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

The Journal of Organic Chemistry

Synthesis and some reactions of 5-aryl-3, 4-dihydro-2H-1, 6-benzoxazocine and 5-aryl-3, 4-dihydro-2H-1, 6-benzothiazocines

JB Press, NH Eudy

Index: Press, Jeffery B.; Eudy, Nancy H. Journal of Organic Chemistry, 1984 , vol. 49, # 1 p. 116 - 122

Full Text: HTML

Citation Number: 5

Abstract

Benzothiazocine lb is most expediently prepared using a two-step procedure wherein amino ketone 5b is isolated; condensation of the mercaptide anion of 2 (preformed from 2 using sodium methoxide) with chloro ketone 3 gives 5b in excellent yield. Subsequent ring closure is accomplished by acid catalysis and azeotropic removal of water. Additional derivatives la, ce are prepared similarly. Structure assignment of 1 via-&-vis 4 is ambiguous using ...

2-Aminothiophenol Structure

2-Aminothiophenol

~%

S-[2-(2-phenylpyrrolidin-1-yl)phenyl] ethanethioate Structure

S-[2-(2-phenylp...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

S-[2-(2-phenylpyrrolidin-1-yl)phenyl] ethanethioate Structure

S-[2-(2-phenylp...

1,2,3,3a-Tetrahydro-3a-phenylpyrrolo(2,1-b)benzothiazole Structure

1,2,3,3a-Tetrah...

~%

S-[2-(2-phenylpyrrolidin-1-yl)phenyl] ethanethioate Structure

S-[2-(2-phenylp...

2-(3-(5,5-dimethyl-2-phenyl-1,3-dioxan-2-yl)propoxy)acetanilide Structure

2-(3-(5,5-dimet...

~92%

N-[2-(4-oxo-4-phenylbutoxy)phenyl]acetamide Structure

N-[2-(4-oxo-4-p...

2-(3-chloropropyl)-5,5-dimethyl-2-phenyl-1,3-dioxane Structure

2-(3-chloroprop...

~%

N-[2-(4-oxo-4-phenylbutoxy)phenyl]acetamide Structure

N-[2-(4-oxo-4-p...

acetoaminophenol Structure

acetoaminophenol

~%

N-[2-(4-oxo-4-phenylbutoxy)phenyl]acetamide Structure

N-[2-(4-oxo-4-p...

5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4-di...

~%

6-methyl-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocine Structure

6-methyl-5-phen...

2-Aminothiophenol Structure

2-Aminothiophenol

~%

6-methyl-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocine Structure

6-methyl-5-phen...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

6-methyl-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocine Structure

6-methyl-5-phen...

5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4,5,...

methyl iodide Structure

~%

6-methyl-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocine Structure

6-methyl-5-phen...

5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-thiophen-2-yl...

~%

1-(5-thiophen-2-yl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(5-thiophen-2...

Ethanoic anhydride Structure

Ethanoic anhydride

5-thiophen-2-yl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-thiophen-2-yl...

~40%

1-(5-thiophen-2-yl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(5-thiophen-2...

4-(2-aminophenoxy)-1-phenylbutan-1-one,hydrochloride Structure

4-(2-aminopheno...

~72%

4-(2-aminophenoxy)-1-phenylbutan-1-one Structure

4-(2-aminopheno...

N-[2-(4-oxo-4-phenylbutoxy)phenyl]acetamide Structure

N-[2-(4-oxo-4-p...

~51%

4-(2-aminophenoxy)-1-phenylbutan-1-one Structure

4-(2-aminopheno...

2-(3-chloropropyl)-5,5-dimethyl-2-phenyl-1,3-dioxane Structure

2-(3-chloroprop...

~%

4-(2-aminophenoxy)-1-phenylbutan-1-one Structure

4-(2-aminopheno...

2-(3-(5,5-dimethyl-2-phenyl-1,3-dioxan-2-yl)propoxy)acetanilide Structure

2-(3-(5,5-dimet...

~%

4-(2-aminophenoxy)-1-phenylbutan-1-one Structure

4-(2-aminopheno...

acetoaminophenol Structure

acetoaminophenol

~%

4-(2-aminophenoxy)-1-phenylbutan-1-one Structure

4-(2-aminopheno...

Ethanoic anhydride Structure

Ethanoic anhydride

5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4,5,...

~72%

1-(5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(5-phenyl-2,3...

5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4-di...

~%

1-(5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(5-phenyl-2,3...

2-Aminothiophenol Structure

2-Aminothiophenol

~%

1-(5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(5-phenyl-2,3...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

1-(5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(5-phenyl-2,3...

Benzenethiol,2-amino-4-chloro-, hydrochloride (1:1) Structure

Benzenethiol,2-...

~%

1-(8-chloro-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(8-chloro-5-p...

4-(2-amino-4-chlorophenyl)sulfanyl-1-phenylbutan-1-one Structure

4-(2-amino-4-ch...

