Chapter 7: Alcohols, Phenols and Thiols

Alcohols: General Formula and Classification

→ General alcohol formula: ROH (R is an alkyl group, OH: hydroxyl group)

→ Classification of alcohols:

Primary (1◦) Secondary (2◦) Tertiary (3◦)

 Nomenclature of Alcohols

IUPAC name: methanol ethanol 1-propanol 2-propanol

Common name: methyl alcohol ethyl alcohol n-propyl alcohol isopropyl alcohol

IUPAC name: 1-butanol 2-butanol 2-methyl-1-propanol 2-methyl-2-propanol

Common name: n-butyl alcohol sec-butyl alcohol iso-butyl alcohol tert-butyl alcohol

IUPAC name: 2-propen-1-ol cyclohexanol phenylmethanol

Common name: allyl alcohol cyclohexyl alcohol benzyl alcohol

Nomenclature of Phenols

IUPAC name: phenol p-chlorophenol 2,4,6-tribromophenol

IUPAC name: m-hydroxybenzoic acid p-hydroxybenzaldehyde p-nitrophenol

 Physical Properties of Alcohols and Phenols (I)
(Hydrogen Bonding)
Boiling Points of Alcohols
→ The boiling point of alcohols is much higher than those of ethers or hydrocarbons with similar molecular weights

Example: CH3CH2OH CH3OCH3 CH3CH2CH3

Mwt.: 46 46 44

Boiling Point (b.p.): +78.5◦C -24◦C -42◦C

Reason: Due to ‘’hydrogen bonding’’ in alcohols

hydrogen bond

Physical Properties of Alcohols and Phenols (II)

(Hydrogen Bonding)

Miscibility of Alcohols in Water

→ Low molecular weight alcohols are complete miscible in water

Reason: → Water is a hydrogen bonded liquid,

the lower molecular weight alcohols can readily replace water
molecules in the hydrogen bonded network

hydrogen bonds
between alcohols
and water molecules
 Boiling Point and Water Solubility of Some Alcohols

Name Formula Boiling Point Solubility in H2O

methanol CH3OH 65 completely miscible

ethanol CH3CH2OH 78.5 completely miscible

1-propanol CH3CH2CH2OH 97 completely miscible

1-butanol CH3CH2CH2CH2OH 117.7 7.9

1-pentanol CH3CH2CH2CH2CH2OH 137.9 2.7

1-hexanol CH3CH2CH2CH2CH2CH2OH 155.8 0.59

Acidity and Basicity Reviewed (I)

Definition:

→ Acid is a proton donor, while base is proton acceptor

Example: Inverse relationship between

The strength of the acid and its
Conjugate base

The strength of an acid in water is measured quantitatively by its

acidity constant or ionization constant, Ka
 Acidity and Basicity Reviewed (II)

The stronger the acid,

the more this equilibrium is shifted to the right,
thus increasing the concentration of H3O+
and increasing the value of Ka

Acidity and Basicity Reviewed (III)

 Acidity and Basicity Reviewed (IV)

→Since the Ka values are very small, we usually use pKa instead
pKa = -log Ka

→ pKa value is inversely proportional to Ka value

→ Stronger acid has larger Ka value and smaller pKa value

→ Weaker acid has smaller Ka value and larger pKa value

Lewis Acid Base Definition

→ Base is an electron donor, while acid is an electron acceptor

Examples: Lewis
acid
Lewis
base

Lewis Lewis
base acid
 The Acidity of Alcohols and Phenols

→ Like water, alcohols and phenols are weak acids.

Dissociation Reaction of Alcohols:

Alcohol Alkoxide ion

Acid (proton donor) (conjugate base)

Conjugate base of ROH is alkoxide ion (RO-)

Conjugate base of CH3OH is methoxide ion (CH3O-)
Conjugate base of CH3CH2OH is ethoxide ion (CH3CH2O-)

The Acidity Comparison of Water, some Alcohols and Phenols

Compound pKa Value

H2O 15.7
CH3OH 15.5
CH3CH2OH 15.9
10.0

Based on the above table:

→ Alcohols (e.g. methanol and ethanol) have acidity strength comparable to water
→ Phenol is much stronger acid than alcohols (has lower pka value)
 Explanation for Acidity Difference between Alcohols and Phenols

