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