Alcohols, Phenols, and Thiols

Wednesday, December 8, 2021

11:38 PM
Bonding Characteristics of final -e from the alkane name and adding
the suffix -ol.
Oxygen Atoms in Organic o Rule 2: Number the chain starting at the
Compounds end nearest the hydroxyl group, and use the
appropriate number to indicate the position
Oxygen
-may have 2 single bonds or 1 double bond of the —OH group.
-In numbering of the longest
carbon chain, the hydroxyl group
has priority over double and triple
bonds, as well as over alkyl,
cycloalkyl, and halogen
substituents.
Carbon Hydrogen Oxygen o Rule 3: Name and locate any substituents
present.
o Rule 4: In alcohols where the —OH group is
attached to a carbon atom in a ring, the
hydroxyl group is assumed to be on carbon
1. Numbering then proceeds in a clockwise
or counterclockwise direction to give the
next substituent the lower number. The
number “1” is omitted from the name since
Alcohol by definition the hydroxyl-bearing carbon is
-organic compound in which an OH (Hydroxyl) carbon 1.
group is bonded to a saturated hydrocarbon

Ex.

Nomenclature for Alcohols

• Common names
-exists for alcohols with simple (generally C1
through C4) alkyl groups.
o Rule 1: name all of the carbon atoms of the
molecule as a single alkyl group
Alcohols with More Than One
o Rule 2: add the word alcohol, separating Hydroxyl Groups
with a space Polyhydroxy alcohols
-possess more than one hydroxyl group.
3 Triol
2 Diol
-final -e of the parent alkane name is retained for
pronunciation reasons

