1. Chapter 19 Substitutions at the Carbonyls
Organic Chemistry II
Fall 1999
Chapter 19 Substitutions at the Carbonyls
 804
Fig. 19.1
reactivity of carbonyls:  807 Table 19.1
resonance, inductive & steric effects:  806 bottom
stability of Y-: equilibrium,  807 mid. (Prob. 19.2)
practice:  , Problem
OrgChem-Chap19
Chapter 15

2. Carboxylic Acid Derivatives: RCO-Y (I)
Organic Chemistry II
Fall 1999
Carboxylic Acid Derivatives: RCO-Y (I)
acyl (acid) chlorides: RCO-Cl (chloride)
SOCl2, PCl3, PCl5;  809 Figure 19.2 ( 360)
the most reactive: preparation of other derivatives
anhydrides: RCO-OCOR’ (carboxylic acid)
from acyl chlorides: with a base,  810 bottom
dehydration of acids: equilibrium,  811 top
practice:  , Problem
OrgChem-Chap19
Chapter 15

3. Carboxylic Acid Derivatives: RCO-Y (II)
Organic Chemistry II
Fall 1999
Carboxylic Acid Derivatives: RCO-Y (II)
esters: RCO-OR’ (alcohol)
from acyl chlorides / anhydrides:  811 bot.-812 top
Fischer esterification: acid & alcohol,  812 middle
mechanism: acid catalyst/equilibrium,  813 Figure 19.3
lactones: cyclic esters,  813 top
practice:  814, Problem
OrgChem-Chap19
Chapter 15

4. Carboxylic Acid Derivatives: RCOY (III)
Organic Chemistry II
Fall 1999
Carboxylic Acid Derivatives: RCOY (III)
amides: RCO-NR’R’’ (amine)
from acyl chlorides / anhydrides:  824 top
1 eq. of base required not to protonate the amine
from acids: lactams / imides,  824 bottom
5- or 6-membered rings favored
type of amides: 1o: -NH2, 2o: -NHR, 3o: -NR1R2
practice:  825, Problem 19.15
OrgChem-Chap19
Chapter 15

5. Preparation of Carboxylic Acids
Organic Chemistry II
Fall 1999
Preparation of Carboxylic Acids
hydrolysis of acid derivatives: RCOY  RCO2H
acyl chlorides & anhydrides: reactive,  815 middle
esters: acidic / basic conditions,  816 Figure 19.4
preparation of soap: saponification,  , Focus On
cleavage of the acyl C-O bond: isotopic exp.;  817 top
amides: harsh conditions, Figure 19.5 &  819 top
nitriles: amide intermediate,  822 & Figure 19.6
R-CO2H  R-CH2X  R-CH2CO2H:  823 top
practice:  , Problem
OrgChem-Chap19
Chapter 15

6. Hydride Addition: LiAlH4, Alcohols
Organic Chemistry II
Fall 1999
Hydride Addition: LiAlH4, Alcohols
RCOCl/RCO2COR’/RCO2R’/(RCO2H): RCH2OH
1o alcohols: 2(3) eq. of H-, Figure &  827 bot.
NaBH4: slow with esters,  828 middle reaction
RCONR’R”/RCN: amines,  829 & Figure 19.9
RCOCl  RC(O)H: LiAlH(OtBu)3 (LTBA),  831
RCO2R’  RC(O)H: (i-Bu)2AlH (DIBALH),  832
practice:  , Problem
OrgChem-Chap19
Chapter 15

7. Organometallic Addition
Organic Chemistry II
Fall 1999
Organometallic Addition
organolithium/Grignard reagents: alcohols
RCOCl/RCO2COR’/RCO2R’:  833 & Fig 19.10
addition to RCN: ketone,  834 bot & Fig 15.11
organocuprates: slow with RCHO/RCOR’
RCOCl:  834 middle reactions
practice:  , Problem
OrgChem-Chap19
Chapter 15

8. Sulfur & Phosphorus Analogues
Organic Chemistry II
Fall 1999
Sulfur & Phosphorus Analogues
sulfonic acid: RSO2-OH
RSO2-Cl (sulfonyl chloride), RSO2-OR’ (sulfonate), RSO2-NR’R” (sulfonamide): 
phosphoric acid: (O)P(OH)3; 
(O)P-Cl3 (phosphoryl chloride), (HO)2P(O)-O-(O)P(HO)2 (pyrophosphoric acid), (O)P-(OR)3’ (triphosphate), (O)P-(NR2)3’ (phosphoric triamide)
nerve gases & pesticides:  Focus On
review:  841-2, Table 19.2
OrgChem-Chap19
Chapter 15