1. THE SOLVENTLESS ALDOL-TYPE CONDENSATION
Experiment 22:
THE SOLVENTLESS ALDOL-TYPE CONDENSATION

2. Objectives:
To synthesize an a,b unsaturated ketone from an aldehyde and a ketone using solvent-free conditions.
To purify the product through a recrystallization.
To identify and analyze purity through TLC and melting point analysis.
To analyze the product using IR spectra.

3. Before coming to lab… Review these techniques: Recrystallization
TLC Analysis
Melting Point Analysis

4. ALDOL CONDENSATIONS
Aldol condensations are nucleophilic additions of an enolate ion, which are strong nucleophiles, to another C=O group under basic conditions.
Protonation gives the aldol product.
Once formed, the aldol product undergoes dehydration in base.
Abstraction of an a proton gives an enolate that can expel an –OH ion to give a conjugated product.
Dehydration is usually exothermic because it leads to a very stable conjugated product.

5. CHEMICAL EQUATION
3,4-dimethoxy benzaldehyde
1-indanone
Aldol Product

6. MECHANISM Base removes a proton to form enolate ion.
Resonance stabilized enolate forms carbanion, which attacks C=O of aldehyde
Oxygen anion removes proton from water, releasing
–OH.
When new C-C bond forms, C=O p bond breaks, electrons stay with oxygen.
Acidic a proton is removed by –OH. Electrons form new p bond.

7. TYPICAL ALDOL CONDENSATION
A typical aldol condensation reaction is carried out in an organic solvent, such as ethanol, requiring eventual waste disposal.
Isolation of the product requires a much more involved work up, not to mention the hazards to the experimenter and the environment due to waste disposal.
Another challenge is that solution phase reaction is reversible, so low product yields may result.

8. GREEN CHEMISTRY CONCERNS
One of the main themes of greener chemistry is to cut down on the use of solvent, and hence cut down on solvent waste. The best way to do this is simply not to use any solvent at all.
Workup is generally easier since as the reaction proceeds, the product separates from the melt as a solid, making work up much less complicated.
Another benefit is that unlike a solution phase reaction, the solid-state reaction is irreversible, resulting in higher chemical yields.

9. OVERVIEW Synthesize aldol product in test tube.
Recrystallize solid in propanol/water to purify.
Suction filter to isolate solid.
Dry product in oven.
Obtain product mass, calculate % yield, do melting point analysis.

10. EXPERIMENTAL PROCEDURE (Synthesis)
Place aldehyde and ketone in large test tube.
Crush solids with glass rod until liquefied.
Add NaOH. Mix and scrape sides of test tube until pale green solid forms.
Continue to react for 15 minutes at room temperature.

11. EXPERIMENTAL PROCEDURE (Purification and Product Isolation)
Place test tube in a 90oC water bath.
Add 90:10 PROPANOL/WATER and heat until solid dissolves.
Suction filter.
Transfer solid to PREWEIGHED WATCH GLASS AND PLACE IN OVEN 15 MINUTES to dry.
Obtain final product mass and calculate % yield.
Proceed to PRODUCT ANALYSIS (TLC, mp, IR).

12. Table 22.1 Theoretical yield (g)
Determine limiting reagent first, then calculate theoretical yield.
HINT: Don’t round too soon!
Actual yield (g)
% yield
Melting range (oC)
Start temperature dial on setting of 5. Back down one tic mark ~ 150oC and watch closely. Record Ti-Tf range.
Compare to literature value to determine purity of product.
Product Appearance
Record the physical state and color of product.

13. Experimental Atom Economy (%)
Table 22.4
Atom Economy (%)
Calculate based on reactants ONLY!
Review Experiment 13 for calculation.
Experimental Atom Economy (%)
“Eproduct”
Cost Per Synthesis ($)
Costs of stock bottles of compounds on p. 192.
Remember to use reactants and catalyst in this calculation!
Cost per Gram ($/g)
CPS/actual yield (g)

14. 3,4-dimethoxybenzaldehyde
Table 22.2
Compound
TLC Rf values
Standard
Sample
1-indanone
Rf values are UNITLESS!
Rf values are 2 decimal places ONLY!
3,4-dimethoxybenzaldehyde
Aldol Product

15. Product Analysis (IR)

16. aromatic C=C stretch (2)
Table 22.3
Functional
Group
Base
Values
(cm-1)
1-Indanone
3,4-dimethoxy
-benzaldehyde
Aldol
Product
Frequency (cm-1)
Frequency
sp3 CH stretch
sp2 CH stretch
C=O stretch
C-O stretch
aromatic C=C stretch (2)
aldehyde CH stretch (2)

17. SAFETY CONCERNS
Solid NaOH is very corrosive! Immediately flush skin with water if any gets on your skin!
Propanol is very flammable! Use extreme caution during purification!

18. WASTE MANAGEMENT
Place all liquid waste in container labeled “LIQUID ORGANIC WASTE”.
Place all solid waste in container labeled “SOLID WASTE”.
Place all used TLC capillaries and melting point capillaries in broken glass container, NOT TRASHCAN!
Leave TLC chambers with lids off in your lab drawer.

19. CLEANING
Clean all glassware with soap, water, and brush, followed by a rinse with wash acetone before returning to lab drawer.
DO NOT return any glassware to lab drawer dirty or wet!

20. LABORATORY NOTEBOOK (Pre-lab)
OBJECTIVE (Must clearly state…)
What compounds will be made and how
How the compounds will be purified
How the purity of the product will be determined
CHEMICAL EQUATION
Include the chemical equation from the top of page 185.
TABLE OF PHYSICAL DATA (Complete the following table using a site listed on WWW Links ONLY. Wikipedia is unacceptable!)
REFERENCE TO PROCEDURE (Must include…)
full title including edition and author names
page numbers where actual procedure can be found
Compound
MW (g/mol)
mp(oC)
bp(oC)
d (g/mL)
HAZARDS
3,4-dimethoxybenzaldehyde X
1-indanone
Sodium hydroxide
1-propanol
Diethyl ether
hexane

21. LABORATORY NOTEBOOK (In-lab)
DATA/CALCULATIONS
Initial weights of 1-indanone and 3,4-dimethoxybenzaldehyde used
Weights of filter paper and watch glass
Weight of watch glass + filter + product
Final weight of dry product
Physical state and color of product
Theoretical yield calculation
% yield calculation
TLC diagram including all cm measurements
Atom economy calculation
Experimental atom economy calculation
“Eproduct” calculation
Cost per synthesis and cost per gram calculations
EXPERIMENTAL PROCEDURE
In paragraph form, BRIEFLY describe the procedure that you actually followed during the lab.
Paragraph must be written in PAST TENSE, PASSIVE VOICE.
Include any volumes or weights of chemicals used during the experiment.
Include any mistakes, accidents or observations if applicable.