Oxygen Containing Organic Compounds

OXYGEN CONTAINING
ORGANIC COMPOUNDS
Compounds of oxygen
 Carbohydrates,fats, proteins, nucleic acids

are complex molecules containing oxygen.
 Firstis necessary to study simpler organic

compounds:
 Alcohols, phenols, ethers, aldehydes,
ketones, acids, esters.

Electron configuration of oxygen atom:
1s2 2s2 2p4
In organic molecule oxygen is attached covalently

with two pairs of atoms
O
O
 Alcohols and phenols (hydroxy derivates)
– compounds with the hydroxyl (-OH)
R-O-H
 Ethers – compounds with alcoxyl group (-OR)
R-O-R
 Aldehydes and ketones – carbonyl group
-
C= O
-
R - R -
C= O C=O
H - R -
 Carboxylic acids – carbonyl + hydroxyl group
R -
- C = O-
H -O
-
Alcohols
Role of alcohols in organic chemistry
Alcohols
Some Common Alcohols
Alcohols
Classification
 In 1o alcohol, only one carbon atom is attached to the carbon carrying the -OH
group (primary carbon).
 In 2o alcohol two carbon atoms are attached to the carbon carrying the -OH
group (secondary carbon).
 In 3o alcohol three other carbon atoms are attached to the carbon atom carrying
the -OH group (tertiary carbon).
Alcohols
The number of hydroxyl groups, there are:
Monohydroxyderivatives (monohydroxy alcohols)
Polyhydroxy alcohols
 Diols (dihydroxyderivatives,)
 Triols (trihydroxyderivatives)
 Tetrols (tetrahydroxyderivatives)
 Polyols belongs to a group of carbohydrates (sugars)
Phenols -OH attached primary to aromatic ring

Nomenclature of Alcohols
The lower molecular weight alcohols have common names.
Word alcohol is added after the name of the alkyl group to
which the hydroxyl group is attached.
methanol – methyl alcohol CH3-OH

ethanol – ethyl alcohol CH3-CH2-OH
1-propanol – propyl alcohol CH3-CH2-CH2-OH
2-propanol – isopropyl alcohol CH3-CH-CH3
OH
1-butanol – n-butyl alcohol CH3-CH2-CH2-CH2-OH
Properties
 Low MW alcohols are colorless liquids of specific
odour (unpleasant from C4), narcotic effect, toxic.
 Polyhydroxy alcohols have sweet taste.
 Higher alcohols (from C12) are solid compounds
 H-bonds → solubility in water, higher boiling points

than alkanes.
Properties
 Liquids at room temperature (up to 11 or 12 C-atoms)
 Methanol and ethanol are free flowing volatile liquids; the

higher alcohols are somewhat viscous
 Some of the highly branched isomers are solids at room

temperature
Solubility in Water at O
25 C
Alcohol Solubility in water

Methyl Miscible
Ethyl Miscible
N-propyl Miscible
Tert-butyl Miscible
Isobutyl 10%
N-pentyl 2.7%
Cyclohexyl 3.6%
N-hexyl 0.6%
Phenol 9.3%
Hexane-1, 6 -diol Miscible
Preparation of Alcohols
 Dehydration of alkenes
 Grignard synthesis to form 1O alcohol
Ether
 R –MgX + HCHO R – CH2OH (1O alc)
H3O+
Ether
CH3CH2CH2MgBr + HCHO H3O+ CH3CH2CH2CH2OH
Grignard synthesis

Ether
 R – MgX + aldehyde H3O+
R – CH (R’) OH
CH3
│
Ether
CH3CH2MgBr + CH3CHO CH3CH2 CHOH
H3O+
Grignard synthesis

Ether
 R – MgX + ketone H O 3O alcohol
3
+
Ether
CH3CH2MgBr + CH3CH2CH2 COCH3
H3O+
CH2CH2CH3
│
CH3CH2COH
│
CH3
Grignard synthesis
 With acyl chlorides

Ether
2 R – MgX + RCOCl H3 O+
3O alcohols
Ether
2 CH3CH2CH2MgBr + CH3COCl
H3O+
CH2CH2CH3
│
CH3CH2CH2COH
│
CH3
Reaction of Alcohols
1. Breaking the oxygen-hydrogen bond.
H H An acid-base reaction.
C C O H
2. Breaking the carbon-oxygen bond.
A substitution reaction by a nucleophile.

H H
C C O H
3. Breaking both the oxygen-hydrogen bond and the carbon-
hydrogen bond at the carbon atom bearing the -OH group.
An oxidation reaction.
H H
C C O H
4. Breaking both the carbon-oxygen bond and the carbon-

hydrogen bond at a carbon atom adjacent to the carbon atom
bearing the –OH group
H H An elimination reaction.
C C O H
Types of reactions of alcohols
 The –OH group generally makes the alcohol
molecule polar.
 The -OH group can form hydrogen bonds to one

another and to other compounds.
 Alcohols, like water, act as acids or bases
http://en.wikipedia.org/wiki/Alcohol#Physical_and_chemical_properties
Dehydration of Alcohols
 Alcohols undergo combustion with O2 to produce

CO2 and H2O.
2CH3OH + 3O2 2CO2 + 4H2O + Heat
 Dehydration removes H- and -OH from adjacent
carbon atoms by heating with an acid catalyst.
H OH
| | H2SO4
H—C—C—H H—C=C—H + H2O
| | 180OC | |
H H H H
alcohol alkene
Dehydration of Alcohols
 Ethers form when dehydration takes place

at low temperature.
H2SO4
CH3—OH + HO—CH3 CH3—O—CH3 + H2O
Two methanol 140OC Dimethyl ether
Oxidation of Alcohols
 1O and 2O alcohols are easily oxidized (by chromium

oxides, permanganate, nitric acid, Household bleach,
NaOCl)
 Chromic reagent is often used for lab oxidation
procedures, Na2Cr2O7 dissolve in a mixture of H2SO4
and water resulting to chromic acid, H2CrO4
Oxidation of Primary Alcohols
 In the oxidation [O] of a primary alcohol, one H is

lost from the –OH and another H from the carbon
bonded to the OH.
[O]
Primary alcohol Aldehyde
OH O
| [O] ||
CH3—C—H CH3—C—H + H2O
|
H
Ethanol Ethanal
(ethyl alcohol) (acetaldehyde)
Oxidation of Primary Alcohols
 Aldehydes can easily be oxidized to produce
acids
[½ O2]
Aldehyde Carboxylic acid
O O
|| [½ O2] ||
CH3—C—H CH3—C—OH
Ethanal Acetic acid
(acetaldehyde)
Oxidation of Secondary Alcohols
 The oxidation of a secondary alcohol removes one

H from –OH and another H from the carbon
bonded to the –OH.
[O]
Secondary alcohol Ketone
OH O
| [O] ||
CH3—C—CH3 CH3—C—CH3 + H2O
|
H
2-Propanol Propanone
(Isopropyl alcohol) (Dimethylketone; Acetone)
Oxidation of Tertiary Alcohols
 Tertiary alcohols are resistant to oxidation.

[O]
Tertiary alcohols no reaction
OH
| [O]
CH3—C—CH3 no product
|
CH3 no H on the C-OH to oxidize
2-Methyl-2-propanol
Summary of Alcohol Oxidations
To oxidize Product Chromium Chromium-
Reagent free reagent
2O alcohol ketone Chromic NaOCl, Swern,
acid (or DMP (Dess-
PCC, Martin
pyridinium periodinane)
chlorochrom
ate)
1O alcohol Aldehyde PCC Swern, DMP
1O alcohol Carboxylic Chromic NaOCl
acid acid
Swern – uses dimethyl sulfoxide (DMSO) at low temp

Reactions of Alcohols
 Formation of sodium and potassium alkoxides
 R – O – H + Na → R – O Na + ½ H2 ↑
 Formation of alkyl halides

Reactions of Alcohols
 Fischer esterification H+
alcohol + carboxylic acid ⇄ ester
Commercially Important Alcohols
 Methanol, also known as wood alcohol
One of the most common industrial solvent; also used

as a starting material for a wide variety of methyl ethers,
methyl esters, and used in plastics, medicines, and fuels
for internal combustion engines
 Obtained by heating wood to a high temperature in the

absence of air.
 Toxic substance, temporary blindness (15 ml),

permanent blindness or death (30 ml)
Common Alcohols
 Ethanol (grain alcohol, spiritus, alcohol)
 Obtained by fermentation from sugar juices
 Fermentation from sugar from the hydrolysis of
starch in the presence of yeast and temperature
of less than 37°C
C6H12O6 (hexose) 2 CH3CH2OH + 2H2O
 Acts as a depressant.
 Lethal dose is 6-8 g/kg ( 1 L of vodka)
Oxidation of Alcohol in the Body
 Enzymes in the liver oxidize ethanol to acetaldehyde

 The aldehyde produces impaired coordination.
Ethanol acetaldehyde acetic acid
Oxidation of methanol in the liver produces formaldehyde
CH3OH H2C=O
Ethanol – An Antidote for Methanol Poisoning
 Formaldehyde reacts very rapidly with proteins.

