8chapter 21

Chapter 21
Amines
Dr. Wolf's CHM 201 & 202
21-1
Amine Nomenclature
21-2
Classification of Amines
Alkylamine
N attached to alkyl group
Arylamine
N attached to aryl group
Primary, secondary, or tertiary
determined by number of carbon atoms
directly attached to nitrogen
21-3
Nomenclature of Primary Alkylamines (RNH2)

Two IUPAC styles
1)
analogous to alcohols: replace -e

ending by -amine
2)
name alkyl group and attach -amine

as a suffix
21-4
Examples: some primary alkylamines

(RNH2: one carbon directly attached to N)
CH3CH2NH2
ethylamine or ethanamine
NH2
CH3CHCH2CH2CH3
NH2
cyclohexylamine or
cyclohexanamine
1-methylbutylamine or
2-pentanamine
21-5
Nomenclature of Primary Arylamines (ArNH2)

Name as derivatives of aniline.
NH2
NH2
p-fluoroaniline
Br
CH2CH3
5-bromo-2-ethylaniline
21-6
Amino groups as substituents

amino groups rank below OH groups and higher
oxidation states of carbon
in such cases name the amino group as a
substituent
O
HOCH2CH2NH2
HC
2-aminoethanol
p-aminobenzaldehyde
NH2
21-7
Secondary and Tertiary Amines

Name as N-substituted derivatives of parent
primary amine.
(N is a locant-it is not alphabetized, but
is treated the same way as a numerical
locant)
Parent amine is one with longest carbon
chain.
21-8
Examples
CH3NHCH2CH3
N-methylethylamine
NHCH2CH3
4-chloro-N-ethyl-3-nitroaniline
NO2
Cl
CH3
N
CH3
N,N-dimethylcycloheptylamine
21-9
Ammonium Salts
A nitrogen with four substituents is positively
charged and is named as a derivative of
ammonium ion (NH4+).
+
CH3NH3 Cl
methylammonium
chloride
CH3
+
CF
CO
CH
CH
N
3
2
2
3
H
N-ethyl-N-methylcyclopentylammonium
trifluoroacetate
21-10
Ammonium Salts
When all four atoms attached to N are carbon,
the ion is called a quaternary ammonium ion and
salts that contain it are called quaternary
ammonium salts.
CH3
+
CH2 N
CH3
CH3
benzyltrimethylammonium iodide
21-11
Structure and Bonding
21-12
Alkylamines
147 pm
112
106
21-13
Alkylamines
Most prominent feature is high electrostatic

potential at nitrogen. Reactivity of nitrogen lone
pair dominates properties of amines.
21-14
Geometry at N
Compare geometry at N of methylamine, aniline,
and formamide.
H
H
H
sp3
sp2
NH2
NH2
C
C
O
H
Pyramidal geometry at sp3-hybridized N in
methylamine.
Planar geometry at sp2-hybridized N in formamide.
21-15
Geometry at N
Compare geometry at N of methylamine, aniline,
and formamide.
sp3
sp2
Pyramidal geometry at sp3-hybridized N in

methylamine.
Planar geometry at sp2-hybridized N in formamide.
21-16
Geometry at N
Angle that the CN bond makes with bisector of
HNH angle is a measure of geometry at N.
sp3
~125
sp2
180
Note: this is not the same as the HNH bond angle
21-17
Geometry at N
Angle that the CN bond makes with bisector of
HNH angle is a measure of geometry at N.
sp3
sp2
180
~125
142.5
21-18
Geometry at N
Geometry at N in aniline is pyramidal; closer to
methylamine than to formamide.
142.5
21-19
Geometry at N
Hybridization of N in aniline lies between sp3 and sp2.
Lone pair of N can be delocalized into ring best if N is
sp2 and lone pair is in a p orbital.
Lone pair bound most strongly by N if pair is in an sp3
orbital of N, rather than p.
Actual hybridization is a compromise that maximizes
binding of lone pair.
142.5
21-20
Electrostatic Potential Maps of Aniline
Nonplanar geometry at
N. Region of highest
negative potential is at N.
Planar geometry at N.
High negative potential
shared by N and ring.
21-21
Physical Properties
21-22
Physical Properties
Amines are more polar and have higher boiling
points than alkanes; but are less polar and
have lower boiling points than alcohols.
CH3CH2CH3 CH3CH2NH2 CH3CH2OH
dipole
moment ():
0D
1.2 D
1.7 D
boiling point:
-42C
17C
78C
21-23
Physical Properties
CH3CH2CH2NH2
boiling
point:
50C
CH3CH2NHCH3
34C
(CH3)3N
3C
Boiling points of isomeric amines decrease in

