Chapter 3.
Compounds bearing Oxygen
Functional group
compounds
Compounds Compounds
bearing Oxygen bearing Nitrogen
Alcohol and Aldehyde and
Acid and ester
phenol Ketone
1. Alcohols and Phenols
Alcohols contain an OH group connected to a
saturated C (sp3). General formula of aliphatic
alcohol is ROH.
Phenols contain an OH group connected to a
carbon in a benzene ring or called Aromatic
alcohols
Classification of Alcohols
Primary: Carbon with —OH is bonded to one other
carbon.
Secondary: Carbon with —OH is bonded to two other
carbons.
Tertiary: Carbon with —OH is bonded to three other
carbons.
C H3 OH C H3
*
C H3 CH C H 2OH C H3 CH C H 2C H 3 C H3 C OH
* *
C H3
IUPAC (Systematic) Nomenclature
Method
Find the longest carbon chain containing the carbon with the
—OH group.
Drop the “–e” from the alkane name; add “–ol”.
Number the chain, giving the —OH group the lowest number
possible.
Number and name all substituents and write them in alphabetical
order.
C H3 OH C H3
2 1
C H3 CH C H 2OH C H3 CH C H 2C H 3 C H3 C OH
3 2 1 1 2 3 4 C H3
Old: 2-methyl-1-propanol Old: 2-butanol Old: 2-methyl-2-propanol
New: 2-methylpropan-1-ol New: butan-2-ol New: 2-methylpropan-2-ol
Examples
Examples
Common names of alcohol
Common names are the name of alkyl group
followed by the word “alcohol”
Useful only for small alkyl groups
C H3 OH
C H3 CH C H 2OH C H3 CH C H 2C H 3
isobutyl alcohol sec-butyl alcohol
IUPAC: 2-methylpropan-1-ol IUPAC: butan-2-ol
Naming polyalcohols
Use –diol, triol, tetraol, etc. for alcohols bearing two,
three, four, etc as suffix instead of –ol in polyalcohol
compounds.
1 3 5
2 4 6
hexane-1,6-diol
1,2-diols (vicinal diol) are called glycols. Common names
for glycols use the name of the alkene from which they
were made.
OH
OH
IUPAC: ethane-1,2-diol IUPAC: propane-1,2-diol
ethylene glycol propylene glycol
Phenol Nomenclature
Method
—OH group is assumed to be on carbon 1.
For common names of di-substituted phenols, use ortho-
for 1,2; meta- for 1,3; and para- for 1,4.
OH OH CH2OH
H3C
Cl
4-methylphenol
3-chlorophenol (para-methylphenol Phenylmethanol
(meta-chlorophenol) Or Para-cresol)
Use “phene” (the French name for benzene) as the
parent hydrocarbon name, not benzene
If it is substituent, called “phenyl”
Properties of Alcohols and Phenols
Alcohols and phenols can form Hydrogen Bonds
hold the two molecules together
Alcohols and phenols have much higher boiling points than
similar alkanes and alkyl halides
Small alcohols are miscible in water, but solubility
decreases as the size of the alkyl group increases.
Acidity of alcohol and phenols
They can transfer a proton to water to a very small extent
Produces H3O+ and an alkoxide ion, RO, or a phenoxide
ion, ArO
and pKa = -log Ka
pKa Values for Typical OH Compounds
pKa range of
alcohols :
15.5–18.0
(water: 15.7)
pKa range of
Phenols :
around 10.0
(water: 15.7)
Phenols is
weak acid
Reactions of Alcohols and phenols
Two general classes of reaction
At the carbon of the C–O bond
At the proton of the O–H bond
Because phenols are weak acids (reacted with strong
bases, reaction at proton of O-H bond is easier.
