Organic II ‫المرحله الثانيه‬

Lec. 9 & 10 ‫طارق الحكيم‬.‫د‬.‫ا‬

Carboxylic acids and derivatives:

These compounds contain the carboxyl group –COOH,

Ar-C-OH
Formic acid Aliphatic acid Aromatic acid

Acid halid x=Cl, Br Acid anhydride

Ester Amide Thioester

Example/

Propionic acid 4-methyl pentanoic acid ( γ-methyl pentanoic acid)

3-bromo-cyclohexane carboxylic acid 1-cyclopentene carboxylic acid

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Benzoic acid Acrylic acid

Succinic acid (dicarboxylic acid) Butyric acid

Q1/ 4-methyl pentanoic acid can be called:
a) α-methyl pentanoic acid
b) γ- methyl pentanoic acid
c) β-methyl pentanoic acid
R
R

Palmitic acid Stearic acid

Oleic acid

Linoleic acid

2-methylbutyric acid ( α -methylbutyric acid)

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Properties:
Like alcohols, carboxylic acids form strong hydrogen bonds that are soluble in
water. Solubility decreases with increasing molecular weight. Their boiling point is
greater than that of alkenes with similar m.wt.

solubility

They are weaker than mineral acids and stronger than alcohols and they have Ka
values because thay are weak acids
Ka= 1.7* 10-5 Ka= 1* 10-16
- +
Acetic acid Alcohol (ethanol)
R-C-O Na

They react with bases to give salts (carboxylates):

RCOOH + NaOH + H2O

Long chain carboxylic acid also called fatty acids ‫ احماض دهنيه‬such as palmitic,
stearic and oleic acids.
RCOOH …R is a long saturated, unsaturated aliphatic, or aromatic.

+ NaOH + H2O

Na-benzoate (salt)
In carboxylate anion, the charge spread equally over both oxygens by two
resonance forms: -
-
R-C-O R-C R-C -

i.e delocalized negative charge.

-

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In alkoxide R-O
- , the negative charge is localized on one oxygen atom,
therefor; alkoxides are LESS stable than aromatic alkoxides (carboxylates)

- +
- +

Benzoate Ethoxide
So, carboxylates are more stable than alkoxides

- + - +

More stable than

Anything that stabilizes the carboxylate anion, increase dissociation and increase
acidity:
CH3COOH Cl-CH2COOH Cl2CH-COOH
pKa= 4.7 pKa= 2.8 pKa=1.5
Increases acidity
Cl CH2-COOH
Cl
CH-COOH
Cl
Cl
Cl C-COOH
Cl Increase acidity

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 Cl Aromatic carboxylic acid is more acidic than aliphatic
acid. Aliphatic and aromatic acids are more acidic than
Cl-C-COOH alcohols.
Cl
pKa= 0.6
x
x= electronegative group (inductive effect) -CH3 is electron donating group

Q/ Arrange the following

> CH -COOH
3
according to acidity:

CH3COOH, CH3CH2OH,
pKa= 3.8 pKa= 4.7 benzoic acid, p-nitrobenzoic
acid

>

Q1// Why carboxylic acids are more acidic than alcohols? Both contain OH
Answer// Due to delocalization in carboxylate as mentioned

Synthesis of carboxylic acids:

1) For acetic acid, the most important one ‫طرق تجاريه‬
O2
Hydrocarbons
Catalyst
Q/ Benzoic acid (A) and p-
nitrobenzoic acid (B):
O2
CH3CHO CH3COOH a) B is more acidic
Aldehyde Catalyst b) A is more acidic
c) A & B have same
acidity
Methanol + CO
Rh-I2

Rh-I2 : Iodenic rhodium

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 2) Fermentation of sugars:
Enzyme
Sugars Acetic acid
Fermentation
o

Cl2
3) Petroleum Heat
Reforming

)‫(النفط الخام‬
OH- H2O

Benzoic acid
Preparation: (lab) ‫طرق مختبريه‬
1- Oxidation of primary alcohols and aldehydes

KMnO4
RCH2- OH RCOOH

AgNO3
RCHO NH4OH RCOOH

2- Oxidation of alkyl benzene

K2Cr2O7

KMnO4

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 3- Carbonation of Grignard reagent

Mg CO2
R-X RMgX R-C-OMgX
1 2

R: Aliphatic or aromatic 3 H+

RCOOH

CH2CH3 1 2 3 CH2CH3
Mg, CO2, H+
CH3-C-Cl CH3-C-COOH
CH3
CH3

‫زياده بدرة كاربون واحده متمثله في مجموعة‬-COOH

‫المتكونه‬
Mg, CO2, H+

CH3-CH
CH3

p-sec. butylbenzoic acid

4- Hydrolysis of nitriles R-C = N CN, C=N Nitrile
H+
R-C = N RCOOH+ NH3
H2O

H+
Ar-C = N H2O Ar-COOH+ NH3

**Increasing the length of carbon chain by one carbon atom.

R H+ Q/ acetic acid can be prepared from:
CH3CN CH3-COOH
H2O a) Benzo nitrile
b) Methyl nitrile
c) c) both

