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Chapter Amines and Amides1. Amines
2. Naming Amines
3. Physical Properties of Amines
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AminesAmines are organic compounds in which
one or more H in ammonia, NH3, is
replaced with alkyl or aromatic groups.
H H H| | |
H
N
H CH3
N
H CH3
N
CH3ammonia
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Classification of AminesAmines are classified as primary, secondary, ortertiary.
In a primary(1) amine, one carbon group isbonded to the nitrogen atom.
Asecondary(2) amine has two carbon groups.Atertiary(3) amine has three carbon groups.
H CH3 CH3| | |
CH3NH CH3NH CH3NCH3
1 2 3
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Models of Amines The three-dimensional models show the
shapes of amine molecules with one or
more alkyl groups bonded to the nitrogenatom.
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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 ofamine.CH3CH2NH2 CH3NHCH3Ethylamine Dimethylamine
CH3|
CH3NCH2CH3Ethyldimethylamine
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IUPAC Names of Amines In the IUPAC system, amines are named as
alkanamines.
The
e in the alkane name of the longestchain is changed toamine.
The chain is numbered to locate theamine group and substituents.
NH2
|CH3CH2NH2 CH3CHCH3Ethanamine 2-Propanamine
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Naming Secondary and Tertiary Amines Each alkyl groups bonded to the N atom is
named asN-alkylgroups in front of the
amine name for the longest chain.HNCH3|
CH3CH2CH2NHCH3 CH3CHCH2CH3
N-Methyl-1-propanamine N-Methyl-2-butanamine
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Aromatic Amines The amine of benzene is named aniline.
Aniline 3-Chloroaniline N-Methylaniline
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NH CH3 NH2
Cl
NH2
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Heterocyclic Amine:
Pyridine Pyrole Quinoline Indole
N N N N
H
PyrolidinePiperidine
N
H
N
H
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NH2
NH2
C6H5NH2
(CH3)2NC2H5
CH3CH2CH2NH2
CH3NHCH
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1. Beri nama sistematis atau nama umum serta
klasifikasikan senyawa-senyawa amina di bawah
ini menjadi amina primer, sekunder atau tersier
LATIHAN
2-metil-1-butanamina
3-metil-3-pentanamina
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LATIHAN2. Tuliskan struktur senyawa amina di bawah ini:
a. Isopropilamina
b. 3-pentanamina
c. Siklopentanamina
d. Fenilamina
e. 2-metil-sikloheksanamina
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Physical Properties of AminesThe boiling points of amines are higher than
alkanes, but lower than alcohols of similar
mass.
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Solubility in WaterAmines with 1-5 carbon atoms are soluble in
water.
The N atom in amines forms hydrogenbonds with the polar O-H bond in water.
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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 notas polar as the O-H bonds in alcohols.
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Learning CheckConsider the following compounds:
1. CH3CH2CH2NH2
2. CH3CH
2NHCH
3
3. CH3CH2CH2CH3
A. Which compound has the highest boiling point?
B. Which compound(s) is(are) soluble in water?
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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
CH3NH2 + H2O CH3NH3+ + OH
methylammonium hydroxide16
Chemical Properties of Amines
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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.
CH3
NH2 + HCl CH3
NH3+
Cl
Methylamine methylammonium
chloride
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Copyright 2007 by Pearson
Education, Inc.
Publishing as Benjamin Cummings
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Learning CheckWrite the equation for ethylamine when it reacts
with
each of the following:
1. + H2O
2. + HCl
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Preparation of amines
1. Nucleophilic Substitution
C
O
C
O
N HKOH
C
O
C
O
N K+ RCH 2X
C
O
C
O
N CH 2R
CO
C
O
N CH 2ROH
-/H 2O
RCH 2NH 2 +
CO
C
O
O
O
RCH 2X+ NH 3 RCH 2NH 2
RCH 2NH 2RCH 2X
RCH 2NHCH 2R
RCH 2NHCH 2RRCH 2X
(RCH 2)3N
(RCH 2)3NRCH 2X
(RCH 2)4N+
X
GabrielSynthesis
Alkylation
OH-
OH-
OH-
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CH3CH2CH2NH2CH3Cl
CH3CH2CH2NHCH3
n-propylaminemethyl-n-propylamine
NH22 CH3CH2Br
NEt
Et
aniline N,N-diethylaniline
H2C NH2
benzylamine
(xs) CH3I H2C N
CH3CH3
CH3 I
benzyltrimethylammonium iodide
Propanamine N-methyl-1-propanamine
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Ar H HNO3 Ar NO2[ H]
Ar NH2H2SO4
Preparation of amines
2. Reduction
NO2
1) Fe, HCl2)OH
NH2
Reduction of nitroaromatic compound
