Preparation of 

Dibenzalacetone by Aldol Condensation

Adapted from Williamson, 5th ed.

     This experiment is an aldol  condensation of two molecules of benzaldehyde with acetone to

form dibenzalacetone. The solvent is ethanol; 3M sodium hydroxide is used to generate the
acetone enolate.. The acetone has already been added to the ethanol (58 mg acetone/1.6 mL
solution). This is a quick and easy synthesis. The challenging part of the experiment is to
determine the stereochemistry of the product.  Since the double bonds can be cis or trans; there
are three diastereomeric isomers: cis, cis, trans, trans and cis, trans. However the problem is
complicated by the stereochemistry about either of the two single bonds between the alkene and
carbonyl.  This stereochemistry is designated by s-cis or s-trans for single bond cis or trans.
(Remember s-cis and s-trans conformations of 1,3-butadiene.) The stereochemistry about the
single bonds can be changed by rotation of 180o and represent conformations. Altogether there
are 10 possible stereoisomers:  1) trans, s-trans, s-trans, trans; 2) trans, s-trans, s-cis, trans; 3)
trans, s-cis, s-cis, trans; 4) trans, s-trans, s-trans, cis; 5) trans, s-trans, s-cis, cis; 6)trans, s-cis, s-
trans, cis; 7)trans, s-cis, s-cis, cis; 8) cis, s-trans, s-trans, cis; 9) cis, s-trans, s-cis, cis; 10) cis, s-
cis, s-cis, cis. 

Procedure:

            It is very important that the ratio of benzaldehyde to acetone be exactly two to one.  Add
0.20 mL of benzaldehyde to a tarred reaction tube and record the mass of the
benzaldehyde.  This should be approximately 0.212 g (2.00 mmol).  Add a solution of acetone in
ethanol to the benzaldehyde so that the mole ratio is exactly 2:1.  The concentration of the
ethanol solution of acetone  is 0.625 M.  After the addition of the acetone solution add 2.0 mL of
3 M sodium hydroxide.  A yellow precipitate should form very quickly.  Cap the tube and shake
occasionally for thirty minutes.  Remove the liquid from the tube by filtration with a dispo pipet
placed against the bottom of the tube.  Wash the product with 3-mL portions of water three
times. 
            After the third washing add 3 mL water and filter the crystals onto a Hirsch funnel by
vacuum filtration. Press the crystals to help dry to dry. Recrystallize the crude from a 70:30
solution of ethanol/water. Remember to use a boiling stick.  Allow the tube to cool to room
temperature and continue cooling in an ice bath.  Vacuum filter the pure crystals and wash them
on the filter with a small portion of cold ethanol/water. Allow the crystals to dry on the
filter.  After the crystals are dry transfer them to a tarred vial and record the mass.  Calculate the
percent yield and determine the melting point.

Molecular Modeling:

     A brief discussion of Computational Chemistry may be found at the Organic Chemistry

Virtual Tutor.  A longer discussion is in Mohrig, Technique 8. 
Read about local versus global energy minima. 

Questions:  1) Open the molecule found at /3322/Spartan Student/benzalacetone.Profile2.sxf).

This is a .sxf confomation file for trans-benzalacetone. To see it the file type in the open files
window must be set to all files  Thedifferent conformations are viewed by toggling from one
frame to another. The toggle is at the bottom left of the screen. Frame 1 (the s-cis
conformer).  For benzalacetone look at the 1,2,3,4 dihedral angle by clicking on geometry,
dihedral and then the four atoms (C10, C9, C8, C7). The dihedral angle should be 179.93o.  Click
on display properties to see the
energy. 

Make a graph of energy vs. dihedral angle as follows:

1) open display spreadsheet
2)add relative energy then ok to add the relative energy to the spreadsheet
3) click on geometry on the top task bar and then measure dihedral 
4) click on C10, C9, C8, and C7 in order and then click on the yellow P at bottom right of the
screen.  This enters the dihedral angles into the spreadsheet
5) In the spreadsheet click on the 179 angle in the top entry and enter -180 in the top box.  This
changes 179 to -180 so the angles change in an orderly fashion.
6) Display plots and select dihedral for the x-axis and relative energy for the y-axis.  Enter ok
and a plot of dihedral energy vs. relative energy is displayed.
7) Go to print to print the graph.
You may click on the squares on the plot to change the molecule to the conformation with that
energy. 
What is the structure of the energy maximum?  Why is this a maximum. 
What is the structure of the conformer with the dihedral of 0?  Why does it have a higher energy
than the conformer at 180?
Turn in a copy of your plot with your lab notebook.

2) There are three diastereotopic isomers possible for dibenzalacetone:  trans-trans, cis-trans, and
cis-cis (stereochemistry at the two C=C). These molecules are in the Spartan database and may
be retrieved.  They are (E,E), (Z,E), and (Z,Z)-1,5-diphenyl-1,4-pentadien-3-one isomers.

The melting points, maximum absorbance wavelengths, and molar absorptivities are different for
each isomer:

isomer melting point lambda max molar absorptivity energy

A 110-111 oC 330 nm 34,300  
B 60 oC 295 nm 20,000  
C liquid 287 11,000  

 You should have isolated the stereoisomer with the melting point 110-111. Which isomer is it? 
Most likely the isolated stereoisomer is the one that is the most stable.  Molecular modeling can
tell you which one this is.  You need to retrieve the three isomers and calculate the equilibrium
geometry at the PM3 level. When you do the calculations select Print Orbitals and Energies
before submitting the calculation.. Record the energy and HOMO and LUMO energies for each
isomer. To find the HOMO and LUMO energies go to display output and scroll down to where
the energies of the MO energies are listed (look for eigenvalues). Each of these are a molecular
orbital.  Since the molecule has 88 electrons with two electrons in each MO, orbital number 44 in
the HOMO and number 45 is the LUMO.  Record the energies for the HOMO and LUMO for
each molecule. An alternate way to determine orbital energies is to display a spreadsheet and
then add E HOMO and E LUMO. 
3) Which isomer is the most stable? Which is least stable?  
4) The energy difference between the HOMO and LUMO is inversely related to the absorption
wavelength [energy = (Planck's constant)(c)/(wavelength)].  It appears that the absorption
wavelength for each isomer in nm is equal to 2550/difference in energy between LUMO and
HOMO (energies in electron volts). Calculate the wavelength for each isomer.  Use the
wavelengths in the lab text to determine the identity of each isomer.
4) Is there a correlation between lambda max and stability?  Explain
5) Which is the highest melting, lowest? Look at the geometry of the three isomers and explain
the difference in energies and melting points.

Additional Questions:

6) Why is it important that the molar ratios of benzaldehyde to acetone be 2:1?

7) How would you change the experimental procedure if you wanted to prepare benzalacetone
rather than dibenzalacetone?
8) The infrared absorption for the carbonyl bond in dibenzaldehyde is at a larger wavenumber
that that of acetone.  Explain.