Remaining Schedule Carboxylic Acids & Derivatives
2/18/2010
Remaining Schedule
Carboxylic Acids & Derivatives
Carboxylic Acids & Derivatives de ydes and a d Ketones eto es Aldehydes
Acids1.pdf
Amines
Midterm 2 - 15 March (alcohols, ethers, acids & derivs)
Structure, Nomenclature & Preparation of Acids
1
2
O H
O H
O
formic
H
CH3
CH3
CH3CH2
O H O O H O
formic acetic
O H
ACIDS
ACIDS
3
4
O H
O H O
O
formic
H
acetic propionic
CH3
ACIDS
O H
CH3CH2 CH3CH2CH2
5
O H O O H O O H O
formic acetic propionic
ACIDS
butyric
O H
6
1
2/18/2010
O H CH3
CH3CH2 CH3CH2CH2
O H O
formic acetic
O H O
propionic
O H O
CH3
CH3CH2 CH3CH2CH2
acetic
O H O
CH3
CH3CH2 CH3CH2CH2
O H O O H O O H O
CH3CH2CH2CH2
IUPAC
-OIC ACID
propionic
acetic
O H O
CH3
butyric
CH3CH2CH2
11
CH3CH2CH2CH2
-OIC ACID
butyric
O H
valeric
O H
10
O H O
methanoic
O H O O H O
ethanoic
IUPAC
-OIC ACID
propanoic butyric
O H O
valeric
IUPAC
propionic
O H O
O H
CH3CH2
O H
O H
O H O
methanoic
O 9
ethanoic
CH3
CH3CH2CH2
valeric
methanoic
O H
CH3CH2
butyric
O CH3CH2CH2CH2
-OIC ACID
O H
O H
8
IUPAC
propionic
O H O
O H
COMMON NAME 7
formic
O CH3CH2CH2CH2
O H
-chloro--methylbutyric acid
valeric
O H
O H O
O
butyric
O H
CH3
ACIDS
O H O
CH3CH2CH2CH2
Cl-CH2CH2CH
O H
valeric 12
2
2/18/2010
O H CH3
CH3CH2 CH3CH2CH2
methanoic
O H O
ethanoic
O H O
-OIC ACID
4 3 2 1O Cl-CH2CH2CH CH3
propanoic
O H O
butanoic IUPAC
pentanoic
O H
13
14
O R
R
O
O- M +
SALTS
O
ESTERS
OR'
H
CH3
CH3CH2 CH3CH2CH2
O O
methanoate ethanoate
O O
15
O
CH3CH2CH2CH2
SALTS ESTERS
propanoate
O O
butanoate
O
O
CH3CH2
O H
4-chloro-2-methylbutanoic acid
O H O
CH3CH2CH2CH2
IUPAC
pentanoate
O
16
SALTS
SALTS
ESTERS
ESTERS ammonium propanoate
O
propanoic
CH3CH2
O H
O
-
+
NH4
17
18
3
2/18/2010
O
-
SALTS
ESTERS
ESTERS
Ammonium 3,3di hl dichloropropionate i t
O Cl2CHCH2
SALTS
O Cl2CHCH2
Methyl 3,3di hl dichloropropionate i t
O CH3
+
NH4
19
O H O
20
O O H
O
oxalic
H O
O O H
oxalic
Rhubarb
DIACIDS
Sorrel
21
O
O
H O O H O O CH2 O H H O
22
O
oxalic malonic
DIACIDS
23
DIACIDS
O
H O O H O O CH2 O H H O O O ( CH2)2 O H H O
oxalic malonic succinic
DIACIDS
24
4
2/18/2010
O
O
O
H O O H O O CH2 O H H O O O ( CH2)2 O H H O
oxalic malonic succinic
DIACIDS
succinum = amber in Latin 25
O
O
O
H O O H O
H O O H O
( CH2 )4 ( CH2 )5
O H O O H
malonic succinic
DIACIDS
glutaric
( CH2 )4 ( CH2 )5
pimelic
H O
DIACIDS
glutaric adipic
O H O
pimelic
O H
26
oh
H O O H O O CH2 O H H O O O ( CH2)2 O H H O O O ( CH2 )3 O H H O
H O O 27
succinic
O
my such
( CH2 )4 ( CH2 )5
DIACIDS
good
O
O
adipic
malonic
O
O
O
H O O H O O CH2 O H H O O O ( CH2)2 O H H O O O ( CH2 )3 O H H O
oxalic
