AMINES

Amines
– Amines contain a nitrogen atom that is bonded to at least one carbon
group
– Can think of amines as derivatives of ammonia, NH3

– aliphatic amine: all carbons bonded to nitrogen are derived from alkyl
groups
– aromatic amine: one or more of the groups bonded to nitrogen are aryl
groups
 Classification of Amines
– Amines are classified as 1°, 2°, or 3° depending on the
number of carbon groups attached to nitrogen
– Aliphatic amine: Only alkyl groups bonded to the nitrogen
– Aromatic amine: One or more aromatic (or aryl) groups
bonded to the nitrogen
Seatwork
 Heterocyclic Amines
– Heterocyclic amine: Amine in which the nitrogen atom is
part of a ring
– Heterocyclic aliphatic amine: Heterocyclic amine in which
the ring is saturated (has no C=C bonds)
– Heterocyclic aromatic amine: Amine nitrogen is part of an
aromatic ring
• Important in nature
 Common Names (easier)
• Aliphatic amines: List the groups bonded to
nitrogen in alphabetical order followed by the
suffix –amine
• Entire name given in one word
 IUPAC Nomenclature
• IUPAC names
– IUPAC names for aliphatic amines derived in similar
way as alcohol names
– Drop the final -e of the parent alkane and replace it by -
amine
– Use a number to locate the amino group on the parent
chain
 IUPAC Nomenclature
– Uses common name aniline for C6H5NH2, the simplest
aromatic amine
– Use numbers to locate substituents OR
– Use the prefixes ortho (o), meta (m), and para (p)
– Several aniline derivatives have common names that are
still widely used
 IUPAC Nomenclature
– Name unsymmetrical secondary and tertiary amines as N-substituted
primary amines
– Take the largest group bonded to nitrogen as the parent amine
– Name the smaller group(s) bonded to nitrogen
– Show their location on nitrogen by using the prefix N (indicating that
they are bonded to nitrogen)
Seatwork
Seatwork
 Ammonium salts
N is group 5

5 valence electrons

NH3 has an unshared pair

that can form a fourth bond
but with a + charge on N
 Nomenclature of Amine Salts
• Amine salts
– Have four atoms or groups of atoms bonded to a nitrogen atom i.e.,
CH3NH3+
– Nitrogen bears a positive charge
– Ion is a quaternary ion-4 bonds to N with + charge
– Positive ion is associated with an anion as a salt
– Compound named as a salt of the corresponding amine
• Replace the ending -amine (or aniline or pyridine etc.) by -ammonium (or
anilinium or pyridinium etc.)
• Add the name of the anion
Seatwork
Seatwork
 Physical Properties
• Small amines have very nasty, sharp,
penetrating odors
– Trimethylamine smells like rotting fish
– Names sometimes reflect their odors:
• 1,4-butanediamine is putrescine
• 1,5-pentanediamine is cadaverine
 Physical Properties
• Amines are polar compounds
– 1° and 2° amines have N-H bonds and can form
hydrogen bonds with one another
– 3° amines have no N-H bond and cannot form
hydrogen bonds with one another
 Physical Properties
– Hydrogen bonds between amines are weaker than hydrogen
bonds between alcohols, because O is more electronegative
than N
– Boiling points of amines lower than those of comparable
alcohols
– Boiling points of amines higher than those of comparable
alkanes
– Compare ethane, methanamine and methanol:
 Physical Properties
– Amines form hydrogen bonds with water and are
more soluble in water than are hydrocarbons of
comparable molecular weight
– Most small amines are completely soluble in water
– Larger amines are only moderately soluble in
water or are insoluble
 Basicity of Amines
• Amines are weak bases
• Aqueous solutions of amines are basic
– Acid-base reaction between an amine and water
involves transfer of a proton from water to the amine

Base Conjugate acid

 Reactions of Amines
• Basicity is most important chemical property of
amines
– Amines, whether soluble or insoluble in water, react
quantitatively with strong acids to form water-soluble
salts
 Basicity of Amines
• Aliphatic amines
– Weak base
– Basicity similar to ammonia
– Stronger than aromatic amines

• Aromatic or Heterocyclic aromatic amines

– Very weak base
– Weaker than aliphatic amines
Basicity of Amines
 Basicity of Amines
• Which form of an amine exists in blood?
– pH of blood is approximately 7.40, which is slightly basic
– Thus an aliphatic amine dissolved in blood exists
predominantly in its protonated (conjugate acid) form
 Physical Properties of
Quaternary Ammonium
Salts
• Unlike 1o, 2o and 3o amines, quaternary nitrogens
have 4 bonds and a +1 charge
• They are associated with an anion
– Cocaine exists as “free base” or “crack” (smoked) and as
HCl salt (injected)
 Physical Properties of
Quaternary Ammonium
Salts
• Melting and Boiling points much higher than amines
(held together by charges)
• Salts are much more soluble in water
– Many drugs are made as hydrochloride salts rather than
just free amines
– Cocaine exists as “free base” or “crack” (smoked) and as
HCl salt (injected)
 Seatwork
– example: complete each acid-base reaction
and name the salt formed
 Seatwork
– example: complete each acid-base reaction
and name the salt formed
– solution:
 Aminoalcohols found in Lipids
• Ethanolamine

• Choline

• Sphinogosine
 Alkaloids
• Alkaloids are basic compounds obtained
from plants
• Alkaloids contain nitrogen
• Alkaloids frequently have physiological
effects
• Alkaloids are often poisonous
• Common names often end in “ine”
 Alkaloids

Cocaine

Caffeine Coniine (from hemlock)

 Properties of Cocaine
Property Free Base HCl Salt
freebase/crack

Melting point oC 98 195

Solubility in H2O Low high

Solubility in High none

fats/oils
Volatility High Low
Smoked Injected/inhaled
 Related Alkaloids
• Many compounds are related
– Heroin: H’s replaced by acetate
– Codeine: Blue H replaced by methyl

• Codeine
• Heroin
• Demerol
• Methadone
Common Drugs

• Amphetamine

• Methamphetamine