selective oxidation of 25,27-di-(3’-formylphenoxylethoxy)- p - tert -butylcalix[4]arene
DESCRIPTION
Selective Oxidation of 25,27-di-(3’-formylphenoxylethoxy)- p - tert -butylcalix[4]arene. Selective Oxidation of 25,27-di-(3’-formylphenoxylethoxy)- p - tert -butylcalix[4]arene. Selective Oxidation of 25,27-di-(3’-formylphenoxylethoxy)- p - tert -butylcalix[4]arene. - PowerPoint PPT PresentationTRANSCRIPT
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Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Mr. Rojrit Rojanathanes
Assist.Prof.Dr. Tawatchai Tuntulani
Dr. Mongkol Sukwattanasinitt*
By
http://www.student.chula.ac.th/~b3819023
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
Selective Oxidation of25,27-di-(3’-
formylphenoxylethoxy)-p-tert-butylcalix[4]arene
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2
Overview
Introduction
Experiment
Application
Discovery
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3
Introduction
Calix[4]arene,the molecular platformO O O OH H HH
Dialdehyde Calix[4]arene,the key intermediate
O
O
H
O
O
H
Na+
O O O O
O O
N N
HH O O O O
O O
NN
R R
HH
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4Synthesis of (1)
O O O OH H HH
O O O O
O O
O
H
O
H
HHK2CO3, CH3CN,Bu4N+Br-
OBr
O
H
Compound (1)60 %
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5
Stilbene Formation
N
O
OH
Ph3P=CH2 Grubb’s catalyst
hAniline
KCN Zn(Hg)/HCl
O
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6
Aldehyde Coupling
OMe
O
H
OMe
O
OMe
OH
KCNEtOH
Compound (7)42 %
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7
O O O O
O O
O
H
O
H
HH
KCN Coupling
KCN
EtOH
O OH
O O
O O O OHH
The SerendipityThe SerendipityThe SerendipityThe SerendipityThe Serendipity
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8
1H-NMR
9.93
1.409.96
OH
O
O
O
O
OH
OH
OH
( ) 4
OH
OH
( ) 4
OH
O
O
O
O
X
OR
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9
13C-NMR
192.1
192.1
53.214.2
OH
O
O
O
O
OH
OH
OH
( ) 4
166.4
OH
O
O OH
OH
( ) 4
O
O
O
XOEt
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10
2D-NMRO
H
O
O OH O OH
O
O
O
NOESY
HMBC
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11
O O O O
O O
O
H
O
H
HH
Surprise Oxidation
KCN
EtOH
Compound (2)50 %
O O O O
O O
O
O
O
H
HH
Surprise OxidationSurprise OxidationSurprise OxidationSurprise Oxidation
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12
Synthesis of (3)
O O O O
O O
O
H
O
H
HH
KCN
i-PrOH
Compound (3)31 %
O O O O
O O
O
OiPr
O
H
HH
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13
Aldehyde Coupling
OMe
O
H
OMe
O
OMe
OHOMe
O
OH+
KCN
EtOH
Compound (9)20 %
Compound (8)42 %
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14
Cannizzaro Reaction
O O O O
O O
O
OHHO
HHO O O O
O O
O
H
O
H
HH
KOH
EtOH
Compound (4)4 %
O O O O
O O
O
OHHO
O
HHO O O O
O O
OH O
HH
H
Compound (5)16 %
Compound (6)< 16 % >
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15
O O O O
O O
O
H
O
H
HH
Selective Oxidation
KCN
EtOH
Compound (2)50 %
O O O O
O O
O
O
O
H
HH
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16
Related Oxidation
R
O
H R CN
O H-
R
OH
CN-N
O
O+-
O O
R
HO CN
- -HO O
R
O CN
-
-
R
O
CN
NO
OH-
+
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17
Possible Mechanism
-CNH
O
R
-CN
R
O
CN
R
HOH -CN
R
OH
-
CN
R
OO
H O
O O
O
R
O
O
H
HO
R
O
H+ -H+
O
H
R
Baeyer - VilligerMechanism
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18
Esterification
EtOH
+
-O O O O
O
R'
O
O
H
H
H-
+
O O O O
O
R'
O
H
HO OH
H O O O O
O
R'
OH
HO O
H
HO O O O
O
R'
O
O
H
H
HO O O O
O
R'
OH2
HO O
H-
+
O O O O
O
R'
O
O
H
H-
+
O O O O
O
R'
O
O
HH
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19
Discovery
Selective oxidation of dialdehyde calix[4]arene via KCN catalyst in the presence of O2
The in situ esterification of acid calix[4]arene via phenolic protons on the lower rim
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20
Potential Application
Synthesis new calix[4]arene derivatives
De-symmetrized calix[4]arene
Synthesis new selective ionophore
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21
AcknowledgementNational Science and TechnologyDevelopment Agency
The Thailand Research Fund
Scientific and TechnologicalResearch Equipment Centre
Dr.Pornthep Sompornpisut
Assist.Prof.Dr.Theerayut Wilaiwan
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Thank you for your attention
Available on the web
www.student.chula.ac.th/~b3819023