GUIDED BY: PRESENTED BY:

MR.SAYAN DUTTA GUPTHA G.SHRAVANI

R.NO:170213884010

ASEMINAR ON HETROCYLIC APPLICATIONS OF ETHYL ACETOACETATE, ETHYL CYANO ACETATE

ETHYLACETOACETATE

OO

O

ETHYL ACETOACETATE

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HETEROCYLCIC APPLICATIONS• PYROLE(HANTZ SYNTHESIS):

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MECHANISM• The mechanism starts with amine (1) attacking the β- carbon of β-

keto esters (2) & forms an enamine(3).The enamine attacks the carbonyl carbon of α-ketones(4).This is followed by the loss of H2O,giving the imine(5).This intermediate undergoes an intramolecular nucleophilic attack forming 5-membered ring (6).Hydrogen is eliminated and the π-bonds are rearranged in the ring ,yielding the final product.

• The other mechanism includes the enamines (3) attacks the α-carbon of the α-halo ketone(4) as a part of a nucleophilic substitution instead of carbonyl carbon.

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MECHANISM

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Hantzsch pyridine Synthesis

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Intermediate -1

R H

O

+

OR"R'

OO -H2O

OR'

R

O OR"

Intermediate-2

OR"R'

OO

+ NH3

-H2O

R'

NH2

O

OR"

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Reaction between two intermediates

R'

NH2

O

OR"

OR'

R

OR"+

-H2O

O

NH

R'

"ROOC COOR"

R'

HR

Oxidation

NH

R'

"ROOC COOR"

R'

HR

NR'

R

R"OOC COOR"

R'

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FUSED RINGQUINOLINE SYNTHESIS

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MECHANISM

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A 2007 study revised the reaction mechanism and based on NMR spectroscopy and theoretical calculations favors an O,O-dicationic intermediate (a super electrophile) over the N,O dicationic intermediate . For preparative purposes triflic acid is recommended:

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PERKIN REACTION

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MECHANISM

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HETROCYCLIC APPLICATIONS OF ETHYLCYANO ACETATE• PYRIMIDINE:

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THEOBROMINE

NH2

O

H2N

UREA

COOC2H5

CH2-CN

NaNH2 HN

NO

CH3

NH2

NH4SH HNO2

HN

N

CH3

NH2

NH2

O

Fused

with acetic acid

HN

NH

N

HN

O

CH3I

NaOC2H5

N

CH3

NN

HN

O

THEOBROMINE

CH3

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THEOPHYLINE

COOC2H5

CH2-CN

N

NO

CH3

NH2

H3C

OHO

FORMIC ACID

N

NO

CH3

O

H3C

N

HN

H-N-CO-N-H

CH3CH3

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REFERENCES • Organic chemistry reactions and reactants :Heterocyclic

compounds

• Organic chemistry portal

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