Vous êtes sur la page 1sur 44

Chapter Amines and Amides

1. Amines 2. Naming Amines 3. Physical Properties of Amines

Amines
Amines are organic compounds in which one or more H in ammonia, NH3, is replaced with alkyl or aromatic groups.

H | HNH ammonia

H H | | CH3NH CH3NCH3

Classification of Amines
Amines are classified as primary, secondary, or tertiary. In a primary (1) amine, one carbon group is bonded to the nitrogen atom. A secondary (2) amine has two carbon groups. A tertiary (3) amine has three carbon groups. H CH3 CH3 | | | CH3NH CH3NH CH3NCH3 1 2 3
3

Models of Amines
The three-dimensional models show the shapes of amine molecules with one or more alkyl groups bonded to the nitrogen atom.

Common Names of Amines


Simple amines are named as alkylamines. The alkyl groups bonded to the N atom are listed in alphabetical order in front of amine.

CH3CH2NH2 Ethylamine

CH3NHCH3 Dimethylamine

CH3 | CH3NCH2CH3 Ethyldimethylamine


5

IUPAC Names of Amines


In the IUPAC system, amines are named as alkanamines. The e in the alkane name of the longest chain is changed to amine. The chain is numbered to locate the amine group and substituents. NH2 | CH3CH2NH2 CH3CHCH3 Ethanamine 2-Propanamine
6

Naming Secondary and Tertiary Amines


Each alkyl groups bonded to the N atom is named as N-alkyl groups in front of the amine name for the longest chain. HNCH3 | CH3CH2CH2NHCH3 CH3CHCH2CH3
N-Methyl-1-propanamine butanamine N-Methyl-2-

Aromatic Amines
The amine of benzene is named aniline.
NH2 NH2 NH CH3

Cl

Aniline

3-Chloroaniline

N-Methylaniline
8

Heterocyclic Amine:
N
Pyridine

N
Pyrole

N
Quinoline

N
Indole

N H
Pyrolidine

N H
Piperidine

LATIHAN
1. Beri nama sistematis atau nama umum serta klasifikasikan senyawa-senyawa amina di bawah ini menjadi amina primer, sekunder atau tersier
CH3CH2CH2NH2 CH3NHCH3 C6H5NH2 (CH3)2NC2H5
NH2

NH2

2-metil-1-butanamina

3-metil-3-pentanamina
10

LATIHAN
2. Tuliskan struktur senyawa amina di bawah ini: a. Isopropilamina b. 3-pentanamina c. Siklopentanamina d. Fenilamina e. 2-metil-sikloheksanamina

11

Physical Properties of Amines


The boiling points of amines are higher than alkanes, but lower than alcohols of similar mass.

12

Solubility in Water
Amines with 1-5 carbon atoms are soluble in water. The N atom in amines forms hydrogen bonds with the polar O-H bond in water.

13

Hydrogen Bonding for Amines


The polar N-H bond provides hydrogen bonding in 1and 2 amines, but not 3. However, the N-H bonds in amines are not as polar as the O-H bonds in alcohols.

14

Learning Check
Consider the following compounds: 1. CH3CH2CH2NH2 2. CH3CH2NHCH3 3. CH3CH2CH2CH3
A. Which compound has the highest boiling point? B. Which compound(s) is(are) soluble in water?

15

Chemical Properties of Amines


Amines are Bronsted-Lowry bases that attract a H+ from H2O to the N atom. Weak bases in water.
NH3 + H2O NH4+ + OH ammonium hydroxide CH3NH3+ + OH methylammonium hydroxide
16

CH3NH2 + H2O

Chemical Properties of Amines


An amine salt Forms when an amine is neutralized by acid. Is named by replacing the amine part of the name with ammonium followed by the name of the negative ion.
CH3NH2 + HCl Methylamine CH3NH3+Cl methylammonium chloride
Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

17

Learning Check
Write the equation for ethylamine when it reacts with each of the following: 1. + H2O

2. + HCl
18

Preparation of amines 1. Nucleophilic Substitution


O C N H C O KOH C O O C N C O
OH-

O C N K+ RCH 2 X

O C N CH 2 R C O O

Gabriel Synthesis

CH 2 R

OH /H 2 O

C O RCH 2 NH 2 + C O O

RCH 2 X + NH 3 RCH 2 NH 2
OH-

RCH 2 NH 2 RCH 2 NHCH 2 R


OH-

Alkylation
(RCH 2 )3 N

RCH 2 X RCH 2 X (RCH 2 )3 N + X

RCH 2 NHCH 2 R

RCH 2 X

(RCH 2 )4 N

CH3CH2CH2NH2 n -propylamine Propanamine

CH3Cl

CH3CH2CH2NHCH3 methyln-propylamine N-methyl-1-propanamine

NH2 aniline

2 CH3CH2Br

Et N Et N,N-diethylaniline

(xs) CH3I H2 C NH2 benzylamine

H2 CH3 C N CH3 CH3 I benzyltrimethylammonium iodide

Preparation of amines 2. Reduction


Reduction of nitroaromatic compound

Ar

HNO3 H H2SO4

Ar NO2
NH2

[ H]

