Bioorganic Chemistry
Amines
Chapte 16
Amines
 Amine
Nomenclature
– Amines are derivatives of Ammonia, NH3
– Classified as 1o, 2o, and 3o amines
H
R
N H
a primary amine
R''
H
R
N R'
a secondary amine
(Count R groups on Nitrogen.)
R
N R'
a tertiary amine
IUPAC Nomenclature
Amines are named by naming the “R” groups
And adding “amine” as a suffix
CH 3
CH 3
CH 2
H2N C CH 3
CH 3 CH 2 N CH 2 CH 3
triethylamine
CH 3
t-butylamine
CH 3
CH 3 NH CH 2 CH 3
H2 N
CH
methylethylamine
CH 3
isopropylamine
Nomenclature
 Aromatic
amines
– Aniline is parent
– Substitution on N is named as a
“N-alkyl” or “N,N-dialkyl” aniline
HN CH 3
NH 2
aniline
CH 3 CH 2 N CH 2 CH 3
Br
N-methylaniline
meta-bromo-N,N-diethylaniline
3
Nomenclature
 Nomenclature
– Use a “N” to locate alkyl groups
– More complicated amines are use “amino” to
name the N group as a substituent
COOH
HN CH 2 CH 2 CH 3
Cl
2o-chloro-N-propylaniline
NH 2
O
CH 3 CH CH 2 C OH
3-aminobutanoic acid
NH 2
p-aminobenzoic acid
Nomenclature
 Heterocyclic
N
H
N
QuickTime™ and a
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Amines
N
H
N
H
N
Pyrrole
Pyrrolidine
N
Pyridine *
Piperidine
Pyrimidine *
A Little Organic Fun
 http://www.youtube.com/watch?v=mAjrnZ-
znkY
 http://www.youtube.com/watch?v=HPGE_
GJkLJA
Physical Properties
 Amine
Physical Properties
– Boiling points slightly
lower than alcohols
– Hydrogen bonding
H
CH 3 N CH 2 CH 3
methylethylamine
» occurs with 1o and 2o amines
» not possible with 3o amines
– Water solubility is similar to same MW
alcohols
Physical Properties
 Amine
Physical Properties
– Strong odors
» simple amine have an odor similar to ammonia
» resemble the odor of raw fish
» some diamines have especially bad odors
H2C CH 2 CH 2 CH 2
NH 2
NH 2
Putrescine
(1,4-diaminobutane)
H2C CH 2 CH 2 CH 2 CH 2
NH 2
NH 2
N
Pyridine
Cadaverine
(1,5-diaminopentane)
Reaction of Amines
 Amines
are BASES!
– React with acids and accept a proton (H+) to
Form alkyl ammonium salts
H3C NH 2 + HCl
methylamine
CH 3 CH 2 NH CH 2 CH 3 + HCl
H3C NH 3+ Clmethylammonium chloride
+
CH 3 CH 2 NH 2 CH 2 CH 3 Cl diethylammonium chloride
diethylamine
+
CH3 NH CH 3 Cl -
CH 3 N CH 3
+ HCl
N,N-dimethylaniline
N,N-dimethylanilinium chloride
Reaction of Amines
 Amines
are BASES!
CH 3 CH 2 NH CH 2 CH 3 + CH 3COOH
diethylamine
acetic acid
?
+
CH 3 CH 2 NH 2 CH 2 CH 3 CH 3COO diethylammonium acetate
Reaction of Amines
 Amines
are BASES!
CH 3 CH 2 NH CH 2 CH 3 + CH 3COOH
diethylamine
acetic acid
+
CH 3 CH 2 NH 2 CH 2 CH 3 CH 3COO diethylammonium acetate
Nomenclature
 Nomenclature
H3C NH 2 + HCl
methylamine
H3C NH 3+ Clmethylammonium chloride
Quaternary Ammonium Salts
 Four
alkyl groups on N
– only with ammonium salts
– NOT made by acidifying an amine
+CH 3
H3 C CH 2 N CH 2 CH 3 Br
CH 3
diethyldimethylammonium bromide
So……. Tell me about some Way
Cool far out Amines…………..
From Yahoo Images
Alkaloids
 Nitrogen
containing compounds found in
roots, bark, leaves, berries, or fruit.
 Thousands have been extracted (in
containers or by chewing) and used to
produce physiological effects in humans
and animals
 Some are deadly poisons, some cure
diseases and some are addictive drugs
N CH 3
H
O C CH
O CH 2OH
atropine
Alkaloid Example
 Coniine
– Simple alkaloid
– Very poisonous
– Hemlock plant
N
H
» Socrates (469-399 BC)
Hemlock From Yahoo Images
CH 2 CH 2 CH 3
coniine
Socrates (469-399 BC) was found guilty
of corrupting the minds of the youth
of Athens and sentenced to death
by drinking a mixture containing
poison hemlock.
Alkaloid Example
 Nicotine
–
–
–
–
Found in smoking, chewing
Stimulant in small doses
Habit forming
Tars, CO, carcinogens
present in smoke
How do you know how much
Nicotine is in a smoke?
From Yahoo Images
N
N
CH 3
nicotine
Alkaloid Example
 Caffeine
– Stimulating action
– Found in:
» coffee
» tea (black, green)
» colas
» No-Doz
» chocolate (theobromine)
O
H3C
O
N
C
CH 3
C
N
N
N
CH 3
caffeine
From Yahoo Images
Alkaloid Example
 Atropine
– Plants:
» henbane
» Belladonna- (deadly nightshade)
From Yahoo Images
– Dilate pupils of eyes
» “used by Cleopatra and
Roman Women to
Enlarge the pupils to
Look more attractive
N CH 3
H
O
C CH
O CH 2OH
atropine
Alkaloid Example
 Morphine
– Found in Opium Poppy
– Simular compounds include
Codeine, Heroin, Demerol, Methadone
– Valuable pain killer
– Troubled drug for abuse
HO
O
N
CH 3
HO
morphine
From Yahoo Images
Other Alkaloid Example
 Quinine
– Cinchona bark
– Used to treat
Malaria
 Strychnine
CH=CH 2
OH
N
HC
CH 3O
N
quinine
– Nux Vomica
– rat poison
 Reserpine
– Indian Snake Root
– lowers bp
Indian Snake Root from Yahoo Images
Amphetamines
 Amphetamines
– Synthetic amines
– Powerful stimulants CNS
» reduce fatigue
» raise glucose blood level
» control mild depression
» reduce hyperactivity in children
» appetite depressant
CH 2 CH CH 3
NH 2
amphetamine (benzedrine)