Hydrolysis of Nitriles -

Carboxylic acids can be prepared from nitriles on heating with aqueous acid or base by a mechanism that we'll discuss in Section 20.7. Since nitriles themselves are usually made by $\mathrm{S}_{\mathrm{N}} 2$ reaction of a primary or secondary alkyl halide with $\mathrm{CN}^{-}$, the two-step sequence of cyanide displacement followed by nitrile hydrolysis is a good way to make a carboxylic acid from an alkyl halide ( $\mathrm{RBr} \rightarrow \mathrm{RC} \equiv \mathrm{N} \rightarrow \mathrm{RCO}_{2} \mathrm{H}$ ). Note that the product acid has one more carbon than the starting alkyl halide. One example occurs in a commercial route for the synthesis of the nonsteroidal anti-inflammatory drug ibuprofen. (See Chapter 15 Chemistry Matters.)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0709.jpg?height=252&width=972&top_left_y=1552&top_left_x=571)
$\downarrow$ 1. $\mathrm{NaOH}, \mathrm{H}_{2} \mathrm{O}$
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Hydrolysis of Nitriles -

Ibuprofen


Carboxylation of Grignard Reagents -

Another method for preparing carboxylic acids is by reaction of a Grignard reagent with $\mathrm{CO}_{2}$ to yield a metal carboxylate, followed by protonation to give a carboxylic acid. This carboxylation reaction is usually carried out by bubbling a stream of dry $\mathrm{CO}_{2}$ gas through a solution of the Grignard reagent. The organomagnesium halide adds to a $\mathrm{C}=\mathrm{O}$ bond of carbon dioxide in a typical nucleophilic carbonyl addition reaction, and protonation of
the carboxylate by addition of aqueous HCl in a separate step then gives the free carboxylic acid. For example:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0710.jpg?height=332&width=1183&top_left_y=249&top_left_x=471)


Carboxylation of Grignard Reagents -

As noted previously, there are no Grignard reagents inside living cells, but there are other types of stabilized carbanions that are often carboxylated. One of the initial steps in fatty-acid biosynthesis, for instance, involves the formation of a carbanion from acetyl CoA, followed by carboxylation to yield malonyl CoA.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0710.jpg?height=519&width=1177&top_left_y=722&top_left_x=471)


WORKED EXAMPLE 20.2 -


Devising a Synthesis Route for a Carboxylic Acid -

How would you prepare phenylacetic acid $\left(\mathrm{PhCH}_{2} \mathrm{CO}_{2} \mathrm{H}\right)$ from benzyl bromide $\left(\mathrm{PhCH}_{2} \mathrm{Br}\right)$ ?


Strategy -

We've seen two methods for preparing carboxylic acids from alkyl halides: (1) cyanide ion displacement followed by hydrolysis and (2) formation of a Grignard reagent followed by carboxylation. The first method involves an $\mathrm{S}_{\mathrm{N}} 2$ reaction and is therefore limited to use with primary and some secondary alkyl halides. The second method involves formation of a Grignard reagent and is therefore limited to use with organic halides that have no acidic hydrogens or reactive functional groups elsewhere in the molecule. In the present instance, either method would work well.


Strategy -

Solution
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0710.jpg?height=375&width=1362&top_left_y=1875&top_left_x=376)


Strategy -

PROBLEM How would you prepare the following carboxylic acids?
20-10 (a) $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CCO}_{2} \mathrm{H}$ from $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CCl}$
(b) $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CO}_{2} \mathrm{H}$ from $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{Br}$


Strategy - 20.6 Reactions of Carboxylic Acids: An Overview

We commented earlier in this chapter that carboxylic acids are similar in some respects to both alcohols and
ketones. Like alcohols, carboxylic acids can be deprotonated to give anions, which are good nucleophiles in $\mathrm{S}_{\mathrm{N}} 2$ reactions. Like ketones, carboxylic acids undergo addition of nucleophiles to the carbonyl group. However, carboxylic acids also undergo other reactions characteristic of neither alcohols nor ketones. FIGURE 20.3 shows some of the general reactions of carboxylic acids.
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Deprotonation
<img class="imgSvg" id = "m6sn3ourlqobfss79a" 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Reduction
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0711.jpg?height=391&width=869&top_left_y=626&top_left_x=628)


FIGURE 20.3 Some general reactions of carboxylic acids.
Reactions of carboxylic acids can be grouped into the four categories indicated in FIGURE 20.3. Of the four, we've already discussed the acidic behavior of carboxylic acids in Section 20.2 through Section 20.4, and we mentioned reduction by treatment with $\mathrm{LiAlH}_{4}$ in Section 17.4. The remaining two categories are examples of fundamental carbonyl-group reaction mechanisms-nucleophilic acyl substitution and $\alpha$ substitution-that will be discussed in detail in Chapters 21 and 22.


