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SYNTHESIS OF OXACYCLIC DERIVATIVES USING IONIC LIQUIDS AS A REACTION
MEDIUM
ALIGARH MUSLIM UNIVERSITY
PRESENTED BY-ANAM ANSARI
INTRODUCTION.
IONIC LIQUIDS: PREPARATION AND PROPERTIES.
SYNTHESIS AND APPLICATION OF: FURAN AND DERIVATIVES. PYRAN AND DERIVATIVES. COUMARINS AND DIOXANES.
APPLICATION OF IONIC LIQUIDS IN SYNTHESIS.
CONCLUSION.
REFERENCES.
CONTENTS
Oxacycles are part of an extensive group of organic structures which are used as a synthetic intermedia.
They are also important because of biological, pharmacological and industrial value of some of the structures in which they are present.
Most of the reaction media used in traditional chemistry utilize volatile organic compounds which have several disadvantages.
Room temperature ionic liquids were introduced as a novel reaction media in synthesis of oxacyclic derivatives.
Utilization of RTILs meant some improvement in relation to reaction yield, reagents selectivity, and diminution in the reaction time, recyclability, as well as improvement in environmental condition.
IONIC LIQUIDS: PROPERTIES AND
PREPARATION Ionic liquid is a salt in the liquid state. Largely made of ions and short-lived ion pairs. They are conductors of electricity, non-ionizing, highly viscous
and frequently exhibit low vapor pressure. They show: Low combustibility. Wide liquid range.
Excellent thermal stability. Favorable solvating
properties. They are used in:
Organic Synthesis. Chemical Industry. Food and Bio
products. Gas Handling.
Waste Recycling. Pharmaceuticals. Dispersant. Batteries
PREPARATION
IONIC LIQUIDS ARE PREPARED BY METATHESIS OF HALIDE SALTS.
N N
Me
+ MeCN
800C N
N
Me
Bu
ClCl
STRUCTURE:
N
N
Me
Bu
Cl
+ KBF4 N
N
Me
Bu
BF4
N
N
Me
Bu
BF4
B:Butylm:Methylim:Imidazolium
[Bmim][BF4]
N
N
Me
Bu
BF4
N
N Bu
Me BF4
1. SYNTHESIS OF FURAN IN Mn(oAc)3 AS CATALYST AND [Bmim][BF4] AS REACTION MEDIUM
SYNTHESIS OF FURAN AND DERIVATIVES
O
OH
+Ph
Mn(OAc)3, 400C
[Bmim][BF4]:Cl2CH2
O Ph
O
GENERALLY SYNTHESISED BY 1, 4- DICARBONYL COMPOUNDS OR
β-KETOESTER UNDER ACID CATALYSIS.
MECHANISM
Mn(OAc)3
O
O
Ph
O
O
Ph
O
OH
Mnn+ II Eq
O
O
Ph
+
O
H
+O
O
Ph Ph
-H+
O
2.SYNTHESIS WITH β-KETOESTERS WITH SAME REACTION CONDITION
R
O
COOEt +R2
R1
Mn(OAc)3,400C
[Bmim][BF4]:Cl2CH2
OR2
R1
R
COOEt
MECHANISM
R
OH
COOEtMn(OAc)3
R
COOEt
R2R1
R
O
R1 R2
COOEt
Mnn+ II Eq
R
O
COOEt
R1 R2+R1
R2EtOOC
RO+
H
R1
R2EtOOC
RO
3.SYNTHESIS OF BENZOFURAN IN Ln(OTf)3 AS CATALYST IN IONIC LIQUID.
OH
Ln(OTf)3
RTIL O
80-90%
SYNTHON
SOLVENT
INSECTI-CIDE
FURAN RESIN
PHARMA-CEUTICALS
1.SYNTHESIS OF PYRAN IN [Bmim][PF6]
SYNTHESIS OF PYRAN AND DERIVATIVES
70-80%
R
O
H
+ OH H.ZSM-5[Bmim][PF6]
O
OH
R
2. MULTICOMPONENT SYNTHESIS IN [Bmim][BF4]
R
O
H
+
X OMe
OH
+NC CN
X
O
O R
CN
NH2Me
[Bmim][BF4]
800C
S NO.
SOLVENT TEMPERATURE (0C)
TIME (h) YIELD (%)
1 [Bmim][BF4] 80 0.5 98
2 EtOH Reflux 5 76
3 Toluene 80 5 75
4 THF Reflux 5 71
5 [Bmim][BF6] 80 1 90
6 [Bmim][BF4] 80 1 90
TABLE: SOLVENT AND REACTION CONDITIONS FOR PYRAN DERIVATIVES SYNTHESIS
SYNTHON
ANTIFUNGAL
AGENTS
PHARMAC-
EUTICALS
SYNTHESIS OF COUMARINS
1.PECHMAN CONDENSATION IN [Bmim]Cl.2ALCl3
OHX
[BMIM] Cl2AlCl3
Ethyl acetoacetateO O
CH3
X
MECHANISM
X
CH2
C
C
H3C
O
O
O
AlCl2
EtOX O
O EtO
HH3C OH
HO
CH3HO
EtO
OX
condensation
-H2O
HO
EtO
OX
CH3
O+ O-
OEt
X
CH3
H
O
CH3
OX
-EtOH
XO
H
LCl2A
Cl+ _
2.SYNTHESIS OF BENZOCOUMARIN IN [Bmim][Al2Cl7]
OMe
MeO2C
O O
[Bmim][Al2Cl7]
MECHANISM
MeO2C
O
Al2Cl6
Cl
MeClO O
OMe
Al2Cl6
O O
OMe
Al2Cl6
MeOAl2Cl6
O O
DYES AND BRIGHTNERS
FLAVOURING
AGENT
PERFUMERY AND
COSMETICS
PHARMAC-
EUTICALS
INSECTICIDE
SYNTHESIS OF DIOXANE
SYNTHESIS BY THE REACTION OF FORMALDEHYDE AND STYRENE IN IONIC LIQUID.
+ 2
H
O
HO
OTSILS
MECHANISM
C
O
HH
H+
C
+O
HH
H
O
+
Ph
HO
H
H
O O+
Ph
HH2C
C+
O
H
H
HPh
Ph
O
+H2C
O
H
O O
HH
Ph
_H
DIOXANE
APPLICATION OF IONIC LIQUID IN SYNTHESIS
Use of RTILs introduces most significant advances in synthesis of Oxacyclic derivatives.
From the simplest monooxacycles to most polyoxacycles both are synthesized using RTILs.
The main effects reported by using ionic liquids were the improvement of reaction yields and the reduction of reaction time.
Other beneficial effects have been also reported when used as supported for other media or reaction catalyst such as silica gel and in microwave assisted synthesis.
RTILs are eco-friendly reaction media and help to reduce pollution.
CURRENT ORGANIC SYNTHESIS, 2012, 9, 65-73. MARTA TEIJEIRA AND MORALES-HELGUERA.
CHEMICAL COMMUNICATION, 2001, 1350-1351. PARSON AND THOMAS. JOURNAL OF ORGANIC CHEMISTRY, 2003, 68,4406-4409. TETRAHEDRON LETT. 2004, 45, 5873-5876. TETRAHEDRON LETT. 2003, 59, 1599-1604. TETRAHEDRON LETT. 2007, 48, 7926-7929. APPL.CATAL.A GEN. 2009, 363, 93-99. CATAL.COMMUNICATION.2005, 6, 57-60. TERAHEDRON LETT. 2005, 46, 3931-3933. BIOORG.MED.CHEM.LETT.2010, 20, 809-813.