H O O H O O CH2 O H H O O O ( CH2)2 O H H O O O ( CH2 )3 O H H O
O
oxalic
O
apple
O H O
pie
O H
28
SOME FAMOUS ACIDS O HO
Citric
C
OH CH2 C C
EDTA
O
O CH2 C
OH
OH
Glutamic
Citric acid 29
30
5
2/18/2010
HO
O C
H 2C
EDTA N
CH2
CH2
O
N
C
CH2 CH2
H 2C
C
O
HO
OH
C
OH
O
Ethylenediaminetetraacetic acid 31
32
EDTA
Glutamic acid O
O HO
C
CH
CH2
CH2
C
OH
NH2
NaOH O HO
C
O CH
CH2
CH2
C
-
O Na
+
NH2
Monosodium glutamate
CHELATING AGENT
33
MSG
34
Preparation of Carboxylic Acids 1. Oxidation of alcohols (RCH2OH RCO2H) 2 Oxidation of alkenes (RCH=CHR 2. (RCH=CHR’ RCO2H + R’CO R CO2H) 3. Oxidation of alkylbenzenes (Ph-Alk PhCO2H) 4. Grignard reaction with CO2 (RMgX + CO2 RCO2H) 5. Hydrolysis of nitriles (R-CN RCO2H) 35
36
6
2/18/2010
Oxidation of alcohols H R C OH H
[O]
O R C OH
H R C R OH
[O]
Oxidation of aldehydes O R C OH
O R C H
[O]
37
Oxidation of alkenes
O R C OH
38
KMnO4
KMnO4
39
KMnO4
40
KMnO4
41
42
7
2/18/2010
Oxidation of alkylbenzenes KMnO4
+
43
44
Oxidation of alkylbenzenes
Grignard Reaction with CO2
O OH
45
46
Example:
What substrate WILL NOT react with Grignard reagent B
3.
C
4.
D H3C CH CH2
5.
E H3 C C C H
6.
F
N
7.
G
O N+ O-
CH3
H H 0%
0%
0%
0%
0%
0%
F
5
O CH3 H3 C C O H
0%
G
47
2.
E
CH3
O C O H3C C CH3
D
CH3
A
C
1.
A
OH
B
O
8
2/18/2010
Preparation of Nitriles
Hydrolysis of Nitriles R C N
H2O
O R
+
NH3
OH
49
50
9
Remaining Schedule
Carboxylic Acids & Derivatives
Carboxylic Acids & Derivatives de ydes and a d Ketones eto es Aldehydes
Acids1.pdf
Amines
Midterm 2 - 15 March (alcohols, ethers, acids & derivs)
Structure, Nomenclature & Preparation of Acids
1
2
O H
O H
O
formic
H
CH3
CH3
CH3CH2
O H O O H O
formic acetic
O H
ACIDS
ACIDS
3
4
O H
O H O
O
formic
H
acetic propionic
CH3
ACIDS
O H
CH3CH2 CH3CH2CH2
5
O H O O H O O H O
formic acetic propionic
ACIDS
butyric
O H
6
1
2/18/2010
O H CH3
CH3CH2 CH3CH2CH2
O H O
formic acetic
O H O
propionic
O H O
CH3
CH3CH2 CH3CH2CH2
acetic
O H O
CH3
CH3CH2 CH3CH2CH2
O H O O H O O H O
CH3CH2CH2CH2
IUPAC
-OIC ACID
propionic
acetic
O H O
CH3
butyric
CH3CH2CH2
11
CH3CH2CH2CH2
-OIC ACID
butyric
O H
valeric
O H
10
O H O
methanoic
O H O O H O
ethanoic
IUPAC
-OIC ACID
propanoic butyric
O H O
valeric
IUPAC
propionic
O H O
O H
CH3CH2
O H
O H
O H O
methanoic
O 9
ethanoic
CH3
CH3CH2CH2
valeric
methanoic
O H
CH3CH2
butyric
O CH3CH2CH2CH2
-OIC ACID
O H
O H
8
IUPAC
propionic
O H O
O H
COMMON NAME 7
formic
O CH3CH2CH2CH2
O H
-chloro--methylbutyric acid
valeric
O H
O H O
O
butyric
O H
CH3
ACIDS
O H O
CH3CH2CH2CH2
Cl-CH2CH2CH
O H
valeric 12
2
2/18/2010
O H CH3
CH3CH2 CH3CH2CH2
methanoic
O H O
ethanoic
O H O
-OIC ACID
4 3 2 1O Cl-CH2CH2CH CH3
