Preparation of carboxylic acid - جامعة البصرة
Transcript of Preparation of carboxylic acid - جامعة البصرة
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Preparation of carboxylic acid
1. Oxidation of primary alcohols
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2. Oxidation of alkylbenzenes (arenes)
.
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CH3
CH3
H3C
CH2CH3
KMnO4, heat
KMnO4, heat
KMnO4, heat
COOH
COOH
HOOC
COOH
toluene benzoic acid
p-xylene terephthalic acid
ethylbenzene benzoic acid
+ CO2
note:! aromatic acids
only
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3-Carbonation of Grignard reagents
The Grignard reagent can be prepared from primary, secondary,
tertiary, or aromatic halides; the method is limited only by the presence
of other reactive groups in the molecule.
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3-Carbonation of Grignard reagents
.
Increases the carbon chain by one carbon
H+
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4- Hydrolysis of nitriles.
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4- Hydrolysis of nitriles
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Reactions of carboxylic acids
The characteristic chemical behaviour of carboxylic
acids is, of course, determined by their functional group,
carboxyl COOH(This group is made up of a carbonyl group
(C= O) and a hydroxyl group (OH)).
1. Acidity. Salt formation.
a-with active metals
b)with bases
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Acidity :the most characteristic property of the carboxylic acids
is the one that gives them their name.
The OH of an acid can be replaced by a number of
groups Cl, OR', NH2 to yield compounds known as
acid chlorides, esters, and amides. These compounds
are called functional derivatives of acids; they all
contain the acyl group:
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lonization of carboxylic acids. Acidity constant
As for any equilibrium, the concentrations of the components are
related by the expression:
Ka = acidity constant.
Ka for carboxylic acids 10-5
Why are carboxylic acids more acidic than alcohols?
ROH + H2O H3O+ + RO-
RCOOH + H2O H3O+ + RCOO-
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Effect of substituent groups on acid
strength of benzoic acids? Electron withdrawing groups will stabilize the anion, decrease the ΔH, shift
the ionization to the right, increasing the Ka, increasing acid strength.
Electron donating groups will destabilize the anion, increase the ΔH, shift
the ionization in water to the left, decreasing the Ka, decreasing acid
strength
COO-
G
COO-
G
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HA + H2O
H3O+ + A-
pote
ntial ene
rgy
ionization
The smaller the ΔH, the more the equilibrium lies to the right, giving a larger Ka ( a
stronger acid ).
ΔH
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R C
O-
O
R C
O-
O
R CO
O
Resonance stabilization of the carboxylate ion decreases the ΔH, shifts the
ionization in water to the right, increases the Ka, and results in carboxylic
acids being stronger acids.
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Effect of substituent groups on acid strength?
CH3COOH 1.75 x 10-5
ClCH2COOH 136 x 10-5
Cl2CHCOOH 5,530 x 10-5
Cl3CCOOH 23,200 x 10-5
-Cl is electron withdrawing and delocalizes the negative charge on the
carboxylate ion, decreasing the ΔH, shifting the ionization to the right and
increasing acid strength.
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-NH2, -NHR, -NR2
-OH
-OR
electron donating
-NHCOCH3
-C6H5
-R
-H
-X=Cl,F,Br
-CHO, -COR
-SO3H
-COOH, -COOR electron withdrawing
-CN
-NR3+
-NO2
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Relative acid strength?
Ka
p-aminobenzoic acid 1.4 x 10-5
p-hydroxybenzoic acid 2.6 x 10-5
p-methoxybenzoic acid 3.3 x 10-5
p-toluic acid 4.2 x 10-5
benzoic acid 6.3 x 10-5
p-chlorobenzoic acid 10.3 x 10-5
p-nitrobenzoic acid 36 x 10-5
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Reduction of acids to alcohol Lithium aluminum hydride, LiAlH4 , is one of the few
reagents that can reduce an acid to an alcohol; the initial
product is an alkoxide from which the alcohol is
liberated by hydrolysis:
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Halogenation of aliphatic acids. Substituted
acids
This is the Hell-Volhard-Zelinsky reaction. Aliphatic
carboxylic acids react smoothly with chlorine or
bromine to yield a compound in which a-hydrogen has
been replaced by halogen(Cl2or Br2 ).
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Halogenation of aliphatic acids. Substituted
acids