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Chapter 21:Chapter 21:

Carboxylic Acid DerivativesCarboxylic Acid DerivativesCarboxylic Acid DerivativesCarboxylic Acid Derivatives

284
?Class I carbonyl compounds are those that will react by acyl substitutions. They are all derivatives of carboxylic acids: RH O RR O cannot be replaced by a nucleophile 285

Class II

aldehydeketone R OH O ROR O RO O RX O RNH2 OO R carboxylic acidesteranhydrideacyl halides amidescompounds with groups that can be replaced by a nucleophile

Class I

?Physical Properties (21-3) ?Boiling points increases with the strength of the dipolar interactions. 286

?The large boiling points of nitriles, acids and amides is due to the strong dipolar forces that are found in these compounds.

287
?Interconversion of Acid Derivatives(21-5)

Acid derivatives normally react by nucleophilic

acyl substitution. The general mechanism of this process is given below. Following this mechanism, it is possible to transform one acid derivative into another one. 288

?The reactivity of acid derivatives can be correlated to the leaving group ability of the base that is expelled. The better the leaving group, the more reactive will be the acid derivative. Not surprising

that acid chloride are the most reactive derivatives. 289
?This is the reason ketones and aldehydes will not react by acyl substitutions. The leaving group is either R -or H-, which are very basic, therefore poor leaving groups OO 290
RH poor leaving groups

?In theory, it is possible to go from one acid derivatives to another one. In practice, only the following reactions are normally used.

Rule: a more

Rule: a more

reactive intermediate can be converted into a less reactive one. 291
Conversion of Acid Chloride to AnhydrideConversion of Acid Chloride to Anhydride 292
Conversion of Acid Chloride to EstersConversion of Acid Chloride to Esters 293
Conversion of Acid Chloride to AmidesConversion of Acid Chloride to Amides 294
Conversion of Anhydrides to EstersConversion of Anhydrides to Esters 295
Conversion of Anhydrides to AmidesConversion of Anhydrides to Amides 296

Practice QuestionsPractice Questions

?If you were starting with acetyl chloride, what nucleophile would you use to prepare the following compounds.

O O 297

NHCH2CH3

O ?Write a detailed stepwise mechanism of the reaction taking place between acetyl chloride and water. 298
Conversion of Esters to Amides Conversion of Esters to Amides ((AmmonolysisAmmonolysis)) 299

?In all of these reactions, the key feature was the basicity of the nucleophile and leaving group. If the nucleophile is more basic than the leaving group, the reaction will proceed. However, if the nucleophile is less basic than the leaving group, no reaction will occur. Hence, knowing pKa is important.

NH2 O

NaClCl

O NaNH2 300
this reaction will not proceed since Cl- is a weaker base than NH 2- Cl O

NaNH2NH2

O NaCl however this reaction is easy since the leaving group Cl -is a weaker base than NH 2- •Transesterification(21-6)

This reaction is very similar to the hydrolysis

reaction (see 21-7). The only difference is that an alcohol is used in large excess instead of water.

This results in the formation of a new ester, one

that has the structure of the alcohol that was used in excess. The reaction can be performed under basic or acidic conditions, the latter being more common.common. 301
Mechanism of Mechanism of TransesterificationTransesterification 302
?Hydrolysis of Acid Derivatives(21-7)

This reaction is the reason all of these

compounds are considered acid derivatives...because they produce carboxylic acids upon hydrolysis. This reaction can be performed under acidic or basic conditions. Acid Chlorides/AnhydridesAcid Chlorides/Anhydrides

These two compounds are so reactive that the

hydrolysis can be performed under neutral conditions. 303

Esters

Esters can be hydrolyzed under acidic or

basic conditions. Under basic conditions, the reaction is known as " saponification" 304
?Under acidic conditions, the mechanism of hydrolysis is the reversed of the Fisher Esterification. H OCH3 OH+OH OCH3 OH H OH OCH3 OH H+ OCH3 O H2O 305
OH O B-H OH OCH3 OH+ HH+B- OH O

Amides

Amides also hydrolyze to acids

under basic or acidic conditions. 306
Base Catalyzed Hydrolysis of AmidesBase Catalyzed Hydrolysis of Amides 307
Acid Catalyzed Hydrolysis of AmidesAcid Catalyzed Hydrolysis of Amides 308

Nitriles

Nitriles are considered acid derivatives

because they generate the corresponding acids under hydrolysis conditions.

Reactions can be performed under acidic

or basic conditions. 309
Base Catalyzed Hydrolysis of Base Catalyzed Hydrolysis of NitrilesNitriles 310

Practice QuestionPractice Question

?What product would be formed from the acid- catalyzed hydrolysis of the following esters? 311
•Reduction(21-8)

Like other compounds bearing C=O functions,

acid derivatives can be reduced easily using reagents such as (LiAlH

4). The majority of the

reductions of acid derivatives give the corresponding primary alcohols. Aldehydes and amines can also be generated. Esters(formation of 1o alcohol)Esters(formation of 1o alcohol) 312
Mechanism of Ester ReductionMechanism of Ester Reduction 313

Acid Chlorides

They can be reduced to the

corresponding primary alcohols with LiAlH

4. However, the use of a bulkier

reagent prevents the reduction to continue past the aldehyde product. 314

Amides(formation of amines)

Amides are reduced to 1

o, 2oor 3oamines with LiAlH 4. 315
Mechanism of Amide ReductionMechanism of Amide Reduction 316

Nitriles

In a similar reactions, nitriles can also be

reduced to the corresponding primary alcohols. 317
?Reactions of Acids Derivatives with Grignards (21-9)

We have seen that esters and acid chlorides add

two equivalents of Grignard reagent to give tertiary alcohols. 318

Nitriles

Nitriles also react with Grignard reagent

to give the corresponding imine. Under acidic conditions, imines are easily converted to the corresponding ketones (see Chapter 18-16) 319
SummarySummary: Acid Chlorides (21: Acid Chlorides (21--10)10) 320
321
SummarySummary: Anhydrides (21: Anhydrides (21--11)11) 322

SummarySummary: Esters (21: Esters (21--12)12)

323

SummarySummary: Amides (21: Amides (21--13)13)

324

SummarySummary: : NitrilesNitriles (21(21--14)14)

325
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