going from primary to secondary to tertiary amines.
Primary amines have two hydrogens on N capable
of being involved in intermolecular hydrogen
bonding. Secondary amines have one. Tertiary
amines cannot be involved in intermolecular
hydrogen bonds.
21-24
Basicity of Amines
21-25
Effect of Structure on Basicity
1. Alkylamines are slightly stronger bases than

ammonia.
21-26
Table 22.1 (page 920)

Basicity of Amines in Aqueous Solution
Amine
Conj. Acid
pKa
NH3
NH4+
9.3
CH3CH2NH2
CH3CH2NH3+
10.8
CH3CH2NH3+ is a weaker acid than NH4+;

therefore, CH3CH2NH2 is a stronger base
than NH3.
21-27

ammonia.
2. Alkylamines differ very little in basicity.
21-28

Amine
Conj. Acid
pKa
NH3
NH4+
9.3
CH3CH2NH2
CH3CH2NH3+
10.8
(CH3CH2)2NH
(CH3CH2)2NH2+
11.1
(CH3CH2)3N
(CH3CH2)3NH+
10.8
Notice that the difference separating a primary,

secondary, and tertiary amine is only 0.3 pK units.
21-29

ammonia.
2. Alkylamines differ very little in basicity.
3. Arylamines are much weaker bases than
ammonia.
21-30

Amine
Conj. Acid
pKa
NH3
NH4+
9.3
CH3CH2NH2
CH3CH2NH3+
10.8
(CH3CH2)2NH
(CH3CH2)2NH2+
11.1
(CH3CH2)3N
(CH3CH2)3NH+
10.8
C6H5NH2
C6H5NH3+
4.6
21-31
Decreased basicity of arylamines
H
+
N
Stronger pKa = 4.6

acid
H + H2N
NH2 +
Stronger
base
Weaker
base
+
H3N
pKa =10.6
Weaker
acid
21-32
H
+
N
H + H2N
H
Stronger
acid When anilinium ion loses a proton, the
resulting lone pair is delocalized into the ring.
NH2 +
+
H3N
Weaker
acid
21-33
H
+
N
H + H2N
H
Aniline is a weaker base because its
lone pair is more strongly held.
Stronger
base
NH2 +
+
H3N
Weaker
base
21-34

Increasing delocalization makes diphenylamine a
weaker base than aniline, and triphenylamine a weaker
base than diphenylamine.
C6H5NH2
(C6H5)2NH
(C6H5)3N
0.8
~-5
pKa of conjugate acid:

4.6
21-35
Effect of Substituents on Basicity of Arylamines

1. Alkyl groups on the ring increase basicity, but
only slightly (less than 1 pK unit).
X
X
H
CH3
NH2
pKa of conjugate acid
4.6
5.3
21-36
Effect of Substituents on Basicity of Arylamines

2. Electron withdrawing groups, especially ortho
and/or para to amine group, decrease basicity
and can have a large effect.
X
X
H
CF3
O2N
NH2
pKa of conjugate acid
4.6
3.5
1.0
21-37
p-Nitroaniline
+
N
NH2

