Carboxylic Acid

Among important examples are :

OH H H H

COOH HOOC

NH2

NH2

COOH

Djenkolic acid Was first isolated by Van Veen and Hyman from the urine of the natives of Java who had eaten the djenkol bean and were suffering from poisoning.

H HO H H H OH

Cholic acid (a major component of human bile)

Carboxylic Acid
also, biological precursors of fats and other lipids :

HH

C
CH3(CH2)7

C
(CH2)7COOH CH3(CH2)4

C
CH2

C
(CH2)7COOH

Oleic acid

Linoleic acid

Carboxylic Acid
This compounds contain the carboxylic group attached to :
A hydrogen Alkyl group A ryl group

O and

O or

C
OH

C
OH

Ar C

OH

example
HCOOH
Formic acid

CH3COOH
Acetic acid Benzoic acid

COOH

CH3(CH2)10COOH
Lauric acid

CH2COOH
Penylic acetic acid

Carboxylic Acid
IUPAC name

Nomenclature

Carboxylic acid that are derivated from open-chain alkanes are systematically named by replacing the terminal e of the corresponding alkane with oic acid.
The carboxylic carbon atom is always numbered C1 in the system.

Propanoic acid

4-Methylpentanoic acid

3-Ethyl-6-methyloctanedioic acid

Carboxylic Acid
COMMON name

Nomenclature

To indicate the position of attachment, the Greek letters, , , , , etc are used. The -carbon is the one bearing the carboxyl group.

C-C-C-C-COOH

CH3
CH3CH2CH-COOH
- Methylbutyric acid

CH3 CH3
CH3CH2CH-CHCOOH
, -Dimethylvaleric acid

Carboxylic Acid

Physical Properties

Gugus C=O pada asam karboksilat mempunyai ikatan , sehingga dapat terjadi resonansi.
Hal yang sama tidak terjadi pada gugus OH dari alkohol.
+ Atom O pada karboksilat lebih bermuatan negatif daripada R-OH Atom H pada karboksilat lebih bersifat sebagai proton daripada R-OH

Kesimpulan Ikatan hidrogen pada karboksilat lebih kuat dari

ikatan hidrogen pada alkohol.

Carboxylic Acid

Physical Properties

2 Hydrogen bond

1 Hydrogen bond

O H3C C O H

O O

O H

CH3

O H

Still MONOMER

Acetic acid DIMER

The Fact

Boiling point of asetic acid = 118 Co Boiling point of n-Propylalcahol = 97 Co

Carboxylic Acid

Dissociation

Like other Bronsted-Lowry acids, carboxylic acid dissociate slightly in dilute aqueous solution to give H3O+ and carboxylic anion, RCOOO R C OH O

+ H2O

O-

+ H3O+

As with all acids, we can define an acidity constant, Ka:

[RCOO-][H3O+] [RCOOH]

Ka =

and

pKa = -log Ka

pKa = -7

pKa = 4,72

pKa = 16

acidity

Carboxylic Acid

Resonance Efect

CH3CH2OH
Ethanol

+ H2O

CH3CH2OUnstabilized

+ H3O+

O H3C C O H

+ H 2O

OH3C C O

H3C

O-

+ H3O+

Resonance stabilized carboxylic ion

Carboxylic Acid

Substituent Efect

STRUCTURE HCl F3CCOOH Cl3CCOOH HCOOH CH3COOH

Ka 107 0,59 0,23 1,77 x 10-4 1,8 x 10-5

pKa -7 0,23 0,64 3,75 4,72

acidity

Carboxylic Acid
1. Oxidation of primary alcohol. R-CH2OH
KMnO4

Preparation
R-COOH

CH3 CH3CH2CHCH2OH
2-Methyl-1-butanol KMnO4

CH3 CH3CH2CHCOOH
2-Methylbutanoic acid

CH3 CH3CHCH2OH
Isobutyl alcohol KMnO4

CH3 CH3CHCOOH
Isobutylic acid

Carboxylic Acid
2. Hydrolysis of Nitriles. R-C
or

Preparation
N
+ H2O

Acid or base

R-COOH
or + NH3

Ar-C CH2CN

Ar-COOH CH2COOH

70% H2SO4

Phenylacetonitrile

Phenylacetic acid

3. Carbonation of Grignard Reagents. 4. Oxydation of Alkylbenzenes. 5. Malonic Ester Syntesis.

Carboxylic Acid
R

Derivatives of

C
OH O

O R

O R

R R

C
Cl

C
OR
Ester

C
O

O R

C
NH2
Amide

Acid chloride

C
O
Anhydride

More reactive

Less reactive

Carboxylic Acid
R
H3C C O OH
Benzoic acid

Derivatives of

Nomenclature

Ar
O C OH
O C Cl
Benzoyl chloride

Acetic acid

Acid chloride

H3C C

O Cl
O

Change: -ic acid to yl chloride

Acetyl chloride

H3C C
Anhydride

O C O C O
Benzoic anhydride

O O

H3C C

Change: acid to anhydride

Acetic anhydride

Carboxylic Acid
R
H3C C O OH
O C NH2
Benzamide

Derivatives of

Nomenclature

Ar
O C OH
Benzoic acid

Acetic acid

Amide

O H3C C NH2

Change: -ic acid to amide

Acetamide

Ester
Change: acid to -ate

H3C C

O
C

O OC2H5
Ethylbenzoate

OC2H5

Ethylacetate

Carboxylic Acid
Carboxylic Acids

Derivatives of

1.Acid Chloride [an Acyl)

are converted into acid chlorides [an acyl group] by

teratment with thyonyl chloride (SOCl2), phosphorus trichloride (PCl3), or oxalyl chloride (ClCOCOCl).

