Chem 22 Spring 2001 Second Review Sheet Chapter 15-Chapter 16
Reactions Covered in Chapter 15
1. Acyl Halide: nucleophilic acyl substitution--no catalyst needed
KNOW MECHANISM for these reactions
+ carboxylate yields ____________ + alcohol yields _____________
+ water yields _____________ + amine yields ______________
Synthesis from acids: ____________________
2. Anhydride: nucleophilic acyl substitution--no catalyst needed
KNOW MECHANISM for these reactions
+ alcohol yields _____________ + water yields ______________
+ amine yields _____________ Synthesis from acids: ____________
3. Esters: nucleophilic acyl substitution-- catalyst and/or Le Chatelier needed
KNOW MECHANISM for acid catalyzed and base promoted reactions
+ alcohol yields _____________ + water yields _____________
+ amine yields ____________________
4. Carboxylic acids: nucleophilic acyl substitution-- catalyst and/or Le Chatelier needed
KNOW MECHANISM for acid catalyzed and base promoted reactions
+ alcohol yields _____________ + amine yields ______________
5. Nitriles and amides: KNOW MECHANISM for acid-cat. and base-prom. hydrolysis
Can use SN2 with CN- to extend carbon chain of alkyl halide
Synthesis of Nitrile from primary amide uses: ____________________
6. Gabriel Synthesis: Good synthesis of primary amines: Reactants: __________
Reagents: Step 1___________________________
Step 2___________________________
Step 3___________________________
7. Diacids/Derivatives and their reactions (similar to reactions above)
Reactions covered in Chapter 16
1. Addition of oxygen nucleophiles: equilibrium reactions, know acid catalyzed mechanism
Water + aldehyde or ketone yields _________________
Alcohol + aldehyde yields _________________ then _________________
Alcohol + ketone yields _________________ then _________________
Be able to recognize internal reactions to make these products.
Be able to predict conditions favoring forward and reverse reactions.
2. Addition of sulfur nucleophiles: equilibrium reactions, Lewis acid catalyzed
Complete reaction of thiol + aldehyde or ketone yields _________________
Be able to recognize internal reactions to make these products.
Reaction of the product with Raney Ni yields ___________________.
3 Addition of nitrogen nucl.: equilibrium reactions, know acid catalyzed mechanism
Complete reaction of 1° amine or ammonia + aldehyde or ketone yields _________.
Complete reaction of 2° amine + aldehyde or ketone yields _________________.
Be able to recognize internal reactions to make these products.
Reaction of the product with Raney Ni or NaBH3CN yields _________________.
Wolff-Kishner mechanism.
4. Addition of carbon nucleophiles: generally the strongest, least reversible reactions.
Addition of HCN yields ________________.
Product can be catalytically hydrogenated to make _______________.
Product can be hydrolyzed to make _______________.
Addition of Grignard or RLi to CH2O followed by acidic workup yields ________.
Addition of Grignard or RLi to aldehyde followed by acidic workup yields ______.
Addition of Grignard or RLi to ketone followed by acidic workup yields ________.
Addition of acetylide to ald. or ket. followed by acidic workup yields ___________.
Addition of phosphorous ylides to aldehydes or ketones yields _______________.
mixture of E,Z.
ylide is formed by the reaction sequence ____________________________
5. Nucleophilic Acyl Substitution of carbon nucleophiles:
Addition of RMgX or RLi to esters/acyl halides, (acidic workup) yields _________.
This synthesis always yields 2 of the same R-group added to the carbonyl.
6. Reactions of hydride nucleophiles:
________ or _________ will add to aldehydes and ketones to make ___________.
Only ________ will react with acids, esters, or acyl halides to make ____________.
Only _________ will react with amides to make ______________.
Only ________________ will react with acyl halides to make ______________.
Only ________________ will react with esters to make ______________.
Which reactions performed in protic solvents? Performed in ether (w/ aqueous workup)?
7. Conjugate Additions to a,b-unsaturated carbonyls
Nucl. that add to the b-carbon___________ Nucl. that add directly ___________
NaBH4 gives a mixture of direct and conjugate addition.
Concepts Covered in Chapter 15/16
1. Nomenclature: carboxylic acids, acyl halides, anhydrides, esters, amides, nitriles, aldehydes, ketones, carboxylates. Common (1-6 carbons) and IUPAC
2. Principle of reactivity for acids and derivatives: general nucleophilic acyl substitution equilibrium reaction. How do you know which direction is favored?
3. Soaps and micelles: What is a fatty acid? What is a triglyceride? How are soaps made? How do they work?
4. Reactivity of aldehydes and ketones: general mechanism of Nucleophilic Addition and Nucleophilic addition-elimination sequence. Why not nucleophilic substitution?
5. Relative reactivity of carbonyl compounds with nucleophiles.
6. The acid catalyzed mechanism to make hemiacetals and acetals: intermediacy of resonance stabilized carbocations (oxonium ions).
7. When is ald. or ket favored over the addition product in an equilibrium reaction?
8. Understand the stereochemical aspects of addition reactions to carbonyl compounds.
9. Use of aldehyde and ketone protecting groups in synthesis. When are they necessary?
10. Synthesis of cyclic compounds from acyclic starting materials.
11. The role of resonance of the a,b-unsaturated carbonyl and reversibility of the addition reaction determines whether conjugate or direct addition reactions occur.
12. Synthesis, synthesis and more synthesis!