propanoic
O H O
butanoic IUPAC
pentanoic
O H
13
14
O R
R
O
O- M +
SALTS
O
ESTERS
OR'
H
CH3
CH3CH2 CH3CH2CH2
O O
methanoate ethanoate
O O
15
O
CH3CH2CH2CH2
SALTS ESTERS
propanoate
O O
butanoate
O
O
CH3CH2
O H
4-chloro-2-methylbutanoic acid
O H O
CH3CH2CH2CH2
IUPAC
pentanoate
O
16
SALTS
SALTS
ESTERS
ESTERS ammonium propanoate
O
propanoic
CH3CH2
O H
O
-
+
NH4
17
18
3
2/18/2010
O
-
SALTS
ESTERS
ESTERS
Ammonium 3,3di hl dichloropropionate i t
O Cl2CHCH2
SALTS
O Cl2CHCH2
Methyl 3,3di hl dichloropropionate i t
O CH3
+
NH4
19
O H O
20
O O H
O
oxalic
H O
O O H
oxalic
Rhubarb
DIACIDS
Sorrel
21
O
O
H O O H O O CH2 O H H O
22
O
oxalic malonic
DIACIDS
23
DIACIDS
O
H O O H O O CH2 O H H O O O ( CH2)2 O H H O
oxalic malonic succinic
DIACIDS
24
4
2/18/2010
O
O
O
H O O H O O CH2 O H H O O O ( CH2)2 O H H O
oxalic malonic succinic
DIACIDS
succinum = amber in Latin 25
O
O
O
H O O H O
H O O H O
( CH2 )4 ( CH2 )5
O H O O H
malonic succinic
DIACIDS
glutaric
( CH2 )4 ( CH2 )5
pimelic
H O
DIACIDS
glutaric adipic
O H O
pimelic
O H
26
oh
H O O H O O CH2 O H H O O O ( CH2)2 O H H O O O ( CH2 )3 O H H O
H O O 27
succinic
O
my such
( CH2 )4 ( CH2 )5
DIACIDS
good
O
O
adipic
malonic
O
O
O
H O O H O O CH2 O H H O O O ( CH2)2 O H H O O O ( CH2 )3 O H H O
oxalic
H O O H O O CH2 O H H O O O ( CH2)2 O H H O O O ( CH2 )3 O H H O
O
oxalic
O
apple
O H O
pie
O H
28
SOME FAMOUS ACIDS O HO
Citric
C
OH CH2 C C
EDTA
O
O CH2 C
OH
OH
Glutamic
Citric acid 29
30
5
2/18/2010
HO
O C
H 2C
EDTA N
CH2
CH2
O
N
C
CH2 CH2
H 2C
C
O
HO
OH
C
OH
O
Ethylenediaminetetraacetic acid 31
32
EDTA
Glutamic acid O
O HO
C
CH
CH2
CH2
C
OH
NH2
NaOH O HO
C
O CH
CH2
CH2
C
-
O Na
+
NH2
Monosodium glutamate
CHELATING AGENT
33
MSG
34
Preparation of Carboxylic Acids 1. Oxidation of alcohols (RCH2OH RCO2H) 2 Oxidation of alkenes (RCH=CHR 2. (RCH=CHR’ RCO2H + R’CO R CO2H) 3. Oxidation of alkylbenzenes (Ph-Alk PhCO2H) 4. Grignard reaction with CO2 (RMgX + CO2 RCO2H) 5. Hydrolysis of nitriles (R-CN RCO2H) 35
36
6
2/18/2010
Oxidation of alcohols H R C OH H
[O]
O R C OH
H R C R OH
[O]
Oxidation of aldehydes O R C OH
O R C H
[O]
37
Oxidation of alkenes
O R C OH
38
KMnO4
KMnO4
39
KMnO4
40
KMnO4
41
42
7
2/18/2010
Oxidation of alkylbenzenes KMnO4
+
43
44
Oxidation of alkylbenzenes
Grignard Reaction with CO2
O OH
45
46
Example:
What substrate WILL NOT react with Grignard reagent B
3.
C
4.
D H3C CH CH2
5.
E H3 C C C H
6.
F
N
7.
G
O N+ O-
CH3
H H 0%
0%
0%
0%
0%
0%
F
5
O CH3 H3 C C O H
0%
G
47
2.
E
CH3
O C O H3C C CH3
D
CH3
A
C
1.
A
OH
B
O
8
2/18/2010
Preparation of Nitriles
Hydrolysis of Nitriles R C N
H2O
O R
+
NH3
OH
49
50
9