PROBLEM How might you prepare 2-phenylethanol from benzyl bromide? More than one step is needed.
20-11
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0711.jpg?height=147&width=668&top_left_y=1371&top_left_x=411)


PROBLEM How might you carry out the following transformation? More than one step is needed.
20-12
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0711.jpg?height=112&width=670&top_left_y=1597&top_left_x=413)


Strategy - 20.7 Chemistry of Nitriles

Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain a $\pi$ bond. Thus, some reactions of nitriles and carboxylic acids are similar. Both kinds of compounds are electrophiles, for instance, and both undergo nucleophilic addition reactions.


Strategy - 20.7 Chemistry of Nitriles

$$
\mathrm{R}-\mathrm{C} \equiv \mathrm{~N}
$$


A nitrile-three bonds to nitrogen -


A nitrile-three bonds to nitrogen -

An acid-three bonds to two oxygens


A nitrile-three bonds to nitrogen -

Nitriles occur infrequently in living organisms, although several hundred examples are known. Cyanocycline A, for instance, has been isolated from the bacterium Streptomyces lavendulae and was found to have both antimicrobial and antitumor activity. In addition, more than 1000 compounds called cyanogenic glycosides are known. Derived primarily from plants, cyanogenic glycosides contain a sugar with an acetal carbon, one oxygen of which is bonded to a nitrile-bearing carbon (sugar-O-C-CN). On hydrolysis with aqueous acid, the acetal is cleaved (Section 19.10), generating a cyanohydrin (HO-C-CN), which releases hydrogen cyanide. It's thought that the primary function of cyanogenic glycosides is to protect the plant by poisoning any animal foolish enough to eat it. Lotaustralin from the cassava plant is an example.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0712.jpg?height=367&width=497&top_left_y=193&top_left_x=565)


A nitrile-three bonds to nitrogen -

Lotaustralin
(a cyanogenic glycoside)


Preparation of Nitriles -

The simplest method of nitrile preparation is the $\mathrm{S}_{\mathrm{N}} 2$ reaction of $\mathrm{CN}^{-}$with a primary or secondary alkyl halide, as discussed in Section 20.5. Another method for preparing nitriles is by dehydration of a primary amide, $\mathrm{RCONH}_{2}$. Thionyl chloride is often used for this reaction, although other dehydrating agents such as $\mathrm{POCl}_{3}$ also work.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0712.jpg?height=218&width=1289&top_left_y=926&top_left_x=418)


Preparation of Nitriles -

The dehydration occurs by initial reaction of $\mathrm{SOCl}_{2}$ on the nucleophilic amide oxygen atom, followed by deprotonation and a subsequent E2-like elimination reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0712.jpg?height=365&width=1558&top_left_y=1246&top_left_x=281)


Preparation of Nitriles -

Both methods of nitrile synthesis- $\mathrm{S}_{\mathrm{N}} 2$ displacement by $\mathrm{CN}^{-}$on an alkyl halide and amide dehydration-are useful, but the synthesis from amides is more general because it is not limited by steric hindrance.


Reactions of Nitriles -

Like a carbonyl group, a nitrile group is strongly polarized and has an electrophilic carbon atom. Nitriles therefore react with nucleophiles to yield $s p^{2}$-hybridized imine anions in a reaction analogous to the formation of a $s p^{3}$-hybridized alkoxide ion by nucleophilic addition to a carbonyl group.


Carbonyl compound -


Carbonyl compound -

Some general reactions of nitriles are shown in FIGURE 20.4.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0713.jpg?height=598&width=860&top_left_y=254&top_left_x=624)


Carbonyl compound -

Hydrolysis: Conversion of Nitriles into Carboxylic Acids
Among the most useful reactions of nitriles is their hydrolysis to yield first an amide and then a carboxylic acid plus ammonia or an amine. The reaction occurs in either basic or acidic aqueous solution:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0713.jpg?height=218&width=1121&top_left_y=1016&top_left_x=502)


Carbonyl compound -

As shown in FIGURE 20.5, base-catalyzed nitrile hydrolysis involves nucleophilic addition of hydroxide ion to the polar $\mathrm{C} \equiv \mathrm{N}$ bond to give an imine anion in a process similar to the nucleophilic addition to a polar $\mathrm{C}=\mathrm{O}$ bond to give an alkoxide anion. Protonation then gives a hydroxy imine, which tautomerizes (Section 9.4) to an amide in a step similar to the tautomerization of an enol to a ketone. Further hydrolysis gives a carboxylate ion.