Ar NH2

NO2
1) Fe, HCl 2) OH

Preparation of amines 2. Reduction


Reduction of nitriles to amines

CH2C

N + 2 H2
LiAlH4

Raney Ni 140

CH2CH2NH2
(71%)

Reduction of amides to amines:

O N CCH3 + LiAlH41) Et2O CH3


2) H2O

N CH2CH3 CH3
22

Reductive amination from aldehyde or ketone

R (R')H

C O + NH3(or R''NH2)
H2, Ni

-H2O

R (R')H

C NH(R'')

R CH NH2(R'') (R')H

Imine

H C O + NH3

H2, Ni 90 atm 40 ~ 70
H2, Ni, EtOH 95

CH2NH2
(89%)
(CH3)2CNHCH2CH2OH

(CH3)2C O + H2NCH2CH2OH

Reductive Amination Examples


O CCH2CH3 + CH3CH2NH2 propiophenone NaBH3CN CH2CH3 NH CHCH2CH3

1-(N-ethylamino)-1-phenylpropane

CH3NH2, H2/Ni

NHCH3

cyclohexanone

cyclohexylmethylamine

Preparation of amines 2. Reductive Amination


Hofmann Rearrangement
R C NH O
Primary amide X2
2

OH /H 2O

RNH

+ CO 2

+ R C N N N O
Acyl azide

H 2O

RNH

+ CO 2

+ N2

25

1. Reactions of primary alkyl amines with nitrous acid (Diazotization)


Nitrosating agent:

HCl NaNO2 + 1/2 H 2SO4

HNO2 + NaCl 1/2 Na2SO4


Nitrous acid + R- N = N Cl + NaCl + H2O diazonium salt

R-NH2 + NaNO2

+ 2HCl

CH3CH2CH2NH2
Primary alkyl amines

NaNO2, HCl

CH3CH2CH2 N
diazonium salt

NCl

CH3CH2CH2 + N2 + HCl
carbocation

2. Reactions of primary arylamines with nitrous acid (Diazotization)


NH2 + NaNO2 + 2 HCl
0 ~ 5

N Cl + H2O + NaCl

diazonium salt

Flowchart Reaction
A. Sandmeyer reaction B. Hydrolisis Primary amine Diazonium salt C. Deamination D. Azo coupling Alkyl halide/cyanide Alcohol

Alkane/Arene Azo compound

28

A. The Sandmeyer reaction:


Aryl diazonium salts react with cuprous chloride, cuprous bromide, cuprous cyanide, potassium iodide

B. Hydrolysis of the diazonium group by OH


Aryl diazonium ion is converted to phenols
(CH3)2CH 1. NaNO2, H2SO4, H2O (CH3)2CH NH2 2. H2O, heat OH

p-Isopropylaniline

p-Isopropylphenol
(73%)

+ N2 :Electron-withdrawing group
OH

Question: Design a synsthesis of

Br

C. Deamination
Aryl diazonium salts react with hypophosphorous acid (H3PO2)

D. Azo Coupling
Contain the -N=N- group. Result of a coupling

reaction between a diazonium salt and a coupling agent.

Azo group

Azo coupling
Aryl diazonium salts are weak electrophiles, they react with highly reactive aromatic compounds, to yield azo compounds
+ CH3COO -Na+ 0 H2O

N2 Cl +

N(CH3)2

N N

N(CH3)2

Azo dyes

Orange II

N N OH

SO3 Na

Coupling with phenols


Benzenediazonium salt and alkaline phenol gives a yellow orange azo compound

Benzenediazonium salt and alkaline naphthalen2-ol gives a red azo compound.

Tartrazine

35

Azo memiliki ikatan rangkap terkonjugasi


Gugus kromofor adalah gugus fungsional yang

menyerap cahaya pada daerah UV-Vis sehingga menyebabkan senyawanya memiliki warna Salah satu gugus kromofor adalah ikatan rangkap terkonjugasi Maka, senyawa azo memiliki warna Maka, azo dapat dianalisis kadarnya dengan cara spektrofotometri

36

TUGAS
Cari definisi, rumus umum dan contoh dari :

A. Asam amino B. Asam lemak C. Asam hidroksi

37

Alkaloids
Alkaloids are Physiologically active nitrogen-containing compounds. Produced by plants. Used as stimulants, anesthetics, and antidepressants. Often habit forming.

38

Cocaine

Cocaine Is reacted with NaOH to produce the free amine form known as crack.

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

39

Caffeine
Caffeine Is a stimulant of the central nervous system. Is found in coffee beans, tea, chocolate, and soft drinks. Contains an imidazole ring.

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

40

Nicotine
Nicotine Increases the adrenaline level in the blood. Causes addiction to tobacco. Contains a pyrrolidine ring.

N CH3

41

Alkaloids Related to Morphine


Alkaloids Such as morphine and codeine are produced by the poppy. Have been used for centuries as painkillers. Such as heroin and codeine are modifications of morphine.

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

42

Morphine and Codeine

Copyright 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

43

Important Aromatic Amines


N N H

N N

N H

Purine (Adenine, Guanine) A, G

Pyrimidine

(Cytosine, Thymine)
C, T