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O R-COOH, R-CO2H, R C OH
Common names: HCO2H CH3CO2H CH3CH2CO2H CH3CH2CH2CO2H CH3CH2CH2CH2CO2H formic acid acetic acid L. formica ant L. acetum vinegar
propionic acid G. first salt butyric acid valeric acid L. butyrum butter L. valerans
Carboxylic acids, common names: CH3(CH2)4CO2H CH3(CH2)5CO2H CH3(CH2)6CO2H CH3(CH2)7CO2H CH3(CH2)8CO2H CH3(CH2)9CO2H CH3(CH2)10CO2H caproic acid --caprylic acid --capric acid --lauric acid oil of lauryl L. caper goat
E bromovaleric acid
F -methylbutyric acid
isovaleric acid
COOH benzoi i
special names
COOH CH3
COOH
COOH
CH3 CH3
o ol i
m ol i
p ol i
IUPAC nomenclature for carboxylic acids: parent chain = longest, continuous carbon chain that contains the carboxyl group alkane, drop e, add oic acid HCOOH CH3CO2H CH3CH2CO2H CH3 CH3CHCOOH Br CH3CH2CHCO2H methanoic acid ethanoic acid propanoic acid
2-methylpropanoic acid
2-bromobutanoic acid
dicarboxylic acids: HOOC-COOH HO2C-CH2-CO2H HO2C-CH2CH2-CO2H HO2C-CH2CH2CH2-CO2H HOOC-(CH2)4-COOH HOOC-(CH2)5-COOH Oh, my! Such good apple pie! oxalic acid malonic acid succinic acid glutaric acid adipic acid pimelic acid
CO2H
CO2H
H H
C C
COOH COOH
H HOOC
C C
COOH H
maleic aci
f maric aci
salts of carboxylic acids: name of cation + name of acid: drop ic acid, add ate
CH3CO2Na
CH3CH2CH2CO2NH4
(CH3CH2COO)2Mg
HO
O C
OH
HO
O C
ONa
carbonic aci
NaO
O C
ONa
physical properties: polar + hydrogen bond water insoluble exceptions: four carbons or less acidic turn blue litmus red relatively high mp/bp
soluble in 5% NaOH
RCO2H + NaOH
stronger acid stronger base
RCO2-Na+ + H2O
weaker base weaker acid
Carboxylic acids are insoluble in water, but soluble in 5% NaOH. 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.
Carboxylic acids, syntheses: 1. oxidation of primary alcohols RCH2OH + K2Cr2O7 2. oxidation of arenes ArR + KMnO4, heat ArCOOH RCOOH
3. carbonation of Grignard reagents RMgX + CO2 4. hydrolysis of nitriles RCN + H2O, H+, heat RCOOH RCO2MgX + H+ RCOOH
1. oxidation of 1o alcohols:
CH3CH2CH2CH2-OH + CrO3
n-butyl alcohol 1-butanol
CH3CH2CH2CO2H
butyric acid butanoic acid
CH3 CH3CHCOOH
isobutyric acid 2-methylpropanoic acid
2. oxidation of arenes:
CH3 tol ene KMnO4, heat COOH benzoic acid
CH3
KMnO4, heat
COOH
H3C p-xylene
RMgX +
O C O
O R C O-
MgX
O R C OH
CH3
CH3 C
2
CH3 H+
Br
MgBr
4. Hydrolysis of a nitrile: H2O, H+ R-C|N heat H2O, OHR-C|N heat R-X + NaCN
1o alkyl halide
R-CO2H
R-CO2- + H+
R-CO2H
RCOOH
CH3 toluene
Br2, hv
CH2 C
CH2 H Mn
4
CH3 Mn
4,
heat C
2H
Br
Mg
MgBr C
2;
then H+
C N H2 , H+, heat
carboxylic acids, reactions: 1. as acids 2. conversion into functional derivatives a) b) c) acid chlorides esters amides
as acids: a) with active metals RCO2H + Na b) with bases RCO2H + NaOH c) relative acid strength? CH4 < NH3 < HC|CH < ROH < HOH < H2CO3 < RCO2H < HF d) quantitative HA + H2O ' H3O+ + AKa = [H3O+] [A-] / [HA] ionization in water RCO2-Na+ + H2O RCO2-Na+ + H2(g)
Ka for carboxylic acids } 10-5 Why are carboxylic acids more acidic than alcohols? ROH + H2O ' H3O+ + RORCOOH + H2O ' H3O+ + RCOOGo = -2.303 R T log Keq The position of the equilibrium is determined by the free energy change, Go. Go = H-T S
Go } H @Ka is inversely related to H, the potential energy difference between the acid and its conjugate base. The smaller the H, the larger the Ka and the stronger the acid.
