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Chapter 22 Naming Acid hadides (Remove- ic acid and add -yl chloride) O

Cl acetyl chloride or ethanoyl chloride (see also benzoyl chloride)

Anhydrides Symmetrical (Remove acid and add ahydride)

O O

O or ethanoic anhydride Mixed Anhydride (Use both acid names, out in alphabetical order)

O O

O

Acetic benzoic anhydride or Benzoic ethanoic anhydride

Esters (The acid part becomes the root. Remove- ic acid and use –ate as the ending. The alkyl group on the oxygen becomes the first part of the name.) O Cl O O

O Ethyl 2-Chloroethyl benzoate

Amides (Remove- ic acid, oic acid or ylic acid and add -amide) O

N

N-ethyl-N-methylbenzamide Nitriles ( Use alyl name and add nitrile or remove- ic acid and add-onitrile)

N C N C H C Benzonitrile 3 Acetonitile (ethanenitrile)

Lactones and Lactams & other strange examples

O O

O NH 4-Butanolactone or γ-Butyrolactone 4-Butanolactam or γ-Butyrolactam

O OEt EtO

O Diethylsuccinate O O

O NH

O sucinnic anhydride O succinamide

Reactions of acids halides.

Preparation O O SOCl2 OH Cl

Sample Mechanism: Acetyl chloride plus dimethyl . O O 2 eq. (CH3)2NH CH N 3 Cl H C 3 CH N 3 H C 3 H

O : O : Cl Cl H C H C + 3 3 N N

H3C H CH3

.. CH NH 3 Other acid halide reactions:

O O CH 3 OMe O

OH

H2O Me2CuLi MeOH (pyr) (pyr) O OH O CH3 Li(tBuO)3AlH H

CH3 1. 2eq MeMgBr Cl

+ O 2. H3O wkup Et2NH O O O (2 eq) O 2 eq NH3 O O NEt2

NH2

+NH Cl 4

Anhydrides Made from the acid chloride. Reacts in a similar way to the acid halide. A cyclic anhydride can be made from the diacid.

O O

OH heat O OH

O O

O O O H2O OH O

O O O CH3OH OMe O pyridine

O O O CH3NH2 (2 eq)

NHCH3 O

Carboxyllic acids

O CH3OH O

OH H2SO4 OMe

O 1. NH3 O

OH 2. heat NH2

O CH3NH2 O

OH DCC NHCH 3 see mechanism on page 803

Fisher esterification/transesterification mechanism.

H+

O CH3OH O

OH H2SO4 OMe

:OH2 H + O

OMe H .. H H + O : O O + H O OH OH H .. + O O H C H C H 3 CH3OH 3

CH3OH H O

OH O H H3C + H C O H 3

Esters O

O HO OH O H H+, H O 2 OH H O 1. LiAlH 4 + + H , H2O 2. H , H2O wkup - OH , H2O

O 1. CH3Li O HO 2. H+, H O O HO 2 OCH CH wkup 2 3 H+ CH3

CH3 NH3

CH3NH2 1. EtMgBr O 2. H+, H O 2 NH wkup 2 O HO Et NHCH3 Et

Amides

1. LiAlH 4 O 2. H+, H O + H2N 2 O H , H O H 2 wkup OH + + NH4 H NH2

DIBAL-H 2. water OH-, H O O 2

H O O H+, H O 2 OH O

O

CH3

1. CH3MgBr 2. water

1. LiAlH 4 O 2. H+, H O + H2N 2 H , H O H N 2 wkup C OH H

goes through amide DIBAL-H OH-, H O 2. water 2 O O O H H+, H O 2 OH O

goes through amide Acid catalyzed hydrolysis of a nitrile (Compare to the catalyzed hydrolysis on page 818.) H+ :NH3 O H2O H H3C C N + H+ O H O

O H O

+ H C C N 3 H N H H H O H H2O + N H H O H

H H N + H N H + H O + O O H O N H N H + H H H O H H H O H 2