FIGURE 20.5 MECHANISM -

Mechanism for the basic hydrolysis of a nitrile to yield an amide, which is then hydrolyzed further to a carboxylic acid anion.
(1) Nucleophilic addition of hydroxide ion to the CN triple bond gives an imine anion addition product.
(2) Protonation of the imine anion by water yields a hydroxyimine and regenerates the base catalyst.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0714.jpg?height=133&width=326&top_left_y=931&top_left_x=1230)
(3) Tautomerization of the hydroxyimine yields an amide in a reaction analogous to the tautomerization of an enol to give a ketone.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0714.jpg?height=145&width=346&top_left_y=1196&top_left_x=1223)
(4) Further hydrolysis of the amide gives the anion of a carboxylic acid by a mechanism we'll discuss in Section 21.7.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0714.jpg?height=114&width=280&top_left_y=1488&top_left_x=1237)


FIGURE 20.5 MECHANISM -

Carboxylate ion


FIGURE 20.5 MECHANISM -

The further hydrolysis of the amide intermediate takes place by a nucleophilic addition of hydroxide ion to the amide carbonyl group, which yields a tetrahedral alkoxide ion. Expulsion of amide ion, $\mathrm{NH}_{2}{ }^{-}$, as leaving group gives the carboxylate ion, thereby driving the reaction toward the products. Subsequent acidification in a separate step yields the carboxylic acid. We'll look at this process in more detail in Section 21.7.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0714.jpg?height=256&width=1443&top_left_y=1929&top_left_x=341)


Reduction: Conversion of Nitriles into Amines -

Reduction of a nitrile with $\mathrm{LiAlH}_{4}$ gives a primary amine, $\mathrm{RNH}_{2}$. The reaction occurs by nucleophilic addition of hydride ion to the polar $\mathrm{C} \equiv \mathrm{N}$ bond, yielding an imine anion, which still contains a $\mathrm{C}=\mathrm{N}$ bond and therefore undergoes a second nucleophilic addition of hydride to give a dianion. Both monoanion and dianion intermediates are undoubtedly stabilized by Lewis acid-base complexation to an aluminum species, facilitating the second addition that would otherwise be difficult. Protonation of the dianion by addition of water in a subsequent step gives the amine.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0715.jpg?height=289&width=1548&top_left_y=189&top_left_x=283)


Reaction of Nitriles with Grignard Reagents
Grignard reagents add to a nitrile to give an intermediate imine anion that is hydrolyzed by addition of water to yield a ketone. The mechanism of the hydrolysis is the exact reverse of imine formation (see FIGURE 19.7).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0715.jpg?height=225&width=985&top_left_y=641&top_left_x=570)


This reaction is similar to the reduction of a nitrile to an amine, except that only one nucleophilic addition occurs rather than two and the attacking nucleophile is a carbanion ( $\mathrm{R}:^{-}$) rather than a hydride ion. For example:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0715.jpg?height=310&width=893&top_left_y=973&top_left_x=616)


WORKED EXAMPLE 20.3 -


Synthesizing a Ketone from a Nitrile -


Strategy -

A ketone results from the reaction between a Grignard reagent and a nitrile, with the $\mathrm{C} \equiv \mathrm{N}$ carbon of the nitrile becoming the carbonyl carbon. Identify the two groups attached to the carbonyl carbon atom in the product. One will come from the Grignard reagent and the other will come from the nitrile.


Solution -

There are two possibilities.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0715.jpg?height=253&width=1139&top_left_y=1993&top_left_x=493)


Solution -


Solution -

PROBLEM How would you prepare 1-phenyl-2-butanone, $\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \mathrm{COCH}_{2} \mathrm{CH}_{3}$, from benzyl bromide,
20-14 $\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{2} \mathrm{Br}$ ? More than one step is needed.