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Reduction of nitriles to amines
CH2C N + 2 H2Raney Ni
140CH2CH2NH2
(71%)
Preparation of amines
2. Reduction
LiAlH4
N
CH3
CCH3
O
+ LiAlH4Et2O
2)H2ON CH2CH3
CH3
1)
Reduction of amides to amines:
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CR
(R')HO + NH3(or R''NH2)
-H2O
C
R
(R')HNH(R'')
ImineH2, Ni
CHR
(R')H
NH2(R'')
C O
H
+NH3
H2, Ni
90 atm40 ~ 70
CH2NH2(89%)
(CH3)2C O + H2NCH2CH2OHH2, Ni, EtOH
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(CH3)2CNHCH2CH2OH
Reductive amination from aldehyde or ketone
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CCH2CH3
O
propiophenone
+ CH3CH2NH2NaBH3CN
CHCH2CH3
NH
CH2CH3
1-(N-ethylamino)-1-phenylpropane
O
cyclohexanone
CH3NH2, H2/NiNHCH3
cyclohexylmethylamine
Reductive Amination Examples
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Preparation of amines
2. Reductive Amination Hofmann Rearrangement
R CO
NH 2X2
OH-/H 2O
RNH 2 CO 2+
Primary amide
R C
O
N N N+
Acyl azide
H 2ORNH 2 CO 2+ + N 2
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1. Reactions of primary alkyl amines
with nitrous acid (Diazotization)
NaNO2 + HCl1/2 H2SO4HNO2 +
NaCl
1/2 Na2SO4
Nitrosating agent:
Nitrous acid
R-NH2 + NaNO2 + 2HClR- N = N Cl
+ -+ NaCl + H2O
diazonium salt
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CH3CH2CH2NH2NaNO2,HCl
CH3CH2CH2N NCl
CH3CH2CH2 + N2 + HCl
2. Reactions of primary arylamineswith nitrous acid (Diazotization)
NH2 + NaNO2 + 2 HCl0 ~ 5 N N Cl + H2O + NaCl
Primary alkyl aminesdiazonium salt
carbocation
diazonium salt
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Flowchart Reaction
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Primary amineDiazonium
salt
A. Sandmeyerreaction
Alkylhalide/cyanide
B. Hydrolisis Alcohol
C.Deamination
Alkane/Arene
D. Azocoupling
Azocompound
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A. The Sandmeyer reaction:
Aryl diazonium salts react with cuprous
chloride, cuprous bromide, cuprous cyanide, potassiumiodide
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:Electron-withdrawing group
B. Hydrolysis of the diazonium
group byOHAryl diazonium ion is converted to phenols
(CH3)2CH NH21. NaNO2, H2SO4, H2O
2. H2O, heat(CH3)2CH OH
Question: Design a synsthesis of
OH
Br
N2+
p-Isopropylaniline p-Isopropylphenol(73%)
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C. Deamination
Aryl diazonium salts react withhypophosphorous acid (H3PO2)
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D. Azo Coupling
Contain the -N=N- group.
Result of a couplingreaction between adiazonium salt and acoupling agent. Azo group
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Azo couplingAryl diazonium salts are weak electrophiles,they react with highly reactive aromatic
compounds, to yield azo compounds
N2+Cl + N(CH3)2
CH3COO-Na+
0H2O
N N N(CH3)2
Azo dyes
OH
N N SO3 NaOrange II
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Coupling with phenols
Benzenediazonium salt and alkaline phenol gives ayellow orange azo compound
Benzenediazonium salt and alkaline naphthalen-2-ol gives a red azo compound.
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Tartrazine
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Azo memiliki ikatan rangkap
terkonjugasi Gugus kromofor adalah gugus fungsional yang
menyerap cahaya pada daerah UV-Vis sehinggamenyebabkan senyawanya memiliki warna
Salah satu gugus kromofor adalah ikatan rangkapterkonjugasi
Maka, senyawa azo memiliki warna
Maka, azo dapat dianalisis kadarnya dengan caraspektrofotometri
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TUGAS Cari definisi, rumus umum dan contoh dari :
A. Asam amino
B. Asam lemakC. Asam hidroksi
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AlkaloidsAlkaloids are Physiologically active nitrogen-containing
compounds.
Produced by plants.
Used as stimulants, anesthetics, andantidepressants.
Often habit forming.
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CocaineCocaine Is reacted with NaOH to produce the free amine form
known as crack.
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Caffeine
Caffeine
Is a stimulant of thecentral nervous system.
Is found in coffeebeans, tea, chocolate,and soft drinks.
Contains an imidazole
ring.
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NicotineNicotine Increases the adrenaline level in the blood.
Causes addiction to tobacco.
Contains a pyrrolidine ring.
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N
CH3
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Alkaloids Related to MorphineAlkaloids 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.
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Morphine and Codeine
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Important Aromatic Amines
N
NN
H
N
N
NH
Purine
(Adenine, Guanine)
Pyrimidine
(Cytosine, Thymine)