Chapter 24.

Amines and
Heterocycles
胺與雜環

Based on McMurry’s Organic Chemistry, 9th edition

Amines – Organic Nitrogen Compounds
 Organic derivatives of ammonia, NH3,
 Nitrogen atom with a lone pair of electrons, making
amines both basic and nucleophilic
 Occur in plants and animals

2
 Why this Chapter?

 Amines and carbonyl compounds are the

most abundant and have rich chemistry

 In addition to proteins and nucleic acids, a

majority of pharmaceutical agents contain
amine functional groups

3
 24.1 Naming Amines
 Alkyl-substituted (alkylamines) or aryl-substituted (arylamines)
 Classified as primary 1° (RNH2), secondary 2° (R2NH), and tertiary 3°
(R3N)
 Depends on number of organic substituents attached to nitrogen

4
 Quaternary Ammonium Ions
 Quaternary ammonium salts 四級胺鹽 :
Compounds that carry a positively charged
nitrogen atom with four attached groups

5
 Structure & Classification
 Amines are further divided into aliphatic, aromatic,
and heterocyclic amines 雜環胺 :
 aliphatic amines 脂肪族胺 : amines in which nitrogen is
bonded only to alkyl groups
 aromatic amines 芳香族胺 : amines in which nitrogen is
bonded to one or more aryl groups
CH 3 CH 3
NH2 N -H CH 2 - N- CH 3

Aniline N-Methylaniline Benzyldimethylamine

(a 1o aromatic (a 2o aromatic (a 3o aliphatic amine)
amine) amine)
 Structure & Classification

 Heterocyclic amines 雜環胺 : amines in which

nitrogen is one of the atoms of a ring

N N N N
H H H
Piperidine Pyrrolidine Pyrrole Pyridine
(heterocyclic (heterocyclic
aliphatic amines) aromatic amines)

六氫吡啶 四氫吡咯 吡咯 吡啶
 IUPAC Names – Simple Amines
1° amine
 For Aliphatic amines: the suffix -amine is added to the name of the alkyl
substituent
 The IUPAC system retains the name aniline 苯胺 , the simplest aromatic amine

8
 IUPAC Names – “-amine” Suffix
1° amine
 The suffix -amine can be used in place of the
final -e in the name of the parent compound

2
3 1

9
IUPAC Names – Amines As Substituent

 Amines with more than one functional group are named by

considering the –NH2 as an amino substituent on the parent molecule

10
 Order of Precedence
 Order of prcedence : ranking function groups in order of
priority for the purposes of IUPAC nomemclature
 For compounds that contain more than one functional group
indicated by a suffix

Functional Suffix if Higher Prefix if Lower

Group in Precedence in Precedence
-CO 2 H -oic acid
-CHO
Precedene

-al oxo-
C=O -one oxo-
-OH -ol hydroxy-
-NH 2 -amine amino-
-SH -thiol mercapto-
 IUPAC Names – Multiple Alkyl Groups

 Symmetrical secondary and tertiary amines are

named by adding the prefix di- or tri- to the alkyl group

12
IUPAC Names – Multiple, Different Alkyl Groups
 Unsymmetrically substituted secondary and
tertiary amines
 Named as N-substituted primary amines
 Largest alkyl group is the parent name, and other
alkyl groups are considered N-substituents

13
 Common Names of Heterocyclic Amines
• Heterocyclic amines 雜環胺 : Compound in which
the nitrogen atom occurs as part of a ring
• Each ring system has its own parent name
• Nitrogen atom is always numbered as position 1

吡啶 吡咯 喹啉 嘧唑

吲哚 嘧啶 四氫吡咯 六氫吡啶 14
24.2 Structure and Properties of Amines

 Bonding to N is similar to that in ammonia

 N is sp3-hybridized

 C–N–C bond angles are close to 109° tetrahedral

value

15
 Chirality Is Possible (But Not Observed)
 An amine with three different substituents on nitrogen is chiral (in
principle but not in practice): the lone pair of electrons is the fourth
substituent
 The two enantiomeric forms rapidly interconvert by a pyramidal inversion
(ammonia, 2 x1011 inversions / second)
 Enantiomers cannot be resolved
 Chrial amines are optical inactive

16
 補充
Chiral Amines
Chiral cyclic amines: Amines in which the nitrogen is
restricted in rotation so it cannot interconvert.
•If the nitrogen atom is contained in a small ring, for example, it
is prevented from attaining the 120° bond angle that facilitates
inversion.
•Such a compound has a higher activation energy for inversion,

the inversion is slow, and the enantiomers may be resolved.

17
 Amines Form H-Bonds
 Amines with fewer than five carbons are water-soluble
 Primary and secondary amines form hydrogen bonds,
increasing their boiling points

18
 24.3 Basicity of Amines
 The lone pair of electrons on nitrogen makes amines
basic and nucleophilic
 They react with acids to form acid–base salts and
they react with electrophiles

19
 Basicity of Amines
 Amines are stronger bases than alcohols, ethers, or water
 Amines establish an equilibrium with water in which water
acts as an acid and transfers a proton to the amine
 The most convenient way to measure the basicity of an
amine (RNH2) is to look at the acidity of the
corresponding ammonium ion (RNH3+)
 acidity of corresponding conjugate acid
 High pKa → weaker acid and stronger conjugate base.

• the basicity of amines by reference to

Kb : base-dissociation constant of the amine
Ka: acid-dissociation constant of the corresponding
conjugate acid
20
 Basicity of Amines
• The basicity of an amine (RNH2)
RNH 2 + H 2 O RNH 3 + + OH -
[RNH 3+ ][OH - ]
Kb =
[RNH 2 ]
pK b = -logK b
• The acidity of the corresponding conjugate acid
ammonium ion (RNH3+)
RNH 3 + H 2 O RNH 2 + H 3O +
[RNH 2 ][H 3O + ]
Ka =
[RNH 3 ]
 pKa + pKb = 14
 Weaker base Smaller pKa for conjugate acid
Stronger base Larger pKa for conjugate acid
21
pKb

4.74

3.36
3.25

3.02

2.73

3.24

9.37

22
23
 General Patterns of Basicity
 Most simple alkylammmonium ions have pKa's of 10 to 11(pKb
3~4)
 Lone pair of electrons on nitrogen can accept a proton from an
acid
胺類鹼性在強弱取決於 N 上電子雲密度的高低和與質子結合能力的大小
 Arylamines and heterocyclic aromatic amines are considerably
less basic than alkylamines (conjugate acid pKa 5 or less)

24
 Effects on Amine Basicity
1. Substitution by alkyl group
 Alkyl groups are electron-donating toward cations
and methylamine has a methyl group to stabilize
the positive charge on nitrogen and make
methylamine a stronger base than ammonia.

25
 Effects on Amine Basicity

2. Resonance Effects
 Aromatic amines 芳香族胺 are considerably
weaker bases than aliphatic amines 烷基胺

N H2 + H2 O N H3 + OH - pK a = 10.66

Cyclohexylamine Cyclohexylammonium
hydroxide

N H2 + H2 O N H3 + OH - pK a = 4.63

Aniline Anilinium hydroxide

26
 Basicity-Aromatic Amines

 Aromatic amines are weaker bases than

aliphatic amines because of two factors
 resonance stabilization of the free base, which
is lost on protonation

H H + H H + H H + H
:N H N N N
:

:
:

Interaction of the electron pair on

nitrogen with the pi system of the
aromatic ring

27
 Effects on Amine Basicity
3.Hybridization Effects
 In pyridine the non-bonding electrons occupy an sp2
orbital, with greater s character and more tightly
held than those in the sp3 orbital of an aliphatic
amine.
 Electrons are held more tightly in orbitals with more
s character, so those compounds are weaker
bases.
Heterocyclic aromatic amines Heterocyclic aliphatic amines

Basicity:

<

吡啶 哌啶
 Basicity of Amides 醯胺
 Amides (RCONH2) are nonbasic, in contrast with
amines
 Amides are stabilized by delocalization of the nitrogen
lone-pair electrons with The C=O group
 Making the N a very weak base
 Amides are more stable than amines
 Stability is lost when protonated
Separation and purification of an amine component from a mixture

30
 Basicity of Amines
 Primary and secondary amines can act as very
weak acids
 N-H proton can be removed by a sufficiently
strong base
 24.4 Basicity of Substituted Arylamines
 Arylamines are less basic than alkylamines
 The N lone-pair electrons in arylamines are

delocalized by interaction with the aromatic ring’s 

electron system
 Are less able to accept H+

 Energy difference between protonated and

nonprotonated forms is higher for arylamines

32
 (larger positive ΔG°) (smaller positive ΔG°)

