Prerequisite: Chemistry 51
Grading Scheme
Recitation Grade:
Laboratory Grade
Lecture Exams
100 pts
Final
100 pts
Total
400 pts
or
Now for the student D who is outside of the desirable limits (50
95). We move his raw grade up to 70 so that D does not skew the
scaling process. D receives a scaled grade of about 51.
Aqueous Solution
Totally ionized in
aqueous solution.
Example
Recall
OH
CH3CH2OH
pKa = 9.95
Stronger
acid
H2O + PhOH
phenol, PhOH
H3O+ + PhO-
Ka = [H3O+][PhO-]/[PhOH] = 10-
ethanol, EtOH
H2O + EtOH
pKa = 15.9
Weaker acid
H3O+ + EtO-
Ka = [H3O+][EtO-]/[EtOH] = 10-15.9
9.95
CH3O - + H+
CH3OH
CH3NH2
CH3NH - + H+
CH3CH3
CH3CH2- + H+
Increasing
Increasing basicity
electronegativity
of
of anion.
atom bearing negative
charge. Increasing
stability of anion.
CH3OH
CH3SH
Increasing
Increasingsize
basicity
of
atom
of anion.
holding
negative charge.
Increasing stability of
anion.
Acidity
OH
Increasing
resonance
basicity
of
stabilization
the
anion.
. Increased
anion
stability.
phenol, PhOH
CH3CH2OH
ethanol, EtOH
CH3CH2O - + H+
No resonance structures!!
Note that phenol itself enjoys resonance but
charges are generated, costing energy, making
the resonance less important. The more
important resonance in the anion shifts the
equilibrium to the right making phenol more
acidic.
OH
OH
etc.
H+
H
H
acetic acid
Nonbonding
electrons
converted
to pi O H
bonding.
O
Which conjugate
acid is favored?
No valid
resonance
structures for this
cation.
H+
H
acetic acid
Acidity.
H3CCH2OH
F3CCH2OH
H3CCH2O - + H+
Increasing anion
Increasing anion
stability.
basicity.
F3CCH2O - + H+
Due to electronegativity
of F small positive
charges build up on C
resulting in stabilization
of the anion.
Effect drops off with distance. EtOH pKa = 15.9
Increasing Acidity of HA
Increasing Basicity of A-
Note. The NH25. Hybridization of the atom bearing the charge. H-A H+ + A:-.
is more basic
than the RCCsp3
sp2
sp
ion.
More s character, more stability, more electronegative,
H-A more acidic, A:- less basic.
Example of hybridization
Effect.
terminal alkyne
RCCH + LiCH2CH2CH2CH3
base
acid
RCCH + AgNO3
HCH2CH2CH2CH3 + RCCLi
AgCCR (ppt)
non-terminal alkyne
RCCR + LiCH2CH2CH2CH3
RCCR + AgNO3
NR
No Reaction
O
H
H
O
Solvation
provides
stabilization.
OH
OH
H
O
pKa = 15.9
ethanol
17
propan-2-ol
18
2-methylpropan-2-ol
(CH3)3CO -,
crowded
Example
para nitrophenol is more acidic than phenol. Offer an explanation
OH
+ H
OH
+ H
N
O
OH
+ H
N
O
OH
N
O
OH
OH
OH
N
O
Now look at the anion. What does the nitro group do?
Remember we are interested to compare with the phenol
phenolate equilibrium.
O
OH
+ H
N
O
O
O H
COOH
CO2H
Nomenclature - IUPAC
names: drop the -e from the
parent alkane and add the suffix -oic
acid.
acid
IUPAC
O
HCOOH
CH3COOH
Methanoic acid
(Formic acid)
Ethanoic acid
(Acetic acid)
OH
3-Methylbutanoic acid
(Isovaleric acid)
O
OH
OH
OH
trans-3-Phenylpropenoic acid
(Cinnamic acid)
Nomenclature - IUPAC
The carboxyl group takes precedence
over most other functional groups.
OH
OH
(R)-5-Hydroxyhexanoic
acid
OH
5-Oxohexanoic acid
O
H2 N
OH
4-Aminobutanoic acid
Nomenclature - IUPAC
Dicarboxylic acids: add the suffix -dioic
acid to the name of the parent alkane
containing both carboxyl groups.
O
HO
O
OH
O
Ethanedioic acid
(Oxalic acid)
O
HO
O
OH HO
O
Butanedioic acid
(Succinic acid)
HO
O
OH
Propanedioic acid
(Malonic acid)
O
O
OH
HO
OH
O
Pentanedioic acid
(Glutaric acid)
Hexanedioic acid
(Adipic acid)
Nomenclature - IUPAC
COOH
2-Cyclohexenecarboxylic
acid
HOOC
COOH
trans-1,3-Cyclopentanedicarboxylic
acid
to show
the location of substituents.
