_x=727)