• IUPAC Nomenclature
-for alcohols containing a single hydroxyl
group
o Rule 1: Name the longest carbon chain to
which the hydroxy group is attached. The
chain name is obtained by dropping the
Important Commonly
Encountered Alcohols
6 commonly encountered alcohols:
1. Methyl Alcohol (Methanol)
-one carbon atom and one -OH group
-simplest alcohol
-colorless liquid
-good fuel for internal combustion engines
-methyl alcohol fuel fires are easier to
put out than gasoline fires bc water
mixes with and dilutes methyl alcohol).
-has excellent solvent properties
-solvent of choice for paints, shellacs,
varnishes
-AKA wood alcohol
-terminology draws attention to an
early method for its preparation -
heating of wood to a high temperature
in the absence of air.
-drinking this is very dangerous
-it is oxidized by the liver enzyme
alcohol dehydrogenase to the toxic
metabolites formaldehyde (for
embalming) and formic acid.
Formaldehyde - can cause
temporary or permanent
blindness
Formic acid - causes acidosis
2. Ethyl Alcohol (Ethanol)
-safe to ingest but at a certain degree
-2-carbon monohydroxy alcohol
-alcohol present in alcoholic beverages
-commonly known as alcohol or drinking
alcohol
-like methanol, it is oxidized by the liver
enzyme alcohol dehydrogenase
-Acetaldehyde - first oxidation product,
largely responsible for symptoms of
hangover, further converted into acetic
acid
-oxidation products are less toxic than those
of methyl alcohol
-extracted from grains (ex. Rice, etc.)
-may cause birth defects to babies (when
ingested during pregnancy)
-Fetal Alcohol Syndrome
-decrease of IQ points of babies
-ingestion of this: lead to liver cirrhosis,
memory loss, addiction
-Proof - percentage of alcohol present divided
by 2
3. Isopropyl Alcohol (2-Propanol)
-70% isopropyl and 30% water - marketed as
the rubbing alcohol.
-has a rapid evaporation rate that creates a
dramatic pulling effect when it is applied to
the skin, hence its use for alcohol rubs to
combat high body temperature.
-has bitter taste
-toxicity is twice that of ethyl alcohol
-fewer fatalities as it often induces
vomiting and thus doesn't stay down to
long enough to be fatal.
-large amount (about 150mL) of ingested
isopropyl alcohol can be fatal
-death occurs from paralysis of the CNS.
4. Ethylene Glycol (1,2-Ethanediol)
5. Propylene glycol (1,2-Propanediol)
-two simplest alcohols possessing 2 -OH
groups
-examples of diol
-also classified as glycols
-glycol - diol in which the 2 -OH groups
are on adjacent carbon atoms.
-both are colorless odorless, high-boiling
liquids that are completely miscible with
water.
-major uses - main ingredient in automobile
"year-round" antifreeze and airplane "de-
icers"
-Ethylene glycol
-extremely toxic when ingested
-oxidized by liver enzymes into oxalic
acid
Oxalic acid -calcium salt,
crystallizes in the kidneys leading
to renal problems, enveloped-
shaped crystals under microscope
 -Propylene glycol
-essentially nontoxic and has been used
as a solvent for drugs.
6. Glycerol (1,2,3-Propanetriol)
-example of triol
-AKA glycerin
-clear, thick liquid that has the consistency of
honey
-molecular structure - 2 -OH groups on 3
different carbon atoms.
-normally present in human body bc it is a
product of fat metabolism
-present, in combined form, in all animal fats
and vegetable oils
-"biological antifreeze" for Arctic species
-bc it has great affinity for water vapor
(moisture)
-it is often added to pharmaceutical
preparations such as lotions and soaps.
-florists sometimes use it to cut flowers to
help regain water and maintain freshness.
-lubricates properties also make it useful in
shaving creams and in applications such as
glycerol suppositories for rectal
administration medicine.
Monohydroxy alcohols
-only on hydroxyl group
-ex. Methyl and ethyl
Classification of Alcohols
1. Primary Alcohol (1°)
-an alcohol in which the hydroxyl-bearing
carbon atom is bonded to only 1 other carbon
atom.
2. Secondary Alcohol (2°)
-the hydroxyl bearing carbon atom is bonded
to 2 other carbon atoms
3. Tertiary Alcohol (3°)
-the hydroxyl bearing carbon atom is bonded
to 3 other carbon atoms
Chemical Reactions of Alcohols
Combustion
-hydrocarbons of all types undergo combustion in
air to produce CO2 and H2O
-alcohols are also flammable; combustion products
are CO2 and H2O
Intramolecular Alcohol Dehydration
-dehydration reaction
-chemical reaction in which the components
of water (H and OH) are removed from a
single reactant or from 2 reactants (H from
one and OH from the other).
-both water components are removed from the
same molecule.
-reaction conditions: temperature of 180°C and
presence of sulfuric acid as a catalyst
-dehydration product: an alkene
-is an example of elimination reaction
-elimination reaction - reaction in which two
groups or two atoms on neighboring carbon
atoms are removed, or eliminated, from a
molecule, leaving a multiple bond between
the carbon atoms.
-lower temp. (140°C)
-an intermolecular rather than an
intramolecular alcohol dehydration process
can occur to produce as ether
Ether - a compound with the general
structure R-O-R
-ether formation
-2 alcohol molecules interact, an H atom being
lost from one and an -OH group from the
other
-resulting "leftover" of the 2 alcohol
molecules join to from the ether
Intermolecular Alcohol Dehydration
-Condensation
-a chemical reaction in which 2 molecules
combine to form a larger one while liberating
a small molecule usually water
-2 alcohol molecules combine to give an ether and
water
Halogenation
-alcohols undergo halogenation reactions in which
a halogen atom is substituted for the hydroxyl
group, producing and alkyl halide.

Structural Characteristics of
Phenols
Phenols
-organic compound in which an -OH group is
attached to a carbon atom that is part of an
aromatic carbon ring system.
-general formula: Ar-OH, where Ar represents aryl
group
-aryl group - an aromatic carbon ring system from
which one hydrogen atom has been removed.
-hydroxyl group - thus the functional group for both
phenols and alcohols
-Physical and Chemical Properties of Phenols
• Generally low-melting solids
• Oily liquids at room temperature
• Most of them are only slightly soluble in
water
• Many have antiseptic and disinfectant
properties
• Simplest phenol - phenol itself, is a colorless
solid with a medicinal odor
• Melting point is 41°C
• More soluble in water that are most other
phenols
Alcohol Phenols

-Nomenclature for Phenols Flammable Flammable

• Simply extensions of the rules used to name Dehydration is only for No dehydration
benzene derivatives with hydrocarbon or alcohols
halogen constituents
• Parent name is phenol Undergoes halogenation Undergoes
-Ring numbering always begins with the halogenations
hydroxyl group and proceeds in the direction
that gives the lower number to the next
-Occurrence of and Uses of Phenols
carbon atom bearing a substituent. The
• Dilute (2%) solutions of phenol have been
numerical position of the hydroxyl group is
used as antiseptics
not specified in the name because it is 1 by • Concentrated phenol solution may cause
definition.
sever skin burn
• Today, it has been replaced by phenol for
more effective phenol derivatives (ex. 4-
hexylressorcinol)
4-hexylresssorcinol - ingredient in many
mouthwash and throat lozenges

