e.g. Filippa Pettersson or Cancer Res. 75(6) , 1102-12, (2015) or 10.1002/anie.201600521

Liebigs Annalen der Chemie

Dimere Naphthochinone, IX. Isodiospyrin und Elliptinon.—Synthese 6, 6′??dimerer Bijuglone durch Phenoloxidation

H Laatsch

Index: Laatsch, Hartmut Liebigs Annalen der Chemie, 1984 , # 2 p. 319 - 339

Full Text: HTML

Citation Number: 5

Abstract

Abstract Durch oxidative Kupplung des Naphthols 37b wurde der potentielle Naturstoff 7, 7′-Dimethyl-6, 6′-bijuglon (5) und in kleinerer Ausbeute Isodiospyrin (21) erhalten. Regiospezifische Synthesen von 5, Elliptinon (10) und 6, 6′-Bijuglon (45a) gelangen durch Phenoloxidation geeignet substituierter p-Chlornaphthole.

NAPHTHALENEDIONE, 5-CHLORO-8-HYDROXY- Structure

NAPHTHALENEDION...

(Iodomethyl)benzene Structure

(Iodomethyl)benzene

~93%

5-chloro-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-8-phen...

4-Chlorophenol Structure

~%

5-chloro-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-8-phen...

1,1'-Diacetoxy-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~65%

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

1,4-Naphthalenedione,5-chloro-8-hydroxy-6-methyl- Structure

1,4-Naphthalene...

~%

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

5-chloro-6-methyl-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-6-meth...

~%

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

~%

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

4-chloro-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

~%

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

4,4'-Dichlor-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl-1,1'-diol Structure

4,4'-Dichlor-5,...

~%

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

1,1'-Diacetoxy-4,4'-dichlor-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~%

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

1,4-Naphthalenedione,5-chloro-8-hydroxy-6-methyl- Structure

1,4-Naphthalene...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

5-chloro-6-methyl-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-6-meth...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

NAPHTHALENEDIONE, 5-CHLORO-8-HYDROXY- Structure

NAPHTHALENEDION...

~%

1-chloro-5,8-dimethoxy-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

4-Chlorophenol Structure

~%

1-chloro-5,8-dimethoxy-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

5-chloro-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-8-phen...

Dimethyl sulfate Structure

Dimethyl sulfate

~%

1-chloro-5,8-dimethoxy-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

5-chloro-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-8-phen...

Dimethyl sulfate Structure

Dimethyl sulfate

~%

5-chloro-4-methoxy-8-phenylmethoxynaphthalen-1-ol Structure

5-chloro-4-meth...

1-chloro-5,8-dimethoxy-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

NAPHTHALENEDIONE, 5-CHLORO-8-HYDROXY- Structure

NAPHTHALENEDION...

~%

5-chloro-4-methoxy-8-phenylmethoxynaphthalen-1-ol Structure

5-chloro-4-meth...

4-Chlorophenol Structure

~%

5-chloro-4-methoxy-8-phenylmethoxynaphthalen-1-ol Structure

5-chloro-4-meth...

5-chloro-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-8-phen...

Dimethyl sulfate Structure

Dimethyl sulfate

~%

5-chloro-4-methoxy-8-phenylmethoxynaphthalen-1-ol Structure

5-chloro-4-meth...

1-chloro-5,8-dimethoxy-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

4-chloro-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

4,4'-Dichlor-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl-1,1'-diol Structure

4,4'-Dichlor-5,...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

1,1'-Diacetoxy-4,4'-dichlor-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

[2-(1-acetyloxy-3-methyl-5,8-dioxonaphthalen-2-yl)-3-methyl-5,8-dioxonaphthalen-1-yl] acetate Structure

[2-(1-acetyloxy...

~68%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

2,3-Dihydro-5,5'-dihydroxy-7,7'-dimethyl-2,2'-binaphthyl-1,4:1',4'-dichinon Structure

2,3-Dihydro-5,5...

7-methyl-5-phenylmethoxynaphthalene-1,4-dione Structure

7-methyl-5-phen...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

5,8-dimethoxy-3-methyl-1-phenylmethoxynaphthalene Structure

5,8-dimethoxy-3...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

1,1'-Diacetoxy-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~%

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

5,8-dimethoxy-3...

Ethanoic anhydride Structure

Ethanoic anhydride

~%

isodiospyrin Structure

5-hydroxy-6-(1-hydroxy-3-methyl-5,8-dioxonaphthalen-2-yl)-7-methylnaphthalene-1,4-dione Structure

5-hydroxy-6-(1-...

Citraconic anhydride Structure

Citraconic anhydride

4-Chlorophenol Structure

(Iodomethyl)benzene Structure

(Iodomethyl)benzene

Dimethyl sulfate Structure

Dimethyl sulfate

~%

Detail

8-chloro-1,4-dimethoxy-2-methyl-5-phenylmethoxynaphthalene Structure

8-chloro-1,4-di...

~%

2,4-dibenzyl-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

2,4-dibenzyl-5,...

Citraconic anhydride Structure

Citraconic anhydride

~%

2,4-dibenzyl-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

2,4-dibenzyl-5,...