Reactions of alcohols (not phenols)
Oxidation of Alcohols: Can be accomplished by inorganic
reagents, such as KMnO4, CrO3, and Na2Cr2O7
Reactions of alcohols (not phenols)
According to Zaixep’s rule
H3C OH H2SO4
H3CHC CHCH3 + H2O
CH3
CH3 H 3P O 4 H 3C C H 3 H 2C
C H 3 C H C H 2C H 3 CH + CH2
OH H 3C H 3C CH3
84 % 16 %
Reactions of alcohols (not phenols)
Substitution Reactions: OH group of alcohols can be
substituted by halogen group or alcohol with acid catalyst
H+
R-OH + R-OH R-O-R + H2O
C2H5-OH + C2H5-OH H+ C2H5-O-C2H5 + H2O
diethyl ether
Reactions of phenols
ONa
ONa
OR
Na NaOH
RX,
NaOH OH
OCOCH3 OH SO3H
CH3COCl Conc. H2SO4
Pyridine
Dilute Br2, CCl4
HNO3
Conc.
OH HNO3 OH
NO2 Br Br
OH
O2N NO2
Br
NO2
Preparation of alcohols
Addition of water
CH3
CH3 Conc. H2SO4
H3C C
+ H2O H3C
HC C H2C CH3
OH
CH3
2. Aldehydes and Ketones (Carbonyl Group)
Carbonyl Group C=O: Present in aldehydes and ketones
Aldehydes have abbreviated formulas RCHO Containing
at least one H connected to the C
O H2C O
formaldehyde
O
O C H
R C H CH 3 CH
acetaldehyde
Aldehydes benzaldehyde
Ketones have abbreviated formulas RCOR’ and Carbonyl
C is connected to two alkyl groups.
O O
CH 3 C CH 3 CH 3
R C R' acetone CH 3 CH 2 C O
Ketones methyl ethyl ketone
Nomenclature of aldehydes and ketones (IUPAC)
IUPAC Name:
Suffix is “-al” for the aldehydes
Suffix is “-one” for the ketones
indicates position of ketone
O O
CH 3 CH 2 CH CH 3 CH 2 CH 2 C CH 2 CH 3
propanal 3-hexanone
An Aldehyde or Ketone takes precedence over any
previously considered group
OH O O
Cl CH 2 CH CH 2 CH 2 CH H 2 C CH CH 2 C CH 2 Cl
5-chloro-4-hydroxypentanal 1-chloro-4-penten-2-one
Common names of aldehydes
Using “aldehyde”
O O O O
H H H3C H CH3CH2 H CH3CH2CH2 H
Methanl ethanl propanal butanal
(formaldehyde) (acetaldehyde) (propionaldehyde) (n-butyraldehyde)
O H
O H O H
OH
OMe
OH
salicylaldehyde
benzaldehyde (2-hydroxybenzenecarbaldehyde) Vanillin
H
cyclopentanecarbaldehyde
Common names of Ketones
Named as alkyl attachments to —C═O.
Use Greek letters instead of numbers.
Historical Common Names
O O O
CH3 H3C CH3
H3C CH3 H3C
propanone 2-butanone 3-pentanone
(acetone) (ethyl methyl ketone) (diethyl ketone)
H3C O
O O
acetophenone benzophenone
cyclohexanone (methyl phenyl ketone) (diphenyl ketone)
Carbonyl structure
Carbon is sp2 hybridized.
C═O bond is shorter, stronger, and more polar than
C═C bond in alkenes.
C=O is more stable than C=C
Physical Properties
Carbonyl compounds cannot form H bonding with each
other Because there is NOT an H connected to a F, N,
O
Aldehydes and Ketones are POLAR molecules and form
dipole interactions
Aldehydes and Ketones give higher boiling and melting
points than hydrocarbon which have the same carbon
number
C O
Physical Properties
Aldehydes and Ketones
can form H bonds with water!
solubility in water is about the same as alcohols.
Acetone and acetaldehyde are miscible in water.
yes!
C O
C O
C O
H O
H
Good solvent for alcohols.
