Ketones and Aldehydes

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Ketones and Aldehydes

• Properties
• Nomenclature
• Preparation
• Reactions
• Synthesis

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Carbonyl Functional Groups
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Large Dipole Controls Properties and Reactivity
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Boiling PointsDipole-Dipole Interactions
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Adrogenic/Anabolic Steroids
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Anabolic Steroids
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IUPAC NomenclatureKetones
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IUPAC NomenclatureAldehydes
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Preparation of Ketones and Aldehydes

• Friedel-Crafts Acylation (ketones)
• Hydration of Alkynes (ketones with
  oxymercuration, aldehydes with hydroboration)
• Ozonolysis of Alkenes (aldehydes and ketones
  depending on
• Reduction of acids, acid chlorides and nitriles
• Oxidation of alcohols

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Friedel-Crafts Acylation
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IsoflavonesHighly Sought After Natural Products
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Acylation occurs ortho to OH
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Oxymercuration HydrationMarkovnikov
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Hydroboration HydrationAnti-Markovnikov
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OzonolysisAlkene Cleavage
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DIBAHDiisobutyl Aluminum Hydride
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Nucleophilic Addition ReactionsStrong
Nucleophiles
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Carbonyl Reactivity
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NaBH4 Reduction
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Some Examples
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Grignard Reagents React With Ketones to form
tertiary alcohols
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Grignard Summary
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Nucleophilic Addition ReactionsWeak Nucleophiles
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Acetal Formation
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Acetal Mechanism
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Use of Ethylene Glycol to Protect Ketones and
Aldehydes
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Synthesis
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Synthesis
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Aldehydes React Preferentially
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Imine Formation
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Imines and Enamines
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Enamine Mechanism (same as imine mech. until
last step)
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Imine Derivatives
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Conjugate Addition toa,b-Unsaturated CO groups
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1,2- vs. 1,4-Addition
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Gilman Reagents add 1,4
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Synthesis
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Carry Out Conjugate Addition 1st
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Propose a Sequence of Steps
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Enols and Enolatesa Substitutions and
Condensations of Ketones and Aldehydes
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Tautomerization Accelerated in Acid
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Reaction Occurs via Enol
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Tautomerization Acceleration in Base
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Alkylation in BaseReaction with 1o RX