Alcohols

1
Alcohols

• Nomenclature
• Properties
• Preparation
• Reactions
• Spectroscopy

2
Alcohol Nomenclature

• IUPAC
• Common
• Carbinol

3
Preparation Reactions

• Reduction of carbonyl compounds
• Hydration of Alkenes
• Grignard reactions

4
Reduction of Carbonyl Compounds

• Reduction of Aldehydes/ketones
• Reduction of Carboxylic acids/Esters

5
Reduction of Aldehydes/Ketones

• Hydrogenation

6
Reduction of Aldehydes/Ketones

• Hydride Reductions

7
Reduction of Carboxylic Acids and Esters

• Lithium Aluminum Hydride Reduction

8
Hydration of Alkenes

• Acid catalyzed Hydration
• Oxymercuration-Demercuration
• Hydroboration-Oxidation

9
Acid-Catalyzed Hydration of Alkenes

• Markovnikov addition
• Formation of most stable carbocation
• Shifts/rearrangements possible

10
Hydration of Alkenes via Oxymercuration/Demercurat
ion

• Markovnikov addition
• Typically no shifts/rearrangements
• Mercurinium ion involvement

11
Hydroboration-Oxidation of Alkenes

• Anti-Markovnikov addition
• No shifts/rearrangements
• Syn addition

12
Grignard Addition Reactions

• Addition to Aldehydes/Ketones
• Addition to Esters
• Addition to Epoxides

13
Grignard Additions to Aldehydes/Ketones

• Formation of primary, secondary, and tertiary
  alcohols

14
Grignard Additions to Esters

• Formation of secondary and tertiary alcohols

15
Grignard Addition to Epoxides
16
Typical Alcohol Reactions

• Salt formation
• Dehydration
• Oxidation
• Alkyl halide formation
• Ester formation

• Ether synthesis
• Periodic acid cleavage of glycols
• Haloform reaction of methyl carbinols
• THP acetal formation

17
Conversion of Alcohols to Salts

• Reaction with Active Metals

18
Dehydration of Alcohols
19
Oxidation of Alcohols
20
Alcohol Conversion to Alkyl Halides

• Reaction with Hydrogen halides
• Reaction with Thionyl chloride
• Reaction with Phosphorus trihalides or
  pentahalides

21
Hydrogen Halide Conversion of Alcohols to Alkyl
Halides
22
Conversion of Alcohols to Alkyl Chlorides via
Thionyl Chloride
23
Conversion of Alcohols to Alkyl Halides via
Phosphorus Halides
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Ester Formation from Alcohols
25
Periodic Acid Cleavage of Glycols
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Haloform Reaction

• Methyl carbinol cleavage to give Carboxylic acids
  and Haloform

27
Disguising an Alcohol

• Creating a tetrahydropyranyl acetal

28
Spectroscopic Characteristics of Alcohols

• Infrared
• Pmr
• Cmr

29
Ethers

• Nomenclature
• Properties
• Preparation
• Reactions

30
Ether Nomenclature
31
Preparation of Ethers

• Dehydration of Alcohols
• Williamson synthesis
• Alkoxymercuration- Demercuration
• Peroxyacid Epoxidation of Alkenes

32
Ether Formation via Acid Catalyzed Dehydration of
Alcohols
33
Williamson Synthesis of Ethers

• Bimolecular Substitution by Alkoxide on a
  suitable substrate

34
Alkoxymercuration-Demercuration of Alkenes

• Markovnikov Addition
• Typically no rearrangements/shifts
• Mercurinium ion involvement

35
Epoxidation of Alkenes

• Prilezhaev reaction

36
Ether Reactions

• HX Cleavage
• Epoxide Ring Opening

37
HX Cleavage of Ethers

• Unimolecular or Bimolecular Cleavage Pathways

38
Epoxide Ring Opening

• Unimolecular or Bimolecular