Organic Chemistry

Chapter 10
Structure and Synthesis
of Alcohols

Structure of Alcohols

Hydroxyl (OH) functional group

Oxygen is sp3 hybridized.
Chapter 10

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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.
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Chapter 10

Classify these:
CH3
CH3

CH3

CH CH2OH

CH3

C OH
CH3

OH

OH
CH3

CH CH2CH3

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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

Name these:
CH3
CH3

CH CH2OH

2-methyl-1-propanol

OH
CH3

CH CH2CH3

2-butanol

CH3
CH3

OH

C OH
CH3

2-methyl-2-propanol

Br

CH3

3-bromo-3-methylcyclohexanol
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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)
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Chapter 10

Naming Priority

Acids
Esters
Aldehydes
Ketones
Alcohols
Amines

Alkenes
Alkynes
Alkanes
Ethers
Halides
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Chapter 10

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
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Chapter 10

Common Names
Alcohol can be named as alkyl alcohol.
Useful only for small alkyl groups.
Examples:
CH3
CH3

CH CH2OH

isobutyl alcohol

OH
CH3

CH CH2CH3

sec-butyl alcohol
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Chapter 10

10

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

HO

1,6-hexanediol
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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
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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.
OH
Methyl phenols are cresols.
OH

H3C

4-methylphenol
para-cresol

Cl

3-chlorophenol
meta-chlorophenol

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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.
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Boiling Points

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15

Solubility in Water

Solubility decreases as the size

of the alkyl group increases.
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16

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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
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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
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Chapter 10

18

2-Propanol
Rubbing alcohol
Catalytic hydration of propene
CH2 CH CH2 + H2O

100-300 atm, 300C

catalyst

CH3 CH CH3
OH

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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!
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Chapter 10

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Table of Ka Values
CH3

OH

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21

Formation of Alkoxide
Ions
React methanol and ethanol with sodium
metal (redox reaction).
CH3CH2OH +

Na

CH3CH2O

Na

1
+ /2 H2

React less acidic alcohols with more

reactive potassium.
(CH3)3C OH +

(CH3)3CO

+ 1/2 H2

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22

Formation of Phenoxide
Ion
Phenol reacts with hydroxide ions to form
phenoxide ions - no redox is necessary.
O

O H
+

OH

HOH
pKa = 15.7

pKa = 10

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23

Synthesis (Review)
Nucleophilic substitution of OH- on alkyl
halide
Hydration of alkenes
water in acid solution (not very effective)
oxymercuration - demercuration
hydroboration - oxidation
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Glycols (Review)
Syn hydroxylation of alkenes
osmium tetroxide, hydrogen peroxide
cold, dilute, basic potassium
permanganate

Anti hydroxylation of alkenes

peroxyacids, hydrolysis
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25

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.

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26

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

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Some Grignard
Reagents
Br
+

Mg

Cl
CH3CHCH2CH3

Mg

CH3C CH2
Br

MgBr

ether

Mg

ether

MgCl
CH3CHCH2CH3

ether

CH3C CH2

=>

MgBr

Chapter 10

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Organolithium Reagents
Formula R-Li (reacts like R:- +Li)
Can be produced from alkyl, vinyl, or aryl
halides, just like Grignard reagents.
Ether not necessary, wide variety of
solvents can be used.

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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

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30

OH

Synthesis of 1 Alcohols
Grignard + formaldehyde yields a primary
alcohol with one additional carbon.
CH3
H3C C CH2

CH3

H
MgBr

C O

CH3

CH2

C O

MgBr

CH3
CH3

CH CH2

CH CH2

CH2

C O H

HOH

Chapter 10

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Synthesis of 2 Alcohols
Grignard + aldehyde yields a secondary
alcohol.
CH3
H3C C CH2

CH3

H3C

H
MgBr

C O

CH3

CH2

C O

MgBr

CH3
CH3

CH CH2

CH3

CH3

CH CH2

CH2

C O H

HOH

Chapter 10

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Synthesis of 3 Alcohols
Grignard + ketone yields a tertiary alcohol.
CH3
H3C C CH2