• Methyl and Hydroxy group derivatives of

phenol have IUPAC-accepted common
names
• Methylphenols are called cresols
-cresol applies to all 3 isomeric
methylphenols
• Phenol derivatives a-phenylphenol and 2-
benzyl-4-chlorophenol - active ingredients
in Lysol

• Hydroxyphenols - for hydroxyphenols, each

of the 3isomers has a different common
name
 • A number of phenols found in plants are
used as flavoring agents and/or
antibacterial.
• Thymol - obtained from the herb thyme,
possesses both flavorant and antibacterial
properties. It is used as an ingredient in
several mouthwash formulations.
• Eugenol - is responsible for the flavor of
cloves. Dentists traditionally used clove oil
as an antiseptic because of eugenol’s
presence
• Vanillin, which gives vanilla its flavor, is
extracted from the dried seed pods of the
vanilla orchid.
• Lower boiling points than alcohols of
similar size and a strong disagreeable odor
• The familiar odor of natural gas results
from the addition of a low concentration of
methanethiol (CH3—SH) to the gas
• The exceptionally low threshold of
detection for this thiol enables consumers
to smell a gas leak long before the gas,
which is itself odorless, reaches dangerous
levels.

Sulfur Analogs of Alcohols

Sulfur analogs
-many organic compounds containing oxygen have
-a sulfur atom has replaced an oxygen atom

Thiols
-sulfur analogs of alcohols
-contain -SH functional groups instead of -OH
functional groups
-sulfhydryl group - thiol functional group, SH
functional group
-organic compound in which a sulfhydryl is bonded
to a saturated carbon atom
-older term is mercaptans

-Nomenclature
• Thiols are named in the same way as
alcohols in the IUPAC system, except that
the –ol becomes -thiol. The prefix thio-
indicates the substitution of a sulfur atom
for an oxygen atom in a compound
• As in the case of diols and triols, the -e at the
end of the alkane name is also retained for
thiols.

• Common names for thiols are based on

use of the term mercaptan, the older
name for thiols. The name of the alkyl
group present (as a separate word)
precedes the word mercaptan.

-Properties
Aldehydes and Ketones
Thursday, December 9, 2021
7:50 AM
Aldehydes
-have a carbonyl group bonded to a carbon atom on
one side and a hydrogen atom on the other side
Carbonyl group - carbon with double bond
with oxygen
-Formaldehyde - an exception bc it has hydrogen
atoms on both sides
Ketones
-have carbonyl group bonded to carbon atoms on
both sides
Nomenclature of Aldehydes and
Ketones
• Aliphatic aldehydes are named
substitutively in the IUPAC system by
replacing the final -e of the name of
corresponding alkane with -al
• Since the aldehyde group must be at the end
of carbon chain, there is no need to indicate
its position.
-When other substituents are present the
carbonyl group carbon is assigned position 1.
• Common names are derived from the
common names for the corresponding
carboxylic acids, and some of them are
retained by IUPAC as the acceptable names
• Aldehydes in which CHO group is attached
to a ring system are named substitutively by
adding the suffix carbaldehyde
• Aliphatic ketones are named substitutively
by replacing final -e of the name of the
corresponding alkane with -one.
• The chain is then numbered in the way that
gives the carbonyl carbon atom, the lower
possible number, and this number used to
designate its position.
Common functional group names for ketones
are obtained simply by separately naming the
two groups attached to the carbonyl group
and adding the word ketone as a separate
word.
• Some ketones have common names that are
retained in the IUPAC system
Physical Properties
-the carbonyl group is a polar group; therefore,
aldehydes and ketones have higher boiling
point than hydrocarbons of the same molecular
weight.
-they cannot have strong hydrogen bonds
between their molecules, they have lower boiling
points that the corresponding alcohols
-the carbonyl oxygen atom allows molecules of
aldehydes and ketones to form strong hydrogen
binds to molecules of water. As a result, low-
molecular-weight aldehydes and ketones show
appreciable solubilities in water.
-short chains are more soluble than long
chains (high molecular weight