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 H+

H2O

Example//
Br2 CN-
CH3CH2OH CH3CH2Br CH3CH2CN
H2O H+

CH3CH2COOH
Q/ 1-convert methanol to acetic acid

2-convert ethanol to propionic acid

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1- Acidity, salt formation
2- Conversion reactions
a- to acid chloride
RCOOH R-C-Cl + HCl
CH3COOH + SOCl2 CH3-C-Cl + SO2 + HCl
Thionyl chloride
Acetyl & acetyl

b- to alcohols, by reduction
LiALH4
CH3COOH CH3CH2OH
c- to esters
d- to amides
R-C-OH + NH3 R-C-NH2 + H2O

Acid Halides

R-C-OH + SoCl2 R-C-Cl

Derivatives:

H2O R--C-ONa
HCL+ R-C-OH R-C-Cl R-C-O-C-R- +NaCl
(4) (1)
anhydride

R-C-OR- R-C-NH2
Ester Amide

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 :
1) R-C-O added
:

2) –NH2 added
They replace Cl
: :

3) RO: added

4) OH- added
All are nucleophilic substitution reactions.
:

R-C-Cl +:NU R-C-NU + Cl

R-C-Cl More reactive

R-C-O-C-R-

R-C-OR-

R-C-NH2 Less reactive

* More reactive derivative can be converted to less reactive ones but

not vice versa

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Substitution in alkyl or aryl group
1- α-halogenation
Cl2
CH3COOH Cl-CH2COOH
Cl2

Cl-CH-COOH
Cl

2- Ring Substitution

Benzoic acid

-COOH is m-directing group (lec.2)

HNO3

H2SO4 m-nitro benzoic ACID

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Chemistry of acid anhydrides:

R-C-O-C-R-

2ROH
R-C-OH R-C-OR R-C-NH2

Carboxylic
Acid Ester Amide

+ CH3C-O-C-CH3
Salicylic Acid
Acetic
o-hydroxy benzoic anhydride
acid
pyridine

Aspirin

Acetyl Salicylic Acid

Ester

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 + CH3-C-O-C-CH3
p-hydroxy Acetic
aniline anhydride
pyridine

Acetaminophenol (para acetol)

Q/ Start from acetic acid and prepare ethyl acetate via anhydride

-H2O
2CH3COOH CH3C-O-C-CH3

2CH3CH2OH

2CH3-C-O-CH2CH3
Ethyl acetate

Via acid chloride:

CH3COOH + SOCl2 CH3-C-Cl

CH3CH2OH

CH3-C-OCH2CH3
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Some reactions of esters:

NaOH NH3
R-COO-Na+ R-C-OR- R-C-NH2
Salt

Saponification Reduction LiAlH2

RCOOH RCH2OH+R-OH
LiAlH4
CH3CH2-C-OCH3 CH3CH2OH + CH3OH
Some reactions of amides:
Amides are usually prepared by reaction of an acid chloride with NH3

R-C-Cl
R-NH2

R-C-NR2- + HCl R-C-NHR- + HCl R-C-NH2 + HCl

Amides are less reactive than acid chloride, anhydrides and esters. In
addition, amides are reduced by LiAlH4 to produce amine RNH2 rather
than alcohol.
LiAlH4
R-C-NH2 RNH2

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Reactions of nitriles:
The chemistry of nitriles is similar to the chemistry of carbonyl
compounds:
R-C=N
[H]

H2O
R-C-OH RCH2NH2 R-C-R
Ketone

Q/ Start from methane and prepare dimethyl ketone

CH4 CH3-C-CH3
CH4 CH3Cl + HCl
CH3Cl + NaCN CH3CN
CH3CN + CH3MgX H2O CH3-C-CH3
Acetone

Dimethyl ketone

Dicarboxylic acids:
HOOC-CH2-COOH HOOC-CH2-CH2-COOH
Malonic acid
Succinic acid

Oxalic acid

Sodium Oxalate (salt)

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 CN-
Cl-CH2COONa CN-CH2COONa
Sodium Chloroacetate
H2O H+

C-OCH2CH3 COOH
2CH3CH3OH
CH2 CH2 + NH4+
C-OCH2CH3 COOH

Ethyl Malonate

(Ester)
Some pharmaceutical derivatives:
-Aspirin
-Antacids .. mix of carboxylic acids
CH2-COOH COOH
HO-C-COOH + HO-C-H + NaHCO3
CH2COOH HO-C-H
COOH
Estilic acid Tartaric acid

(16g) (26g)

-Facial cream… lactic acid + lemon juice

CH3-C-COOH
Ketonic acid

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-vit. C.

H 3 2 1
- Omega-3,6 RCH2- - - C=C-CH2-COOH
H

-Triglycerides (Triesters)
-Waxes.

Thank you
Prof. Dr. Tareq Alhakeem

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