Solution - 20.8 Spectroscopy of Carboxylic Acids and Nitriles


Infrared Spectroscopy -

Carboxylic acids have two characteristic IR absorptions that make the $-\mathrm{CO}_{2} \mathrm{H}$ group easily identifiable. The $\mathrm{O}-\mathrm{H}$ bond of the carboxyl group gives rise to a very broad absorption over the range 2500 to $3300 \mathrm{~cm}^{-1}$. The $\mathrm{C}=\mathrm{O}$ bond shows an absorption between 1710 and $1760 \mathrm{~cm}^{-1}$. The exact position of $\mathrm{C}=\mathrm{O}$ absorption depends both on the structure of the molecule and on whether the acid is free (monomeric) or hydrogen-bonded (dimeric). Free carboxyl groups absorb at $1760 \mathrm{~cm}^{-1}$, but the more commonly encountered dimeric carboxyl groups absorb in a broad band centered around $1710 \mathrm{~cm}^{-1}$. As with other carbonyl-containing functional groups, conjugation with an alkene or benzene ring lowers the frequency of the $\mathrm{C}=\mathrm{O}$ stretch by 20 to $30 \mathrm{~cm}^{-1}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0716.jpg?height=120&width=182&top_left_y=1024&top_left_x=462)
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Infrared Spectroscopy -

Associated carboxyl (usual case), $1710 \mathrm{~cm}^{-1}$


Infrared Spectroscopy -

Both the broad $\mathrm{O}-\mathrm{H}$ absorption and the $\mathrm{C}=\mathrm{O}$ absorption at $1710 \mathrm{~cm}^{-1}$ (dimeric) are identified in the IR spectrum of butanoic acid shown in FIGURE 20.6.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0716.jpg?height=481&width=1382&top_left_y=1261&top_left_x=369)


Infrared Spectroscopy -

FIGURE 20.6 IR spectrum of butanoic acid, $\mathbf{C H}_{3} \mathbf{C H}_{2} \mathbf{C H}_{2} \mathbf{C O}_{2} \mathbf{H}$.
Nitriles show an intense and easily recognizable $\mathrm{C} \equiv \mathrm{N}$ bond absorption near $2250 \mathrm{~cm}^{-1}$ for saturated compounds and $2230 \mathrm{~cm}^{-1}$ for aromatic and conjugated molecules. Few other functional groups absorb in this region, so IR spectroscopy is highly diagnostic for nitriles.


Infrared Spectroscopy -

PROBLEM Cyclopentanecarboxylic acid and 4-hydroxycyclohexanone have the same formula $\left(\mathrm{C}_{6} \mathrm{H}_{10} \mathrm{O}_{2}\right)$, and
20-15 both contain an -OH and a $\mathrm{C}=\mathrm{O}$ group. How could you distinguish between them using IR spectroscopy?


Nuclear Magnetic Resonance Spectroscopy -

Carboxyl carbon atoms absorb in the range 165 to $185 \delta$ in the ${ }^{13} \mathrm{C}$ NMR spectrum, with aromatic and $\alpha, \beta$-unsaturated acids near the upfield end of the range ( $\sim 165 \delta$ ) and saturated aliphatic acids near the downfield end ( $\sim 185 \delta$ ). Nitrile carbons absorb in the range 115 to $130 \delta$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0717.jpg?height=313&width=1175&top_left_y=185&top_left_x=472)


In the ${ }^{1} \mathrm{H}$ NMR spectrum, the acidic $-\mathrm{CO}_{2} \mathrm{H}$ proton normally absorbs as a singlet near $12 \delta$. The chemical shift of the carboxyl proton is concentration and solvent dependent, as these variables can change the extent of hydrogen-bonding in the sample. In some cases, the carboxyl-proton resonance is broadened to the point of being nearly undetectable. Traces of water in the sample can exacerbate the situation. As with alcohols (Section 17.11), the $-\mathrm{CO}_{2} \mathrm{H}$ proton can be replaced by deuterium when $\mathrm{D}_{2} \mathrm{O}$ is added to the sample tube, causing the absorption to disappear from the NMR spectrum. FIGURE 20.7 shows the ${ }^{1} \mathrm{H}$ NMR spectrum of phenylacetic acid. Note that the $-\mathrm{CO}_{2} \mathrm{H}$ absorption occurs at $12.0 \delta$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0717.jpg?height=529&width=1405&top_left_y=806&top_left_x=360)


FIGURE 20.7 Proton NMR spectrum of phenylacetic acid, $\mathbf{C}_{\mathbf{6}} \mathbf{H}_{\mathbf{5}} \mathbf{C H}_{\mathbf{2}} \mathbf{C O}_{\mathbf{2}} \mathbf{H}$.
PROBLEM How could you distinguish between the isomers cyclopentanecarboxylic acid and 20-16 4-hydroxycyclohexanone by ${ }^{1} \mathrm{H}$ and ${ }^{13} \mathrm{C}$ NMR spectroscopy? (See Problem 20-15.)


