Chapter 7: Alcohols, phenols and thiols.

Alcohols

 Numbering of OH group has priority over multiple bonds.

Phenols

 Carboxylic and carbonyl groups have priority over alcohols.

 Boiling Point: H-OH > R-OH > R-OR > R-H

 Alcohols have high BP due to hydrogen bonding just like water.
  In an alcohol, as the carbon length increases, BP increases but solubility in water
decreases.

Acidity and basicity

Bronsted Lowry definition

 Acid: Proton donor

 Base: Proton acceptor

 Ka: Equilibrium acidity constant (ionization constant)

 More Ka (or less pKa) means stronger acid.
 If an acid is strong, its conjugate base is weak and vice versa.

Lewis definition

 Acid: Can accept electron pair (BF3, AlCl3, FeCl3, positively charged ions)
 Base: Can donate electron pair (NH3, negatively charged ions)
 Amphoteric: Can act as acid or base (ex: water)

Acidity of alcohols and phenols

 Alcohols are weak acids because the alkoxides ions are unstable
 Phenols are also weak acids but stronger acids compared to alcohols because the
phenoxide ions are stable due to resonance.

 Increasing carbon length in ROH makes decreases acidity.

 Electron withdrawing groups (such as F) increases acidity by stabilizing conjugate
base. Electron donating groups decrease acidity by destabilizing conjugate base.

Inductive effect

 In phenols, electron withdrawing groups increase acidity by induction and

resonance.
 Producing alkoxides

 Alcohols react with metals to form alkoxides which are white solids.

 Since alkoxides are strong conjugate bases compared to NaOH, the following
reactions is shifted backwards.

 Phenol reacts with NaOH to form phenoxides.

Basicity of alcohols and phenols

 They act as lewis base (donate electrons).

 These weak bases can react with strong acids.
Dehydration of alcohols

 Small amounts of strong acids remove water from alcohols when heated.

 Tertiary alcohols dehydrate by E1 mechanism.

 Primary alcohols dehydrate by E2 mechanism.

 In dehydration, alcohols act as base.

 The ease of alcohol dehydration is tertiary > secondary > primary (similar to stability
of carbocation)
 If more than one alkene is produced, the alkene with most substituted double bond
(most R groups) will be the major product.

Reaction with HX

 Since halide ions are good nucleophiles, substitution occurs.

 Speed of reaction: Tertiary > Secondary > Primary

 Tertiary alcohols undergo SN1 mechanism.
 Mechanism:

 Primary alcohols undergo SN2 mechanism.

Mechanism:

Other ways to prepare RX

 Pure RX can be obtained since SO2 and HCl leave as gases. This method is not
effective for preparing low boiling RX (less C).

 For low boiling RX, the following method can be used since phosphorus acid has a
high BP. The RX can be recovered by distillation.

Comparison of alcohols and phenols

 For substitution, the C-OH group in alcohols can be easily broken with the help of an
acid catalyst.
 C-OH bond is difficult to break in phenols because the positive carbon in the phenyl
cation is sp-hybridized and must be linear. But this is prevented due to the ring
structure. Thus phenyl cations are unstable.

 Therefore phenols cannot undergo SN1 and SN2 mechanisms.

Oxidation of alcohols

 Tertiary alcohols do not undergo the above kind of oxidation.

 Jones reagent: CrO3 dissolved in sulfuric acid. Acetone used as solvent.

 PCC: Pyridinium chlorochromate

- Prepared as follows:

- Oxidation of primary alcohols can be stopped at aldehyde stage by using PCC

Multiple OH groups

 Ethylene glycol: used as antifreeze

 Glycerol: Its nitration produces a shock-sensitive explosive

 Sorbitol: Used in candy making and as a sugar substitute for diabetics.

Electrophillic aromatic substitution in phenols

 OH groups strongly activates the ring to allow electrophillic substitution

Oxidation of phenols

1,4-dihydroxybenzene  quinone

Phenols as antioxidants

 Phenols react with and destroy peroxy (ROO.) and (.OH) radicals which could
otherwise oxidize food.
 The resulting phenoxy radical is stable due to resonance.

 BHA (butylated hydroxyanisole) and BHT (butylated hydroxytoluene) are examples

of commercial antioxidants.

Thiols

 Thiols are also called mercaptans because they react with mercuric ion to form
mercaptides.
 They are formed by nucleophillic displacement of RX with SH (sulfhydryl ion)

 R-SH are more acidic than R-OH

 Thiols oxidize to disulfides.

 The odor of fresh garlic is caused by diallyl disulfide: