Alcohols

Contain a hydroxyl (-OH) group

R
O
H
+

Intermolecular forces: dipole-dipole, H-bonding
H-bonds between alcohol molecules: high boiling points
H-bonds with water: up to 4-carbon alcohols soluble in water
-OH group can act as a weak base or a weak acid
R OH R O
H
H
R O
+ Strong acid + Strong base
H
3
C
O
H
H
3
C
O
H
H
O
H
alkoxide oxonium ion alcohol
Alcohol Nomenclature
Parent chain = longest chain containing C with -OH
Root name: replace e with ol
ethane ethanol, butene butenol, etc.
Give OH the smallest possible number
OH has priority over double bonds, alkyl groups
Two OH groups -diol; three OH groups -triol
Add to end of root name (propane propanediol)
OH
5-methyl-3-hexanol
OH HO
1,2-ethanediol
(ethylene glycol)
antifreeze
Alcohol Naming Practice
OH
OH
OH
OH
OH
2-propanol
(isopropyl alcohol)
2,4-dimethyl-3-pentanol
4-penten-2-ol 3,5-dimethyl-2,4-heptanediol
Classes of Alcohols
Primary (1) alcohol
Secondary (2) alcohol
Tertiary (3) alcohol
OH
OH
OH
CH
3
1-butanol
4-phenyl-2-hexanol
1-methylcyclohexanol
OH C attached to 1 other C
OH C attached to 2 other Cs
OH C attached to 3 other Cs
Reactions of Alcohols
Reaction with strong bases
alcohol as proton donor (weak acid)
Reaction with strong acids
alcohol as proton acceptor (weak base)
Dehydration
reverse of hydration of alkenes
requires H
+
catalyst
Oxidation
increase # of C-O bonds
R OH R O
H
H
R O
Strong acid
Strong base
alkoxide
oxonium ion
R OH
- H
2
O
alkene
H C C CH
3
OH
H
H
H
C C
CH
3
H H
H
R R'
O
R H
O
aldehyde ketone
or
R OH
oxidizing
agent
H
+

Dehydration Mechanism
Step 1: electrophilic H
+
catalyst attacks nucleophilic O atom
Step 2: H
2
O dissociates, leaving behind a carbocation
Step 3: Electrons from neighboring C-H bond form bond,
regenerating H
+
catalyst
H
2
O +
H C C CH
3
O
H
H
H
H H
H C C
H
H
CH
3
H
H C C
H
H
CH
3
H
C C
CH
3
H H
H
H
+
H C C CH
3
O
H
H
H
H H
H C C CH
3
OH
H
H
H
H
Hydration and Dehydration
C C
CH
3
H H
H
H
2
O + H C C CH
3
OH
H
H
H
H
+
Hydration and dehydration are in equilibrium
Can change [H
2
O] to favor one reaction or the other
Change Favors
Increase [H
2
O]
Formation of Alcohol (hydration)
Decrease [H
2
O]
Formation of Alkene (dehydration)
Possible Dehydration Products
The most-substituted alkene product is favored (most stable)
OH
H
OH
H
OH H
OH
H
+
?
Major
product
Least Hs on
double bond
Oxidation of Alcohols
Oxidation: increases oxidation number
More C-O bonds (add O) or increases bond order
Fewer C-H bonds (remove H)
Needs an oxidizing agent
CrO
3
, Cr
2
O
7
2-
, MnO
4
-

1 alcohol
R
C
H
O
R
C
OH
O
C OH R
H
H
aldehyde carboxylic acid
PCC stops at
aldehyde
oxidizing
agent
oxidizing
agent
+1
+1
-1
-2
+1
+1
-2
-2
-2
+3
+1
+1
0
0 0
CrO
3
(Cr
6+
)
Cr
3+

,or PCC (pyridinium chlorochromate)
Breathalyzer Tests
ethanol ethanal
(acetaldehyde)
ethanoic acid
(acetic acid)
CH
3
C OH
H
H
CH
3
C
H
O
CH
3
C
OH
O
+ Cr
6+
+ Cr
3+

oxidized oxidized
Breathalyzer Tests
ethanol ethanal
(acetaldehyde)
ethanoic acid
(acetic acid)
CH
3
C OH
H
H
CH
3
C
H
O
CH
3
C
OH
O
+ Cr
6+
+ Cr
3+

oxidized oxidized
methanol methanal
(formaldehyde)
methanoic acid
(formic acid)
H C OH
H
H
H
C
H
O
H C
OH
O
oxidized oxidized
R
C
R
O
C OH R
H
R
Oxidation of Alcohols
2 alcohol
ketone
oxidizing
agent
C OH R
R
R
3 alcohol
oxidizing
agent
No reaction
-2
+1
0
-2
+2
0
0
0 0
+1
CH
3
C
CH
3
O
CH
3
C OH
CH
3
H
2-propanol propanone
(acetone)
Cl
O
Naming aldehydes and ketones
Parent chain = longest chain containing C=O (carbonyl)
Aldehyde Ketone
Prefix
Suffix
Numbering
Naming Priority: Aldehydes > Ketones > Alcohols
-OH (alcohol) substituent hydroxy
oxo
e becomes al
C=O is always C #1
(dont have to number it)
oxo
e becomes one
C=O is lowest possible number
(must number it)
H
O OH
3-hydroxy-4-methylpentanal 3-chloro-2-butanone
Naming Practice
O O
O O
O O
propanedial 2,4-pentanedione
3-oxopentanal
Has both an
aldehyde and a
ketone
Aldehyde
has priority
Ketone = oxo
Condensation of Alcohols
Condensation reaction: two molecules
combine to form a larger molecule (+ water)
Catalyzed by acid (H
+
)
CH
3
OH H-OCH
3

