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Adhveer Domanlall 217010961 15/07/19

Experiment 4 Preparation of 5,5-dimethylcyclohexan-1,3 Dione(dimedone)

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)

Dimedone is a cyclic diketone. It can be to identify whether a compound contains


an aldehyde group.(4,5 In general) Cyclohexanediones have use as catalysts in the formation of
transition-metal complexes as well as have applications in colorimetry, crystallography,
luminescence and spectrophotometric analysis.(4,5) It also has use in chemistry involving organic
compounds of low electrical resistance. (4,5)
Tautomerism(5,6)

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)

Results and Calculations:


Diethyl propanedioate/Diethyl malonate (C7H12O4)

Molar mass: 160.17g/mol

Volume: 8.5 mL

Density: 1.05 g/mL

Mass = Density × Volume= 1.05g/mL × 8.5mL= 8.93g

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)

Molar mass: 98.14g/mol

Volume: 6 mL

Density: 0.858 g/mL

Mass = Density × Volume= 0.858g/mL ×6mL= 5.15g

Number of moles: mass/molar mass = 5.15g / 98.14g. mol−1=0.0524mol= 52.4 mmol

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)

Mass of product :5.64g

Molar mass=140.18g/mol

Number of moles: mass/ molar mass = 5.64g / 140.18g. mol−1=0.0402mol=40.23mmol

Percentage yield = (experimental yield / theoretical yield) ×100%

= (40.23mmol / 52.4mmol) × 100%= 76.77 %

TLC

Rf=Distance travelled by the compound/Distance covered by the solvent front

Starting material Rf=3.7cm/4.1cm=0.902

Product(dimedone) Rf=1.5cm/4.1cm=0.366

Melting point (from literature): 146-148 °C(lit.) (7)

The product formed were crystals light orange in colour

.
Discussion

Overall reaction (2)

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

Mechanism and explanation (9)

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.

Lastly, decarboxylation will yield dimedone

The reaction can also be performed with dimethyl malonate and mesityl oxide (8)-mechanism

Conjugate addition followed by intramolecular acylation(8)


Base catalysed ester hydrolysis, protonation and thermal decarboxylation.(8)

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

4.R. L. Shriner and H. R. Todd (1935). "5,5-dimethyl-1,3-cyclohexanedione". Organic Syntheses. 15:


16. doi:10.1002/0471264180.os015.06.
5.Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter(2001). Organic Chemistry (1st
ed.). Oxford University Press. p. 532. ISBN 978-0-19-850346-0.

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