CHO CHEMISTRY MATTERS -


Vitamin C -

The word vitamin, despite its common usage, is actually an imprecise term. Generally speaking, a vitamin is an organic substance that a given organism requires in small amounts to live and grow but is unable to synthesize and must obtain in its diet. Thus, to be considered a vitamin, only a small amount of the substance is needed-anywhere from a few micrograms to 100 mg or so per day. Dietary substances needed in larger amounts, such as some amino acids and unsaturated fats, are not considered vitamins.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0718.jpg?height=624&width=1020&top_left_y=672&top_left_x=550)


Vitamin C -

FIGURE 20.8 In addition to the hazards of weather, participants in early polar expeditions often suffered from scurvy, caused by a dietary vitamin C deficiency. (credit: "Shackleton's expedition to the Antarctic last moments of the Endurance" by Underwood \& Underwood/ Wikimedia Commons, Public Domain)


Vitamin C -

Furthermore, different organisms need different vitamins. More than 4000 species of mammals can synthesize ascorbic acid in their bodies, for instance, but humans are not among them. Ascorbic acid is therefore a human vitamin-what we all know as vitamin C -and must be provided by our diet. Small amounts of more than a dozen other substances are similarly required by humans: retinol (vitamin A), thiamine (vitamin $B_{1}$ ), and tocopherol (vitamin E), for instance.


Vitamin C -

Vitamin C is surely the best known of all human vitamins. It was the first to be discovered (1912), the first to be isolated (1928), the first to be structurally characterized (1933), and the first to be synthesized in the laboratory (1933). Over 121,000 tons of vitamin C is synthesized worldwide each year, more than the total amount of all other vitamins combined. In addition to its use as a supplement, vitamin C is used as a food preservative, a "flour improver" in bakeries, and an animal-food additive.
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Vitamin C -

Vitamin C (ascorbic acid)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0718.jpg?height=481&width=421&top_left_y=1882&top_left_x=1031)


Vitamin C -

Vitamin C is perhaps most well-known for its antiscorbutic properties, meaning that it prevents the onset of scurvy, a bleeding disease affecting those with a deficiency of fresh vegetables and citrus fruits in their diet. Sailors in the Age of Exploration were particularly susceptible to scurvy, and the death toll was high. The


Vitamin C -

Portuguese explorer Vasco da Gama lost more than half his crew to scurvy during his two-year voyage around the Cape of Good Hope in 1497-1499.


Vitamin C -

More recently, large doses of vitamin $C$ have been claimed to prevent the common cold, cure infertility, delay the onset of symptoms in acquired immunodeficiency syndrome (AIDS), and inhibit the development of gastric and cervical cancers. None of these claims have been backed by medical evidence, however. In the largest study yet of the effect of vitamin $C$ on the common cold, a meta-analysis of more than 100 separate trials covering 40,000 people found no difference in the incidence of colds between those who took supplemental vitamin C regularly and those who did not. When taken during a cold, however, vitamin $C$ does appear to decrease the cold's duration by perhaps a day.


Vitamin C -

The industrial preparation of vitamin $C$ involves an unusual blend of biological and laboratory organic chemistry, beginning with glucose and following the five-step route shown in FIGURE 20.9. Glucose, a pentahydroxy aldehyde, is first reduced to sorbitol, which is then oxidized by the microorganism Acetobacter suboxydans. No chemical reagent is known that is selective enough to oxidize only one of the six alcohol groups in sorbitol, so an enzymatic reaction is used. Treatment with acetone and an acid catalyst then converts four of the other hydroxyl groups into acetal linkages, and the remaining hydroxyl group is chemically oxidized to a carboxylic acid by reaction with aqueous NaOCl (household bleach). Hydrolysis with acid then removes the two acetal groups and causes an internal ester-forming reaction to give ascorbic acid. Each of the five steps has a yield better than $90 \%$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0719.jpg?height=909&width=1674&top_left_y=1042&top_left_x=231)


Vitamin C -

FIGURE 20.9 The industrial synthesis of ascorbic acid from glucose.


Key Terms -

- carboxyl group - Henderson-Hasselbalch equation
- carboxylation
- nitrile
- carboxylic acid, $\mathrm{RCO}_{2} \mathrm{H}$


Key Terms -


Summary -

Carboxylic acids are among the most useful building blocks for synthesizing other molecules, both in nature and in the laboratory. Thus, an understanding of their properties and reactions is fundamental to understanding biological chemistry. In this chapter, we've looked both at acids and at their close relatives, nitriles ( $\mathrm{RC} \equiv \mathrm{N}$ ).