H
2
SO
4
catalyst
CH
3
OCH
3
+ H
2
O +
alcohol alcohol ether water + +
Ethers
Intermolecular forces:
Dipole-dipole
No H-bonding between ether molecules
Lower boiling point than alcohols
Water or alcohols can H-bond to ether oxygen
Somewhat soluble in water and other polar solvents
R
O
R
R
O
H
H
O
H
water
alcohol

H-bond acceptor
No H-bond donor
Two alkyl groups (Cs) bound to oxygen
Naming Ethers
Common names: name both R groups, add ether
diethyl ether
(anesthetic)
O
ethyl ethyl
Naming Ethers
Common names: name both R groups, add ether
diethyl ether
(anesthetic)
tert-butyl methyl ether
(used as gasoline additive)
propyl people ether
O
O O
O
one-eyed, one-horned, flying...
methyl tert-butyl
ethyl ethyl
O
CH
3
propyl
O
O
O
H
Reactions of Ethers
Reactions of peroxides:
Explosive!
Formation of peroxides
diisopropyl ether
peroxide
Controlled
detonation
Resulting crater:
3 feet wide,
one foot deep
+ O
2
peroxide
O
diisopropyl ether
R
C
H
O
R
C
R'
O
Aldehydes and Ketones
C=O group called a carbonyl group
C and O both
sp
2
hybridized
120
120
aldehyde ketone
R
C
H
O
+

R
C
H
O
Very polar C=O bond
Higher boiling point than alkanes
H-bond acceptor
Soluble in polar solvents
No H-bond donor
Lower boiling point than alcohols
Structural Isomers
Draw all the possible structural isomers for
the following formulas:
C
4
H
10
O
C
5
H
12
O
C
4
H
8
O
C
5
H
10
O
Alcohols and Ethers
Aldehydes and Ketones
(contain a double bond)
Notice that all formulas contain one oxygen
What functional groups do you know that contain one
oxygen?
Does the atom ratio of carbon to hydrogen make a
difference?
C
4
H
10
O Isomers
OH
OH
OH
OH
O
O
O
1-butanol
2-butanol
2-methyl-2-propanol 2-methyl-1-propanol
diethyl ether methyl propyl ether
isopropyl methyl ether
C
5
H
12
O

Isomers
OH
OH
OH
OH
OH
OH
O H
OH
1-pentanol
2-pentanol
3-pentanol
2-methyl-1-butanol
3-methyl-2-butanol
3-methyl-1-butanol
2-methyl-2-butanol
2,2-dimethyl-1-propanol
C
5
H
12
O

Isomers
O
O
O
O
O
O
butyl methyl ether tert-butyl methyl ether sec-butyl methyl ether
isobutyl methyl ether ethyl propyl ether
ethyl isopropyl ether
C
4
H
8
O Isomers
O
O
O
butanal
2-butanone
2-methylpropanal
C
5
H
10
O Isomers
O
O
O
O
O
O
O
pentanal 2-pentanone
3-pentanone
3-methylbutanal 3-methyl-2-butanone
2,2-dimethylpropanal 2-methylbutanal
Reactions of Aldehydes and Ketones
Oxidation of aldehydes to carboxylic acids
CrO
3
, MnO
4
-
Reduction of aldehydes and ketones to alcohols
Decrease C-O bonds, increase C-H bonds
Reducing agents: LiAlH
4
, NaBH
4
, H
2
/Pt
OH
H
O
propanal 1-propanol
CH
3
CH
2
CHO CH
3
CH
2
CH
2
OH
LiAlH
4
O OH
NaBH
4
2-methyl-3-pentanone 2-methyl-3-pentanol
Reduction of Aldehydes/Ketones
O
O
OH
OH
O
3-oxopentanal
1,3-pentanediol
LiAlH
4
NaBH
4
cyclohexanone
cyclohexanol
H
2
/Pt

OH
O O O H OH
pentanedial
1,5-pentanediol
Carboxylic Acid Nomenclature
Parent chain: longest containing carboxyl group (COOH)
Name of parent: replace e with oic acid
Numbering starts at carboxyl carbon
Priority: Carboxylic acid > aldehydes > ketones > alcohols

hydroxy
substituent
oxo
substituents
OH
O
trans-3-methyl-2-hexenoic acid
(human armpits)
OH
O O
3-oxobutanoic acid
(diabetes)
HO OH
O O
propanedioic acid
(apples)
R C
O
O H
O
OH O
O
aspirin
OH
HN O
CH
3
Tylenol
Can irritate your stomach Gentle on the stomach
A carboxylic acid Just an alcohol
Carboxylic Acid Reactions
Reduction to 1 alcohols
Only LiAlH
4
reduces carboxylic acids
(not NaBH
4
or H
2
/Pt)
butanoic acid
1-butanol
OH
OH
O
LiAlH
4
butanoic acid
OH
O
NaBH
4
or H
2
/Pt

NO RXN
OH
O
Reactant remains
unchanged
What are the products?
3-oxo-4-pentenoic acid
LiAlH
4
H
2
/Pt NaBH
4
OH
O OH
OH
O O
OH
O OH
OH
OH
3-hydroxypentanoic acid
4-pentene-1,3-diol
3-hydroxy-4-pentenoic acid