O
R

O
+ SOCl2

C
OH

C
Cl

+ HCl + SO2

Carboxylic Acid
Conversion to :
H2O ROH

Derivatives of

O R C
NH3

Cl
[H]

RMgX

O R C
Acid

O OH R C
Ester

O
NH2

O
H

OR

Amide

Aldehyde
[H]

Ketone
RMgX

OH R CH H

OH R C R OR

Alcohol

t-alcohol

Carboxylic Acid
With H2 O can converted back into carboxylic acid.
O H3C C Cl

Derivatives of

HOH

H3C C

O OH

+ HCl

Acetyl chloride

Acetic acid

With alcohol can..

Cl

HOCH3

OCH3

+ HCl

Ester
Benzoyl chloride Methylbenzoate

Amide formation with amonia.

O H3C C Cl

+ 2NH3

Acetyl chloride

H3C C

NH2

+ NH4Cl

Acetamide

Carboxylic Acid
O H C O-Na+

Derivatives of

2.Acid Anhydrides

reparation :

O Cl C CH3

O H C O

O C CH3

Sodium formate

Acetyl chloride

Acetic formic anhydride

Carboxylic Acid
Conversion to :
H2O ROH

Derivatives of

O R C O

O C R
NH3 [H]

O R C
Acid

O OH R C
Ester

O
NH2

OR

H
Aldehyde
[H]

Amide

OH R CH H

Alcohol

Carboxylic Acid
In drugs industry :
H

Derivatives of

NH2 HO
p-Hydroxyaniline

O H3CC O

O CCH3
NaOH

N HO

CH3
Acetaminophen

H3CC

O-

O C OH
Salicylic acid

O
OH

O O CCH3
NaOH

C O O C

H3CC

OH

H3CC

O-

CH3

Aspirin

Carboxylic Acid
Ester is hydroxy group ini acid change into some alkyl or aryl:
The ester linkage is also present in animal fats and many biologically important molecules.

Derivatives of

3. Ester

O H2C O C R O

O CH3CH2CH2C-OCH3
Methylbutanoate [from pineaples]

CH3

HC

R O

CH3CO-CH2CH2CHCH3
Isopentyl acetate [from bananas]

H2C

A fat

Carboxylic Acid
O

Derivatives of

Conversion to :
H2O RMgX

OR
NH3

[H]

O R C
Acid

OH
OH

O
NH2

R OR
R

H
Aldehyde
[H]

t-alcohol

Amide

OH R CH H

Alcohol

Carboxylic Acid
Esters are usually prepared by the reaction of alcohols or phenols with acids or acid derivatives.

Derivatives of

ESTERIFICATION

O R

O OH + H-OR
alcohol

C
ESTER

OR

+ H-OH

Carboxylic acid

CH2OH + HOOCCH3

CH2OOCCH3

+ H-OH

Benzyl alcohol

Acetic acid

Benzyl acetat

Carboxylic Acid

Derivatives of

SAPONIFICATION

O R C
H2O

O R C
An acid

OR

NaOH

+ ROH

OH

O R C
A soap

O-Na+

Amine
Amine is derivates of ammonia, when one or more of hydrogen change into alkyl (R) or aryl (Ar).

H H

H H R

H H R

N
Ammonia

N
Primary 1o

N
Secondary 2o

N
Tertiary 3o

Amine
H3C
N N
Nicotine

O N N CH3
Caffeine

CH3

CH3

H3 C H2 C N CH2CH2OH

OH OH OH H2C H3C N C H C H N N O C H O CH2OH

N H3 C

N+

Vitamin B1

H3C

Vitamin B2

Amine
Aliphatic amine are named by naming the alkyl group or groups attached to nitrogen, and following these by the word amine.

Nomenclature

CH3 H3C C CH3

H H3CH2C N CH3

NH2
tert-Butylamine Etrhylmetylamine

Amine
Aromatic amine those in which nitrogen is attached directly to an aromatic ring, are generally named as derivatives of the simple aromatic amine, -aniline.

Nomenclature

NH2
aniline

Br

NH2 Br

H3C

C2H5

H3C

CH3

NH2

Br
2,4,6-Tribromoaniline

N-Ethyl-N-methylaniline

NO
p-Nitroso-N, N-dimethylaniline

CH3
p-Touidine

Amine
Amine are highly polar and therefore have higher boiling point than alkanes of equivalent molecular weight have, but lower boiling point than alcohol or carboxylic acids.
R R N N R R R H H N R R H N R H R N H R

Physical Properties

CPs CH3CH3 CH3NH2 CH3OH

BP (oC) -88,6 -6,3 +65,0

Mr 30 31 32

Amine

Reaction

CH3COOH
Acetic acid

Cl2

CH2COOH Cl
Chloroacetic acid

NH3

CH2COOH NH2
GLYSINE [an amino acid]

O O R R R

C
Cl

C
O

O R

O R

C
NH2
Amide

C
OR
Ester

Acid chloride

C
O
Anhydride

R-C

N HCl

O
1 2

CH2CH3
3 4 5

CH3
6 7

O
8

HOCCH2CHCH2CH2CHCH2COH CH3CH2OH