→ Phenols are stronger acids than alcohols because of the corresponding phenoxide ions
are stabilized by resonance (negative charge is delocalized)
→ While the negative charge of an alkoxide ion is concentrated on the oxygen atom

Charge localized
on the oxygen atom Charge delocalized
in alkoxide ions in phenoxide ion

→ Because phenoxide ion stabilized this way, the equilibrium for their formation is more favorable
than that of alkoxide ion

The Acidity Comparison between Different Types of Phenols

Compound pKa Value

10.4 weakest acid

10.0

7.2

0.25 strongest acid

“picric acid”

→ Electron donating groups decrease the acidity

→ Electron withdrawing groups increase the acidity
 The Acidity Comparison between Ethanol and Trifluoroethanol

pKa values
weakest acid
Ethanol CH3CH2OH 15.9

2,2,2-trifluoroethanol CF3CH2OH 12.4 strongest acid

Reason:

Inductive effect of fluorine atom accounts for the acidity difference

Reaction of Alcohols and Phenols as Acids

No reaction

but
stronger acid
 The Basicity of Alcohols and Phenols

→ Alcohols can function as weak bases

Lewis Base acid protonated alcohol

Reactions of Alcohols (I)

Dehydration of alcohols to alkenes

Reaction of alcohols to form alkyl halide

X: Cl or Br

3◦ or 2◦ alcohol Alkyl halide

Any class of alcohol Alkyl chloride

 Reactions of Alcohols (II)

Reaction of alcohols to form alkyl halide

X: Cl or Br

Oxidation of alcohols to aldehydes, ketones and carboxylic acids

1◦ alcohol aldehyde carboxylic acid

Oxidizing Agents:
- Jone’s reagent (CrO3/H2SO4)
- KMnO4/ H2SO4

2◦ alcohol ketone

PCC Oxidizing Agent

→ PCC is a special oxidizing agent will oxidize 1◦ alcohols to aldehydes

Aldehyde
1◦ alcohol
PCC: pyridinium chlorochromate
 Exercise

Complete the following six reactions:

Alcohols with More Than One Hydroxyl Group

→ Compounds with two adjacent alcohol groups are called glycols. e.g. ethylene glycol.

→ Examples of compounds with more than one hydroxyl group:

IUPAC: 1,2-ethanediol 1,2,3-propanetriol 1,2,3,4,5,6-hexanehexaol

Common: ethylene glycol glycerol (glycerine) sorbitol

 Properties and Applications of Alcohols with More Than One Hydroxyl Group (I)

ethylene glycol

→ Used as permanent antifreeze in automobile radiators

Because of its increased → It is completely miscible with water
capacity for hydrogen bonding
→ Has an exceptionally high boiling point for its molecular weight (much higher than ethanol)

Properties and Applications of Alcohols with More Than One Hydroxyl Group (II)

glycerol (glycerine)

→ Colorless, water-soluble, high boiling point liquid

→ Has a sweet taste.
→ Used in shaving and toilet soaps, and in cough drops and syrups
→ Triesters of glycerol are fats and oils.
 Properties and Applications of Alcohols with More Than One Hydroxyl Group (III)

sorbitol

→ With its many hydroxyl groups is water soluble.

→ It is almost sweet as cane sugar
→ Used in candy making and as a sugar substitute for diabetics

Aromatic Substitution in Phenols

→ Some reactions will occur with phenols, but not with alcohols.
Examples:

(1)

(2)
 Oxidation of Phenols

Thiols, the Sulfur Analogs of Alcohols and Phenols

→ The sulfhydryl group (-SH) is the functional group of thiols.

→ Thiols are named as follows:

CH3SH
methanethiol 1-butanethiol 2-pentanethiol

thiophenol 3-bromobenzenethiol
 Reactions Involving Thiols (I)

→ Preparation of alkyl thiols:

Examples:

Reactions Involving Thiols (II)

→ Reactions of alkyl thiols:

Thiols are more acidic than alcohols

Examples:
 Reactions Involving Thiols (III)

→ Oxidation reaction of thiols:

Examples: