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Organic Chemistry, 5th Edition

L. G. Wade, Jr.

Chapter 10
Structure and Synthesis
of Alcohols

Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
2003, Prentice Hall
Structure of Alcohols

• Hydroxyl (OH) functional group


• Oxygen is sp3 hybridized.
=>
Chapter 10 2
Classification
• 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.
• Aromatic (phenol): -OH is bonded to a
benzene ring.
=>
Chapter 10 3
Classify these:
CH3 CH3
CH3 CH CH2OH CH3 C OH
CH3

OH OH
CH3 CH CH2CH3 =>

Chapter 10 4
IUPAC Nomenclature
• Find the longest carbon chain
containing the carbon with the -OH
group.
• Drop the -e from the alkane name, add -
ol.
• Number the chain, starting from the end
closest to the -OH group.
• Number and name all substituents. =>
Chapter 10 5
Name these:
CH3
OH
CH3 CH CH2OH
CH3 CH CH2CH3
2-methyl-1-propanol
2-butanol
CH3 OH
CH3 C OH
CH3
Br CH3
2-methyl-2-propanol
3-bromo-3-methylcyclohexanol
=>
Chapter 10 6
Unsaturated Alcohols
• Hydroxyl group takes precedence. Assign
that carbon the lowest number.
• Use alkene or alkyne name.

OH
CH2 CHCH2CHCH3 4-penten-2-ol (old)

pent-4-ene-2-ol
(1997 revision of IUPAC rules)
=>
Chapter 10 7
Naming Priority
• Acids • Alkenes
• Esters • Alkynes
• Aldehydes • Alkanes
• Ketones • Ethers
• Alcohols • Halides
• Amines

=>

Chapter 10 8
Hydroxy Substituent
• When -OH is part of a higher priority class of
compound, it is named as hydroxy.
• Example:

OH
CH2CH2CH2COOH
also known as GHB
4-hydroxybutanoic acid
=>
Chapter 10 9
Common Names
• Alcohol can be named as alkyl alcohol.
• Useful only for small alkyl groups.
• Examples:
CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
isobutyl alcohol sec-butyl alcohol

=>
Chapter 10 10
Naming Diols
• Two numbers are needed to locate the two
-OH groups.
• Use -diol as suffix instead of -ol.

HO OH

1,6-hexanediol

=>
Chapter 10 11
Glycols
• 1, 2 diols (vicinal diols) are called glycols.
• Common names for glycols use the name of
the alkene from which they were made.

CH2CH2 CH2CH2CH3
OH OH OH OH
1,2-ethanediol 1,2-propanediol
ethylene glycol propylene glycol
Chapter 10
=> 12
Naming Phenols
• -OH group is assumed to be on carbon 1.
• For common names of disubstituted phenols,
use ortho- for 1,2; meta- for 1,3; and para- for
1,4.
• Methyl phenols are cresols. OH
OH

H3C

Cl
4-methylphenol
3-chlorophenol para-cresol
=>
meta-chlorophenol Chapter 10 13
Physical Properties
• Unusually high boiling points due to
hydrogen bonding between molecules.
• Small alcohols are miscible in water, but
solubility decreases as the size of the
alkyl group increases.

=>

Chapter 10 14
Boiling Points

=>
Chapter 10 15
Solubility in Water

Solubility decreases as the size


of the alkyl group increases.

=>
Chapter 10 16
Methanol
• “Wood alcohol”
• Industrial production from synthesis gas
• Common industrial solvent
• Fuel at Indianapolis 500
Fire can be extinguished with water
High octane rating
Low emissions
But, lower energy content
Invisible flame =>
Chapter 10 17
Ethanol
• Fermentation of sugar and starches in grains
• 12-15% alcohol, then yeast cells die.
• Distillation produces “hard” liquors
• Azeotrope: 95% ethanol, constant boiling
• Denatured alcohol used as solvent
• Gasahol: 10% ethanol in gasoline
• Toxic dose: 200 mL ethanol, 100 mL methanol

=>
Chapter 10 18
2-Propanol
• “Rubbing alcohol”
• Catalytic hydration of propene

100-300 atm, 300°C


CH2 CH CH2 + H2O CH3 CH CH3
catalyst
OH

=>
Chapter 10 19
Acidity of Alcohols
• pKa range: 15.5-18.0 (water: 15.7)
• Acidity decreases as alkyl group
increases.
• Halogens increase the acidity.
• Phenol is 100 million times more acidic
than cyclohexanol!

