hetreocyclic applications of ethyl aceto acetate & ethyl cyano acetate
TRANSCRIPT
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
10/25/2014 2
HETEROCYLCIC APPLICATIONS• PYROLE(HANTZ SYNTHESIS):
10/25/2014 3
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.
10/25/2014 4
MECHANISM
10/25/2014 5
Hantzsch pyridine Synthesis
10/25/2014 6
Intermediate -1
R H
O
+
OR"R'
OO -H2O
OR'
R
O OR"
Intermediate-2
OR"R'
OO
+ NH3
-H2O
R'
NH2
O
OR"
10/25/2014 7
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'
10/25/2014 8
FUSED RINGQUINOLINE SYNTHESIS
10/25/2014 9
MECHANISM
10/25/2014 10
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:
10/25/2014 11
PERKIN REACTION
10/25/2014 12
MECHANISM
10/25/2014 13
HETROCYCLIC APPLICATIONS OF ETHYLCYANO ACETATE• PYRIMIDINE:
10/25/2014 14
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
10/25/2014 15
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
10/25/2014 16
REFERENCES • Organic chemistry reactions and reactants :Heterocyclic
compounds
• Organic chemistry portal
10/25/2014 17
10/25/2014 18
10/25/2014 19
10/25/2014 20
10/25/2014 21
10/25/2014 22
10/25/2014 23