O
+
N
+
NH2
Lone pair on amine nitrogen is conjugated with

p-nitro groupmore delocalized than in aniline
itself. Delocalization lost on protonation.
21-38
Effect is Cumulative
Aniline is 3800 times more basic than
p-nitroaniline.
Aniline is ~1,000,000,000 times more basic than
2,4-dinitroaniline.
21-39
Heterocyclic Amines
is more basic than
H
piperidine
11.2
(an alkylamine)
pyridine
5.2
(resembles an
arylamine in
basicity)
21-40
Heterocyclic Amines
is more basic than
imidazole
7.0
pyridine
5.2
21-41
Imidazole
Which nitrogen is protonated in imidazole?
H+
H+
+
H N
+ H
N
H
21-42
Imidazole
Protonation in the direction shown gives a
stabilized ion.
N
H+
+
H N
+
N H
21-43
Tetraalkylammonium Salts
as Phase-Transfer Catalysts
21-44
Phase-Transfer Catalysis
Phase-transfer agents promote the solubility of
ionic substances in nonpolar solvents. They
transfer the ionic substance from an aqueous
phase to a non-aqueous one.
Phase-transfer agents increase the rates of
reactions involving anions. The anion is relatively
unsolvated and very reactive in nonpolar media
compared to water or alcohols.
21-45
Quaternary ammonium salts are phase-transfer
catalysts. They are soluble in nonpolar solvents.
CH2CH2CH2CH2CH2CH2CH2CH3
H3C
+
N CH2CH2CH2CH2CH2CH2CH2CH3
Cl
CH2CH2CH2CH2CH2CH2CH2CH3
Methyltrioctylammonium chloride
21-46
Quaternary ammonium salts are phase-transfer
catalysts. They are soluble in nonpolar solvents.
CH2CH3
+
N CH2CH3
Cl
CH2CH3
Benzyltriethylammonium chloride
21-47
Example
The SN2 reaction of sodium cyanide with butyl
bromide occurs much faster when benzyltriethylammonium chloride is present than when
it is not.
CH3CH2CH2CH2Br +
NaCN
benzyltriethylammonium chloride
CH3CH2CH2CH2CN
NaBr
21-48
Mechanism
Mechanism
CH2CH3
+
N CH2CH3 Cl
CH2CH3
CN
(aqueous)
(aqueous)
CH2CH3
+
N CH2CH3 CN
CH2CH3
(aqueous)
Cl
(aqueous)
21-49
CH2CH3
Mechanism
Mechanism
+
N CH2CH3 CN
CH2CH3
(in butyl bromide)
CH2CH3
+
N CH2CH3 CN
CH2CH3
(aqueous)
21-50
CH2CH3
Mechanism
Mechanism
+
N CH2CH3 CN + CH3CH2CH2CH2Br
CH2CH3
(in butyl bromide)
CH2CH3
+
N CH2CH3 Br + CH3CH2CH2CH2CN
CH2CH3
(in butyl bromide)
21-51
Reactions of Amines:
A Review and a Preview
21-52
Preparation of Amines
Two questions to answer:

1) How is the CN bond to be formed?
2) How do we obtain the correct oxidation
state of nitrogen (and carbon)?
21-53
Methods for CN Bond Formation

Nucleophilic substitution by azide ion (N3) (Section 8.1, 8.13)
Nitration of arenes (Section 12.3)
Nucleophilic ring opening of epoxides by ammonia (Section
16.12)
Nucleophilic addition of amines to aldehydes and ketones
(Sections 17.10, 17.11)
Nucleophilic acyl substitution (Sections 19.4, 19.5, and 19.11)
Nucleophilic substitution by ammonia on -halo acids
(Section 20.15)
21-54
Preparation of Amines
by Alkylation of Ammonia
21-55
Alkylation of Ammonia
Desired reaction is:
2 NH3
+ RX
RNH2 +
NH4X
+
H3N
via:
H3N + R
then:
H3N + H
H
+
N R
H
R +
H
+
H3N
H + N
H
R
21-56
Alkylation of Ammonia
But the method doesn't work well in practice.
Usually gives a mixture of primary, secondary,
and tertiary amines, plus the quaternary salt.
NH3
RX
RNH2
RX
R2NH
RX
+
R4N
X
RX
R3N
21-57
Example
CH3(CH2)6CH2Br
NH3
CH3(CH2)6CH2NH2
(45%)
+
CH3(CH2)6CH2NHCH2(CH2)6CH3
(43%)
As octylamine is formed, it competes with ammonia for
the remaining 1-bromooctane. Reaction of octylamine
with 1-bromooctane gives N,N-dioctylamine.
21-58
The Gabriel Synthesis of