Arylamines have a larger positive ΔG° for protonation and are therefore
less basic than alkylamines, primarily because of resonance stabilization
of the ground state.
33
 Basicity of Arylamines
 Substituted arylamines can be more basic or less basic than
aniline
 Electron-donating substituents (such as CH3, NH2,
OCH3) increase the basicity of the corresponding arylamine
 Electron-withdrawing substituents (such as Cl, NO2,
CN) decrease arylamine basicity

芳香族胺取代基中，給電子基使鹼性增強，拉電子基使鹼性降低

34
35
 24.5 Biological Amines and the Henderson-
Hasselbalch Equation
Henderson-Hasselbalch Equation:
A  A 
pH  p K a  log   so log    pH  p K a
 HA   HA 
 To reflect structures at physiological pH:
 Cellular amines are written in their protonated form
 Amino acids in their ammonium carboxylate form

36
 胺的製備
O
O
1.Amine + O (Imine) 1. Amine + (Amide) NH
2.reduction 2. reduction R Cl
O

Reductive Acylation-reduction Gabrial

amination synthesis
LiAlH4 New
1 0, 2 0 , 3 0
New 10, 20 , 30
10 New
胺 NaOH+Br2
Azide LiAlH4 10 10 Amide
RN3 1 0
New 1 0

Sn/H2SO4 Hoffmann
LiAlH4
Reduction rearrangement
Nitrile Nitro
compound
RCN
Reduction Reduction 37
 24.6 Synthesis of Amines

Reduction of nitriles 氰化物 , amides, and nitro
compounds
 Amines can be prepared by reduction of nitriles
(CH 20-7) and amides (CH 21-7) with LiAlH4

(10 amine)

(10 , 20 , 30 amine)

Br CN CH2NH2
NaCN 1) LiAlH4
2) H2O
38
 Synthesis of Amines
 Reduction of Nitro group (CH 16-2)
 Arylamines are prepared from nitration of an aromatic compound and

reduction of the nitro group

 Reduction by catalytic hydrogenation over platinum is suitable if no other

groups can be reduced

 Iron, zinc, tin, and tin(II) chloride are effective in acidic solution

39
 SN2 Reactions of Alkyl Halides
Alkylation
 Simplest method of alkylamine synthesis is by S 2
N
alkylation of ammonia or an alkylamine with an
alkyl halide
 Ammonia and other amines are good nucleophiles

40
 Uncontrolled Multiple Alkylation
 Primary, secondary, and tertiary amines all have similar reactivity
 the initially formed monoalkylated substance undergoes further reaction to

yield a mixture of products (disadvantage of direct alkylation)

 Secondary and tertiary amines undergo further alkylation

41
 Selective Preparation of Primary Amines:
the Azide Synthesis

Azide ion, N3 疊氮化合物 displaces a halide ion from a primary
or secondary alkyl halide to give an alkyl azide, RN3
 Alkyl azides are not nucleophilic (but they are explosive),
overalkylation can not .

Reduction with LiAlH4 gives the primary amine

10 amine
42
 Gabriel Synthesis of Primary Amines
 Gabriel amine synthesis: A phthalimide 鄰苯二醯亞胺 alkylation for
preparing a primary amine from an alkyl halide
 only alkylate once.

 The N-H in imides (CONHCO) can be removed by KOH followed

by alkylation and hydrolysis

only alkylate
once

phthalimide anion

pKa= 8.3 鄰苯二醯亞胺負離子

10 amine
NaOH,H2O

10 amine
二醯亞胺負離子是很弱的鹼，它可以作為親核試劑，與鹵反應，取代後再水解，
是製備 1 胺的一種方法 43
 Reductive Aminationof Aldehydes and Ketones

 Reductive amination 還原胺化 : Treatment of an aldehyde or

ketone with ammonia or an amine in the presence of a reducing
agent (NaBH4 or H2/Ni)

44
Mechanism of Reductive Amination

imine

45
 Reductive Amination Is Versatile
 Ammonia, primary amines, and secondary amines yield
primary, secondary, and tertiary amines, respectively

46
 Hofmann and Curtius Rearrangements

 Carboxylic acid derivatives, amide and acyl azide, can

be converted into primary amines with loss of one
carbon atom by both the Hofmann rearrangement and
the Curtius rearrangement

10 amine

47
 Hofmann Rearrangement
 RCONH2 reacts with Br2 and base
 Gives high yields of arylamines and alkylamines
 Figure 24.5 See Mechanism

48
Figure 24.5 - Mechanism
Mechanism

Isocyanate
intermediate
 Curtius Rearrangement
 Heating an acyl azide prepared from an acid chloride
 Migration of R from C=O to the neighboring
nitrogen with simultaneous loss of a leaving group

heat

51
 24.7 Reactions of Amines
 Alkylation and acylation have already been presented
 Primary and secondary amines can also be acylated by
nucleophilic acyl substitution reaction