-melting point is also affected - higher carbon
content, higher melting point
Chemistry of Aldehydes & Ketones
• Used in perfumes
-bc many have pleasant fragrances
• With the development of synthetic organic
chemistry in the 19th century, many
ingredients now used in perfumes result
from the creativity of lab chemists.
Synthesis of Aldehydes
Aldehydes by Oxidation of 18 Alcohols
-oxidation state of an aldehyde lies between that of
an 18 alcohol and a carboxylic acid
-aldehydes can be prepared from 18 alcohols by:
o Swern oxidation
o Oxidation with pyridinium
chlorochromate (C5H5NHCrO3Cl-, or PCC)
The ff are examples of Swern oxidation and
PCC oxidation:
Aldehydes by Ozonolysis of Alkenes
-alkenes can be cleaved by ozonolysis of their
double bond. The products are aldehydes and
ketones.
Aldehydes by Reduction of Acyl Chlorides,
Esters and Nitriles (Acid Derivatives)
-theoretically, it is not possible to prepare
aldehydes by reduction of carboxylic acids.
-In practice, this is possible with the reagent
normally used to reduce a carboxylic acid, lithium
aluminum hydride (LiALH4 or LAH)
o Carboxylic acid treated with LAD - reduced
all the way to the 1*alcohol
o Happens bc LAH is a very powerful
reducing agent and aldehydes are very
easily reduced
Any aldehyde that might be formed in the
reaction mixture is immediately reduced by
LAH to the 1* alcohol. (It does not help to use
a stoichiometric amount of LAH, because as
soon as the first few molecules of aldehyde
are formed in the mixture, there will still be
much unreacted LAH present and it will
reduce the aldehyde.)
The secret to success here is not to use a
carboxylic acid itself, but to use a derivative of
a carboxylic acid that is more easily reduced,
and an aluminum hydride derivative that is
less reactive than LAH.
 Ketones from Arenes by Friedel-Crafts
Acylations
-Arenes - aromatic hydrocarbon

-Acyl chlorides (RCOCl), esters (RCO2R9),

nitriles (RCN)
-easily prepared from carboxylic acids, they
are more easily reduced

-The following scheme summarizes how lithium tri-

tert butoxyaluminum hydride and DIBAL-H can be
used to synthesize aldehydes from acid derivatives:

Ketones from Secondary Alcohols by

Swern Oxidation
and other methods

Ketones from Nitriles

Aldehydes from Acyl Chlorides: RCOCl --->
RCHO
-treating acyl chlorides with LiAlH[OC(CH3)3]3,
lithium tri-tert-butoxyaluminum hydride, at -78°C
-carboxylic acids ---> acyl chlorides by using SOCl2
-treating a nitrile (R-Ci≡N) with either a Grignard
reagent or an organolithium reagent followed by
hydrolysis yields a ketone

-specific example:

Mechanistically, the reduction is brought about by

the transfer of a hydride ion from the aluminum
atom to the carbonyl carbon of the acyl chloride.
Subsequent hydrolysis frees the aldehyde.

Synthesis of Ketones
Ketones (and aldehydes) by Ozonolysis of
Alkenes
-Ozonolysis - organic reaction where the
unsaturated bonds of alkenes, alkynes or azo
compounds are cleaved with ozone.
Carboxylic Acids, Esters, And other Acid
Derivatives
Thursday, December 16, 2021
7:22 AM

Structure of Carboxylic Acids parent chain and the –COOH carbon is

and their Derivatives
• Functional group
-combination of a carbonyl group and a
hydroxyl group (carboxyl group, -COOH)
-however the resulting carboxyl group
possesses properties that are unlike those
present in aldehydes/ketones and alcohols.
-this means that carboxylic acid is very
reactive, even to itself
designated as C-1.
o Name the parent chain by dropping the “e”
from the corresponding alkane name and
changing to “oic acid.
o Indicate the identity and location of
substituents on the parent chain at the front
of the carboxylic acids name.

• Dicarboxylic Acids
-2 carboxylic groups
o For these compounds, both ends of a chain
will end with a –COOH group. The parent
• General formula chain is the one that involves both –COOH
groups.
o The parent chain is named as an alkane and
the term “dioic acid” is added afterwards to
indicate the diacid structure.

