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2nd September 2013 @ 14:43

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Reaction information

*#Reaction file  
Scheme_601.cdx
*Reaction file type CDX
*Procedure  To a stirred solution of ZrCp2Cl2 (0.292 g, 1.0 mmol) in dry THF (5.0 mL) under argon at -80 °C, nBuLi (0.8 mL of 2.5 M solution in hexanes, 2.0 mmol) was added dropwise and stirred for 10 minutes. But-2-ynyl-methyl-(3-phenyl-prop-2-ynyl)-amine (598, 197 mg, 1.0 mmol) as a solution in THF (2.0 mL) was added dropwise, warmed to room temperature stirred for 5 hrs, quenched with a saturated solution of NaHCO3 (8.0 mL) and methanol (5.0 mL).  The product was extracted into diethyl ether (3 x 100 mL), the combined organic layer washed with water (4 x 50 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 colourless oil (156 mg, 0.78 mmol, 78 %).
*Yield (%)  78
*Type of Yield Isolated product yield
Reference(s)  
DM Thesis_2000_pp91-95.pdf
DM Thesis_2000_pp189.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
2nd September 2013 @ 14:42

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Reaction information

*#Reaction file  
Scheme_598.cdx
*Reaction file type CDX
*Procedure  

To a stirring solution of triethylamine (1.0 mL, 10.0 mmol) and methanesulphonyl chloride (3.5 mmol, 354 mg) in DCM (10.0 mL) at 0 °C, 2-butyn-1-ol (3.0 mmol, 211 mg) was added under argon.  The solution was left to stir for 20 minutes at 0 °C, warmed to room temperature and stirred for 20 minutes before quenching with a solution of dietyl ether (30.0 mL), filtered, and the solvent removed under reduced pressure.  The product dissolved in MeCN (10.0 mL), secondary amine (290 mg, 2.0 mmol) added at 0 °C, stirred with K2CO3 (1.0 g, 7.5 mmol), triethylamine (3.0 mL) and the solution refluxed for 30 minutes.  The reaction was quenched with a solution of NaHCO3 (15.0 mL), the product extracted into diethyl ether (3 x 50 mL), the combined organic layer washed with water (30.0 mL), brine (30.0 mL), dried over MgSO4, filtered and the solvent removed under reduced pressure.  Column chromatography (SiO2, 0-100 % Et2O:petroleum including 5 % Et3N) afforded the desired compound as a pale oil (242 mg, 1.2 mmol, 61 %).

*Yield (%)  61
*Type of Yield Isolated product yield
Reference(s)  
DM Thesis_2000_pp91-95.pdf
DM Thesis_2000_pp188.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
2nd September 2013 @ 14:41

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Reaction information

*#Reaction file  
Scheme_597.cdx
*Reaction file type CDX
*Procedure  

To a stirred solution of ZrCp2Cl2 (0.292 g, 1.0 mmol) in dry THF (5.0 mL) under argon at 80 °C, nBuLi (0.8 mL of 2.5 M solution in hexanes, 2.0 mmol) was added dropwise and stirred for 10 minutes. Allyl-[3-(3-methoxy-phenyl)-prop-2-ynyl]-methyl-amine (594, 216 mg, 1.0 mmol) as a solution in THF (2.0 mL) was added dropwise, warmed to room temperature stirred for 5 hrs, before quenching with methanol (5.0 mL) and a saturated solution of NaHCO3 (8.0 mL).  The product was extracted into diethyl ether (3 x 100 mL), the combined organic layer washed with water (4 x 50 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 colourless oil (170 mg, 0.78 mmol, 78 %).

*Yield (%)  78
*Type of Yield Isolated product yield
Reference(s)  
DM Thesis_2000_pp91-95.pdf
DM Thesis_2000_pp187.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
2nd September 2013 @ 14:40

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Reaction information

*#Reaction file  
Scheme_594.cdx
*Reaction file type CDX
*Procedure  

To a stirred solution of [3-(3-methoxy-phenyl)-prop-2-ynyl]-methyl-amine (592, 350 mg, 2.0 mmol), K2CO3 (2.0 g, 14.7 mmol) in MeCN (30.0 mL) at 0 °C, allyl bromide (240 mg, 2.0 mmol) was added dropwise.  The solution was warmed to room temperature, stirred for 1 hour then refluxed for 1 hour, before quenching with a saturated solution of NaHCO3 (50.0 mL).  The product was extracted into diethyl ether (3 x 40 mL), the combined organic layer washed with water (3 x 30 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 an orange oil (164 mg, 1.5 mmol, 76 %).

 

*Yield (%)  76
*Type of Yield Isolated product yield
Reference(s)  
DM Thesis_2000_pp91-95.pdf
DM Thesis_2000_pp186.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
2nd September 2013 @ 14:39

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Reaction information

*#Reaction file  
Scheme_592.cdx
*Reaction file type CDX
*Procedure  

To a stirred solution of triethylamine (1.0 mL, 10.0 mmol) and methanesulphonyl chloride (354 mg, 3.5 mmol) in DCM (10.0 mL), 3-(3-methoxy-phenyl)-prop-2-yn-1-ol (486 mg, 3.0 mmol) was added under argon at 0 °C.  The solution was stirred for 20 minutes at -20 °C, before quenching with a solution of ether (30.0 mL), cold filtered, and the solvent removed under reduced pressure.  The product was dissolved in EtOH (10.0 mL), and methylamine (66 % solution in IMS, 3.0 mL, 10.0 mmol) was added at 0 °C.   The resulting solution was refluxed for 30 minutes, before quenching with a saturated solution of NaHCO3 (15.0 mL).  The product was extracted into diethyl ether (3 x 50 mL), the combined organic layer washed with water (3 x 30.0 mL), brine (30.0 mL), dried over MgSO4, filtered and the solvent removed under reduced pressure.  Column chromatography (SiO2, 0-100 % Et2O:petroleum including 5 % Et3N) afforded the desired compound as a yellow oil (361 mg, 2.1 mmol, 59 %).    

*Yield (%)  59
*Type of Yield Isolated product yield
Reference(s)  
DM Thesis_2000_pp91-95.pdf
DM Thesis_2000_pp185.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