~%

1-(8-chloro-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(8-chloro-5-p...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

1-(8-chloro-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(8-chloro-5-p...

Ethanoic anhydride Structure

Ethanoic anhydride

8-chloro-5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

~91%

1-(8-chloro-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(8-chloro-5-p...

8-chloro-5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

~%

1-(8-chloro-5-phenyl-2,3,4,5-tetrahydro-1,6-benzothiazocin-6-yl)ethanone Structure

1-(8-chloro-5-p...

4-(2-amino-4-chlorophenyl)sulfanyl-1-thiophen-2-ylbutan-1-one Structure

4-(2-amino-4-ch...

~99%

8-chloro-5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-thio...

2-Aminothiophenol Structure

2-Aminothiophenol

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~16%

1,2,3,3a-Tetrahydro-3a-phenylpyrrolo(2,1-b)benzothiazole Structure

1,2,3,3a-Tetrah...

5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4-di...

2-(3-(5,5-dimethyl-2-phenyl-1,3-dioxan-2-yl)propoxy)acetanilide Structure

2-(3-(5,5-dimet...

~86%

4-(2-aminophenoxy)-1-phenylbutan-1-one,hydrochloride Structure

4-(2-aminopheno...

2-(3-chloropropyl)-5,5-dimethyl-2-phenyl-1,3-dioxane Structure

2-(3-chloroprop...

~%

4-(2-aminophenoxy)-1-phenylbutan-1-one,hydrochloride Structure

4-(2-aminopheno...

acetoaminophenol Structure

acetoaminophenol

~%

4-(2-aminophenoxy)-1-phenylbutan-1-one,hydrochloride Structure

4-(2-aminopheno...

4-(2-aminophenoxy)-1-phenylbutan-1-one Structure

4-(2-aminopheno...

~68%

5-phenyl-3,4-dihydro-2H-1,6-benzoxazocine Structure

5-phenyl-3,4-di...

2-(3-chloropropyl)-5,5-dimethyl-2-phenyl-1,3-dioxane Structure

2-(3-chloroprop...

~%

5-phenyl-3,4-dihydro-2H-1,6-benzoxazocine Structure

5-phenyl-3,4-di...

2-(3-(5,5-dimethyl-2-phenyl-1,3-dioxan-2-yl)propoxy)acetanilide Structure

2-(3-(5,5-dimet...

~%

5-phenyl-3,4-dihydro-2H-1,6-benzoxazocine Structure

5-phenyl-3,4-di...

acetoaminophenol Structure

acetoaminophenol

~%

5-phenyl-3,4-dihydro-2H-1,6-benzoxazocine Structure

5-phenyl-3,4-di...

N-[2-(4-oxo-4-phenylbutoxy)phenyl]acetamide Structure

N-[2-(4-oxo-4-p...

~%

5-phenyl-3,4-dihydro-2H-1,6-benzoxazocine Structure

5-phenyl-3,4-di...

4-(2-aminophenoxy)-1-phenylbutan-1-one,hydrochloride Structure

4-(2-aminopheno...

~%

5-phenyl-3,4-dihydro-2H-1,6-benzoxazocine Structure

5-phenyl-3,4-di...

n-Butyllithium Structure

5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4-di...

~53%

5-butyl-5-phenyl-2,3,4,6-tetrahydro-1,6-benzothiazocine Structure

5-butyl-5-pheny...

2-Aminothiophenol Structure

2-Aminothiophenol

~%

5-butyl-5-phenyl-2,3,4,6-tetrahydro-1,6-benzothiazocine Structure

5-butyl-5-pheny...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

5-butyl-5-phenyl-2,3,4,6-tetrahydro-1,6-benzothiazocine Structure

5-butyl-5-pheny...

4-(2-amino-4-chlorophenyl)sulfanyl-1-thiophen-2-ylbutan-1-one Structure

4-(2-amino-4-ch...

~%

2-(6-chloro-3-thiophen-2-yl-1,4-benzothiazin-2-ylidene)acetaldehyde Structure

2-(6-chloro-3-t...

8-chloro-5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-thio...

~43%

2-(6-chloro-3-thiophen-2-yl-1,4-benzothiazin-2-ylidene)acetaldehyde Structure

2-(6-chloro-3-t...

2-(6-chloro-3-(thiophen-2-yl)-2H-benzo[b][1,4]thiazin-2-ylidene)ethyl acetate Structure

2-(6-chloro-3-(...

6-chloro-3-(2-thienyl)-2H-1,4-benzothiazine-ethanol acetate Structure

6-chloro-3-(2-t...

8-chloro-5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

~%

2-(6-chloro-3-phenyl-1,4-benzothiazin-2-ylidene)acetaldehyde Structure

2-(6-chloro-3-p...

Benzenethiol,2-amino-4-chloro-, hydrochloride (1:1) Structure

Benzenethiol,2-...

~%

2-(6-chloro-3-phenyl-1,4-benzothiazin-2-ylidene)acetaldehyde Structure

2-(6-chloro-3-p...

