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)