investigate cleavage

28
Investigate cleavage Investigate cleavage H 3 COOC O OH OH COOH OMe OMe COOH O O COOH O O HOOC COOH HOOC CH 3 + 100 o C WO 4 2- , H 2 O 2 , PTC

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Investigate cleavage. 1) WO 4 2- , H 2 O 2. 100 o C, 10 hrs. 85% yield. O=COCH 3. C. 1) WO 4 2- , H 2 O 2 , 100 o C. 2) H + , H 2 O, 100 o C. 10% yield. H 2 O, H 3 PO 4 , 90 o C. 8%. 13%. 1) HCOOH, H 2 O 2 , 90 o C. 2) NaOH, H 2 O, 100 o C. 50% yield. - PowerPoint PPT Presentation

TRANSCRIPT

Page 1: Investigate cleavage

Investigate cleavageInvestigate cleavage

H3COOC

O

OH

OH

COOH

OMe

OMe

COOH

O

O

COOH

O

O

HOOC COOH

HOOC CH3

+100oC

WO42-, H2O2, PTC

Page 2: Investigate cleavage

H3COOC

O

COOCH3

1) WO42-, H2O2 100oC, 10 hrs

85% yield

Page 3: Investigate cleavage

C O

O=COCH3

Page 4: Investigate cleavage

H3COOC

O

1) WO42-, H2O2, 100oC

HOOC COOH

2) H+, H2O, 100oC

10% yield

Page 5: Investigate cleavage

1122334455667788991010111112121313

Page 6: Investigate cleavage

H3COOC

O

H2O, H3PO4 , 90oC

H3COOC

COOCH3

HO

O

O

H3COOC

OH

H3COOC

COOCH3

HO

O

OH

COOCH3

HO

OH

COOH

HO

OH

8% 13%

Page 7: Investigate cleavage
Page 8: Investigate cleavage
Page 9: Investigate cleavage
Page 10: Investigate cleavage

COOH

OH

OH

COOH

1) HCOOH, H2O2, 90oC 2) NaOH, H2O, 100oC

50% yield

Page 11: Investigate cleavage
Page 12: Investigate cleavage

1) WO42-, H2O2, 100oC

HOOC COOH

1% yield

COOH

OH

OH

Page 13: Investigate cleavage

Ac2O, H3PO4, 100oC

39% yield

COOH

OH

OH

OH

C

O

O

OAc

C

OAc

O

OAc

Page 14: Investigate cleavage
Page 15: Investigate cleavage

KOH, DMSO, MeI 40oC

59% yield

COOH

OH

OH

COOMe

OMe

OMe

Page 16: Investigate cleavage
Page 17: Investigate cleavage

1) WO42-, H2O2, 100oC

HOOC COOH

COOMe

OMe

OMe

OH

C

O

O

OAc

C

OAc

O

OAc

X

Page 18: Investigate cleavage

Investigate cleavageInvestigate cleavage

H3COOC

O

OH

OH

COOH

OMe

OMe

COOH

O

O

COOH

O

O

HOOC COOH

HOOC CH3

+100oC

WO42-, H2O2, PTC

10%

1%

Page 19: Investigate cleavage

O

C O

OH

OH

OH

COOH

n-1

COOH

WO42-, 5eq H2O2 100oC, 24 hrs

70% yield,

Page 20: Investigate cleavage

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

-2E+07

0

2E+07

4E+07

6E+07

8E+07

1E+08

1E+08

1E+08

2E+08

2E+08

2E+08

2E+08

2E+08

3E+08

3E+08

3E+08

3E+08May12-2009Chemist Hoong Sing Soissh1-9 productPROTON.w CDCl3 u SSH 6

1.0

0

5.6

30.5

81.4

4

0.9

9

0.0

3

0.1

0

0.1

0

0.0

3

Page 21: Investigate cleavage

COOH

WO42-, 5eq H2O2 80oC, 24 hrs

Page 22: Investigate cleavage

COOH

WO42-, 5eq H2O2 60oC, 24 hrsX

0.51.01.52.02.53.03.54.04.55.05.5f1 (ppm)

-2E+07

0

2E+07

4E+07

6E+07

8E+07

1E+08

1E+08

1E+08

2E+08

2E+08

2E+08

2E+08

2E+08

3E+08

3E+08

3E+08

3E+08

3E+08

4E+08

4E+08

4E+08

Page 23: Investigate cleavage

COOH

WO42-, 1.5 eq H2O2 100oC, 24 hrs

Page 24: Investigate cleavage

COOH

WO42-, 2.5 H2O2 100oC, 24 hrs

Page 25: Investigate cleavage

H3COOC

O

Glycerol, BF3.Et2O, 65oC

Page 26: Investigate cleavage

COOCH3

O

O

H3COOC

O

COOCH3

OHNa

OH

OH

Page 27: Investigate cleavage

H3COOC

O

Glycerol, BF3.Et2O, 65oC

Page 28: Investigate cleavage

CH2OC

CHOC

O

CH2 CH7 CH

CH2 CH7 CH CH2 CH37

CH2OC

O

CH2 CH7 CH

O

O

O

O

CH2 CH3CH CH

O

4

CH2 CH3CH CH

O

4

Glycerol, BF3.Et2O, 65oC

Sticky Rubber like polymer