COOHUse numbers
COOH
COOH
OH
COOH
COOH
Benzoic 2-Hydroxybenzoic 1,2-Benzenedicarboxylic 1,4-Benzenedicarboxylic
acid
acid
acid
acid
(Salicylic acid)
(Phthalic acid)
(Terephthalic acid)
Nomenclature-Common
When common names are used, the
letters etc. are often used to
locate substituents.
O
5
1 OH
4 3 2
O
H2 N
OH
4-Aminobutanoic acid
(-Aminobutyric acid, GABA)
OH
NH2
(S)-2-Aminopropanoic acid
[(S)--Aminopropionic acid;
L-alanine]
Physical Properties
In the liquid and solid states, carboxylic acids are
associated by hydrogen bonding into dimeric
structures.
Physical Properties
Carboxylic acids have significantly higher
boiling points than other types of organic
compounds of comparable molecular
weight.
They are polar compounds and form very strong
intermolecular hydrogen bonds.
Physical Properties
Table 17.2
Molecular Boiling
Weight
Point
(C)
(g/mol)
Solubility
(g/100 g H2 O)
Structure
Name
CH3 COOH
Acetic acid
60.1
118
Infinite
CH3 CH2CH2OH
1-Propanol
60.1
97
Infinite
CH3CH2CHO
Propanal
58.1
48
16
88.1
163
Infinite
88.1
86.1
137
103
2.3
Slight
205
1.0
176
153
0.2
0.1
Physical Properties
Water solubility decreases as the
relative size of the hydrophobic portion
of the molecule increases.
Acidity
CH3
CH3
Acidity
Electron-withdrawing substituents near the
carboxyl group increase acidity through their
inductive effect.
Acetic
acid
4.76
Cl2CHCOOH
Chloroacetic Dichloroacetic
acid
acid
2.86
1.48
Increasing acid strength
Cl3CCOOH
Trichloroacetic
acid
0.70
Acidity
The form of a carboxylic acid present in
aqueous solution depends on the pH of
the solution.
O
O
O
O
OH
OH
R-C-OH
R-C-OH + R-C-OR-C-O
H+
H+
predominant
present in equal
predominant
species when the
concentrations when
species when
pH of the
the pH of the
the pH of the
solution is
solution is equal to
solution is 7.0
2.0 or less
the pKa of the acid
or greater
H2 O
COO Na
+ H2 O
Sodium benzoate
(60 g/100 mL water)
H2 O
COO NH4
Ammonium benzoate
(20 g/100 mL water)
CH3COO Na + H2 CO3
CO2 + H2O
- +
CH3COO Na + CO2 + H2O
Reaction with
bases
The acid-base
properties of
carboxylic acids
allow an easy
separation of
carboxylic acids
from waterinsoluble
nonacidic
compounds.
Preparation
Carbonation of Grignard reagents
Treatment of a Grignard reagent with
carbon dioxide followed by acidification
gives a carboxylic acid.
O
MgCl + C
O
Carbon dioxide
O
C-O
[ MgCl] +
A magnesium carboxylate
HCl
H2 O
O
C-OH + Mg 2+
Cyclopentanecarboxylic acid
Oxidation
Primary alcohol
Na Cr O
RCH2OH 2 2 7
Na2Cr2O7
RCH=O
RCO 2H
Tertiary
R3COH
NR
Oxidation: Aldehyde
Carboxylic
Recall from the discussion of alcohols.
RCHO
Ag(NH3)2+
RCO2- + Ag
CH3
CX3
CO2-
X2
NaOH
O
CH3
methyl
NaOH
+ HCX3
Example
OH
OH
Na2Cr2O7
acid
HO
CH2OH
CO2H
Secondary
PCC
R2CHOH
R2C=O
O
OH
HIO4
glycol
HIO3
two aldehydes
OH
HIO4
HO
+ HIO3
aldehydes
O
carboxylic acid
O
O
HO
HIO4
+ HIO3
OH
carboxylic acid
carboxylic acid
OH
O
2 HIO4
O
HO
+ 2 HIO3
OH
OH
O
CH3 COH H = -138 kJ(33 kcal)/mol
Product
Reactant
Tetra coordinate
complex
Iodide negative, CO
neutral. Thus Rh(I)
Hexa coordinate
complex
Iodide negative, CO
neutral, CH3
negative. Thus Rh(III).
oxidized.
PentaRh
coordinate
complex
Iodide negative, CO
neutral, CH3CO
Mn+ + X-Y
M(n+2)+
X-
YH
Ph3P
Cl
Ir
CO
PPh3
Vaskas compound
Ox. Addn
+ H2
Reduc. Elim.