Primary Alkylamines
21-59
Gabriel Synthesis
gives primary amines without formation of
secondary, etc. amines as byproducts
uses an SN2 reaction on an alkyl halide to form
the CN bond
the nitrogen-containing nucleophile
is N-potassiophthalimide
21-60
Gabriel Synthesis
gives primary amines without formation of
secondary, etc. amines as byproducts
uses an SN2 reaction on an alkyl halide to form
the CN bond
the nitrogen-containing nucleophile
is N-potassiophthalimide
O
21-61
N-Potassiophthalimide
the pKa of phthalimide is 8.3
N-potassiophthalimide is easily prepared by
the reaction of phthalimide with KOH
NH
O
O
KOH
O
21-62
N-Potassiophthalimide as a nucleophile
+ R
SN2
O
+
21-63
Cleavage of Alkylated Phthalimide
O
N
R + H2O
imide hydrolysis is
nucleophilic acyl
substitution
acid or base
CO2H
+
H2N
CO2H
21-64
Cleavage of Alkylated Phthalimide

hydrazinolysis is an alternative method of releasing the
amine from its phthalimide derivative
O
N
H2NNH2
NH
NH
O
+
H2N
R
21-65
Example
C6H5CH2Cl
DMF
O
N
CH2C6H5
(74%)
O
21-66
Example
O
NH
NH
H2NNH2
C6H5CH2NH2 (97%)
O
N
CH2C6H5
O
21-67
Preparation of Amines by
Reduction
21-68
Preparation of Amines by Reduction

almost any nitrogen-containing compound can
be reduced to an amine, including:
azides
nitriles
nitro-substituted benzene derivatives
amides
21-69
Synthesis of Amines via Azides
SN2 reaction, followed by reduction, gives a

primary alkylamine.
CH2CH2Br
NaN3
CH2CH2N3
(74%)
1. LiAlH4
2. H2O
azides may also be

reduced by catalytic
hydrogenation
CH2CH2NH2
(89%)
21-70
Synthesis of Amines via Nitriles

primary alkylamine.
CH3CH2CH2CH2Br
nitriles may also be
reduced by lithium
aluminum hydride
NaCN
CH3CH2CH2CH2CN
(69%)
H2 (100 atm), Ni
CH3CH2CH2CH2CH2NH2
(56%)
21-71
Synthesis of Amines via Nitriles

primary alkylamine.
CH3CH2CH2CH2Br
NaCN
the reduction also

works with cyanohydrins
CH3CH2CH2CH2CN
(69%)
H2 (100 atm), Ni
CH3CH2CH2CH2CH2NH2
(56%)
21-72
Synthesis of Amines via Nitroarenes
HNO3
Cl
H2SO4
nitro groups may also

be reduced with tin (Sn)
+ HCl or by catalytic
hydrogenation
(88-95%)
1. Fe, HCl
2. NaOH
Cl
NH2
(95%)
NO2
Cl
21-73
Synthesis of Amines via Amides

O
COH
1. SOCl2
CN(CH3)2
2. (CH3)2NH
(86-89%)
only LiAlH4 is an
appropriate reducing
agent for this reaction
1. LiAlH4
2. H2O
CH2N(CH3)2
(88%)
21-74
Reductive Amination
21-75
Synthesis of Amines via Reductive Amination