52
 Hofmann Elimination 霍夫曼脫去反應
 Converts amines into alkenes
 NH2 is very a poor leaving group so it converted to an 4o
alkylammonium ion, which is a good leaving group
 An amine is completely methylated by reaction with an excess amount of
iodomethane to produce the corresponding quaternary ammonium salt

less substituted alkene

4o
53
 Hofmann Elimination
 Silver Oxide Is Used for the Elimination Step
 Exchanges hydroxide ion for iodide ion in the quaternary ammonium
salt, thus providing the base necessary to cause elimination

C H 3 O H-
C H 3 I- +
+ H2 O C H 2 -N - C H 3 + A gI
C H 2 -N - C H 3 + A g2 O
CH3
CH3
(Cyclohexylmethyl)trimethyl-
(Cyclohexylmethyl)trimethyl- Silver
ammonium hydroxide
ammonium iodide oxide
54
 Orientation in Hofmann Elimination
 in the E2 reaction of an alkyl halide , Major
product is the more highly substituted alkene
product (Zaitsev's rule)
 However, Major product is the less highly
substituted alkene in the Hofmann elimination
 Non-Zaitsev result is probably steric
 Due to the large size of the trialkylamine leaving
group
 The base must abstract a hydrogen from the
most sterically accessible
 least hindered position

霍夫曼規則 - 主要脫去產物是取代基較少的烯。這是四級胺鹽特有的規則
55
Steric Effects Control the Orientation

56
 24.8 Reactions of Arylamines
 Electrophilic aromatic substitution
 Amino substituents are strongly activating, ortho- and para-directing
groups in electrophilic aromatic substitution reactions
 May trisubstitute with excess reagent.

苯胺

trisubstitute 57
 Reactions of Arylamines
• Arylamines monosubstitute reactions are
controlled by conversion to amide

胺轉變成醯胺
活性降低
反應為單取代產物
monosubstitute

58
 Arylamines Are Not Useful for Friedel-Crafts
Reactions
 The amino group forms a Lewis acid–base complex
with the AlCl3 catalyst, preventing further reaction
 Therefore we use the corresponding amide

H+ changes -NH2 to -NH3+, a meta-directing deactivator. 在酸中 , 反而為 deactivat

•

59

水解
胺轉變成醯胺
回復
可以進行 friedel-crafts 反應
胺基

59
 Formation of Sulfonamides
• Sulfa drugs ( 磺胺藥 ) are sulfonamides that are the first
pharmaceutical agents to be used clinically against
bacterial infection ( 抗菌藥 )
• Bacterial cannot distinguish between sulfonamide and p-
aminobenzoic acid.

Chlorosulfonic sulfanilamide
acid

NH2

O S O
NH2
60
 Diazonium Salts: The Sandmeyer Reaction
 Primary arylamines react with HNO2 (Nitrous acid 亞硝酸 ) yielding stable arenediazonium salts 芳香重氮鹽
 Corresponding alkanediazonium can not be isolated

 Arenediazonium salts are useful because the diazonium group can be replaced by a nucleophile in a substitution reaction

Aniline 苯胺 diazonium salt

芳香重氮鹽的化學性質非常活潑，能發生許多有機化學反應，可分為兩大類：
1 、取代反應－－重氮基被取代，同時放出氮氣的反應。
2 、偶合反應－－產生偶氮化合物 azo compound
61
 Nitrous Acid Reagent
 The nitrous acid is protonated, loses water to
form the nitrosonium ion (NO+).
 Nitrous acid ( HNO2 亞硝酸 ) can act as a source
of the nitrosonium ion, NO+ 亞硝醯基離子 , a
electrophile.
H
+
H + +
H O N O H O N O H2O + N O N O
+
nitrous acid nitrosonium ion

electrophile

62
 補充

Mechanism of diazotization of amine

63
 Reaction of Arenediazonium Salts
 The N2 group can be replaced by a nucleophile
Arenediazonium Salts 芳香重氮鹽

64
 Reaction of Arenediazonium Salts
Replacement of the diazonium by chloride, bromide,
cyanide with copper(I) salt CuCl , CuBr, CuCN.( 芳
香重氮鹽被溴 , 氯 , 氰基取代 )

