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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 Presentation
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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
2
Overview
Introduction
Experiment
Application
Discovery
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
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 %
5
Stilbene Formation
N
O
OH
Ph3P=CH2 Grubb’s catalyst
hAniline
KCN Zn(Hg)/HCl
O
6
Aldehyde Coupling
OMe
O
H
OMe
O
OMe
OH
KCNEtOH
Compound (7)42 %
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
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
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
10
2D-NMRO
H
O
O OH O OH
O
O
O
NOESY
HMBC
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
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
13
Aldehyde Coupling
OMe
O
H
OMe
O
OMe
OHOMe
O
OH+
KCN
EtOH
Compound (9)20 %
Compound (8)42 %
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 % >
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
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-
+
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
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
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
20
Potential Application
Synthesis new calix[4]arene derivatives
De-symmetrized calix[4]arene
Synthesis new selective ionophore
21
AcknowledgementNational Science and TechnologyDevelopment Agency
The Thailand Research Fund
Scientific and TechnologicalResearch Equipment Centre
Dr.Pornthep Sompornpisut
Assist.Prof.Dr.Theerayut Wilaiwan
Thank you for your attention
Available on the web
www.student.chula.ac.th/~b3819023
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