In reductive amination, an aldehyde or ketone
is subjected to catalytic hydrogenation in the
presence of ammonia or an amine.
R
fast
C
R'
O + NH3
NH + H2O
R'
The aldehyde or ketone equilibrates with the

imine faster than hydrogenation occurs.
21-76
Synthesis of Amines via Reductive Amination

The imine undergoes hydrogenation faster
than the aldehyde or ketone. An amine is
the product.
R
fast
O + NH3
C
R'
C
H
NH + H2O
R'
R
R'
H2, Ni
NH2
21-77
Example: Ammonia gives a primary amine.
H2, Ni
O + NH3
H
NH2
ethanol
(80%)
via:
NH
21-78
Example: Primary amines give secondary amines

O
CH3(CH2)5CH
+ H2N
H2, Ni
ethanol
CH3(CH2)5CH2NH
(65%)
via:
CH3(CH2)5CH
N
21-79
Example: Secondary amines give tertiary amines
O
CH3CH2CH2CH
N
H
H2, Ni, ethanol
N
CH2CH2CH2CH3
(93%)
21-80
Example: Secondary amines give tertiary amines

possible intermediates include:
+
N
N
HO
CHCH2CH2CH3
CHCH2CH2CH3
N
CH
CHCH2CH3
21-81
Reactions of Amines:
A Review and a Preview
21-82
Reactions of Amines
Reactions of amines almost always involve the
nitrogen lone pair.
as a base:
as a nucleophile:
21-83
Reactions of Amines
Reactions already discussed
basicity (Section 21.4)
reaction with aldehydes and ketones (Chapter 17)
reaction with acyl chlorides,
anhydrides, and esters
21-84
Reactions of Amines with Alkyl

Halides
21-85
Reaction with Alkyl Halides

Amines act as nucleophiles toward alkyl halides.
N + R
N R + X
+
21-86
Example: excess amine
NH2
ClCH2
(4 mol)
(1 mol)
NaHCO3
90C
NHCH2
(85-87%)
21-87
Example: excess alkyl halide
CH2NH2
methanol
3CH3I
heat
+
CH2N (CH3)3 I
(99%)
21-88
The Hofmann Elimination
21-89

a quaternary ammonium hydroxide is the reactant
and an alkene is the product
is an anti elimination
the leaving group is a trialkylamine
the regioselectivity is opposite to the Zaitsev rule.
21-90
Quaternary Ammonium Hydroxides

are prepared by treating quaternary ammmonium
halides with moist silver oxide
CH2N (CH3)3 I
Ag2O
H2O, CH3OH
+
CH2N (CH3)3 HO
21-91

on being heated, quaternary ammonium
hydroxides undergo elimination
CH2 +
N(CH3)3
+ H2O
(69%)
160C
+
CH2N (CH3)3 HO
21-92
Mechanism
CH2
CH2
N(CH3)3
+
N(CH3)3
21-93
Regioselectivity
Elimination occurs in the direction that gives
the less-substituted double bond. This is called
the Hofmann rule.
H2C
CH3CHCH2CH3
+ N(CH3)3
HO
CHCH2CH3 (95%)
heat
+
CH3CH
CHCH3 (5%)
21-94
Regioselectivity
Steric factors seem to control the regioselectivity.
The transition state that leads to 1-butene is
less crowded than the one leading to cis
or trans-2-butene.
21-95
Regioselectivity
CH3CH2
CH3CH2
+ N(CH3)3
C
C
major product
largest group is between two H atoms
21-96
Regioselectivity
CH3
H
CH3
H
+ N(CH3)3
CH3
C
C
CH3
minor product
largest group is between an

H atom and a methyl group
21-97
Electrophilic Aromatic
Substitution
in Arylamines
21-98
Nitration of Anililne
NH2 is a very strongly activating group

