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29th August 2013 @ 16:04

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Reaction information

*#Reaction file  
Scheme_312.cdx
*Reaction file type CDX
*Procedure  

To a stirring solution of N-benzyl-N-(3-heptynyl)amine (309, 1.0 g, 4.8 mmol), K2CO3 (1.2 g, 12.0 mmol) and MeCN (10.0 mL), benzenesulfonate (307, 1.33 g, 5.0 mmol) was added dropwise.  The reactants were refluxed for 24 hrs then quenched using NaOH (6M, 30.0 mL).  The product was extracted into diethyl ether (3 x 100 mL), the combined organic layer washed with water (3 x 100 mL), brine (50.0 mL), dried over MgSO4, filtered and the solvent removed under reduced pressure.  Column chromatography (SiO2, 0-100 % Et2O:petroleum including 5 % Et3N) afforded the title compound as a viscous clear oil (1.3 g, 4.4 mmol, 88 %).

*Yield (%)  88
*Type of Yield Isolated product yield
Reference(s)  
DM Thesis_2000_pp40-49.pdf
DM Thesis_2000_pp106.pdf
Further information  

For multistep reactions (or their steps):

Overall reaction? True
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step  
Attached Files
22nd August 2013 @ 16:37

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Reaction information

*#Reaction file  
CSRxnsScheme_136b.cdx
*Reaction file type CDX
*Procedure  

General procedure C (see below) with N-(Dec-9-en-3-yn-1-yl)-N-(hex-1-yn-1-yl)-4-methylbenzenesulfonamide  (372 mg, 1.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 9:1) gave the title compound as the minor product as a pale yellow oil (119 mg, 32%).

 

 The minor product was (E)‑N‑(hex‑1‑yn‑1‑yl)‑4‑methyl‑N‑(3‑(2‑methylcyclohexylidene)propyl)benzenesulfonamide (136b) obtained as a pale yellow oil (102 mg, 26%).  

 

General procedure C: zirconocene mediated cocyclisation of ynamides

n-BuLi (0.88 mL of a 2.5 M solution in hexanes, 2.2 mmol) was added dropwise to a solution of Cp2ZrCl2 (322 mg, 1.1 mmol) in dry THF (5.0 mL) at −78 °C.  A solution of the appropriate ynamide (1.0 mmol) in dry THF (3.0 mL) was added dropwise at −78 °C.  The reaction mixture was warmed to room temperature and stirred for 5 h.  The reaction mixture was cooled to −78 °C and MeOH (10.0 mL) added.  After stirring at −78 °C for 1 h the reaction mixture was stirred at room temperature for 16 h.  The reaction mixture was poured into water (100 mL) and extracted with ether (3 × 50 mL).  The organic extracts were combined, washed sequentially with water (2 × 100 mL) and brine (100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product, which was purified as described.

*Yield (%)  26
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp106.pdf
AH Thesis_2011_pp176-223.pdf
Further information  Compound 136b: (E)‑N‑(hex‑1‑yn‑1‑yl)‑4‑methyl‑N‑(3‑(2‑methylcyclohexylidene)propyl)benzenesulfonamide

For multistep reactions (or their steps):

Overall reaction? True
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step  
Attached Files
22nd August 2013 @ 16:33

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Reaction information

*#Reaction file  
CSRxnsScheme_135b.cdx
*Reaction file type CDX
*Procedure  

General procedure C (see below) with N-(Dec-9-en-3-yn-1-yl)-N-(hex-1-yn-1-yl)-4-methylbenzenesulfonamide  (372 mg, 1.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 9:1) gave the title compound as the minor product as a pale yellow oil (119 mg, 32%).

 

 

 

General procedure C: zirconocene mediated cocyclisation of ynamides

n-BuLi (0.88 mL of a 2.5 M solution in hexanes, 2.2 mmol) was added dropwise to a solution of Cp2ZrCl2 (322 mg, 1.1 mmol) in dry THF (5.0 mL) at −78 °C.  A solution of the appropriate ynamide (1.0 mmol) in dry THF (3.0 mL) was added dropwise at −78 °C.  The reaction mixture was warmed to room temperature and stirred for 5 h.  The reaction mixture was cooled to −78 °C and MeOH (10.0 mL) added.  After stirring at −78 °C for 1 h the reaction mixture was stirred at room temperature for 16 h.  The reaction mixture was poured into water (100 mL) and extracted with ether (3 × 50 mL).  The organic extracts were combined, washed sequentially with water (2 × 100 mL) and brine (100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product, which was purified as described.