X
copper(I) salt
HNO2 , H2SO4

HNO2 , H2SO4

HNO2 , H2SO4

65
 The Sandmeyer Reaction
• Sandmeyer reaction: Reaction of an arenediazonium
salt with the corresponding copper(I) halide to yield aryl
chlorides and bromides
 Aryl iodides can be prepared by direct reaction with
NaI without a copper(I) salt
Ar-NH2  Ar-Cl, Ar-Br, Ar-I
 Aryl Nitriles and Carboxylic Acids
 An arenediazonium salt and CuCN yield the nitrile, ArCN,
which can be hydrolyzed to ArCOOH

Ar-NH2  Ar-CN  Ar-COOH

67
 Formation of Phenols (ArOH)
 The diazonio group can be replaced by –OH to yield a phenol
 Reaction of the arenediazonium salt with copper(I) oxide in an
aqueous solution of copper(II) nitrate yield phenols

Ar-NH2  Ar-OH

68
 Reduction to a Hydrocarbon
 The diazonio group can be replaced by –H to yield an arene
 By treatment of a diazonium salt with hypophosphorous acid, H3PO2 次磷酸

Ar-NH2  Ar-H

69
 Mechanism of Diazonium Replacement

 Diazonium replacement takes place Through radical (rather than polar or ionic) pathways

70
 Diazonium Coupling Reactions
重氮偶合反應
 Arenediazonium salts undergo a coupling reaction with activated
aromatic rings, such as phenols and arylamines, to yield brightly
colored azo compounds 偶氮化合物 , ArN=NAr

electrophile

• Are typical electrophilic aromatic substitutions

71
 How Diazonium Coupling Occurs
 The electrophilic diazonium ion reacts with the electron-
rich ring of a phenol or arylamine
 Usually occurs at the para position but goes ortho if para
is blocked

72
 Azo Dyes
 Azo-coupled products 偶氮化合物 have extended 
conjugation that lead to low energy electronic transitions
that occur in visible light (dyes)

73
 Summary of Diazonium Reactions

Coupling Reaction

芳香重氮鹽的化學性質非常活潑，能發生許多有機化學反應，可分為兩大類：
1 、取代反應－－重氮基被取代，同時放出氮氣的反應。
74
2 、偶合反應－－產生偶氮化合物 azo compound
 24.9 Heterocycles Amines 雜環胺
 A heterocycle 雜環 is a cyclic compound that
contains atoms of two or more elements in its
ring, usually C along with N, O, or S

血紅素

• Possess same chemistry as their open-chain

counterparts 75
 Pyrrole
 Pyrrole 吡咯
 Simplest five-membered unsaturated heterocyclic aromatic amine

 Undergoes electrophilic substitution reactions

 Chemical properties are not consistent with the structural features of amine or a

conjugated diene

2
3
1

76
 Pyrrole
 Also aromatic, but lone pair of electrons is
delocalized, so much weaker base.

Lione pair e- on N involve in the ring
 Non-basic nitrogens in pyrrole

77
Lone-Pair Electrons of Pyrrole and Furan Are
π Electrons
• If a lone pair can be used to form a π bond in a resonance
contributor, the lone-pair electrons are π electrons.
 Chemistry of Pyrrole
 Pyrrole is more reactive toward electrophiles than
benzene
 Electrophilic substitutions occur at C2 next to the
 Reaction leads to intermediate cation having 3
resonance forms
 Reaction at C3 gives 2 resonance forms

79
 Electrophilic Substitutions of Pyrrole

C-2

C-3

80
 Imidazole
Imidazole 嘧唑


 Common five-membered heterocyclic aromatic amine

 Constituent of the amino acid histidine
 One of two nitrogens is basic, one is non-basic
Thiazole 噻唑 , five-memberde hetercyclic aromatic
amine

81
 Imidazole 嘧唑
this pair of electrons
this pair of is a part of the
electrons aromatic sextet
3 1
is not a part
of aromatic
N N H

basic non basic

1
H
N
- pKa = 6.10
Amino acid CH2 CHCO 2
N
3 + +
Histidine NH
H 3
82
82
 Thiazole 噻唑
 Contains six  electrons, aromatic
 Each carbon contributes one electron, nitrogen
contributes one electron, and sulfur contributes
two electrons to the ring  system
 Sulfur and nitrogen have lone electron pairs in sp2
orbitals that lie in the plane of the ring
 Pyridine 吡啶
 Nitrogen-containing heterocyclic analog of benzene
• Heterocyclic aromatic compound.

