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Carboxylic Acids PDF
Carboxylic Acids PDF
Carboxylic acids:
O
R-COOH, R-CO2H, R C
OH
Common names:
HCO2H formic acid L. formica ant
CH3CO2H acetic acid L. acetum vinegar
CH3CH2CO2H propionic acid G. “first salt”
CH3CH2CH2CO2H butyric acid L. butyrum butter
CH3CH2CH2CH2CO2H valeric acid L. valerans
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5 4 3 2 1
C—C—C—C—C=O
δ γ β α used in common names
Br CH3
CH3CH2CH2CHCOOH CH3CHCH2COOH
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COOH
special names
benzoic acid
CH3
CH3
CH3
CH3CHCOOH 2-methylpropanoic acid
Br
CH3CH2CHCO2H 2-bromobutanoic acid
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dicarboxylic acids:
HOOC-COOH oxalic acid
HO2C-CH2-CO2H malonic acid
HO2C-CH2CH2-CO2H succinic acid
HO2C-CH2CH2CH2-CO2H glutaric acid
HOOC-(CH2)4-COOH adipic acid
HOOC-(CH2)5-COOH pimelic acid
CO2H CO2H
CO2H
CO2H CO2H
CO2H
phthalic acid isophthalic acid
terephthalic acid
H COOH H COOH
C C
C C
H COOH HOOC H
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O O
C C
HO OH HO ONa
Na2CO3
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physical properties:
polar + hydrogen bond relatively high mp/bp
water insoluble
exceptions: four carbons or less
acidic turn blue litmus red
soluble in 5% NaOH
RCO2H RCO2-
covalent ionic
water insoluble water soluble
1. Identification.
2. Separation of carboxylic acids from basic/neutral organic
compounds.
The carboxylic acid can be extracted with aq. NaOH and
then regenerated by the addition of strong acid.
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1. oxidation of 1o alcohols:
CH3 CH3
CH3CHCH2-OH + KMnO4 CH3CHCOOH
isobutyl alcohol isobutyric acid
2-methyl-1-propanol` 2-methylpropanoic acid
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2. oxidation of arenes:
KMnO4, heat
CH3 COOH
H3C HOOC
KMnO4, heat
CH2CH3 COOH + CO2
Mg CO2 H+
R-X RMgX RCO2MgX RCOOH
Increases the carbon chain by one carbon.
Mg CO2 H+
CH3CH2CH2-Br CH3CH2CH2MgBr CH3CH2CH2COOH
n-propyl bromide butyric acid
H+
O O O
+ +MgX
RMgX + C R C R C
O- OH
O
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Br MgBr COOH
p-toluic acid
Br2, hv Mg
CH3 CH2Br CH2MgBr
CO2
H+
CH2 COOH
phenylacetic acid
4. Hydrolysis of a nitrile:
H2O, H+
R-CN R-CO2H
heat
H2O, OH-
R-CN R-CO2- + H+ R-CO2H
heat
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Br2, hv NaCN
CH3 CH2Br CH2 CN
toluene
H2O, H+, heat
CH2 COOH
phenylacetic acid
KCN
CH3CH2CH2CH2CH2CH2-Br CH3CH2CH2CH2CH2CH2-CN
1-bromohexane
H2O, H+, heat
CH3CH2CH2CH2CH2CH2-COOH
heptanoic acid
CH2OH
KMnO4
CH3
KMnO4, heat
CO2H
Br MgBr
Mg
CO2; then H+
C N
H2O, H+, heat
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as acids:
a) with active metals
RCO2H + Na RCO2-Na+ + H2(g)
b) with bases
RCO2H + NaOH RCO2-Na+ + H2O
c) relative acid strength?
CH4 < NH3 < HCCH < ROH < HOH < H2CO3 < RCO2H < HF
d) quantitative
HA + H2O H3O+ + A- ionization in water
Ka = [H3O+] [A-] / [HA]
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H3O+ + A-
potential energy
ΔH
HA + H2O
ionization
The smaller the ΔH, the more the equilibrium lies to the
right, giving a larger Ka ( a stronger acid ).
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O O-
R C R C
O- O
O
R C
O
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Electron withdrawing groups will stabilize the anion, decrease the ΔH, shift
the ionization to the right, increasing the Ka, increasing acid strength.
COO-
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-
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O SOCl2 O
R C R C
OH or PCl3 Cl
orPCl5
O PCl3 O
CH3CH2CH2 C CH3CH2CH2 C
OH Cl
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b) esters
―direct‖ esterification: H+
RCOOH + R´OH RCO2R´ + H2O
-reversible and often does not favor the ester
-use an excess of the alcohol or acid to shift equilibrium
-or remove the products to shift equilibrium to completion
―indirect‖ esterification:
RCOOH + PCl3 RCOCl + R´OH RCO2R´
-convert the acid into the acid chloride first; not reversible
O H+ O
C + CH3OH C + H2O
OH O CH3
SOCl2
O CH3OH
C
Cl
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c) amides
―indirect‖ only!
RCOOH + SOCl2 RCOCl + NH3 RCONH2
amide
O O
PCl3 NH3 O
OH Cl NH2
3-Methylbutanoic acid
O PCl3 O NH3 O
C C C
OH Cl NH2
amide
NH3
O
C ammonium salt
O NH4
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3. Reduction:
RCO2H + LiAlH4; then H+ RCH2OH
1o alcohol
LiAlH4 H+
CH3CH2CH2CH2CH2CH2CH2COOH
Octanoic acid
(Caprylic acid)
CH3CH2CH2CH2CH2CH2CH2CH2OH
1-Octanol
O H2, Pt
CH2 C NR
OH
LiAlH4
H+
CH2CH2OH
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COOH
Br2,P
NR (no alpha H)
RCHCOOH RCHCOOH
aminoacid
NH2
OH
KOH(alc)
RCH2CHCOOH RCH=CHCOOH
Br then H+
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NO2
CO2H
H2SO4,SO3
CO2H
SO3H
CO2H
benzoic acid Br2,Fe
Br
CH3Cl,AlCl3
NR
spectroscopy:
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p-toluic acid
-COO—H
stretch
C=O
COOH c
CH3 a
c b a
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