 Enzymes loss of the function.
 Ethanol competes for the oxidative enzymes
and tends to prevent the oxidation of the methanol
to formaldehyde.
Isopropyl Alcohol or 2-propanol
(Propan-2-ol)
 Commonly used as rubbing alcohol

 Has less drying effect on the skin compared
to ethanol
 Also effective as topical antiseptics
Polyhydroxy Alcohols
Ethylene glycol - ethane-1,2-diol
HO–CH2–CH2–OH
 Used as a radiator and automobile antifreez
 toxic: 50 mL, lethal: 100 mL
Glycerol - propane-1,2,3-triol (glycerin)

CH2 - OH
CH - OH
CH2 - OH
 Present as the backbone of several important biological
compounds
Glycerol
 Oxidation of glycerol arises glyceraldehyde – major

metabolite.
 Reaction with acid esters formed - with nitric acid
arises glyceroltrinitrate – nitroglycerin. Nitroglycerin
is administered as a treatment for heart disease.
Glycerol
 The phosphoric acid esterifies primary –OH group

to form 1-glycerophosphate acid.
 1-glycerophosphate acid is an important
metabolite and a structural component of complex
lipids.
Glycerol as a Backbone for Several
Bilogical Compounds
phosphatidylcholine phosphatidylethanolamine
Reactivity of Alcohols
 Reaction with carboxylic acids, acid chlorides

and acid anhydrides to form esters.
 Reaction of primary or secondary alcohol in the

presence of a catalyst (commonly concentrated
sulfuric acid) with carboxylic acid is called
esterification.
 The introduction of acetyl (CH3CO-) group in

alcohols or phenols in known as acetylation.
End Alcohols

Oxygen Containing Organic Compounds

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OXYGEN CONTAINING

 Carbohydrates,fats, proteins, nucleic acids

 Firstis necessary to study simpler organic

ketones, acids, esters.

1s2 2s2 2p4

In organic molecule oxygen is attached covalently

 Ethers – compounds with alcoxyl group (-OR)

 Carboxylic acids – carbonyl + hydroxyl group

Monohydroxyderivatives (monohydroxy alcohols)

Phenols -OH attached primary to aromatic ring

methanol – methyl alcohol CH3-OH

 Polyhydroxy alcohols have sweet taste.

 Higher alcohols (from C12) are solid compounds

 H-bonds → solubility in water, higher boiling points

 Liquids at room temperature (up to 11 or 12 C-atoms)

 Methanol and ethanol are free flowing volatile liquids; the

 Some of the highly branched isomers are solids at room

Alcohol Solubility in water

 Grignard synthesis to form 2O alcohol

 Grignard synthesis to form 3O alcohol

 With acyl chlorides

2. Breaking the carbon-oxygen bond.

A substitution reaction by a nucleophile.

4. Breaking both the carbon-oxygen bond and the carbon-

 The -OH group can form hydrogen bonds to one

 Alcohols, like water, act as acids or bases

 Alcohols undergo combustion with O2 to produce

 Ethers form when dehydration takes place

 1O and 2O alcohols are easily oxidized (by chromium

 In the oxidation [O] of a primary alcohol, one H is

 The oxidation of a secondary alcohol removes one

 Tertiary alcohols are resistant to oxidation.

Swern – uses dimethyl sulfoxide (DMSO) at low temp

 Formation of alkyl halides

One of the most common industrial solvent; also used

 Obtained by heating wood to a high temperature in the

 Toxic substance, temporary blindness (15 ml),

C6H12O6 (hexose) 2 CH3CH2OH + 2H2O

 Enzymes in the liver oxidize ethanol to acetaldehyde

Ethanol acetaldehyde acetic acid

Oxidation of methanol in the liver produces formaldehyde

 Formaldehyde reacts very rapidly with proteins.

 Commonly used as rubbing alcohol

Glycerol - propane-1,2,3-triol (glycerin)

 Oxidation of glycerol arises glyceraldehyde – major

 The phosphoric acid esterifies primary –OH group

 Reaction with carboxylic acids, acid chlorides

 Reaction of primary or secondary alcohol in the

 The introduction of acetyl (CH3CO-) group in

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