-R-radicals/carbon chain
-C with double bond O single bond OH- makes
it a carboxylic acids

• Some simple carboxylic acids

-2-
Bromobutanedio
ic acid
-simplest - formic acid, only one C
-benzoic acid - parent name

• The following molecules have a similar Common Names for Carboxylic

structure to carboxylic acids
Acids

IUPAC Nomenclature for

Carboxylic Acids
• Monocarboxylic Acids
-only one carboxyl group
-carboxyl group-always located at end Acetic acid-vinegar
of the parent chain
o Select the longest, continuous carbon chain
that involves the carboxyl group. This is the
 • Keto Acids
-a carbonyl group is present as part of carbon
chain that involves a carboxyl group

• For common names carboxylic acids and -for IUPAC naming - O-atom of the carbonyl
diacids, substituents are often numbered group is treated as an "oxo" substituent (not
using Greek system as a ketone) and the molecule is called 2-
oxopropanoic acid

-the ff molecule could be called α-

Methylpropionic acid (2-Methylpropanoic
Metabolic Carboxylic
• Polyfunctional acids are intermediates in
acid)
metabolic reactions that occur as food is
processed to obtain energy.
• Eight key intermediates in these processes
are derived from only three carboxylic acids
(Propanoic, Butanoic, and Pentanoic
acids)

Polyfunctional Carboxylic Acids

-carboxylic acids that contains other functional
groups besides the -COOH group.

• Unsaturated Acids
-possess a unit of unsaturation (double/triple
C-C bond) in the structure
-Most common:

• Hydroxy Acids
Physical Properties of Carboxylic
Acids
• Most polar functional group so far
-the presence of the carbonyl group next the
OH causes the O-H bond to be even more
polar and reactive

• Because of the very polar -COOH group,
they exhibit strong intermolecular
attractions.
• Carboxylic acids of a given number of
carbon atoms have a higher boiling point
than alcohols.
• They tend to dimerize, that are twice as
heavy which have enhanced London
forces (thus higher boiling point).
• Dissolve well in water (up to 4 carbon
chains)
-because of the H-bonding
-beyond 4 C chains, water solubility drops off
rapidly
Preparation of Carboxylic Acids
• Carboxylic Acids can be prepared from
aldehydes which can be prepared from
primary alcohols.
• Aromatic carboxylic acids can be made by
oxidizing alkyl-substituted aromatic
molecules
1. By oxidation of the alkenes
-alkenes can be oxidized to carboxylic acids
with hot alkaline KMnO4 (yield up to 2
carboxylic acids)
-alternatively, ozonides can be subjected to an
oxidative work up that yields carboxylic
acids:
2. By oxidation of aldehydes and primary
alcohols
-aldehydes can be oxidized to carboxylic acids
with mild oxidizing agents such as Ag(NH3)2
+HO-
-primary alcohols can be oxidized with
KMnO4
-Aldehydes and primary alcohols are oxidized
to carboxylic acids with chromic acid
(H2CrO4) in aqueous acetone (the Jones
Oxidation)
3. By benzylic oxidation of alkylbenzenes
-primary and secondary alkyl groups (but not
3° groups) directly attached to a benzene ring
are oxidized by KMnO4 to -CO2H group
 4. By oxidation of the benzene ring
-The benzene ring of an alkylbenzene can be
converted to a carboxyl group by ozonolysis,
followed by treatment with hydrogen
peroxide.

5. By hydrolysis of cyanohydrins and other

nitriles
-Aldehydes and ketones can be converted to
cyanohydrins and that these can be
hydrolyzed to α-hydroxy acids. In the
hydrolysis the -CN group is converted to a -
COOH group.

-Nitriles can also be prepared by nucleophilic

Ka-acid dissociation constant
substitution reactions of alkyl halides with
sodium cyanide.
Carboxylic Acid Salts
General Reaction: -when carboxylic acid are reacted with strong
Hydrolysis of the nitrile yields a carboxylic bases, they are converted to salts as follows:
acid with a chain one carbon atom longer
than the original alkyl halide.

6. By carbonation of Grignard Reagents

-Grignard reagents react with carbon
dioxide to yield magnesium carboxylates.
-Acidification produces carboxylic acids:
-Salts of carboxylic acids are much more water-
soluble than the acids themselves. Also, they can be
converted back to the acid form by reacting them
with a strong acid.

