EXPERIMENT NO : 14 DATE : / / 2018

AIM : Preparation of 7 – hydroxy coumarin by Pechhman reaction.

REFERANCE : Comprehensive organic chemistry , preparation and quantitative analysis ;

Alhuwalia V K , Aggarwal Renu ; 1st edition (2000) ,Taj press (India) ; Pg no : 177-178

REQUIREMENTS

 REAGENTS : Ethyl acetoacetate , polyphosphoric acid , conc sulphuric acid

resorcinol , phosphorus pentoxide , ortho phosphoric acid.
 GLASSWARES : Beaker , glass rod , conical flask , stirrer , funnel , graduated
cylinder , pipette
 OTHERS : Filter papers , Thermometer , rough cloth.

THEORY

Coumarin is a chemical compound/poison found in many plants, notably in high

concentration in the tonka bean, woodruff, and bison grass. It has a sweet scent, readily
recognised as the scent of newly-mown hay. It has clinical value as the precursor for several
anticoagulants, notably warfarin.

Coumarins (1-benzopyrane -2-one) are chemical compounds in the benzopyeone class of

organic compounds found in many plants . Coumarin is an organic compound that has two six-
membered rings fused together, with one of the rings being a benzene ring and the other
containing an alkene functionality and an ester functional group. Coumarins play an important
role in both natural systems like plants and also in medicinal applications as drug molecules.

One of the most popular methods of making coumarins is called a Pechmann condensation
reaction. The Pechmann condensation involves taking phenol and reacting it with ethyl
acetoacetate in the presence of a catalyst (usually aluminum chloride is used).
The reaction is called a 'condensation' because literally our two reactant molecules condense with
one another to form our single product molecule. Once the condensation happens, we get our
coumarin product!
Coumarins are classified as a member of the benzopyrone family. all of which consist of a
benzene ring joined to a pyrone ring. The benzopyrones can be subdivided into the benzoalfa-
pyrones to which the coumarins belong and the benzo-gama-pyrones, of which the flavonoids are
principal members.
Umbelliferone, esculetin and scopoletin are the most widespread coumarins in nature. In the
synthesis of these compounds ortho-hydroxylation should respectively take place on p-coumaric,
caffeic and ferulic acid. Their physiological, bacteriostatic and anti-tumor activity makes these
compounds attractive backbone derivatisation and screening as novel therapeutic agents.
Coumarin was initially considered to be a benzoic acid derivative, but its synthesis by W. H.
Perkin, Sr., (160) from salicylaldehyde by means of his classical reaction established its relation
to o-hydroxy cinnamic acid, which loses a molecule of water in forming the lactone ring.
However, different constitutional formulae have been suggested from time to time. Of the
various formulae proposed by Perkin (I), Basecke (II), Strecker, Fittig, and Tiemann (III),
Salkowski (IV), and Morgan and Micklethwait (V), formula III has been found to be in complete
accord with the known reactions of the coumarin derivatives and has been universally accepted
as correct {vide Hugo Schiff (179)).

Thus coumarins and their derivatives are, from the point of view of their chemical constitution, a
group of lactones derived from o-hydroxycinnamic acids: alternately stated, a coumarin ring
system is formed by the fusion of a benzene and a 1,2-pyrone ring, i.e., coumarins are a class of
heterocyclic compounds containing oxygen as a member of the heterocyclic ring.
PROPERTIES OF COUMARIN
PHYSICAL STATE SOLID CRYSTALLINE
MELTING POINT 69 -73˚C
BOILING POINT 296-298˚C
SPECIFIC GRAVITY 0.935
SOLUBLITY OF WATER 1.7 g/l (at 20˚ C)
SOLVENT SOLUBLITY SOLUBLE IN ETEHR AND CHCL3
VAPOUR DENSITY 5.04
LOG P 1.39(OCTANOL / WATER)
HENRY LAW CONSTANT 6.95E-06 (atm-m3/mole at 25˚C)
OTHER RATE CONSTANT 1.32-11(cm3/molecule-sec at 25 C )
FLASH POINT 150
STABILITY STABLE UNDER NORMAL CONDITION

USES OF COUMARIN
1) Coumadin is a brand name for the drug warfarin.
2) Coumarin is also used as a gain medium in some dye lasers.
3) As a sensitizer in older photovoltaic technologies.
4) Coumarin has clinical medical value by itself, as an edema modifier.
5) As potent rodenticides.

PROCEDURE
1) A mixture of poly phosphoric acid [160 g obtained by dissolving P2O5 in 70 g of
commercial ortho phosphoric acid ρ = 1.75) resorcinol ( 11 g ,0.1 mol) and ethyl
acetoacetate (13 g , 0.1 mol) is stirred and heated at 75 – 80 ˚ C .
2) The resulting solution is then poured on the ice water .
3) The separated product is filtered washed with cold water and crystallized from the dilute
alcohol .
ANOTHER PROCEDURE
It can also be prepared by using concentrated sulphuric acid instead polyphosphoric acid .
1) Solution of the resorcinol (11 g ,0.1 mol) and ethyl acetoacetate (13 g , 0.1 mol) is added
to the cold concentrated sulphuric acid ( cold temperature = 10˚C , 100 ml).4
2) The reaction mixture is kept for 20 hours at the room temperature and poured with the
vigorous stirring on the crushed ice .
3) The separated product is filtered , washed with water and crystallized from dilute alcohol.
4) The melting point of the product reported is [184-186 ˚ C].

RESULT
PARTICULARS VALUE
1) PRACTICAL YIELD
2) THEORITICAL YIELD
3) % PRACTICAL YIELD
4) MELTING POINT
5) Rf VALUE

CONCLUSION