4-(2-amino-4-chlorophenyl)sulfanyl-1-phenylbutan-1-one Structure

4-(2-amino-4-ch...

~%

2-(6-chloro-3-phenyl-1,4-benzothiazin-2-ylidene)acetaldehyde Structure

2-(6-chloro-3-p...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

2-(6-chloro-3-phenyl-1,4-benzothiazin-2-ylidene)acetaldehyde Structure

2-(6-chloro-3-p...

7-chloro-3a-phenyl-1,2,3,3a-tetrahydrobenzo[d]pyrrolo[2,1-b]oxazole Structure

7-chloro-3a-phe...

~49%

4-chloro-2-(2-phenylpyrrolidin-1-yl)phenol Structure

4-chloro-2-(2-p...

2-Amino-4-chlorophenol Structure

2-Amino-4-chlor...

~%

4-chloro-2-(2-phenylpyrrolidin-1-yl)phenol Structure

4-chloro-2-(2-p...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

4-chloro-2-(2-phenylpyrrolidin-1-yl)phenol Structure

4-chloro-2-(2-p...

5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-thiophen-2-yl...

~73%

5-thiophen-2-yl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-thiophen-2-yl...

1,2,3,3a-Tetrahydro-3a-phenylpyrrolo(2,1-b)benzoxazole Structure

1,2,3,3a-Tetrah...

~99%

2-(2-phenylpyrrolidin-1-yl)phenol Structure

2-(2-phenylpyrr...

aminophenol Structure

~%

2-(2-phenylpyrrolidin-1-yl)phenol Structure

2-(2-phenylpyrr...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

2-(2-phenylpyrrolidin-1-yl)phenol Structure

2-(2-phenylpyrr...

4-(2-amino-4-chlorophenyl)sulfanyl-1-phenylbutan-1-one Structure

4-(2-amino-4-ch...

~52%

8-chloro-5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

Benzenethiol,2-amino-4-chloro-, hydrochloride (1:1) Structure

Benzenethiol,2-...

~%

8-chloro-5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

8-chloro-5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4-di...

~67%

5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4,5,...

2-Aminothiophenol Structure

2-Aminothiophenol

~%

5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4,5,...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-phenyl-3,4,5,...

8-chloro-5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-thio...

~82%

8-chloro-5-thiophen-2-yl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-thio...

4-(2-amino-4-chlorophenyl)sulfanyl-1-thiophen-2-ylbutan-1-one Structure

4-(2-amino-4-ch...

~%

8-chloro-5-thiophen-2-yl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-thio...

8-chloro-5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-thio...

~99%

8-chloro-5-thiophen-2-yl-3,4-dihydro-2H-1λ4,6-benzothiazocine 1-oxide Structure

8-chloro-5-thio...

4-(2-amino-4-chlorophenyl)sulfanyl-1-thiophen-2-ylbutan-1-one Structure

4-(2-amino-4-ch...

~%

8-chloro-5-thiophen-2-yl-3,4-dihydro-2H-1λ4,6-benzothiazocine 1-oxide Structure

8-chloro-5-thio...

8-chloro-5-(4-fluorophenyl)-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-(4-f...

~66%

8-chloro-5-(4-fluorophenyl)-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-(4-f...

Benzenethiol,2-amino-4-chloro-, hydrochloride (1:1) Structure

Benzenethiol,2-...

~%

8-chloro-5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

4-(2-amino-4-chlorophenyl)sulfanyl-1-phenylbutan-1-one Structure

4-(2-amino-4-ch...

~%

8-chloro-5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

8-chloro-5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

8-chloro-5-phenyl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

~30%

8-chloro-5-phenyl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

8-chloro-5-phen...

8-chloro-5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

8-chloro-5-thio...

~15%

4-(2-amino-4-chlorophenyl)sulfanyl-1-thiophen-2-ylbutan-1-one Structure

4-(2-amino-4-ch...

5-thiophen-2-yl-3,4-dihydro-2H-1,6-benzothiazocine Structure

5-thiophen-2-yl...

~%

6-methyl-5-thiophen-2-yl-2,3,4,5-tetrahydro-1,6-benzothiazocine Structure

6-methyl-5-thio...

5-thiophen-2-yl-3,4,5,6-tetrahydro-2H-1,6-benzothiazocine Structure

5-thiophen-2-yl...

methyl iodide Structure

~%

6-methyl-5-thiophen-2-yl-2,3,4,5-tetrahydro-1,6-benzothiazocine Structure

6-methyl-5-thio...

Benzenethiol,2-amino-4-chloro-, hydrochloride (1:1) Structure

Benzenethiol,2-...

4-Chloro-1-oxo-1-phenylbutane Structure

4-Chloro-1-oxo-...

~%

4-(2-amino-4-chlorophenyl)sulfanyl-1-phenylbutan-1-one Structure

4-(2-amino-4-ch...