Acidity of Carboxylic Acids

-when carboxylic acids are placed in water - they
-USES:
undergo de-protonation
• Many drugs medicine that have acid
groups are marketed as carboxylic acid
salts (sodium, potassium salts)
-bc of their enhanced solubility in water
compared to the acid form.
 -Indicate the structures of the carboxylic acid and
alcohol that are needed to make an ester:

Structure of Esters
Esters
-carboxylic acid derivatives having an alkoxy group IUPAC Nomenclature of Esters
instead of a hydroxyl group. 1. The name for the alcohol portion comes
first; name the alkyl part of the alcohol.
Present the alkyl name separate from the
remainder of ester name.
2. The carboxylic portion is named as if it
were deprotonates changing the "-ic acid"
to "ate" or "oate"

Preparation of Esters
Esterification Reactions
-condensation reactions involving carboxylic acids
and alcohols

Other examples:

-an ester consists of an acid portion and an alcohol

portion:

Cyclic Esters (lactones)

-created from hydroxy acids ( bear both hydroxyl Selected Common Esters
and carboxyl group) in an intramolecular • Flavor/ fragrance agents
esterification reaction:
 • Pheromones Physical Properties of Esters
• Because they do not possess –OH groups,
esters cannot form H- bonds with other
Ester molecules. As a result, esters have
lower boiling point than carboxylic acids
-2-Methylbutane Methanoate and alcohols that have approximately the
• Medications same molar mass.

• Water molecules can H-bond to esters, at

the oxygen atoms. This makes low molecule
weight esters water-soluble.

Chemical Reaction of Esters

Synthesis of Aspirin Ester Hydrolysis
-reacting water with an ester in the presence of an
acid catalyst (reverse of esterification)

Isomerism in Carboxylic Acids and

Esters
• Carboxylic acids and esters that have a
given number of carbon atoms form
another example of functional group Ester Saponification
isomers: -hydrolysis but under basic conditions
-salt is produced instead of carboxylic acid

• For both carboxylic acids and esters,

skeletal isomers are possible

• Positional isomers are possible for esters,

but not carboxylic acids.
Structure of Acid Anhydride
Thursday, January 6, 2022
1:45 AM

Anhydride
-compound derived from another (such as an acid)
by removal of the elements of water

Acid Anhydride
-contains 2 molecules of an acid, with a loss of a
molecule of water.
-addition of water regenerates 2 molecules of
carboxylic acid 2. Acyl Chlorides also react with carboxylic
acid to give acid anhydride

Nomenclature
-"acid" is changed to "anhydride" (in common and Heating Carboxylic Acids with ZnO
IUPAC) -acid anhydride can be prepared from heating
simple carboxylic acids with Zinc Oxide
-oxidation reaction

Mixed Anhydrides
-anhydrides composed of two different acids
-named using names of individual acids
-alphabetize the names for both acids and replacing
the word acid with the word anhydride

Symmetrical Anhydrides
-word "acid" from carboxylic acid to the word Heating Dicarboxylic Acids
"anhydride" -Certain cyclic anhydrides can be prepared by
heating dicarboxylic acid such as succine and
phthalic anhydride.

Preparation of Acid Anhydrides

From Acyl Chlorides
1. Acyl chloride reacts with carboxylate
salts to form acid anhydrides
-can be used to prepare both symmetrical and
asymmetrical anhydrides
Reactivity of Acid Anhydride
Acid Anhydrides vs Acyl Chlorides
• Ethanoic anhydride has a bulky ethanoate,
CH3COO- group attached to the carbonyl
atom
• Ethnaoyl chloride has a simple Cl atom
attached to the carbonyl atom
• Ethanoic anhydride is less reactive

Reaction of the Acid Anhydrides

1. Hydrolysis
-to produce carboxylic acids
-can be carried out in acid or base
-Carboxylate salts are formed if done in basic
solution

2. Alcoholysis
-produce esters and carboxylic acids
-does not require catalyst but still require
heating

3. Ammonolysis
-ammonolysis of anhydrides with ammonia,
primary and secondary amines

-acetamide -
ammonium acetate
Amines and amides
Thursday, January 6, 2022
3:23 AM

Bonding Characteristics of -nitrogen is bonded to 2 hydrocarbon groups and

one hydrogen atom
Nitrogen atoms in Organic -R2NH
Compounds
Tertiary Amine
-nitrogen atom is bonded to 3 hydrocarbon groups
and no hydrogen atoms
-R3N

• The basis for the amine primary-secondary-

tertiary classification system differs from
that for alcohols
Nitrogen
-member of group VA Alcohols Amines
-5 valence electrons, form 3 covalent bonds to
We look at how We look at how many
complete its octet of electrons.
many R groups are R groups are on the
on a carbon atom, nitrogen atom
Carbon - 4 bonds
the hydroxyl
Nitrogen - 3 bonds
bearing carbon atom
Oxygen - 2 bonds
• Tert-butyl alcohol - tertiary alcohol,
4 Most abundant Elements in Living Organisms whereas tert-butylamine is a primary amine
• Carbon
• Hydrogen
• Oxygen
• Nitrogen

