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Alcohols - Structure and Synthesis - Chapter 10

This document summarizes key information about alcohols and their synthesis. It discusses the nomenclature, acidity, and synthesis of alcohols. The primary synthetic methods covered are nucleophilic addition reactions of organometallic reagents like Grignard reagents to carbonyl compounds, addition of hydride reagents to carbonyls, and catalytic hydrogenation of aldehydes and ketones. Thiols are also introduced as sulfur analogs of alcohols.

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126 views

Alcohols - Structure and Synthesis - Chapter 10

This document summarizes key information about alcohols and their synthesis. It discusses the nomenclature, acidity, and synthesis of alcohols. The primary synthetic methods covered are nucleophilic addition reactions of organometallic reagents like Grignard reagents to carbonyl compounds, addition of hydride reagents to carbonyls, and catalytic hydrogenation of aldehydes and ketones. Thiols are also introduced as sulfur analogs of alcohols.

Uploaded by

lotanna
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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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

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