Chemical properties
1. Oxidation - Tollens Test
- Benedicts Test
2. Reduction – Hydrogen addition
– NaBH4 reagent
R CHO
Tollen's Test Oxidation
RCOOH O RCOOH
or Benedict's Test
R R'
Reduction
R CH2OH
OH
R R'
Oxidation by common reagents
Only aldehyde is oxidized
O Oxidation
R R' NO
Tollen’s Test
The Silver Mirror Test: Oxidation of Aldehydes
Ag+ ion in aq. ammonia
NO reaction with KETONES
Ag(NH3)2+ + aldehyde Silver Mirror
Ag+ + 2 NH3 → Ag(NH3)2+
Ag(NH3)2+ +RCHO → Ago + RCOO- +4NH3
Benedict’s Test
Oxidation of Aldehydes
Cu2+ ion, aqueous
NO reaction with KETONES
Cu2+ + aldehyde Cu+(oxide) + acid
Cu2+ Cu+
O
R C H + 2 Cu2+ + 5 OH-
aldehyde
O
R C O- + 2 Cu2O + 3 H2O
carboxylic acid (ion)
Addition of H2 (reduction)
Reduction to Alcohols:
Both aldehyde and ketone is reduced by Hydrogen gas
and a catalyst (Ni, Pd, Pt)
Similar to alkene to alkane reduction
Aldehyde → primary alcohol
Ketone → second alcohol
H2
CH3 CH CH CHO CH3 CH2 CH2 CH2OH
Pt
2-butenal 1-butanol
O OH
H2
CH 3 C CH 3 CH 3 CH CH 3
acetone Pt 2-propanol
Reduction using NaBH4 or LiAlH4
NaBH4 can reduce ketones and aldehydes, but NOT
esters, carboxylic acids, acyl chlorides, or amides.
LiAlH4 can reduce ANY carbonyl because it is a very
strong reducing agent.
NaBH4
ROOC CHO ROOC CH2OH
LiAH4
ROOC CHO HOH2C CH2OH
Preparation of aldehyde
Oxidation of Primary Alcohols to Aldehydes:
Pyridinium chlorochromate (PCC) is selectively used to
oxidize primary alcohols to aldehydes.
Hydroboration–oxidation of an alkyne gives anti-
Markovnikov addition of water across the triple bond.
R H OH
1. BH3
R CH2 CHO
R
2. H2O2 H OH
Alkyne enol (not isolated) Aldehyde
Example 1. BH3
CH2 CHO
2. H2O2, OH-
Alkyne Aldehyde
Preparation of Ketones
Secondary alcohols are readily oxidized to ketones
with sodium dichromate (Na2Cr2O7) in sulfuric acid or
by potassium permanganate (KMnO4).
The double bond is oxidatively cleaved by ozone followed
by reduction. Ketones and aldehydes can be isolated as
products.
Preparation of Ketones
Reaction between an acyl halide and an aromatic ring
will produce a ketone.
The initial product of Markovnikov hydration is an enol,
which quickly tautomerizes to its keto form.
3. Carboxylic acid and esters
Carboxylic acids are strong organic acids which contain
the carboxyl group (-COOH, -CO2H)
O
C
O H
Esters are derivatives of organic acid which contain the
group -COOR
O
C O R
3.1. Carboxylic acid
Carboxylic acids are classified as aliphatic or aromatic depending
on whether R or an Ar is attached to the carboxylic group
R-COOH or Ar-COOH COOH
COOH
Cl
Aliphatic acid Aromatic acid
Nomenclature
Formula IUPAC Common
alkan -oic acid prefix – ic acid
HCOOH methanoic acid formic acid
CH3COOH ethanoic acid acetic acid
CH3CH2COOH propanoic acid propionic acid
CH3CH2CH2COOH butanoic acid butyric acid
Nomenclature
Naming Rules
Identify longest chain
(IUPAC) Number carboxyl carbon as 1
(Common) Assign , , , to carbon atoms adjacent to
carboxyl carbon
Examples:
Nomenclature
Naming Cyclic Carboxylic Acids
Cyclic compounds containing one or more COOH groups attached
to the ring are named by identifying the name of the ring
followed by the word carboxylic acid or dicarboxylic acids etc.
The carbon atom bearing the carboxylic group is numbered 1
and the substituents are numbered relative to it.
Nomenclature
Naming Aromatic Carboxylic Acids
The simplest aromatic carboxylic acid is benzoic acid.
Substituted benzoic acids are named with benzoic
acid as the parent name.
Derivatives are named using numbers to show the location
of substituents relative to the carboxyl group.
The ring carbon attached to the carboxyl group is the
#1 position.
Benzoic acid
Salicylic acid
Benzene carboxylic acid 2-Hydroxybenzoic acid
Physical Properties of Carboxylic Acids
Solubility
The carboxylic acid are highly polar organic compounds.
This polarity results from the presence of a strongly
polarized carbonyl (C=O) group and hydroxyl (O-H) group.
As the number of carbons in a carboxylic acid series becomes
greater, the solubility in water decreases.
Aromatic carboxylic acids are insoluble in water.
Physical Properties of Carboxylic Acids
Boiling Point
Carboxylic acids are polar compounds and form very strong
intermolecular hydrogen bonds to form a dimer.
As the number of carbons in a carboxylic acid series becomes
greater, the boiling point increases.
Chemistry Properties of Carboxylic Acids
Acidity and Acid Strength
The most important chemical property of carboxylic acids
chemistry is their acidic nature.
The mineral acids (HCl, HBr, HI, H2SO4, H3PO4 ) are defined as
"strong acids" because they undergo complete dissociation.
Carboxylic acids are strong organic acids , they are much more
acidic than alcohols.
Carboxylic acids are stronger acids than phenols.
Chemistry Properties of Carboxylic Acids
Reaction with Bases : Salt formation and The carboxyl
hydrogen is replaced by metal ion, M+
With strong base:
+
With weak base
Weaker acids like phenols react only with strong bases like
(NaOH or KOH) and will not react with NaHCO3
Chemistry Properties of Carboxylic Acids
Reaction with reagents (Nucleophiles) to form acid
derivatives:
When the OH of a carboxylic acid is replaced by a nucleophile
(:Nu), a carboxylic acid derivative is produced.
Preparation of Carboxylic Acids
Oxidation
Oxidation of primary alcohols and aldehydes
KMnO4/ H+ / Δ KMnO4/ H+ / Δ
K2Cr2O4 / H+ K2Cr2O4 / H+
Oxidation of Alkylbenzene
KMnO4 / OH-
Δ / H+
Preparation of Carboxylic Acids
Hydrolysis of Nitriles:
Nitriles:
They are prepared by reacting a 1° or 2° alkyl halide with cyanide
salt.
Acid hydrolysis of a nitriles yields a carboxylic acids.
+ NH3
+ NH3
+ NH3
Derivatives of Carboxylic acids
3.2 Esters
Nomenclature
the functional derivatives’ names are derived from
the common or IUPAC names of the corresponding
carboxylic acids.
Naming Ester: Change –ic acid to –ate preceded by
the alkyl is derived from the alcohol, R'OH.
alkyl alkanoate
Examples:
Preparation of Esters
Conversion of Carboxylic Acids into Esters
Methods include reaction of a carboxylate anion with a
primary alkyl halide
Esterification (Fisher)
Heating a carboxylic acid in an alcohol solvent containing a
small amount of strong acid produces an ester from the
alcohol and acid
Chemical Properties of Esters
Chemical Properties of Esters
Hydrolysis: Conversion of Esters into Carboxylic Acids
An ester is hydrolyzed by aqueous base or aqueous acid to
yield a carboxylic acid plus an alcohol
Aminolysis of Esters: Ammonia reacts with esters to form
amides
Chemical Properties of Esters
Reduction: Conversion of Esters into Alcohols (Reaction
with LiAlH4 yields primary alcohols)