Summary -

Carboxylic acids are named systematically by replacing the terminal -e of the corresponding alkane name with -oic acid. Like aldehydes and ketones, the carbonyl carbon atom is $s p^{2}$-hybridized; like alcohols, carboxylic acids are associated through hydrogen-bonding and therefore have high boiling points.


Summary -

The distinguishing characteristic of carboxylic acids is their acidity. Although weaker than mineral acids such as HCl , carboxylic acids dissociate much more readily than alcohols because the resultant carboxylate ions are stabilized by resonance between two equivalent forms.


Summary -

Most carboxylic acids have $\mathrm{p} K_{\mathrm{a}}$ values near 5, but the exact $\mathrm{p} K_{\mathrm{a}}$ of a given acid depends on structure. Carboxylic acids substituted by electron-withdrawing groups are more acidic (have a lower $\mathrm{p} K_{\mathrm{a}}$ ) because their carboxylate ions are stabilized. Carboxylic acids substituted by electron-donating groups are less acidic (have a higher $\mathrm{p} K_{\mathrm{a}}$ ) because their carboxylate ions are destabilized. The extent of dissociation of a carboxylic acid in a buffered solution of a given pH can be calculated with the Henderson-Hasselbalch equation. Inside living cells, where the physiological $\mathrm{pH}=7.3$, carboxylic acids are entirely dissociated and exist as their carboxylate anions.


Summary -

Methods of synthesis for carboxylic acids include (1) oxidation of alkylbenzenes, (2) oxidation of primary alcohols or aldehydes, (3) reaction of Grignard reagents with $\mathrm{CO}_{2}$ (carboxylation), and (4) hydrolysis of nitriles. General reactions of carboxylic acids include (1) loss of the acidic proton, (2) nucleophilic acyl substitution at the carbonyl group, (3) substitution on the $\alpha$ carbon, and (4) reduction.


Summary -

Nitriles are similar in some respects to carboxylic acids and are prepared either by $\mathrm{S}_{\mathrm{N}} 2$ reaction of an alkyl halide with cyanide ion or by dehydration of an amide. Nitriles undergo nucleophilic addition to the polar $\mathrm{C} \equiv \mathrm{N}$ bond in the same way that carbonyl compounds do. The most important reactions of nitriles are their hydrolysis to carboxylic acids, reduction to primary amines, and reaction with Grignard reagents to yield ketones.


Summary -

Carboxylic acids and nitriles are easily distinguished spectroscopically. Acids show a characteristic IR absorption at 2500 to $3300 \mathrm{~cm}^{-1}$ due to the $\mathrm{O}-\mathrm{H}$ bond and another at 1710 to $1760 \mathrm{~cm}^{-1}$ due to the $\mathrm{C}=\mathrm{O}$ bond; nitriles have an absorption at $2250 \mathrm{~cm}^{-1}$. Acids also show ${ }^{13} \mathrm{C}$ NMR absorptions at 165 to $185 \delta$ and ${ }^{1} \mathrm{H}$ NMR absorptions near $12 \delta$. Nitriles have a ${ }^{13} \mathrm{C}$ NMR absorption in the range 115 to $130 \delta$.


Summary of Reactions -

1. Preparation of carboxylic acids (Section 20.5)
a. Carboxylation of Grignard reagents


Summary of Reactions -

$$
\mathrm{R}-\mathrm{MgX} \stackrel{\text { 1. } \mathrm{CO}_{2}}{\text { 2. } \mathrm{H}_{3} \mathrm{O}^{+}} \quad \stackrel{\stackrel{\mathrm{O}}{\|}}{\mathrm{R}^{-}}{ }_{\mathrm{OH}}
$$


Summary of Reactions -

b. Hydrolysis of nitriles


Summary of Reactions -

$$
\mathrm{R}-\mathrm{C} \equiv \mathrm{~N} \stackrel{\mathrm{or}^{\mathrm{NaOH}, \mathrm{H}_{2} \mathrm{O}}}{\mathrm{R}^{-} \stackrel{\mathrm{O}}{\mathrm{C}} \mathrm{C}_{\mathrm{OH}}^{+}}
$$


