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TetraphenylcyclopentadienoneAn
Example of a Double-Crossed Aldol
Addition Reactions of Carbonyl Groups
The chemical reactivity of aldehydes and ketones is closely associated with
the presence of the carbonyl group in their structures. For example, both aldehydes
and ketones undergo addition reactions such as the addition of a Grignard reagent
to the carbonyl group as shown in Figure 1.
O
RCH + R'MgX
aldehyde
Grignard
reagent
O
RCR'' + R'MgX
ketone
addition
Grignard
reagent
OMgX
RCH
R'
salt
addition
OMgX
RCR''
R'
salt
H+
H2O
acidification
H+
H2O
acidification
OH
RCH
R'
IIo alcohol
OH
RCR''
R'
IIIo alcohol
O-
:Nu
C
Nu
carbon
3 hydrogens
H O
H C C H
H
acetaldehyde
Lab 12
2 hydrogens
3 hydrogens
-C
-C
H H H O H
H C C C C C H
H H H
H
2-pentanone
2
H O
H C C H
H
-OH
step 1
acetaldehyde
O
H C C H
+ HOH
H
carbanion
Lab 12
O
H C C H
OH
C C H
H
H
carbanion
enolate
H O
H C C H
H
acetaldehyde
H OH
H OO
H-OH
H C C H + -OH
H C C H
H C C H
step 2
H CH2CH
H
H CH2CH step 3
O
O
carbanion
aldol
of acetaldehyde
OH
OH O
OH
Figure 7. Aldols.
Acetaldehyde is the simplest compound that has alpha hydrogens. Therefore,
the common name of the aldol made the self-aldol addition reaction of
acetaldehyde is called aldol. All other aldehydes or ketones that contain the hydroxycarbonyl structure are members of the aldol family and are called aldols.
Crossed-Aldol Addition Reaction
In a self-aldol addition reaction, both reactants come from the same
compound. When the two reactants in Step 2 come from different compounds, the
reaction is called a crossed-aldol addition reaction.
A crossed-aldol addition reaction generally involves one aldehyde or ketone
without alpha hydrogens and one with alpha hydrogens; therefore, only the
compound with alpha hydrogens can form an enolate in base. If both compounds
contained alpha hydrogens, then multiple products would be produced. The enolate
is the nucleophile that adds to the carbonyl group of the compound without alpha
hydrogens. Benzaldehyde contains no alpha hydrogens and acetone contains six
equivalent alpha hydrogens; therefore, these two compounds can undergo a
crossed-aldol addition reaction without forming multiple products. Figure 8 shows
the structures of benzaldehyde and acetone. You should know the structures of
these compounds.
O
C
not
H
benzaldehyde
Lab 12
O
CH3CCH3
acetone
5
Step 1
-CH CCH
2
3
Step 2
OCH
HOH
CH2CCH3
Step 3
O
OH
CH
CH2CCH3
O
Lab 12
H C C
H OH H O
H C C C C H
H H H
aldol
Step 4
H H
H
H C
H O
C C H
-unsaturated aldehyde
(conjugated, more stable)
H O
C H
-unsaturated aldehyde
(unconjugated, less stable)
OH
CH
CH2CCH3
O
- H2O
O
CH CHCCH3
aldol
-unsaturated ketone
Lab 12
O
CH2 C CH2
dibenzyl ketone
KOH
- H2O
tetraphenylcyclopenatadienone
Lab 12
5. Heat the mixture on the sand bath until the solids dissolve but do not let the
ethanol boil (bp = 78 oC).
6. Slowly add seven drops of 5% (weight-volume) alcoholic potassium hydroxide
(KOH) through the condenser.
7. Bring the ethanol to a boil and allow the mixture to reflux for 10 min.
8. If a solid begins to form and cake on the round-bottomed flask, add a few drops
of absolute ethanol to keep the solid moist.
9. While the mixture is under reflux, prepare an ice-water bath in a beaker large
enough to hold the round-bottomed flask.
10. Remove the apparatus from the sand bath and allow the round-bottomed flask
to cool to room temperature.
11. Place the flask, still attached to the condenser, in the ice-water bath and allow
the flask to come to the temperature of the ice bath.
12. Remove the condenser and collect the crystals on a Bchner funnel.
13. Continue to apply suction until the crystals are as dry as possible.
14. Weigh the crystals and record the yield directly in your notebook.
15. Show the crystals to your instructor, who will tell you what to do with them.
16. Clean your work area. Replace all equipment to the correct storage location.
Lab 12
Lab 12
10
6.
7.
O
C
8.
CH3CHO
CH3CHO
no heat
O
CH3CCH3
(1)OH(2) heat
OHno heat
O
9.
(1)OH(2) heat
10. What structural feature makes your product in lab purple? _______________
Lab 12
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