CH3

H3C

H
MgBr

C O

CH3

H3C

CH2

C O

MgBr

CH3

CH3
CH3

CH CH2

CH3

CH3

CH CH2

CH2

C O H

HOH

CH3

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Chapter 10

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How would you

synthesize
OH

CH2OH

CH3CH2CHCH2CH2CH3

OH

OH

CH3

C CH3
CH2CH3

Chapter 10

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34

Grignard Reactions
with Acid Chlorides
and Esters
Use two moles of Grignard reagent.
The product is a tertiary alcohol with
two identical alkyl groups.
Reaction with one mole of Grignard
reagent produces a ketone intermediate,
which reacts with the second mole of
Grignard reagent.
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35

Grignard + Acid
Chloride (1)
Grignard attacks the carbonyl.
Chloride ion leaves.
CH3

H3C
R

MgBr

C O
Cl

CH3
R C O
Cl

R C O

MgBr

Cl
CH3

MgBr

R C

MgBrCl

Ketone intermediate
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Grignard and Ester (1)

Grignard attacks the carbonyl.
Alkoxide ion leaves! ? !
CH3

H3C
R

MgBr

C O
CH3O

CH3
R C O
OCH3

R C O

MgBr

OCH3
CH3

MgBr

R C

MgBrOCH3

Ketone intermediate
Chapter 10

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Second step of reaction

Second mole of Grignard reacts with the
ketone intermediate to form an alkoxide ion.
Alkoxide ion is protonated with dilute acid.
CH3

CH3
R

MgBr

R C

R C O

MgBr

HOH
CH3
R C OH
R

Chapter 10

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How would you

synthesize...
Using an acid chloride or ester.
OH

CH3

CH3CH2CCH3

CH3

OH

OH
CH3CH2CHCH2CH3

Chapter 10

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39

Grignard Reagent +
Ethylene Oxide
Epoxides are unusually reactive ethers.
Product is a 1 alcohol with 2 additional
carbons.
O

O
MgBr

CH2

MgBr

CH2CH2

CH2

HOH
O H
CH2CH2

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40

Limitations of Grignard
No water or other acidic protons like
O-H, N-H, S-H, or -CC-H. Grignard
reagent is destroyed, becomes an
alkane.
No other electrophilic multiple bonds,
like C=N, CN, S=O, or N=O.
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Reduction of Carbonyl
Reduction of aldehyde yields 1 alcohol.
Reduction of ketone yields 2 alcohol.
Reagents:
Sodium borohydride, NaBH4
Lithium aluminum hydride, LiAlH4
Raney nickel
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Sodium Borohydride
Hydride ion, H-, attacks the carbonyl
carbon, forming an alkoxide ion.
Then the alkoxide ion is protonated by
dilute acid.
Only reacts with carbonyl of aldehyde or
ketone, not with carbonyls of esters or
carboxylic acids.
O
C
H

H
C

O
+

Chapter 10

H3O

O H
H

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43

Lithium Aluminum Hydride

Stronger reducing agent than sodium
borohydride, but dangerous to work with.
Converts esters and acids to 1 alcohols.
O
C

OCH3

H
LAH

H3O+

Chapter 10

O H
H

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Comparison of
Reducing Agents
LiAlH4 is stronger.
LiAlH4 reduces more
stable compounds
which are resistant
to reduction.
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Catalytic Hydrogenation
Add H2 with Raney nickel catalyst.
Also reduces any C=C bonds.
OH

NaBH4

OH
H2, Raney Ni

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46

Thiols (Mercaptans)

Sulfur analogues of alcohols, -SH.

Named by adding -thiol to alkane name.
The -SH group is called mercapto.
Complex with heavy metals: Hg, As, Au.
More acidic than alcohols, react with
NaOH to form thiolate ion.
Stinks!
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Thiol Synthesis
Use a large excess of sodium
hydrosulfide with unhindered alkyl
halide to prevent dialkylation to R-S-R.
H

_
R X

SH

+ X

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Thiol Oxidation
Easily oxidized to disulfides, an
important feature of protein structure.
R

SH

+ HS

Br2
R

R +

2 HBr

Zn, HCl

Vigorous oxidation with KMnO4,

HNO3, or NaOCl, produces sulfonic acids.

SH

HNO3
boil

Chapter 10

O
S
O

OH

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End of Chapter 10

Chapter 10

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