4-Chlorophenol Structure

~%

2,4-dibenzyl-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

2,4-dibenzyl-5,...

8-chloro-1,4-dimethoxy-2-methyl-5-phenylmethoxynaphthalene Structure

8-chloro-1,4-di...

~88%

4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

Citraconic anhydride Structure

Citraconic anhydride

~%

4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

4-Chlorophenol Structure

~%

4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

Citraconic anhydride Structure

Citraconic anhydride

~%

acetic acid,4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

acetic acid,4-c...

4-Chlorophenol Structure

~%

acetic acid,4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

acetic acid,4-c...

8-chloro-1,4-dimethoxy-2-methyl-5-phenylmethoxynaphthalene Structure

8-chloro-1,4-di...

~%

acetic acid,4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

acetic acid,4-c...

Ethanoic anhydride Structure

Ethanoic anhydride

4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

~%

acetic acid,4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

acetic acid,4-c...

1,1'-Diacetoxy-4,4'-dichlor-5,5',8,8'-tetramethoxy-6,6'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

Maleic anhydride Structure

Maleic anhydride

4-Chlorophenol Structure

~35%

NAPHTHALENEDIONE, 5-CHLORO-8-HYDROXY- Structure

NAPHTHALENEDION...

NAPHTHALENEDIONE, 5-CHLORO-8-HYDROXY- Structure

NAPHTHALENEDION...

~%

acetic acid,4-chloro-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,4-c...

5-chloro-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-8-phen...

~%

acetic acid,4-chloro-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,4-c...

4-Chlorophenol Structure

~%

acetic acid,4-chloro-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,4-c...

1-chloro-5,8-dimethoxy-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

~%

acetic acid,4-chloro-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,4-c...

1,4-Naphthalenedione,5-chloro-8-hydroxy-6-methyl- Structure

1,4-Naphthalene...

(Iodomethyl)benzene Structure

(Iodomethyl)benzene

~80%

5-chloro-6-methyl-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-6-meth...

1,4-Naphthalenedione,5-chloro-8-hydroxy-6-methyl- Structure

1,4-Naphthalene...

~%

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

(Iodomethyl)benzene Structure

(Iodomethyl)benzene

~%

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

5-chloro-6-methyl-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-6-meth...

Dimethyl sulfate Structure

Dimethyl sulfate

~%

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

1,1'-Diacetoxy-4,4'-dichlor-5,5',8,8'-tetramethoxy-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~90%

acetic acid,2-(1-hydroxy-5,8-dimethoxynaphthalen-2-yl)-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,2-(...

NAPHTHALENEDIONE, 5-CHLORO-8-HYDROXY- Structure

NAPHTHALENEDION...

~%

acetic acid,2-(1-hydroxy-5,8-dimethoxynaphthalen-2-yl)-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,2-(...

5-chloro-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-8-phen...

~%

acetic acid,2-(1-hydroxy-5,8-dimethoxynaphthalen-2-yl)-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,2-(...

4-Chlorophenol Structure

~%

acetic acid,2-(1-hydroxy-5,8-dimethoxynaphthalen-2-yl)-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,2-(...

1-chloro-5,8-dimethoxy-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

~%

acetic acid,2-(1-hydroxy-5,8-dimethoxynaphthalen-2-yl)-5,8-dimethoxynaphthalen-1-ol Structure

acetic acid,2-(...

Citraconic anhydride Structure

Citraconic anhydride

4-Chlorophenol Structure

~%

8-chloro-5-hydroxy-2-methylnaphthalene-1,4-dione Structure

8-chloro-5-hydr...

5-chloro-8-hydroxy-2-methylnaphthalene-1,4-dione Structure

5-chloro-8-hydr...

Citraconic anhydride Structure

Citraconic anhydride

4-Chlorophenol Structure

~%

8-chloro-5-hydroxy-2-methylnaphthalene-1,4-dione Structure

8-chloro-5-hydr...

5-chloro-8-hydroxy-2-methylnaphthalene-1,4-dione Structure

5-chloro-8-hydr...

7-methyl-5-phenylmethoxynaphthalene-1,4-dione Structure

7-methyl-5-phen...

Dimethyl sulfate Structure

Dimethyl sulfate

~%

5,8-dimethoxy-3-methyl-1-phenylmethoxynaphthalene Structure

5,8-dimethoxy-3...

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

~90%

4-chloro-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

1,4-Naphthalenedione,5-chloro-8-hydroxy-6-methyl- Structure

1,4-Naphthalene...

~%

4-chloro-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

5-chloro-6-methyl-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-6-meth...

~%

4-chloro-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

1,1'-Diacetoxy-4,4'-dichlor-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~15%

2-(1-hydroxy-5,8-dimethoxy-3-methylnaphthalen-2-yl)-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

2-(1-hydroxy-5,...

1,1'-Diacetoxy-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

1'-Acetoxy-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl-1-ol Structure

1'-Acetoxy-5,5'...

1,4-Naphthalenedione,5-chloro-8-hydroxy-6-methyl- Structure

1,4-Naphthalene...

