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22 Cards in this Set
- Front
- Back
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Enolate - monohalogenation
vs. perchlorination |
acid catalyzed for monohalogenation
base catalyzed for perchlorination |
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Alkylation of an enolate
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Use of a base and R-X (via SN2), but problematic for E2, aldol condensation, and overalkylation with multiple products
Solve by having only one H, good alkyl contingent or enamines |
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Aldol Condensation/Dehydration
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A carbonyl creates a carbonyl with an alpha double bonded carbon
1. Enolate generation 2. Nucleophilic Attack 3. Protonation 4. Dehydration |
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Alpha, beta unsaturated aldehydes and ketones
1. hydrogen cyanide addition 2. O and N nucleophiles 3. organometallics 4. enolate ions as nucleophiles |
1. cyanide at beta position
2. conjugate hydration or ether or amine addition 3. RLi - adds 1,2 R2CuLi - adds 1,4 4. Michael Addition and Robinson Annulation |
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Michael Addition
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1,5 carbonyl addition
creates two carbonyl groups |
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Robinson annulation
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combines michael addition and intramolecular aldol condensation
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make carboxylic acid
1. oxidation of primary alcohol and aldehyde 2. Carbonation 3. Nitrile hydrolysis |
1. KMnO4; CrO3, H20; HNO3; H2O2, Cu or Ag
2. organometallic and carbon dioxide 3. CN (for SN2), followed by aqueous work up |
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reduction of carboxylic acid
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LiAlH4
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Synthesis of Alkanoyl Halides
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SOCl2, PCl5, PBr3
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Synthesis of Anhydridies
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carboxyclic acid and alkanoyl halide, heat
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Synthesis of esters
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alcohol and carboxylic acids, acid catalyzed
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synthesis of amides
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carboxylic acid and amine, plus heat
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reduction by DIBAL
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esters and amides to form aldehydes and amines
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reduction by LiAl(OCCH3)3
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alkanoyl halides and anhydrides become aldehyde
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LiAlH4
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everything to alcohol or amine
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Hell-Vollhard-Zelinsky Reaction
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makes alpha bromocarboxylic acid
1. alkanoyl bromide formation 2. enolization 3. bromination 4. exchange |
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Alkanoyl Halide Reactions
1. water 2. alcohol 3. amines 4. organometallic reagents 5. reduction |
1. carboxylic acid
2. esters 3. amides 4. ketones by RX and R2CuLi 5. use of soft LiAl - aldehyde use of NaBH4 - alcohol |
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anhydride reactions
1. hydrolysis 2. alcohol 3. amines |
1. carboxylic acid
2. ester and carboxylic acid 3. amide and carboyxlic acid |
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Ester reactions
1. hydrolysis 2. alcohol 3. amines 4. grignards 5. reduction 6. alkylation through ester enolates with LDA |
1. carboxylic acid
2. transesterfication - switch between alkyl groups 3. amides 4. alcohols - tertiary or secondary 5. LiAlH4- alcohol DIBAL - aldehyde NaBH4 is unreactive |
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Amides
1. hydrolysis 2. Reduction 3. alkylaation of N or C 4. Hoffman Rearrangement |
1. carboxylic acid
2. LiAlH4 - amine DIBAL - aldehyde 3. Alkylation - LDA, CH3I, NaNH2 and haloalkane |
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Alkanenitrile
1. hydrolysis 2. organometallic reagent 3. reucation |
1. carboxylic acid
2. ketone by RLi and RMgX 3. soft LiAl or DIBAL - aldehyde LiAlH4 or catalytic hydrogenation-amine |
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Synthesis of Amines
1. Alkylation of NH3, primary and secondary amines 2. Via nitriles 3. arenamine via nitroarene |
1. excess RNH2 and limited RX
2. RX and CN, followed by LiAlH4 3. EAS |