Summary of Reactions -

2. Preparation of nitriles (Section 20.7)
a. $\mathrm{S}_{\mathrm{N}} 2$ reaction of alkyl halides


Summary of Reactions -

$$
\mathrm{RCH}_{2} \mathrm{Br} \quad \xrightarrow{\mathrm{NaCN}} \mathrm{RCH}_{2} \mathrm{C} \equiv \mathrm{~N}
$$


Summary of Reactions -

b. Dehydration of amides
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0720.jpg?height=137&width=779&top_left_y=2035&top_left_x=719)
3. Reactions of nitriles (Section 20.7)
a. Hydrolysis to yield carboxylic acids


Summary of Reactions -

$$
\mathrm{R}-\mathrm{C} \equiv \mathrm{~N} \xrightarrow[\text { 2. } \mathrm{H}_{3} \mathrm{O}^{+}]{\stackrel{\text { 1. } \mathrm{NaOH}, \mathrm{H}_{2} \mathrm{O}}{\mathrm{R}^{-\quad}} \stackrel{\mathrm{O}}{\mathrm{C}} \mathrm{OH}_{\mathrm{OH}}}+\mathrm{NH}_{3}
$$


Summary of Reactions -

b. Reduction to yield primary amines
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0721.jpg?height=120&width=494&top_left_y=192&top_left_x=867)
c. Reaction with Grignard reagents to yield ketones


Summary of Reactions -

$$
\mathrm{R}-\mathrm{C} \equiv \mathrm{~N} \quad \stackrel{\text { 1. } \mathrm{R}^{\prime} \mathrm{MgX} \text {, ether }}{\text { 2. } \mathrm{H}_{3} \mathrm{O}^{+}} \quad \stackrel{\text { R }}{\stackrel{\mathrm{O}}{\mathrm{C}}>_{\mathrm{R}^{\prime}}}+\mathrm{NH}_{3}
$$


Additional Problems -


Visualizing Chemistry -

PROBLEM Give IUPAC names for the following carboxylic acids (reddish brown $=\mathrm{Br}$ ):


Visualizing Chemistry -


Visualizing Chemistry -

PROBLEM Would you expect the following carboxylic acids to be more acidic or less acidic than benzoic acid?
20-18 Explain. (Reddish brown $=\mathrm{Br}$.)
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0721.jpg?height=375&width=470&top_left_y=1591&top_left_x=486)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0721.jpg?height=394&width=594&top_left_y=1597&top_left_x=1031)


Visualizing Chemistry -

PROBLEM The following carboxylic acid can't be prepared from an alkyl halide by either the nitrile hydrolysis
20-19 route or the Grignard carboxylation route. Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0721.jpg?height=345&width=467&top_left_y=2148&top_left_x=436)


Visualizing Chemistry -

PROBLEM Electrostatic potential maps of anisole and thioanisole are shown. Which do you think is the 20-20 stronger acid, $p$-methoxybenzoic acid or $p$-(methylthio) benzoic acid? Explain.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0722.jpg?height=367&width=457&top_left_y=321&top_left_x=433)


Visualizing Chemistry -

Anisole $\left(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OCH}_{3}\right)$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0722.jpg?height=367&width=484&top_left_y=321&top_left_x=1013)


Visualizing Chemistry -

Thioanisole $\left(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{SCH}_{3}\right)$


Mechanism Problems -

PROBLEM Predict the product(s) and write the mechanism of each of the following reactions:


Mechanism Problems -


Mechanism Problems -

1. Mg
$\xrightarrow[\text { 3. } \mathrm{H}_{3} \mathrm{O}^{+}]{\text {2. } \mathrm{CO}_{2}}$ ?
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0722.jpg?height=123&width=388&top_left_y=920&top_left_x=950)


20-22 (a) -


20-22 (a) -

PROBLEM Predict the product(s) and write the complete mechanism of each of the following reactions:
20-24 (a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0722.jpg?height=199&width=692&top_left_y=1635&top_left_x=478)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0722.jpg?height=136&width=736&top_left_y=1851&top_left_x=483)


20-22 (a) -

PROBLEM Acid-catalyzed hydrolysis of a nitrile to give a carboxylic acid occurs by initial protonation of the
20-25 nitrogen atom, followed by nucleophilic addition of water. Review the mechanism of base-catalyzed nitrile hydrolysis in Section 20.7 and then predict the products for the following reactions. Write the steps involved in the acid-catalyzed reaction, using curved arrows.
(a)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0722.jpg?height=112&width=424&top_left_y=2199&top_left_x=482)
(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0722.jpg?height=123&width=549&top_left_y=2204&top_left_x=986)


20-22 (a) -

PROBLEM Nitriles can be converted directly to esters by the Pinner reaction, which first produces an
$\mathbf{2 0 - 2 6}$ iminoester salt that is isolated and then treated with water to give the final product. Propose a mechanism for the Pinner reaction using curved arrows to show the flow of electrons at each step.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0723.jpg?height=253&width=1182&top_left_y=180&top_left_x=401)


20-22 (a) -

PROBLEM Naturally occurring compounds called cyanogenic glycosides, such as lotaustralin, release
20-27 hydrogen cyanide, HCN, when treated with aqueous acid. The reaction occurs by hydrolysis of the acetal linkage to form a cyanohydrin, which then expels HCN and gives a carbonyl compound.
(a) Show the mechanism of the acetal hydrolysis and the structure of the cyanohydrin that results.
(b) Propose a mechanism for the loss of HCN, and show the structure of the carbonyl compound that forms.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0723.jpg?height=182&width=448&top_left_y=787&top_left_x=475)


Lotaustralin -

PROBLEM 2-Bromo-6,6-dimethylcyclohexanone gives 2,2-dimethylcyclopentanecarboxylic acid on treatment
20-28 with aqueous NaOH followed by acidification, a process called the Favorskii reaction. Propose a mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0723.jpg?height=205&width=803&top_left_y=1139&top_left_x=409)


Lotaustralin -

PROBLEM Naturally occurring compounds called terpenoids, which we'll discuss in Section 27.5, are
20-29 biosynthesized by a pathway that involves loss of $\mathrm{CO}_{2}$ from 3-phosphomevalonate 5-diphosphate to yield isopentenyl diphosphate. Use curved arrows to show the mechanism of this reaction.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0723.jpg?height=386&width=1294&top_left_y=1515&top_left_x=410)


Lotaustralin -

PROBLEM In the Ritter reaction, an alkene reacts with a nitrile in the presence of strong aqueous sulfuric acid 20-30 to yield an amide. Propose a mechanism.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0723.jpg?height=202&width=747&top_left_y=2016&top_left_x=407)


Naming Carboxylic Acids and Nitriles -


Naming Carboxylic Acids and Nitriles -

PROBLEM Draw structures corresponding to the following IUPAC names:
20-32 (a) cis-1,2-Cyclohexanedicarboxylic acid (b) Heptanedioic acid (c) 2-Hexen-4-ynoic acid
(d) 4-Ethyl-2-propyloctanoic acid (e) 3-Chlorophthalic acid (f) Triphenylacetic acid
(g) 2-Cyclobutenecarbonitrile (h) m-Benzoylbenzonitrile


Naming Carboxylic Acids and Nitriles -

PROBLEM Draw and name the following compounds:
20-33 (a) The eight carboxylic acids with the formula $\mathrm{C}_{6} \mathrm{H}_{12} \mathrm{O}_{2}$
(b) Three nitriles with the formula $\mathrm{C}_{5} \mathrm{H}_{7} \mathrm{~N}$


Naming Carboxylic Acids and Nitriles -

PROBLEM Pregabalin, marketed as Lyrica, is an anticonvulsant drug that is also effective in treating chronic
20-34 pain. The IUPAC name of pregabalin is (S)-3-(aminomethyl)-5-methylhexanoic acid. (An aminomethyl group is $-\mathrm{CH}_{2} \mathrm{NH}_{2}$.) Draw the structure of pregabalin.


Naming Carboxylic Acids and Nitriles -

PROBLEM Isocitric acid, an intermediate in the citric acid cycle of food metabolism, has the systematic name
20-35 ( $2 R, 3 S$ )-3-carboxy-2-hydroxypentanedioic acid. Draw the structure.


Acidity of Carboxylic Acids -

PROBLEM Order the compounds in each of the following sets with respect to increasing acidity:
20-36 (a) Acetic acid, oxalic acid, formic acid
(b) $p$-Bromobenzoic acid, $p$-nitrobenzoic acid, 2,4-dinitrobenzoic acid
(c) Fluoroacetic acid, 3-fluoropropanoic acid, iodoacetic acid


Acidity of Carboxylic Acids -

PROBLEM Arrange the compounds in each of the following sets in order of increasing basicity:
20-37 (a) Magnesium acetate, magnesium hydroxide, methylmagnesium bromide
(b) Sodium benzoate, sodium $p$-nitrobenzoate, sodium acetylide
(c) Lithium hydroxide, lithium ethoxide, lithium formate