• Pyridine has six delocalized electrons in its pi

system.
 The two non-bonding electrons on nitrogen are in
an sp2 orbital, and they do not interact with the pi
electrons of the ring. This pair of electrons on
nitrogen is not involve in aromatic
• Basic nitrogens on pyridine

• The sp2-hybridized nitrogen atom is less basic

than the sp3-hybridized nitrogen in an alkylamine

Pyridine 吡啶

basic

lone pair e- on N
not involve in the ring

85
 Electrophilic Substitutions of Pyridine
•
Underdoes electrophilic aromatic substitutions with
difficulty
• High dipole moment

• Pyridine is less reactive toward electrophiles than

benzene

• Give 3-substituted products

86
 3-substituted for Pyridine
• Electrophilic aromatic substitution reactions of pyridine normally occur at C3
• Reaction at C3 is favored over reaction at C2 or C4

no octet

no octet 87
 Pyrimidine 嘧啶
 Heterocyclic aromatic compound.

88
 Pyrimidine 嘧啶
this pair of electrons
is not a part of the
1. Planar
aromatic sextet
2. Cyclic, p orbital basic
on each atom of
the ring
3. 6  electron
N
• aromatic N
• resonance energy

= 26 kcal/mol
basic
DNA base: aromatic
O O NH 2
4
3 CH3
N 5 HN HN N
2 6
N O N1 O N1 O N1
1
H H H
Pyrimidine Uracil (U) Thymine (T) Cytosine (C) 89
89
Polycyclic Heterocyclic Amines 多環雜環胺
 Polycyclic heterocycles
 Quinoline, isoquinoline, and indole contain both a
benzene ring and a heterocyclic aromatic ring
 Purine contains two heterocyclic rings joined
together
 Quinoline and isoquinoline are less reactive
towards electrophilic substitution
 Indole undergoes electrophilic substitution more
easily than benzene
Polycyclic Heterocycles 多環雜環胺

喹啉 異喹啉 吲哚 嘌呤

91
Electrophilic Substitutions of Quinoline

92
 Electrophilic Substitutions of Indole

• Purine has three basic, pyridine-like nitrogen atoms

93
24.10 Spectroscopy of Amines -Infrared
Infrared Spectroscopy:
 1° and 2° amine are identified by characteristic

N–H stretching absorptions 3300 to 3500 cm1

 Amine absorption bands are sharper and less

intense than hydroxyl bands

 N–H bend (scissor) is noticed above 1600 cm –1

94
Nuclear Magnetic Resonance Spectroscopy

 N–H hydrogens appear as broad signals without clear-

cut coupling to neighboring C–H hydrogens
 In D2O exchange of N–D for N–H occurs, and the N–H
signal disappears

95
 Chemical Shift Effects
 Hydrogens on C next to N and absorb at lower field than
alkane hydrogens
 N-CH3 gives a sharp three-H singlet at  2.2 to  2.6

C7H15N

96
 13
C NMR Spectroscopy

 Carbons next to amine N are slightly deshielded -

about 20 ppm downfield from where they would
absorb in an alkane

97
 Mass Spectrometry
 A compound with an odd number of nitrogen atoms has
an odd-numbered molecular weight
 Presence of N can be detected observing the spectrum

 Alkylamines cleave at the C–C bond nearest the nitrogen

to yield an alkyl radical and a nitrogen-containing cation

98
 Mass Spectrum of N-Ethylpropylamine
 The two modes of a cleavage give fragment ions at
m/z = 58 and m/z = 72.

99
Summary
 Amines are organic derivatives of ammonia
 Basicity of arylamines is lower than that of
alkylamines
 Nitrogen lone-pair electrons are delocalized by
interaction with the aromatic  system
 Compounds that contain one or more nitrogen
atoms as part of a ring are called heterocyclic
amines
 Alkylamines are prepared by SN2 reaction of
ammonia or an amine with an alkyl halide or by
Gabriel amine synthesis
Summary
 Reductive amination is a reaction in which a
ketone or an aldehyde is treated with an amine in
the presence of a reducing agent such as NaBH4
 Amines result from Hofmann and Curtius
rearrangements of carboxylic acid derivatives
 Hofmann elimination - A process in which amines
also undergo E2 elimination to yield alkenes, first
quaternized by treatment with iodomethane and
then heated with silver oxide
Summary
 Arylamines are converted by diazotization with
nitrous acid into arenediazonium salts
 The diazonio group can then be replaced by
other substituents by Sandmeyer reaction
 Diazonium salts undergo coupling with phenols
and arylamines to give brightly colored azo
compounds