Investigate cleavage - University of Warwick

Investigate cleavage O H3COOC OH COOH OH HOOC + 100oC OMe COOH WO42-, H2O2, PTC

OMe O O COOH O O COOH HOOC CH3 COOCH3 1) WO42-, H2O2

100oC, 10 hrs O H3COOC 85% yield O=COCH3 C O O H3COOC 1) WO42-, H2O2, 100oC

2) H+, H2O, 100oC HOOC COOH 10% yield 13 12 11 10 9

8 7 6 5 4 3 2 1 O

H3COOC H2O, H3PO4 , 90oC COOH COOCH3 HO OH OH OH OH HO

COOCH3 COOCH3 O O O HO HO H3COOC 8% 13%

H3COOC H3COOC COOH 1) HCOOH, H2O2, 90oC 2) NaOH, H2O, 100oC OH COOH OH 50% yield OH COOH OH

1) WO42-, H2O2, 100oC HOOC COOH 1% yield OH COOH OH Ac2O, H3PO4, 100oC OAc OH C OAc

O C OAc 39% yield O O OH COOH OH KOH, DMSO, MeI 40oC

OMe COOMe OMe 59% yield OMe COOMe OMe OH OAc C O OAc

C O OAc 1) WO4 , H2O2, 100 C 2- HOOC o X COOH O

Investigate cleavage O H3COOC 10% OH COOH 1% OH HOOC + 100oC

OMe COOH WO42-, H2O2, PTC OMe O O COOH O O COOH HOOC CH3

COOH WO42-, 5eq H2O2 100oC, 24 hrs OH COOH O OH C OH O n-1

70% yield, May12-2009 Chemist Hoong Sing Soi ssh1-9 product PROTON.w CDCl3 u SSH 6 3E+08 3E+08 3E+08 3E+08 2E+08 2E+08 2E+08 2E+08 2E+08 1E+08

1E+08 1E+08 8E+07 6E+07 4E+07 2E+07 0 -2E+07 7.5 7.0 6.5 6.0 5.5

5.0 4.5 4.0 f1 (ppm) 3.5 3.0 2.5 2.0 1.5

1.0 0.5 COOH WO42-, 5eq H2O2 80oC, 24 hrs COOH WO42-, 5eq H2O2 X 60oC, 24 hrs 4E+08 4E+08 4E+08

3E+08 3E+08 3E+08 3E+08 3E+08 2E+08 2E+08 2E+08 2E+08 2E+08 1E+08 1E+08 1E+08 8E+07 6E+07 4E+07 2E+07 0

-2E+07 5.5 5.0 4.5 4.0 3.5 3.0 f1 (ppm) 2.5 2.0

1.5 1.0 0.5 COOH WO42-, 1.5 eq H2O2 100oC, 24 hrs COOH WO42-, 2.5 H2O2 100oC, 24 hrs O

H3COOC Glycerol, BF3.Et2O, 65oC OH OH O COOCH3 O H3COOC O COOCH3 OHNa O H3COOC Glycerol, BF3.Et2O, 65oC

O CH2OC O CHOC CH2OC O CH2 CH2 CH2 7 7 7

CH O CH O CH CH O CH CH CH2

C H 7 CH2 4 CH3 CH3 O CH O

CH C H CH2 Glycerol, BF3.Et2O, 65oC Sticky Rubber like polymer 4 CH3