Chapter

10
Structure and Synthesis of
Alcohols
 Alcohols

OH

Phenol

§ Alcohols are organic compounds containing hydroxyl

groups.
 Rules for Nomenclature of Alkanols and Phenols
• Name the longest chain bearing the –OH group.
• Replace suffix –e from alkane name with –ol; ethane
becomes ethanol.
• Number at the end closest to the –OH group (—OH
outranks C=C and C≡C, halides)
• Name all substituents in alphabetical order indicating their
number positions, as usual.
• For Phenols: The —OH group is assumed to be on carbon 1.
Examples:
OH

Cl
3-chlorophenol
 Acidity of Alcohols and Phenols
• Strong bases react with alcohols and yield alkoxide
anions (RO-)
• Alkyl groups decrease acidity,
 Effects on Acidity

• Groups that stabilize negative charge (Electron

withdrawing groups) increase the acidity of alcohols,
effect diminishes with distance.

Acidity
Increases
 Acidity of Phenols
• Phenols are stronger acids, the phenoxide ion is
resonance stabilized…
 Synthesis of Alcohols-Review from previous
chapters (CH 243)
• SN1 and SN2 reactions of alkyl halides (Chapter 6)

• From alkenes: (Chapter 8)

• Hydration (50% H2SO4-H2O)

• Oxymercuration-demercuration

• Hydroboration-oxidation
 Synthesis of Alcohols-Other Methods
Two types of synthetic methods
Ø Carbon chain size increases: C-C bond formation and alcohol
formation
O OH
R-
R

R = alkyl or phenyl group

Ø Carbon chain size remains same: Alcohol formation.
O OH
H-
H

Both of the above methods involve a unifying concept.

Nucleophilic addition to carbonyl compounds
 Discovery of the Grignard Reagent and Reaction

Awarded Nobel prize in

François Auguste Chemistry (1912)
Victor Grignard

Solvent:

Organolithiums also behave in the same way

Alkyl, alkenyl or aryl magnesium/lithium halides can be prepared from the corresponding
halides (fluorides do not react readily; R—I > R—Br > R—Cl >> R—F)
 Mechanism of Addition of the Organometallic (e.g
Grignard Reagent/Organolithiums) to the Carbonyl
STEP 1

STEP 2
 Reaction with Formaldehyde
• Formaldehyde adds one more C than originally present
in the “R” group and forms a primary alcohol R—CH2—
OH
 Reaction with Other Aldehydes
• Other aldehydes yield secondary alcohol
 Reaction With Ketones
• The product is a tertiary alcohol
 Reaction of Grignards with Carboxylic
Acid Chlorides and Esters
The organometallic attacks the carbonyl. The intermediate expels the
chloride, forming a ketone.

The ketone reacts with a second equivalent of organometallic and forms a

tertiary alkoxide. Protonation of the alkoxide forms the alcohol.
 Mechanism with Esters
The organometallic attacks the carbonyl. The intermediate expels the
chloride, forming a ketone.

The ketone reacts with a second equivalent of organometallic and forms a

tertiary alkoxide. Protonation of the alkoxide forms the alcohol.
 10.10 Side Reactions of Organometallic Reagents
• As strong bases they readily accept protons from a
variety of protic substances
• Small amounts of water, protic solvents and reactants
with OH, NH or SH groups should not be present in
reactions with organometallic compounds
 Synthesis of Alcohols-Other Methods
Two types of synthetic methods
Ø Carbon chain size increases: C-C bond formation and alcohol
formation

Ø Carbon chain size remains same: Alcohol formation.

O OH
H-
H

Both of the above methods involve a unifying concept.

Nucleophilic addition to carbonyl compounds
Synthesis of Alcohol using Hydride Reagents

STEP 1

STEP 2
 NaBH4
• Hydride (nucleophile) adds to the C=O, forms an
alkoxide, protonated to alcohol
LiAlH4 is more powerful than NaBH4
 Catalytic Hydrogenation of Aldehydes and Ketones

• As with alkenes, H2 and a metal catalyst are used

• For carbonyl contain compounds Raney Ni (a form of
finely divided Ni saturated with hydrogen) is used
• In addition to C=O, C=C are also reduced
 Thiols (Mercaptans)
• Thiols are the S containing analogs of alcohols, also
called mercaptans
• They are named by adding the suffix thiol to the alkane
name, e.g., methanethiol = CH3—SH
• They are stronger acids than their R—OH counterparts
 Preparation of Thiols

• Thiols are prepared easily in SN2 reactions