NH2 not only activates the ring toward
electrophilic aromatic substitution, it also
makes it more easily oxidized
attemped nitration of aniline fails because
nitric acid oxidizes aniline to a black tar
21-99
Strategy: decrease the reactivity of aniline by
converting the NH2 group to an amide
O
NH2
O O
CH3COCCH3
CH(CH3)2
NHCCH3
(98%)
CH(CH3)2
(acetyl chloride may be used instead of acetic anhydride)

21-100
Strategy: nitrate the amide formed in the first
step
O
O
NHCCH3
NO2
CH(CH3)2
NHCCH3
HNO3
CH(CH3)2
(94%)
21-101
Strategy: remove the acyl group from the amide
by hydrolysis
O
NHCCH3
NO2
CH(CH3)2
NH2
NO2
KOH
ethanol,
heat
CH(CH3)2
(100%)
21-102
Halogenation of Arylamines
occurs readily without necessity of protecting
amino group, but difficult to limit it to
monohalogenation
NH2
NH2
Br2
Br
Br
acetic acid
CO2H
CO2H
(82%)
21-103
Monohalogenation of Arylamines
Decreasing the reactivity of the arylamine by
converting the NH2 group to an amide allows
halogenation to be limited to monosubstitution
NHCCH3
CH3
NHCCH3
CH3
Cl2
acetic acid
Cl
(74%)
21-104
Friedel-Crafts Reactions
The amino group of an arylamine must be protected
as an amide when carrying out a Friedel-Crafts
reaction.
NHCCH3
CH3
NHCCH3
CH3
CH3CCl
AlCl3
O
CCH3 (57%)
21-105
Nitrosation of Alkylamines
21-106
Nitrite Ion, Nitrous Acid, and Nitrosyl Cation
+
H
N
H
H
O
H
N
+
+
O
H
21-107
Nitrosyl Cation and Nitrosation
N
+
21-108
Nitrosyl Cation and Nitrosation

+
N
N
+
21-109
Nitrosation of Secondary Alkylamines

+
N
+
H
N
+
nitrosation of secondary
amines gives an Nnitroso amine
21-110
Example
(CH3)2NH
NaNO2, HCl
H2O
(CH3)2N
(88-90%)
21-111
Some N-Nitroso Amines
(CH3)2N
N-nitrosodimethylamine
(leather tanning)
N-nitrosopyrrolidine
(nitrite-cured bacon)
N-nitrosonornicotine
(tobacco smoke)
21-112
Nitrosation of Primary Alkylamines

R
H
H
N
+
H
H
N
+
analogous to
nitrosation of
secondary amines to
this point
21-113

R
H
R
N
H
this species reacts further
R
H
N
O
+
H
21-114
nitrosation of a
primary alkylamine
gives an alkyl
diazonium ion
process is called
diazotization
H
R
+
N
H
R
O
+
H
21-115
Alkyl Diazonium Ions
+ +
R
N
+
N
alkyl diazonium ions

readily lose N2 to
give carbocations
21-116
Example: Nitrosation of 1,1-Dimethylpropylamine
+
N
HONO
NH2
OH
(80%)
H2O
N2
+
(3%)
(2%)
21-117
Nitrosation of Tertiary Alkylamines

There is no useful chemistry associated with the
nitrosation of tertiary alkylamines.
R
R
N
R
R
R
+
N
21-118
Nitrosation of Arylamines
21-119
Nitrosation of Tertiary Arylamines

reaction that occurs is
electrophilic aromatic substitution
N(CH2CH3)2
1. NaNO2, HCl,
H2O, 8C
N(CH2CH3)2
2. HO
N
(95%)
21-120
Nitrosation of N-Alkylarylamines
similar to secondary alkylamines;
gives N-nitroso amines
NHCH3
NaNO2, HCl,
H2O, 10C
NCH3
(87-93%)
21-121
Nitrosation of Primary
Arylamines
gives aryl diazonium ions
aryl diazonium ions are much more stable than
alkyl diazonium ions
most aryl diazonium ions are stable under the
conditions of their formation (0-10C)
+
RN
+
ArN
N
N
fast
+
R
+ N2
slow
+
Ar
+ N2
21-122
Example:
(CH3)2CH
NH2
NaNO2, H2SO4
H2O, 0-5C
(CH3)2CH
+
N
N HSO4
21-123
Synthetic Origin of Aryl Diazonium Salts

Ar
H
Ar
NO2
Ar
NH2
Ar
+
N
N
21-124
Synthetic Transformations
of Aryl Diazonium Salts
21-125
Transformations of Aryl Diazonium Salts

Ar
Ar
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
21-126
Preparation of Phenols
+
N
Ar
N
H2O, heat
Ar
OH
21-127
Example
NH2
(CH3)2CH
1. NaNO2, H2SO4
H2O, 0-5C
2. H2O, heat
OH
(CH3)2CH
(73%)
21-128

Ar
Ar
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
21-129
Preparation of Aryl Iodides

reaction of an aryl diazonium salt with
potassium iodide
Ar
+
N
KI
Ar
21-130
Example
NH2
Br
1. NaNO2, HCl
H2O, 0-5C
I
Br
2. KI, room temp.

(72-83%)
21-131

Ar
Ar
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
21-132
Preparation of Aryl Fluorides
Ar
Ar
+
N
heat the tetrafluoroborate salt of a diazonium ion;

process is called the Schiemann reaction
21-133
Example
NH2
1. NaNO2, HCl,
H2O, 0-5C
CCH2CH3
O
2. HBF4
3. heat
CCH2CH3
O
(68%)
21-134

Ar
Ar
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
21-135
Preparation of Aryl Chlorides and

Bromides
Ar
Cl
Ar
Ar
+
N
Br
aryl chlorides and aryl bromides are prepared by

heating a diazonium salt with copper(I) chloride or
bromide
substitutions of diazonium salts that use copper(I)
halides are called Sandmeyer reactions
21-136
Example
NH2
1. NaNO2, HCl,
Cl
H2O, 0-5C
NO2
2. CuCl, heat
NO2
(68-71%)
21-137
Example
1. NaNO2, HBr,
NH2
Cl
H2O, 0-10C
Br
Cl
2. CuBr, heat
(89-95%)
21-138

Ar
Ar
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
21-139
Preparation of Aryl Nitriles
Ar
CN
Ar
+
N
aryl nitriles are prepared by heating a diazonium

salt with copper(I) cyanide
this is another type of Sandmeyer reaction
21-140
Example
1. NaNO2, HCl,
NH2
CH3
H2O, 0C
CN
CH3
2. CuCN, heat
(64-70%)
21-141

Ar
Ar
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
21-142

hypophosphorous acid (H3PO2) reduces diazonium
salts; ethanol does the same thing
this is called reductive deamination
+
N N
Ar
Ar
21-143
Example
NaNO2, H2SO4,
NH2
CH3
H3PO2
CH3
(70-75%)
21-144
Value of Diazonium Salts

1) allows introduction of substituents such as OH,
F, I, and CN on the ring
2) allows preparation of otherwise difficultly
accessible substitution patterns
21-145
Example
NH2
Br2
NH2
Br
NaNO2, H2SO4,
Br
H2O, CH3CH2OH
H2O
Br
Br
Br
(100%)
Br
(74-77%)
21-146
Azo Coupling
21-147
Azo Coupling
Diazonium salts are weak electrophiles.
React with strongly activated aromatic compounds
by electrophilic aromatic substitution.
Ar
+
N
N + Ar'
Ar
Ar'
an azo compound
Ar' must bear a strongly electron-releasing group
such as OH, OR, or NR2.
21-148
Example
OH
+
+ C6H5N
Cl
OH
N
NC6H5
21-149
Spectroscopic Analysis of Amines
21-150
Infrared Spectroscopy
the NH stretching band appears in the range
3000-3500 cm-1
primary amines give two peaks in this region, one
for a symmetrical stretching vibration, the other for
an antisymmetrical stretch
H
R
R
H
symmetric
H
N
H
antisymmetric
21-151
Infrared Spectroscopy
primary amines give two NH stretching peaks,
secondary amines give one
RNH2
R2NH
21-152
H NMR
compare chemical shifts in:
H3C
CH2NH2
H3C
3.9 ppm
N
H is more shielded than O
CH2OH
4.7 ppm
C
H
21-153
C NMR
13
Carbons bonded to N are more shielded than