2 Types of Organic Nitrogen-Containing

Compounds
1. Amines
-carbon-hydrogen-nitrogen containing
compounds
2. Amides
-contain oxygen along with the 3 other • The functional group present in a primary
elements amine, the —NH2 group, is called an amino
group. An amino group is the —NH2
functional group. Secondary and tertiary
Structure and Classification of amines possess substituted amino groups.
Amines
Amine
-organic derivative of ammonia (NH3) in which one
or more alkyl, cycloalkyl, or aryl groups are
attached to the nitrogen atom
-numerous drugs used for the treatment of mental
illness, hay fever, heart problems, and other
physical disorders are amines or amides.

Primary Amine
-nitrogen atom is bonded to one hydrocarbon
group and two hydrogen atoms
-RNH2

Secondary Amine
 • In diamines, the final -e of the carbon chain
name is retained for ease of pronunciation.
Thus the base name for a four-carbon chain
bearing two amino groups is
butanediamine.
• Cyclic amines exist. Such compounds are
always either secondary or tertiary amines.
Cyclic amines are heterocyclic compounds.
Numerous cyclic amine compounds are
found in biochemical systems.

Nomenclature for Amines

Common Names
-list the alkyl group/s attached to the nitrogen in
alphabetical order • Secondary and tertiary amines are named
-add suffix -amine as N-substituted primary amines. The
-prefixes di- and tr- when identical groups are largest carbon group bonded to the
bonded nitrogen is used as the parent amine name.
The names of the other groups attached to
the nitrogen are appended to the front of
the base name, and N- or N,N- prefixes are
used to indicate that these groups are
attached to the nitrogen atom rather than to
the base carbon chain.

IUPAC Rules
-similar to alcohol
-alcohol: alkonols (-ol), amines: alkanamines (-
amine)
1. Select as the parent carbon chain the
longest chain in which the nitrogen atom is
attached.
2. Name the parent chain by changing the -e or
the alkane to -amine
3. Number the parent chain from the end • In amines where additional functional
nearest to the nitrogen atom. groups are present, the amine group is
4. The position of attachment of the nitrogen treated as a substituent. As a substituent, an
atom is indicated by a number in front of —NH2 group is called an amino group.
the parent chain name.
5. The identity and location of any
substituents are appended to the front of
the parent chain.

• Aniline - simplest aromatic amine, a

benzene ring bearing an amino acid
 o Other simple aromatic amines are
named as derivatives of aniline.
• In secondary and tertiary aromatic amines,
the additional group or groups attached to
the nitrogen atom are located using a
capital N-.
Isomerism for Amines
• Constitutional isomerism in amines can
arise from several causes. Different carbon
atom arrangements produce isomers, as in:
• Different positioning of the nitrogen atom
on a carbon chain is another cause for
isomerism, illustrated in the following
compounds.
• For secondary and tertiary amines, different
partitioning of carbon atoms among the
carbon chains present produces
constitutional isomers. There are three C4
secondary amines:
• Carbon atom partitioning can be two ethyl
groups, a propyl group and a methyl group,
or an isopropyl group and a methyl group.
Physical Properties of Amines
• The methylamines (mono-, di-, and tri-) and
ethylamine are gases at room temperature
and have ammonia-like odors.
• Most other amines are liquids, and many
have odors resembling that of raw fish.
• A few amines, particularly diamines, have
strong, disagreeable odors.
• The foul odor arising from dead fish and
decaying flesh is due to amines released by
the bacterial decomposition of the foul ofor
of proteins.
• Two of these “odoriferous” compounds are
the diamines putrescine and cadaverine.
• The simpler amines are irritants to the skin,
eyes, and mucous membranes and are
toxic by ingestion.
• Aromatic amines are generally toxic. Many
are readily absorbed through the skin and
affect both the blood and the nervous
system.
• The boiling points of amines are
intermediate between those of alkanes
and alcohols of similar molecular mass.
• Amines with fewer than six carbon atoms
are infinitely soluble in water. This
solubility results from hydrogen bonding
between the amines and water.
• Even tertiary amines are water-soluble,
because the amine nitrogen atom has a
nonbonding electron pair that can form a
hydrogen bond with a hydrogen atom of
water.
Selected Biochemically
Important Amines
• Neurotransmitter
-chemical substance that is released at the
end of a nerve, travels across the synaptic gap
between the nerve and another nerve, and
then bonds to a receptor site on the other
nerve, triggering nerve impulse.
-most important neurotransmitters:
acetylcholine and amines norepinephrine,
dopamine, serotonin
o Norepinephrine - compound secreted by
the adrenal glands into the blood, helps
maintain muscle tone in the blood vessels
o Dopamine - found in the brain, deficiency
of this results to Parkinson's diseases
(degenerative neurological disease)
o Serotonin - brain chemical involved in
sleep, sensory perception, regulation of
body temperature
 • Administration of dopamine to a • Secondary amide (monosubstituted
patient does not relieve the amides)
symptoms of this disease because -is an amide in which an alkyl (or aryl) group
dopamine in the blood cannot cross and a hydrogen atom are bonded to the amide
the blood–brain barrier. The drug L- nitrogen atom.
dopa, which can pass through the
blood– brain barrier, does give relief • Tertiary amide (disubstituted amides)
from Parkinson’s symptoms. Inside -is an amide in which two alkyl (or aryl)
brain cells, enzymes catalyze the groups and no hydrogen atoms are bonded to
conversion of L-dopa to dopamine. the amide nitrogen atom.
o Epinephrine - AKA adrenaline, has some
neurotransmitter functions but is more
important as a CNS stimulant
o Histamine - responsible for the unpleasant
effects felt by individuals susceptible to hay
fever and various pollen allergies

• Alkaloids
- is a nitrogen-containing organic compound
extracted from plant material.

• Morphine Simplest Amide

- is one of the most effective painkillers -has a hydrogen atom attached to an unsubstituted
known, its painkilling properties are about a amide functional group.
hundred times greater than those of aspirin.

• Codeine
- is less potent than morphine, having a
painkilling effect about one-sixth that of
morphine. Amides in which Methyl Groups are present
1. Methyl group attached to the carbon
• Heroin 2. Methyl group attached to the nitrogen
- is a semi-synthetic compound, the diacetyl
ester of morphine; it is produced from
morphine.

Structure and Classifications of

Amides Simplest Aromatic Amide
Amides -involves benzene ring to which an unsubstituted
-is a carboxylic acid derivative in which the amide is attached
carboxyl —OH group has been replaced with an
amino or a substituted amino group. The amide
functional group is thus depending on the degree of
substitution.

Cyclic Amide Structures

-can be classified as primary, secondary, tertiary,

depending on how many H atoms are attached to
the nitrogen atom. • Lactam
• Primary amide (unsubstituted amides)
-cyclic amide
-is an amide in which two hydrogen atoms are -ring size is indicated using a Greek letter
bonded to the amide nitrogen atom.
 o b-lactam - 4-membered ring, bc the b
carbon from the carbonyl group is bonded
to the heteroatom.
• Members of penicillin family of
antibiotics contain this.
o g-lactam - 5-membered ring
Nomenclature for Amides
-based on name of the parent carboxylic acid:
1. -ic acid (common) or -oic acid (IUPAC) is
changed to -amide
Physical Properties of Amides
2. The names of groups attached to the
nitrogen (20 and 30 amides) are appended to
the front of the base name, using an N-
prefix as a locator.
Selected Amides and Their Uses
• Urea
-one-carbon diamide
-a water soluble white solid produced in the
human body from carbon dioxide and
ammonia through a complex series of
metabolic reactions.
-with malfunctioning kidneys, urea
concentrations in body can build to toxic
levels (condition: uremia)
-Urea formation is the human body’s primary
method for eliminating “waste” nitrogen. The
kidneys remove urea from the blood and
provide for its excretion in urine.
• Melatonin
-is a hormone that is synthesized by the
pineal gland and that regulates the sleep in
humans
-polyfunctional amide; amine and ether
groups are also present
• Acetaminophen
-derivative acetamide, which in 1992
replaced aspirin as the top-selling over-the-
counter pain reliever.
• Barbiturates
-which are cyclic amide compounds, are a
heavily used group of prescription drugs that
cause relaxation (tranquilizers), sleep
(sedatives), and death (overdoses).
-derivatives of barbituric acid - cyclic amide
first synthesized from urea and malonic acid.
• Amides do not exhibit basic properties in
solution as amines do.
• Methanamide and its N-methyl and N,N-
dimethyl derivatives (the simplest 10, 20,
and 30 amides, respectively), are all liquids
at room temp.
• In many cases, the amide melting point is
even higher than that of the corresponding
carboxylic acid.