carboxylic acid derivatives and their...
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Carboxylic Acid Derivatives and Their Reactions.
Carboxylic Acid Esters
R C
O
OH R’HO R C
O
R’O+ + H2OH+
Synthesized from a carboxylic acid and an alcohol:
carboxylic acid alcohol or
phenol
ester
Nomenclature base on parent alcohol and carboxylic acid:
CH3 C
O
OH CH3HO CH3 C
O
CH3OCH2CH2 + + H2O
methanolpropanoic acid methyl propanoate
hydrolysis
condensation
C
O
OHC
O
HO CH3HO + excess
terephthalic acidH+
methyl alcohol
C
O
OCH3
dimethyl terephthalate
C
O
CH3O + 2 H2O
A Diester Synthesis
C
O
OHC
O
HO CH2CH2HO + excess
terephthalic acidH+
ethylene glycolethanediol
OH
C
O
OC
O
CH2CH2 O
n
A polyester
A Polyester Synthesis
Hydrolysis Reaction of Esters
Hydrolysis of Esters Under Acidic Conditions
R C
O
OH R’HOR C
O
R’O ++ H2O H+
ester carboxylic acid alcohol or
phenol
Notice that this is the reverse of the condensation reaction used to synthesize an ester !!
Hydrolysis Reaction of Esters
Hydrolysis of Esters Under Basic Conditions
R C
O
O-Na+ R’HOR C
O
R’O ++ NaOHH2O
esteralcohol
or phenol
carboxylate salt
H2O
R C
O
OH + NaOH[ ] The carboxylic acid is an intermediate but reacts with the
basic NaOH !!
Hydrolysis Worksheet
HCl, H2O
CO
O CH2F
F
CH3
CO
O CH2F
F
CH3H
OH
ethyl-2,4-difluoro benzoate
2,4-difluoro benzoic acid ethyl alcohol
NaOH, H2O
OC
O
CH2 CHCH3
CH3
OC
O
CH2 CHCH3
CH3
H
HO
phenyl-3-methyl butanoate
phenol
3-methyl butanoic acid
C
OO
CH2 CHCH3
CH3Na+
sodium 3-methylbutanoate
COCH2 CH
CH3
CH3
ONaOH, H2O
COCH2 CH
CH3
CH3
O
HHO
isobutyl benzoate
benzoic acid
2-methyl-1-propanol2-methylpropyl benzoate
“isobutyl alcohol”
CO
O
Na+
Soaps
Soaps are produced by a process called “saponification” (technically, “basic hydrolysis of fats”)
H2C
C
H2C
OH
O
O
C
C
O
O
C
O
C
C
O
O
C
O
-O
-O
-O
Na+
Na+
Na+
Hot aq NaOH
H2C
C
H2C
OHH
OH
OH
C
O
CH2CH2
CH2CH2
CH2CH2
CH2CH2
CH2CH2
CH2CH2
CH2CH2
CH3-ONa+
Soaps
Soaps are the sodium or potassium salts of long-chain fatty acids.
hydrophilic region
hydrophobic region
How Do Soaps Work?
micelle micelle+grease
Synthetic Detergents
S
O
O-ONa+
O
S
O
-ONa+
O
S
O
-ONa+
O
Sodium Dodecyl Sulfate (SDS)
Sodium Alkyl Benzene Sulfonate (ABS)
Sodium Dodecyl Benzene Sulfonate (LAS)
N+CH2
N+
Synthetic Detergents
Na+
O
O
O
O
OS
O
O
-O
O
O
O
HO
Amides - Synthesis and Nomenclature
CH3 C
O
OH CH3H N+H
CH3 C
O
CH3 N
H>100o C+ H2O
acetic acid methylamine N-methylacetamide
condensation
Amides - Basic Hydrolysis
O
R C R’ N
HH2O, NaOH R C
O
O Na+ R’ N
H
H
O
R C R’ N
H
Two Products
Amides - Basic Hydrolysis
Example
CN
CH2CH3
CH2CH3
O
+ Na + OH-H2O
H-NCH2CH3
CH2CH3Na+
C
O
O +
N,N-diethylbenzamide
sodium benzoate diethylamine
Amides - Acid Hydrolysis
O
R C R’ N
HH2O, H3O+
O
R C R’ N
H
R C
O
OH R’ N
H
HH2O
H3O+ ??