*Yield (%)  32
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp106.pdf
AH Thesis_2011_pp176-223.pdf
Further information  Compound 135b: (2Z,3E)-3-(Hept-6-en-1-ylidene)-2-pentylidene-1-tosylpyrrolidine

For multistep reactions (or their steps):

Overall reaction? True
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step  
Attached Files
22nd August 2013 @ 16:27

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Reaction information

*#Reaction file  
CSRxnsScheme_136a.cdx
*Reaction file type CDX
*Procedure  

General procedure C (see below) with N-(Hex-1-yn-1-yl)-4-methyl-N-(non-8-en-3-yn-1-yl)benzenesulfonamide (372 mg, 1.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 9:1) gave the product as a pale yellow oil (119 mg, 32%).

The major product (title compound) was (E)‑N‑(hex‑1‑yn‑1‑yl)‑4‑methyl‑N‑(3‑(2‑methylcyclopentylidene)propyl)benzenesulfonamide (136a) obtained as a pale yellow oil (150 mg, 40%)

 

 

General procedure C: zirconocene mediated cocyclisation of ynamides

n-BuLi (0.88 mL of a 2.5 M solution in hexanes, 2.2 mmol) was added dropwise to a solution of Cp2ZrCl2 (322 mg, 1.1 mmol) in dry THF (5.0 mL) at −78 °C.  A solution of the appropriate ynamide (1.0 mmol) in dry THF (3.0 mL) was added dropwise at −78 °C.  The reaction mixture was warmed to room temperature and stirred for 5 h.  The reaction mixture was cooled to −78 °C and MeOH (10.0 mL) added.  After stirring at −78 °C for 1 h the reaction mixture was stirred at room temperature for 16 h.  The reaction mixture was poured into water (100 mL) and extracted with ether (3 × 50 mL).  The organic extracts were combined, washed sequentially with water (2 × 100 mL) and brine (100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product, which was purified as described.

*Yield (%)  40
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp106.pdf
AH Thesis_2011_pp176-223.pdf
Further information  Compound 136b: (E)‑N‑(hex‑1‑yn‑1‑yl)‑4‑methyl‑N‑(3‑(2‑methylcyclohexylidene)propyl)benzenesulfonamide

For multistep reactions (or their steps):

Overall reaction? True
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step  
Attached Files
22nd August 2013 @ 16:26

This post is compatible for submission to ChemSpider Reactions.

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Reaction information

*#Reaction file  
CSRxnsScheme_135a.cdx
*Reaction file type CDX
*Procedure  

General procedure C (see below) with N-(Hex-1-yn-1-yl)-4-methyl-N-(non-8-en-3-yn-1-yl)benzenesulfonamide (372 mg, 1.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 9:1) gave the title compound as the minor product as a pale yellow oil (119 mg, 32%).

 

 

 

General procedure C: zirconocene mediated cocyclisation of ynamides

n-BuLi (0.88 mL of a 2.5 M solution in hexanes, 2.2 mmol) was added dropwise to a solution of Cp2ZrCl2 (322 mg, 1.1 mmol) in dry THF (5.0 mL) at −78 °C.  A solution of the appropriate ynamide (1.0 mmol) in dry THF (3.0 mL) was added dropwise at −78 °C.  The reaction mixture was warmed to room temperature and stirred for 5 h.  The reaction mixture was cooled to −78 °C and MeOH (10.0 mL) added.  After stirring at −78 °C for 1 h the reaction mixture was stirred at room temperature for 16 h.  The reaction mixture was poured into water (100 mL) and extracted with ether (3 × 50 mL).  The organic extracts were combined, washed sequentially with water (2 × 100 mL) and brine (100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product, which was purified as described.

*Yield (%)  32
*Type of Yield Isolated product yield
Reference(s)  
AH Thesis_2011_pp106.pdf
AH Thesis_2011_pp176-223.pdf
Further information  Compound 135a: (2Z,3E)-3-(Hex-5-en-1-ylidene)-2-pentylidene-1-tosylpyrrolidine 

For multistep reactions (or their steps):

Overall reaction? True
For overall reaction - links to child reaction steps  
For step in multistep reaction - link to previous reaction step  
For step in multistep reaction - link to following reaction step  
Attached Files