those bonded to O.
CH3NH2
26.9 ppm
CH3OH
48.0 ppm
21-154
UV-VIS
An amino group on a benzene ring shifts max
to longer wavelength. Protonation of N causes
UV spectrum to resemble that of benzene.
+
NH2
NH3
max
204 nm
256 nm
max
230 nm
280 nm
max
203 nm
254 nm
21-155
Mass Spectrometry
Compounds that contain only C, H, and O have

even molecular weights. If an odd number of N
atoms is present, the molecular weight is odd.
A molecular-ion peak with an odd m/z value
suggests that the sample being analyzed contains
N.
21-156
Mass Spectrometry
Nitrogen stabilizes
carbocations, which
drives the fragmentation
pathways.
(CH3)2NCH2CH2CH2CH3
e
+
(CH3)2NCH2CH2CH2CH3
+
(CH3)2N
CH2
+ CH2CH2CH3
21-157
Mass Spectrometry
Nitrogen stabilizes
carbocations, which
drives the fragmentation
pathways.
CH3NHCH2CH2CH(CH3)2
e
+
CH3NHCH2CH2CH(CH3)2
+
CH3NH
CH2
+ CH2CH(CH3)2
21-158
End of Chapter 21
21-159

8chapter 21

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8chapter 21

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Chapter 21

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Nomenclature of Primary Alkylamines (RNH2)

analogous to alcohols: replace -e

name alkyl group and attach -amine

Dr. Wolf's CHM 201 & 202

Examples: some primary alkylamines

Nomenclature of Primary Arylamines (ArNH2)

Dr. Wolf's CHM 201 & 202

Amino groups as substituents

Dr. Wolf's CHM 201 & 202

Secondary and Tertiary Amines

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Structure and Bonding

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Most prominent feature is high electrostatic

Pyramidal geometry at sp3-hybridized N in

Note: this is not the same as the HNH bond angle

Dr. Wolf's CHM 201 & 202

Electrostatic Potential Maps of Aniline

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Boiling points of isomeric amines decrease in

Dr. Wolf's CHM 201 & 202

Effect of Structure on Basicity

1. Alkylamines are slightly stronger bases than

Dr. Wolf's CHM 201 & 202

Table 22.1 (page 920)

CH3CH2NH3+ is a weaker acid than NH4+;

Effect of Structure on Basicity

1. Alkylamines are slightly stronger bases than

Dr. Wolf's CHM 201 & 202

Table 22.1 (page 920)

Notice that the difference separating a primary,

Effect of Structure on Basicity

1. Alkylamines are slightly stronger bases than

Dr. Wolf's CHM 201 & 202

Table 22.1 (page 920)

Dr. Wolf's CHM 201 & 202

Decreased basicity of arylamines

Stronger pKa = 4.6

Dr. Wolf's CHM 201 & 202

Decreased basicity of arylamines

Dr. Wolf's CHM 201 & 202

Decreased basicity of arylamines

Decreased basicity of arylamines

pKa of conjugate acid:

Dr. Wolf's CHM 201 & 202

Effect of Substituents on Basicity of Arylamines

Effect of Substituents on Basicity of Arylamines

Lone pair on amine nitrogen is conjugated with

Dr. Wolf's CHM 201 & 202

is more basic than

is more basic than

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202

Dr. Wolf's CHM 201 & 202