[ ]
R C
O
OH R’ N
H
H
H
+
Hydrolysis Worksheet
Amides - Acid Hydrolysis
Example
CN
CH2CH3
CH2CH3
O
+ H 2SO4H2O
C
O
OH
N,N-diethylbenzamide
benzoic aciddiethylammoniumhydrogen sulfate
+ NCH2CH3
CH2CH3+
H HSO4
H
H CH2CH3CO
NCH2CH2CH3
HCl, H2O
H CH2CH3CO
NCH2CH2CH3
OH
H
HN
HCH2CH3
CH2CH2CH3Cl-
HCl
formic acid
ethylpropylammonium chloride
NO2
CH2CH3CO
NH
NaOH, H2O
NO2
CH2CH3CO
NH
OH
H
NaOH
Na+
CO
O
NO2
ethylamine
sodium 2-nitro-benzoate
C
O
OHC
O
HO CH2CH2HO + excess
terephthalic acidH+
ethylene glycolethanediol
OH
C
O
OC
O
CH2CH2 O
n
A polyester
A Polyester Synthesis
Amides - Condensation Polymers
H2N CH2CH2CH2CH2CH2CH2 NH2CH2CH2CH2CH2C
O
C
O
OHHO +adipic acid hexamethylene diamine
mix at room temperature
CH2CH2CH2CH2C
O
C
O
OO CH2CH2CH2CH2CH2CH2NH3H3N-- + +
H2Oheat
CH2CH2CH2CH2C
O
C
O
CH2CH2CH2CH2CH2CH2NH
NH
C
O
NH )( n
polyhexamethylenediamine adipate
Nylon 6,6
hexamethylene diammonium adipate
Carboxylic Acids and Their Derivatives
Carboxylic Acid Anhydrides and Halides
R C
O
OH RC
O
HO R C
O
ORC
O
+ H2O+H+
Synthesis from a carboxylic acid:
R C
O
OH Cl”“H+ R C
O
Cl + H2O
Very unstable; very “reactive” Low boiling points and melting points
“Lachrymators” Generate the starting acids upon hydrolysis
carboxylic acid carboxylic acid carboxylic acid anhydride
carboxylic acid carboxylic acid chloride
Carboxylic Acid Anhydrides and Halides
Used to Synthesize Esters
CH3 C
O
OCH3C
O
+C
O
OH
O CH3C
O
C
O
OH
OH
ethyl alcohol acetyl chloride ethyl acetate
salicylic acid acetic anhydridesalicyl acetate
acetyl salicylic acid aspirin
CH3C
O
Cl
CH3CH2OH CH3C
O
CH3CH2O+
Cl H+
C
O
CH3HO+
CH3C
O
Cl
CH3CH2OH CH3C
O
CH3CH2O+
CH3 C
O
OCH3C
O
+C
O
OH
O CH3C
O
C
O
OH
OH
These highly reactive compounds are use to transfer the acetyl group to an alcohol group.
CH3C
O
Carboxylic Acid Anhydrides and Halides
Summary of reactivity of carboxylic acid related functional groups:
Acid Anhydrides
Acid HalidesCarboxylic Acid
EstersCarboxylic Acid
Amides Carboxylic Acids
Similar Derivatives of Inorganic Acids
CH3 C
O
OH HO S
O
OH
O
HO P
O
OH
OH
S
O
OCH3CH3O
O
P
O
OCH3CH3O
OCH3
C
O
OCH3CH3
C
O
OCH3C
O
CH3 OHS
O
O S
O
HO
O O
P
O
O OHP
O
HO
OH OH
acetic acid sulfuric acid phosphoric acid
methyl acetate dimethyl sulfate trimethyl phosphate
acetic anhydride pyrosulfuric acid pyrophosphoric acid
Similar Derivatives of Inorganic Acids
C
O
OCH3C
O
CH3 OHS
O
O S
O
HO
O O
P
O
O OHP
O
HO
OH OH
acetic anhydride pyrosulfuric acid pyrophosphoric acid
ANHYDRIDE LINKAGES
“REACTIVE LINKAGES”
“HIGH ENERGY BONDS”
What is ATP??
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