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SYNTHESIS OF ALCOHOLS AND PHENOLS

Organometallic Reagents for Alcohol Synthesis

o Terminal alkynes can be deprotonated by strong bases such as sodium amide to form acetylide ions.
o The acetylide ion is a strong nucleophile that can react with alkyl halides and carbonyl compounds forming
a C-C bond.
o The reaction of the acetylide ion with aldehydes and ketones produces acetylenic alcohols.

Grignard Reagents

o Grignard reagents are prepared by reacting the alkyl halide with magnesium metal in an ether solvent.
o There are no restrictions on the alkyl halides used but alkyl iodides are the most reactive followed by
bromides and chlorides.
o It is not typical for an alkyl fluoride to form Grignard reagents. The order of reactivity for alkyl halides is R-I
> R-Br > R-Cl >> R-F.

Addition of Organometallics to Carbonyl Compounds

o Grignard and lithium reagents have a nucleophilic carbon and as such can attack an electrophile in solution.
o The carbonyl carbon has a partial positive charge that will be prone to nucleophilic attacks.
o Attack of the organometal carbon on the carbonyl will produce a tetrahedral intermediate with a negatively
charged oxygen atom, i.e., an alkoxide.
o Protonation of the intermediate with dilute acid gives the alcohol.
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Protonation of the Alkoxide Intermediate

o The intermediate alkoxide can be protonated by using a dilute acid solution.

Formation of Primary Alcohols Using Grignard Reagents

o Depending on the carbonyl compound used, primary, secondary or tertiary alcohols can be obtained.
o Reaction of a Grignard with formaldehyde will produce a primary alcohol after protonation.

Formation of Secondary Alcohols Using Grignard Reagents

o Addition of a Grignard reagent to an aldehyde followed by protonation will produce a secondary alcohol.

Formation of Tertiary Alcohols Using Grignard Reagents

o Tertiary alcohols can be easily obtained by addition of a Grignard to a ketone followed by protonation with
dilute acid.