=>
Chapter 10 20
Table of Ka Values

CH3 OH

=>
Chapter 10 21
Formation of Alkoxide
Ions
React methanol and ethanol with sodium
metal (redox reaction).
1
CH3CH2OH + Na CH3CH2O Na + /2 H2

React less acidic alcohols with more


reactive potassium.
(CH3)3C OH + K (CH3)3CO K + 1/2 H2

=>
Chapter 10 22
Formation of Phenoxide
Ion
Phenol reacts with hydroxide ions to form
phenoxide ions - no redox is necessary.
O H O
+ OH
+ HOH
pKa = 15.7
pKa = 10

=>

Chapter 10 23
Synthesis (Review)
• Nucleophilic substitution of OH- on alkyl
halide

• Hydration of alkenes
water in acid solution (not very effective)
oxymercuration - demercuration
hydroboration - oxidation
Chapter 10 24
=>
Organometallic
Reagents
• Carbon is bonded to a metal (Mg or Li).
• Carbon is nucleophilic (partially
negative).
• It will attack a partially positive carbon.
C - X
C = O
• A new carbon-carbon bond forms.
=>
Chapter 10 25
Grignard Reagents
• Formula R-Mg-X (reacts like R:- +MgX)
• Stabilized by anhydrous ether
• Iodides most reactive
• May be formed from any halide
primary
secondary
tertiary
vinyl
aryl =>
Chapter 10 26
Some Grignard
Reagents
Br
ether MgBr
+ Mg

Cl MgCl
ether
CH3CHCH2CH3 + Mg CH3CHCH2CH3

CH3C CH2
ether
Br + Mg CH3C CH2 =>
MgBr

Chapter 10 27
Reaction with Carbonyl
• R:- attacks the partially positive carbon in the
carbonyl.
• The intermediate is an alkoxide ion.
• Addition of water or dilute acid protonates the
alkoxide to produce an alcohol.

R
C O R C O R C OH
HOH
OH
=>
Chapter 10 28
Synthesis of 1° Alcohols
Grignard + formaldehyde yields a primary
alcohol with one additional carbon.
CH3 H H CH3 H
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 H
HOH
CH3 CH CH2 CH2 C O H
H

=>
Chapter 10 29
Synthesis of 2º Alcohols
Grignard + aldehyde yields a secondary
alcohol.
CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H
H H H

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
H

=>
Chapter 10 30
Synthesis of 3º Alcohols
Grignard + ketone yields a tertiary alcohol.
CH3 H H3C CH3 CH3
H3C C CH2 C MgBr C O CH3 CH CH2 CH2 C O MgBr
H3C
H H CH3

CH3 CH3
HOH
CH3 CH CH2 CH2 C O H
CH3

=>
Chapter 10 31
How would you
synthesize…
OH CH2OH
CH3CH2CHCH2CH2CH3

OH OH
C CH3
CH3 =>
CH2CH3

Chapter 10 32
Reactions of Alcohol
(CH3)3COH + HCl (CH3)3CCl + HOH
Alcohol Hydrogen Halide Alkyl Halide Water

Chapter 10 33
Reactions of Alcohol
CH3CH2OH + HBr CH3CH2Br + H2O

Chapter 10 34
Lucas Test

Chapter 10 35
Chemical Equation

Chapter 10 36
How would you
synthesize...
Using an acid chloride or ester.

OH
CH3
CH3CH2CCH3 C
CH3 OH

OH
CH3CH2CHCH2CH3 =>

Chapter 10 37