Alcohols & Phenols

OH OH OH

C C

An alcohol A phenol An enol

Naming Alcohols 4 CH3

HO 1 H
2 1
3
OH 2 CHCHCH3
1 2 3 4 5
CH3CCH2CH2CH3 3
4
OH

CH3 HO H
3-Phenyl-2-butanol
2-Methyl-2-pentanol Cis-1,4-Cyclohexanediol
 Common Names that are accepted by IUPAC
CH2OH CH3
H2C CHCH2OH H3C C OH
Allyl alcohol
Benzyl alcohol (2-Propen-1-ol) CH3
(Phenylmethanol)
Tert-Butyl alcohol
(2-Methyl-2-propanol)

Naming Phenols
Note that -phenol is used as the parent name rather than –benzene.
OH

O2N 2,4-Dinitrophenol
NO2
Properties of Alcohols & Phenols: Hydrogen Bonding
Like water, they form hydrogen bonds in the liquid state.
Acidity & Basicity

- Both are weakly basic.

- React with strong acid as shown below.

[ or ArOH + HX
+ -
ArOH2 X ]
- Both are weakly acidic.
- They dissociate in dilute aqueous solution by donating a
proton to water, generating H3O+ & an alkoxide ion, RO− or
phenoxide ion, ArO− .
Alcohols react with: alkali metals; strong bases like sodium
hydride (NaH), sodium amide (NaNH2) & Grignard Reagents
(RMgX) to form alkoxides.
- +
CH3OH + NaH CH3O Na + H2
Methanol Sodium methoxide

- +
CH3CH2OH + NaNH 2 CH3CH2O Na + NH2
Ethanol Sodium ethoxide

-+
OH + CH3MgBr O MgBr + CH4

cyclohexanol Bromomagnesiumcyclohexoxide
Phenols are more acidic than alcohols because the phenoxide ion
formed, is resonance-stabilized.
The resonance-stabilized phenoxide ion is more stable
than the alkoxide ion.
 Preparation of Alcohols

Some of the methods of alcohol preparation we have already seen.

- By Hydration of Alkenes – not so good.
- Hydroboration/oxidation & Oxymercuration/reduction better.
1,2-Diols can be prepared by direct hydroxylation of an alkene
with OsO4 followed by reduction with NaHSO3.
Summary of Reactions
(b) Grignard reagent addition to Carbonyl compounds
(1) Formaldehyde

+ HOMgBr

Formaldehyde

- + R= 1, 2, 3 alkyl, aryl, or vinylic

R MgX X= Br, Cl, I
POCl3 = Phosphorus oxychloride
 (c) Oxidation
(1) Primary Alcohols

PCC= Pyridinium chlorochromate

ALDEHYDES & KETONES

O O
C C
R H R
R
An aldehyde
A ketone

Naming Aldehydes

Aldehydes are named by replacing the terminal -e of the

corresponding alkane with -al. The parent chain must contain
the CHO group. The CHO carbon is numbered carbon 1.
For example:
For more complex aldehydes in which the –CHO group is
attached to a ring, the suffix -carbaldehyde is used:
Some Common Names of some simple Aldehydes that are recognized
by IUPAC are shown in the table below:
 Naming Ketones

O
O
CH3CH2CCH2CH2CH3
1 2 3 4 5 6 CH3CH CHCH2CCH3
6 5 4 3 2 1
3-Hexanone 4-Hexen-2-one

O O
CH3CH2CCH2CCH3
6 5 4 3 2 1
2,4-Hexanedione
A few ketones are allowed by IUPAC to retain their common names:
Exercises:

1)
2) Draw Structures corresponding to the following names:
(a) 3-Methylbutanal
(b) 4-Chloro-2-pentanone
(c) Phenylacetaldehyde
(d) 2-(1-Chloroethyl)-5-methylheptanal