Enolate Exercises - Organic chemistry II January -May 2018

Prof. Kamil Makowski

1. Explain or define each of following concept (if you want you can use an example)
a. How can we convert electrophilic carbonyl compound into nucleophile

b. Tautomerism

c. How differ tautomerism from resonance

d. Enolate and enol

e. Kinetic enolate and thermodynamic enolate

f. How can we obtain kinetic and thermodynamic silyl enol ethers

g. Why is better acid promoted alpha-mono-halogenation than base promoted

h. Haloform reaction (we talk about it but we didn’t name it like that – do a research) i.
HVZ reaction
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

j. Michael addition, Michael acceptor and Michael donor

k. Aldol reaction, cross aldol reaction

l. Robinson annelation (or anulation)

m. Crossed claisen condensations

n. Stork reaction and Mannich reaction

2. When cis-2,4-dimethylcylohexanone is dissolved in aqueous ethanol containing a trace of

NaOH a mixture of cis and trans isomers results. Give a mechanism for this isomerization.
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

3. Propose mechanism for the reaction of 3-pentanone with sodium hydroxide and bromine to
give 2-bromo-3-pentanone

4. Predict the products of the following reactions:

a. Methyl cyclopentyl ketone + excess Cl2 + excess NaOH
b. Propiophenone + excess Br2 + excess NaOH
c. Cyclohexanone + Cl2 (1 eq) + excess AcOH

5. Acid catalysed halogenaton is synthetically useful for converting ketones to α,β-unsaturated

ketones, which are useful in Michael reactions. Propose a method for converting
cyclohexanone to cyclohex-2-en-1-one, an important synthetic starting material.
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

6. Predict the major products of the following reactions:

7. Predict the products of the Claisen condensation (hint: cyclic Claisen cyclization called
dieckmann cyclization)
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

8. Predict the cross claisen condensation of cyclohexanone and diethyl carbonate using sodium
ethoxide as a base.

9. Propose the mechanism for aldol condensation of cyclohexanone (autocondensation)

Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

10. Propose the mechanism for following reaction:

11. What two reagent would you use that could be joined by an aldol condensation to obtain
following products:

12. What kind of the electrophile would you use to obtain following product using malonate
ester as starting material
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

13. Show how the following products might be synthetized from suitable Micheal donors and
acceptors

14. Show how you would you use Robinson annulation to synthetize the following compounds
(remember that cyclohexenone is a new ring)
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

15. Show how you would accomplish each of conversion using enamine synthesis
a. Cyclopenthanone → 2-allylcyclopentanone
b. 3-pentanone → 2-methyl-1-phenyl-3-pentanone

16. Predict products for following reactions:

Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

17. Propose mechanism of the reactions from exercise 16.

Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

18. How you would accomplish the following conversions. You may use any necessary reagent.
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

19. Sometimes chemists when buy a commercial product they run 1H NMR to check if the
compound is ok and without impurities. Master student have bought a dimedone from
SigmaAldrich and to be sure run the proton NMR. She got surprise when saw the spectra
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

because clearly it was a mixture of two products. Assign the signals of dimedone (in
red) and then try guess what the “impurity” is (black). Should the master student to
be worried about that impurity?

20. Master student performed Clasisen condensation. Analyze the spectra of starting material
and the product. Did he managed to obtain the product of claisen condensation?
Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

Product
 Enolate Exercises - Organic chemistry II January -May 2018
Prof. Kamil Makowski

21. The student performed the aldol reaction at low temperature using LDA as a base, 3methylbutan-2-one
and ethanal as a starting materials. Help him to analyse spectra and convince the student that he
succeed.