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Alcohols
Alcohols
• Aldehydes- *terminal H
• Ester- R-COO-R
• Amides- R-CON-R
Connection between alcohols, ethers, thiols
and phenols
• All of these groups are derived from the structure of water,
with a few substitutions.
• Alcohols- remove one H from water and add an alkyl group
• Thiols- replace the O in an alcohol with an S
• Ethers- remove both H atoms from water and add two alkyl
groups in their place
• Phenols- replace the alkyl group from alcohols with an aromatic
ring
• 2) CH3CH(OH)CH3
• 3)CH3CH(CH3)CH2OH
• 4) CH3C(CH3)2OH
IUPAC Naming of Alcohols
• 1) Select the longest continuous chain of carbon atoms
containing the hydroxyl (OH) group.
• 2) Number the carbons so that the lowest number carbon is
closest to the –OH group.
• 3) Name the parent alcohol by replacing the –e at the end of
the alkane name with an –ol.
• Designate the position of the –OH group by placing the
hyphenated carbon number in front of the parent alcohol
name.
• 4) Name each side chain or branch alphabetically, and use
numbers to designate its position off the main chain.
Cyclicalcohols are named using the prefix
cyclo and considering the —OH group
attached to C–1.
Practice Naming and Drawing Alcohols
• 3)3,3-dimethyl-2-
hexanol
• 1)
• 4) 2-ethyl-1-pentanol
• 5) 2-bromo-4-ethyl-3-
• 2) heptanol
Common Names
• Alcohols have a lot of • 3) sec-butyl alcohol
common names so it is
important to recognize • 4) tert-butyl alcohol
these for safety in lab.
• Examples:
• 1) isopropyl alcohol
• 2) n-butyl alcohol
Physical properties of alcohols
• High boiling points • What part of their structure
compared to their alkanes accounts for their high boiling
points?
• Example:
Methane -162°C • Most are soluble in water.
Methanol 65°C Solubility becomes lessened
as the carbon chain
lengthens. WHY?
• Boiling points of alcohols
increases with the
• Predict the effect of dihydroxy
increasing number of
alcohols on solubility in water.
carbon atoms.
Making alcohols
• Generally, the reverse of the reactions that we have discussed
so far are the ones used to make alcohols.
• 1. Preparation from alkene compound
• 2. Alkaline hydrolysis of an alkyl halide (primary and secondary
alcohols only)
• 3. Alcohol by Grignard reagents
• 4. Preparation of alcohol by fermentation method
• 5. Catalytic reduction of aldehydes and ketones to make
primary and secondary alcohols. Alcohols from carbonyl
compounds.
• 6. Hydrolysis of esters
• These starting materials are expensive, so specific methods are
devised for specific alcohols.
2. Alkaline hydrolysis of an alkyl halide (primary
and secondary alcohols only)
• Alkyl halides react with aqueous spdium
hydroxide to form alcohols.
• R-X + NaOH R-OH +NaX
H2O,Heat
CH3CH2-Br +NaOH CH3CH2-OH + NaBr
Alcohols are produced by the reaction of
Grignard reagents with aldehydes and
ketones.
The first step of the reaction is the
nucleophilic addition of Grignard reagent to
the carbonyl group to form an adduct.
Hydrolysis of the adduct yields an alcohol.
5. By reduction of carboxylic acids and esters:
Carboxylic acids are reduced to primary alcohols
in excellent yields by lithium aluminium
hydride, a strong reducing agent.
However, LiAlH 4is an expensive reagent, and
therefore, used for preparing special chemicals
only.
Commercially, acids are reduced to alcohols by
converting them to the esters , followed by their
reduction using hydrogen in the presence of
catalyst (catalytic hydrogenation).
Diborane (BH 3) 2reacts with alkenes to give
trialkyl boranes as addition product. This is
oxidised to alcohol by hydrogen peroxide in the
presence of aqueous sodium hydroxide.
The addition of borane to the double bond takes
place in such a manner that the boron atom gets
attached to the sp2 carbon carrying greater
number of hydrogen atoms.
The alcohol so formed looks as if it has been
formed by the addition of water to the alkene in a
way opposite to the Markovnikov’s rule.
In this reaction, alcohol is obtained in excellent
yield.
Hydroxyl Group Importance
• The –OH group is a gateway to many organic
reaction AND biochemical reactions as well.
• Example: Fats are degraded from alkanes to
alkenes…then hydrated to form an alcohol.
• Then, the alcohol is oxidized to form a ketone.
This process is necessary to use energy from fats.
• 10% of infants that die of SIDS cannot degrade
fats. It is hypothesized that this lack of ability to
use fat for energy may be a leading cause of SIDS.
Methanol
• Used to be made by heating wood in a non-oxygen
atmosphere…called destructive distillation.
• Early 1920s, began catalytic hydrogenation of carbon
monoxide…
• CO + 2 H2 CH3OH
• Requires catalysts, high temp and high pressure
• Can be made from coal as well, significant as a non-
petroleum source
• Is useful in conversion to manufacture of other
chemicals, polymers, etc.
Ethanol
• Aka: grain alcohol, ethyl alcohol, spirit
• Earliest and most widely known alcohol
• Prepared by fermentation of starch and sugar (for drinking)
• Pure ethanol is hygroscopic (water seeking), reaches
equilibrium at 95.6% ethanol.
• For industrial uses, it is made by acid-catalyzed addition of
water to ethylene.
• Uses: intermediate in manufacture of acetaldehyde, acetic
acid, ethyl acetate and diethyl ether
• Ethanol for industrial use is usually denatured by adding
small amounts of methanol and other chemicals that are
hard to remove and cannot be consumed.
Isopropyl alcohol (2-propanol)
• Synthesized from propene and water,
catalyzed by acid…2 propanol, not 1-propanol,
is produced because of Markovnikov’s rule.
• Example:
2 CH3CH2OH + 2 Na 2 Na+ + -OCH2CH3 + H2(g)
• B) 2-propanol
• C) cyclohexanol
Oppenauer oxidation, named after Rupert Viktor Oppenauer, is a gentle
method for selectively oxidizing secondary alcohols to ketones. The reaction is
the opposite of Meerwein–Ponndorf–Verley reduction. The alcohol
is oxidized with aluminium isopropoxide in excess acetone.
Allyl alcohol