Beruflich Dokumente
Kultur Dokumente
Introduction
The aim of the experiment is to the synthesize dimedone (by means of Robinson annulation), and to
characterize/determine the purity of the product by taking the melting point and performing TLC.
The synthesis is actually a modification of the normal Robinson annulation, in that initial Michael
addition of diethyl malonate with mesityl oxide (4-methylpent-3-en-2-one) is followed by an
intramolecular Claisen condensation rather than aldol condensation.(1,2) The annulation product is
hydrolysed and decarboxylated in the reaction mixture to yield the cyclic 1,3-diketone. (2,3)
In solution dimedone is in equilibrium with its tautomer — it is a 2:1 keto to enol ratio (5,6)
Dimedone in the crystalline enol form contains chains of molecules linked by hydrogen bonds(5,6)
Volume: 8.5 mL
Number of moles: mass/molar mass = 8.93g / 160.17g. mol−1 =0.056mol =56 mmol
4-Methylene pent-3-en-2-one/Mesityl oxide (C6H10O)
Volume: 6 mL
There is a 1:1 stoichiometric ratio between Diethyl propanedioate and 4-Methylene pent-3-en-2-one
when reacting, therefore 4-Methylene pent-3-en-2-one is the limiting reagent. The maximum
amount of 5, 5-dimethylcyclohexan-1,3-dione that can be formed is therefore 52.4 mmol
5, 5-dimethylcyclohexan-1,3-dione /Dimedone(C8H12O2)
Molar mass=140.18g/mol
TLC
Product(dimedone) Rf=1.5cm/4.1cm=0.366
.
Discussion
Brief explanation of the Robinson annulation reaction that occurs in the experiment
Strong bases such as NaOEt (alkoxides)can be used to easily deprotonate Diethyl malonate, which
will a produce a nucleophilic enolate. The nucleophilic enolate then undergoes reversible conjugate
addition with enones (such as mesityl oxide). This is due to the Michael addition step of the
Robinson annulation. Then through a sequence of steps of alpha deprotonation and intramolecular
acyl substitution the six membered ring is formed. This is due to the Claisen condensation step of the
slightly altered Robinson annulation. The ester is hydrolysed with acid and the carboxylic acid
undergoes decarboxylation to afford the product known as dimedone
Basic conditions are needed to start therefore NaOEt is used. Diethyl malonate is a good nucleophile
on account of the two ester groups on either side of the central carbon atom. It has a pKa of 12.36 ,
which is extremely acidic for a C−HC−H bond. The first step is a Michael addition. and mesityl oxide is
a good Michael acceptor.
The resultant enolate will equilibrate, enabling it to form a much more stable 6 membered ring. We
then have a Claisen condensation.
The reaction can also be performed with dimethyl malonate and mesityl oxide (8)-mechanism
The experimental melting point was not determined. The percentage yield was determined to be
76.77% which indicates good yield/amount of product was formed. There may have been loss of
product during recrystallization.
From TLC-The Rf values of the starting material and the product differ enough to conclude that the
product synthesized is dimedone (is pure enough to be dimedone)
Conclusion
We can therefore conclude that dimedone was synthesized and characterized (using TLC), with a
high yield, and that the experimental melting point was not determined. A better understanding of
Robinson annulation reactions was attained
References
1.http://www.chemicalland21.com/specialtychem/finechem/DIMEDONE.htm
2.http://www.orgsyn.org/demo.aspx?prep=cv2p0200
3.https://www.revolvy.com/page/Dimedone
6.M. Bolte and M. Scholtyssik (October 1997). "Dimedone at 133K". Acta Crystallogr. C. 53 (10):
IUC9700013. doi:10.1107/S0108270197099423.
7.https://www.lookchem.com/Dimedone/
8.ht8.tps://www.chemtube3d.com/conjugate-addition-dimedone-synthesis/
9.https://chemistry.stackexchange.com/questions/99049/mechanism-of-dimedone-preparation