Ph3P
Cl
Ir III
CO
H
PPh3
Insertion-deinsertion
M-X + L
M-L-X
O
(CO)5Mn-C-CH3
(CO)5Mn-CH3 + CO
Mn
CO
H3 C
H3 C
CO
CO
CO
O
Mn
OC
CO
CO
CO
CO
C
CO
O
Mn
OC
CO
CO
Tetra coordinate
complex
Rh(I)
Oxidative
Addition.
Hexa coordinate
complex
Rh(III).
Hexa coordinate
complex
Rh(III).
Rh(III)
.
Insertion Reaction, Migratory
Insertion
1. LiAlH4
2. H2O
Selective Reduction
Carboxyl groups are not affected by catalytic
reduction under conditions that reduce
O
Oand ketones.
OH
O
aldehydes
OH + H2
5-Oxohexanoic acid
Pt
25C, 2 atm
OH
5-Hydroxyhexanoic acid
(racemic)
O
OHby NaBH
O
NorOare carboxyl
groups reduced
4.
1. NaBH4
C6 H5
OH
C6 H5
OH
2. H2 O
5-Oxo-5-phenylpentanoic acid
5-Hydroxy-5-phenylpentanoic acid
(racemic)
Fischer Esterification
Esters can be prepared by treating a
carboxylic acid with an alcohol in the
presence of an acid catalyst,
commonly H2SO4, ArSO3H, or gaseous
O
O
H
SO
2
4
HCl.
OH
Ethanoic acid
(Acetic acid)
HO
Ethanol
(Ethyl alcohol)
+ H2 O
O
Ethyl ethanoate
(Ethyl acetate)
Fischer Esterification
Fischer esterification is an equilibrium
reaction.
By careful control of experimental
conditions, it is possible to prepare esters
in high yield.
If the alcohol is inexpensive relative to the
carboxylic acid, it can be used in excess to
drive the equilibrium to the right.
Alternatively, water can be removed by
azeotropic distillation .
Deprotonation
H C N N:
ether
Diazomethane
O
RCOCH3 + N2
A methyl ester
Diazomethane Mechanism
Esterification occurs in two steps.
Step 1: Proton transfer to diazomethane.
O
R C O H +
CH2 N N
R C O:
A carboxylate
anion
CH3 N N
Methyldiazonium
cation
R C O: + CH3 N N
SN2
O
R C O CH3 + N N
Acid Chlorides
The functional group of an acid
halide is a carbonyl group bonded to
a halogen atom.
Among the acid halides, acid chlorides
O
O
O
are by far the most common and
the
C-Cl
-C-X
CH3 CCl
most widely used.
Functional group
of an acid halide
Acetyl
chloride
Benzoyl
chloride
Acid Chlorides
Acid chlorides are most often prepared
by treating a carboxylic acid with thionyl
chloride.
O
+ SOCl2
OH
Cl + SO2 + HCl
Butanoic acid Thionyl chloride Butanoyl chloride
R-C-O-H + Cl-S-Cl
R C O S Cl + H-Cl
A chlorosulfite
group
Acid Halides
Step 2: Attack of chloride ion gives a
tetrahedral carbonyl addition
intermediate, which collapses to give
O theO acid chloride.
R
Cl
Cl -
O R
O
O
O
Cl
Cl
A tetrahedral carbonyl
addition intermediate
R-C-Cl
SO2
Cl
Decarboxylation
Decarboxylation: The loss of CO2
from a carboxyl group.
Most carboxylic acids require a very
high temperature for thermal
decarboxylation.
O
decarboxylation
R-C-OH
R-H + CO2
heat
Decarboxylation
Exceptions are carboxylic acids that
have a carbonyl group beta to the
carboxyl group
This type of carboxylic acid undergoes
decarboxylation on mild heating.
O
warm
OH
3-Oxobutanoic acid
(Acetoacetic acid)
Acetone
+ CO
2
(1)
CO2
(A cyclic six-membered
transition state)
(2)
HO
O
Enol of
a ketone
A ketone
O
OH
HO
O
Oxalosuccinic acid
OH + CO2
HO
O
-Ketoglutaric acid
Decarboxylation of Malonic
Acid
Decarboxylation occurs if there is any
carbonyl group beta to the carboxyl.
Malonic acid and substituted malonic
acids.
O
O
140-150C
HOCCH2 COH
Propanedioic acid
(Malonic acid)
O
CH3COH + CO2
(1)
O
HO
O
+ C
O
(2)
A cyclic six-membered
Enol of a
transition state
carboxylic acid
O
HO
A carboxylic
acid
+ CO2