~%

2-(1-hydroxy-5,8-dimethoxy-3-methylnaphthalen-2-yl)-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

2-(1-hydroxy-5,...

5-chloro-6-methyl-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-6-meth...

~%

2-(1-hydroxy-5,8-dimethoxy-3-methylnaphthalen-2-yl)-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

2-(1-hydroxy-5,...

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

~%

2-(1-hydroxy-5,8-dimethoxy-3-methylnaphthalen-2-yl)-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

2-(1-hydroxy-5,...

4-chloro-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

~%

2-(1-hydroxy-5,8-dimethoxy-3-methylnaphthalen-2-yl)-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

2-(1-hydroxy-5,...

4,4'-Dichlor-5,5',8,8'-tetramethoxy-3,3'-dimethyl-2,2'-binaphthyl-1,1'-diol Structure

4,4'-Dichlor-5,...

~%

2-(1-hydroxy-5,8-dimethoxy-3-methylnaphthalen-2-yl)-5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

2-(1-hydroxy-5,...

Citraconic anhydride Structure

Citraconic anhydride

Ethanoic anhydride Structure

Ethanoic anhydride

4-Chlorophenol Structure

~%

acetic acid,8-chloro-3-methylnaphthalene-1,4,5-triol Structure

acetic acid,8-c...

Detail

Citraconic anhydride Structure

Citraconic anhydride

Ethanoic anhydride Structure

Ethanoic anhydride

4-Chlorophenol Structure

~%

acetic acid,8-chloro-3-methylnaphthalene-1,4,5-triol Structure

acetic acid,8-c...

Detail

Citraconic anhydride Structure

Citraconic anhydride

4-Chlorophenol Structure

(Iodomethyl)benzene Structure

(Iodomethyl)benzene

~%

8-chloro-2-methyl-5-phenylmethoxynaphthalene-1,4-dione Structure

8-chloro-2-meth...

1-chloro-5,8-dimethoxy-2-methyl-4-phenylmethoxynaphthalene Structure

1-chloro-5,8-di...

~60%

5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

5,8-dimethoxy-3...

5,8-dimethoxy-3-methyl-1-phenylmethoxynaphthalene Structure

5,8-dimethoxy-3...

~%

5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

5,8-dimethoxy-3...

1,4-Naphthalenedione,5-chloro-8-hydroxy-6-methyl- Structure

1,4-Naphthalene...

~%

5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

5,8-dimethoxy-3...

7-methyl-5-phenylmethoxynaphthalene-1,4-dione Structure

7-methyl-5-phen...

~%

5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

5,8-dimethoxy-3...

5-chloro-6-methyl-8-phenylmethoxynaphthalene-1,4-dione Structure

5-chloro-6-meth...

~%

5,8-dimethoxy-3-methylnaphthalen-1-ol Structure

5,8-dimethoxy-3...

Citraconic anhydride Structure

Citraconic anhydride

~%

2,2'-Dimethyl-5,5'-dihydroxy-6,6'-bi[1,4-naphthoquinone] Structure

2,2'-Dimethyl-5...

4-Chlorophenol Structure

~%

2,2'-Dimethyl-5,5'-dihydroxy-6,6'-bi[1,4-naphthoquinone] Structure

2,2'-Dimethyl-5...

8-chloro-1,4-dimethoxy-2-methyl-5-phenylmethoxynaphthalene Structure

8-chloro-1,4-di...

~%

2,2'-Dimethyl-5,5'-dihydroxy-6,6'-bi[1,4-naphthoquinone] Structure

2,2'-Dimethyl-5...

1,1'-Diacetoxy-4,4'-dichlor-5,5',8,8'-tetramethoxy-6,6'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~%

2,2'-Dimethyl-5,5'-dihydroxy-6,6'-bi[1,4-naphthoquinone] Structure

2,2'-Dimethyl-5...

4-chloro-5,8-dimethoxy-6-methylnaphthalen-1-ol Structure

4-chloro-5,8-di...

~%

2,2'-Dimethyl-5,5'-dihydroxy-6,6'-bi[1,4-naphthoquinone] Structure

2,2'-Dimethyl-5...

N/A Structure

~85%

2,2'-Dimethyl-5,5'-dihydroxy-6,6'-bi[1,4-naphthoquinone] Structure

2,2'-Dimethyl-5...

1,1'-Diacetoxy-5,5',8,8'-tetramethoxy-6,6'-dimethyl-2,2'-binaphthyl Structure

1,1'-Diacetoxy-...

~%

2,2'-Dimethyl-5,5'-dihydroxy-6,6'-bi[1,4-naphthoquinone] Structure

2,2'-Dimethyl-5...

Citraconic anhydride Structure

Citraconic anhydride

~%

Plumbagin Structure

4-Chlorophenol Structure

~%

Plumbagin Structure

acetic acid,8-chloro-2-methylnaphthalene-1,4,5-triol Structure

acetic acid,8-c...

~%

Plumbagin Structure

Citraconic anhydride Structure

Citraconic anhydride

4-Chlorophenol Structure

(Iodomethyl)benzene Structure

(Iodomethyl)benzene

Dimethyl sulfate Structure

Dimethyl sulfate

~%

Detail