H3
+ A-
potential energy
HA + H2
ionization
The smaller the H, the more the equilibrium lies to the right, giving a larger Ka ( a stronger acid ).
O R C O-
OR C O
O R C O
Resonance stabilization of the carboxylate ion decreases the H, shifts the ionization in water to the right, increases the Ka, and results in carboxylic acids being stronger acids.
-Cl is electron withdrawing and delocalizes the negative charge on the carboxylate ion, lowering the PE, decreasing the H, shifting the ionization to the right and increasing acid strength.
Electron withdrawing groups will stabilize the anion, decrease the H, shift the ionization to the right, increasing the Ka, increasing acid strength.
COOG
Electron donating groups will destabilize the anion, increase the H, shift the ionization in water to the left, decreasing the Ka, decreasing acid strength.
COOG
-NH2, -NHR, -NR2 -OH -OR -NHCOCH3 -C6H5 -R -H -X -CHO, -COR -SO3H -COOH, -COOR -CN -NR3+ -NO2
electron donating
electron withdrawing
Relative acid strength? Ka p-aminobenzoic acid p-hydroxybenzoic acid p-methoxybenzoic acid p-toluic acid benzoic acid p-chlorobenzoic acid p-nitrobenzoic acid 1.4 x 10-5 2.6 x 10-5 3.3 x 10-5 4.2 x 10-5 6.3 x 10-5 10.3 x 10-5 36 x 10-5
CO2H + SOCl2
COCl
O CH3CH2CH2 C OH
PCl3 CH3CH2CH2 C
O Cl
b)
esters H+
direct esterification:
RCOOH + ROH ' 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
-convert the acid into the acid chloride first; not reversible
O C OH SOCl2
H+ + CH3OH
O + H2O C O CH3
O C Cl
CH3OH
c)
amides
RCOCl + NH3
O Cl NH3
RCONH2 amide
O NH2
Directly reacting ammonia with a carboxylic acid results in an ammonium salt: RCOOH + NH3 RCOO-NH4+ acid base
O C OH
PCl3
O C Cl
NH3
O C NH2 amide
NH3
O C O
NH4
ammoni m salt
Li lH4
CH3CH2CH2CH2CH2CH2CH2CH2OH 1-Octanol
Carboxylic acids resist catalytic reduction under normal conditions. RCOOH + H2, Ni NR
O CH2 C OH LiAlH4 H+
H2, Pt
NR
CH2CH2OH
X2 = Cl2, Br2
Br2,P
RCH2COOH + Br2,P
RCHCOOH + HBr
+
nH e ;th OH Na
RCHCOOH OH
aminoacid
NR
spectroscopy:
IR: -COOH
OH stretch 2500 3000 cm-1 (b) C=O stretch 1680 1725 (s)
nmr: -COOH
10.5 12 ppm
p-toluic acid
-COOH stretch
C=O
COOH c b CH3 a
Carboxylic acids, syntheses: 1. oxidation of primary alcohols RCH2OH + K2Cr2O7 2. oxidation of arenes ArR + KMnO4, heat ArCOOH RCOOH
3. carbonation of Grignard reagents RMgX + CO2 4. hydrolysis of nitriles RCN + H2O, H+, heat RCOOH RCO2MgX + H+ RCOOH
carboxylic acids, reactions: 1. as acids 2. conversion into functional derivatives a) b) c) acid chlorides esters amides