Aldol Condensation Web PDF
Aldol Condensation Web PDF
Aldol Condensation Web PDF
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Contents
Objectives
1
Introduction 1
Safety 1
Preparation of 4-(4-methoxyphenyl)-3-buten-2-one (Product A) 2
Preparation of 1,5-bis(4-methoxyphenyl)-1,4-pentadien-3-one (Product B) 6
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Objectives In this experiment, the aldol condensation of
acetone and p-anisaldehyde
The objective of this experiment is to understand (4-methoxybenzaldehyde) is carried out under basic
aspects of carbonyl chemistry and carbon-carbon conditions (Scheme 2). By employing a stepwise
bond formations using the well-known aldol sequence, you will be able to isolate the mono-
condensation reaction. Reaction products formed addition (Product A), and repeat the reaction, this
in this experiment will be primarily characterized time using (Product A) as the source ketone to
by 1H NMR spectroscopy using the Spinsolve form the bis-addition (Product B).
benchtop NMR spectrometer.
Safety
Introduction This experiment must be performed in a fume
hood with adequate ventilation. Acetophenone
Carbon-carbon bond formation is one of the
and benzaldehyde are harmful handle with care.
cornerstones of organic synthesis. One of the
Potassium hydroxide is caustic and corrosive use
key reactions used, the aldol condensation,
with caution. Wear appropriate safety equipment
features the reaction of two carbonyl compounds
before commencing with this experiment.
to form a new -hydroxy carbonyl compound.1
Consult the relevant MSDS for additional safety
This reaction can be performed under acid- or
information.
base-catalyzed conditions, and usually results
in the formation of an ,-unsaturated carbonyl
compound. The general base-catalysed reaction
is shown in Scheme 1. One of the reacting species
must contain a protonated -carbon adjacent to
the carbonyl centre. The proton attached to this
carbon is acidic enough to be abstracted by base
to form an enolate species. Upon reaction with
a second carbonyl compound, the -hydroxy
carbonyl compound is formed, which can undergo
E1cB elimination of water to form an E-alkene.
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Scheme 2. Synthetic two-step preparation of aldol products from acetone and p-anisaldehyde.
Preparation of 4-(4-methoxyphenyl)-
3-buten-2-one (Product A)
In a 100 mL round bottom flask prepare a solution
of p-anisaldehyde (1.2 mL, 10 mmol) in acetone
(15 mL), add a magnetic flea and clamp the flask
above a magnetic stirrer. In a separate beaker,
prepare a solution of potassium hydroxide
(1.0 g) in water (20 mL) and add slowly (over 2
minutes) to the mixture in the round bottom flask
while stirring. Stir the solution for 20 minutes
and add approximately 40 mL of water to the
reaction mixture to ensure that all the product has
precipitated. Filter the resulting solid by vacuum
filtration and wash with water. Dry the solid and
recrystallize from ethanol (Figure 1).
Figure 1. Recrystallized
4-(4-methoxyphenyl)but-3-en-2-one (Product A).
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NMR Spectra
NMR Spectra
The 1H NMR spectrum for the starting material, should account for the remaining six protons in
p-anisaldehyde, is shown in Figure 2. Here, four chemical environments i.e. the two alkene
the resonances for the aldehyde and oxymethyl protons and the two sets of aromatic protons.
proton environments can be easily identified. The overlap of these resonances complicates
The two remaining resonances, belonging to the the assignment of their chemical shifts and
1,4-disubstituted benzene ring, can be assigned multiplicities. By turning to the 2D J-resolved and
based on inductive effects of the substituents, i.e. COSY experiments in Figures 4 and 5, this region
the aldehyde carbonyl group pulls electron density can be observed in more detail.
away from the aromatic ring, deshielding the ortho
In the 2D J-resolved experiment, J-coupling
protons and shields those in the meta position.
constants are mapped against the proton
The oxymethyl group has the opposite effect.
chemical shift. This allows the chemical shifts of
Figure 3 shows the 1H NMR spectrum of proton resonances to be accurately measured by
recrystallized 4-(4-methoxyphenyl)-3-buten-2-one. examining the f2 dimension, while their coupling
The diagnostic methyl resonances at 2.35 ppm constants can be measured in the f1 dimension.
and 3.83 ppm are the terminal methyl at position 1 Thus, in Figure 4, two doublets with 16.4 Hz
and oxymethyl on the aromatic ring, respectively. coupling constants can be identified at 6.56 and
The remaining resonances between 6.377.69 ppm 7.51 ppm, and two doublets of 8.5 Hz at 6.89
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group at C-2 in different ways; the -proton is shielded (lower ppm) and the -
proton is deshielded (higher ppm). Hence, the protons on C-3 and C-4 can be
assigned as 6.56 ppm and 7.51 ppm, respectively. The oxymethyl group attached to
C-4 of the aromatic ring has a similar effect. The protons situated ortho to the ether
group are shielded, while the meta protons are deshielded. This allows the
remaining protons, at positions C-2 and C-3, to be assigned as 7.50 ppm and 6.89
ppm, respectively.
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Preparation of 1,5-bis(4-
methoxyphenyl)-1,4-pentadien-3-one
(Product B)
In a 100 mL round bottom flask, prepare a solution (over 2 minutes) to the mixture in the round bottom
of freshly recrystallized 4-(4-methoxyphenyl)-3- flask while stirring. Stir the solution for 30 minutes.
buten-2-one (0.60 g, 3.4 mmol) and p-anisaldehyde Recover the resulting solid by vacuum filtration and
(0.61 mL, 5.1 mmol) in ethanol (15 mL). In a wash with water. Dry the solid and recrystallize
separate beaker, prepare a solution of potassium from ethanol (Figure 6).
hydroxide (0.8 g) in water (20 mL) and add slowly
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Figure 6. Recrystallized 1,5-bis(4-methoxyphenyl)penta-1,4-dien-3-one (Product B).
NMR Spectra
NMR Spectra
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Figure 8. 2D J-resolved spectrum of 1,5-bis(4-methoxyphenyl)-1,4-pentadien-3-one
(Product B) in CDCl3.
Figure 8. 2D J-resolved spectrum of 1,5-bis(4-methoxyphenyl)-1,4-pentadien-3-one (Product B) in CDCl3.
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Figure 9. COSY spectrum of 1,5-bis(4-methoxyphenyl)-1,4-pentadien-3-one (Product B) in CDCl3.
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References
1) Jones, Jr., M. Organic Chemistry, 2nd ed., W. W. Norton & Company, Inc., 2000.
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