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31st July 2013 @ 16:49

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SOURCE

Author 1 is the author of this LabTrove post (and has contributor role of "Abstracter").

  *First name *Last name Email Organization Role
Author 2 Alan Henderson   University of Southampton Doer
Author 3 Richard Whitby   University of Southampton Conceiver
Author 4          

TEXT

*Procedure or Transformation Zirconocene mediated cocyclisations of ynamides
*Compound(s) being made 4-Methyl-N-(4-(trimethylsilyl)but-3-yn-1-yl)-N-((trimethylsilyl)ethynyl)benzenesulfonamide
*Chemicals used (delimited by semicolons ;)

4-Methyl-N-(non-4-yn-1-yl)benzenesulfonamide1-Bromohex-1-yne ;DMFK2CO3CuSO4.5H2O1,10-phenanthrolineetherMgSO4 

*Procedure  

General procedure A (see below) with 4-Methyl-N-(non-4-yn-1-yl)benzenesulfonamide  (1.47 g, 5.0 mmol) and 1-Bromohex-1-yne (886 mg, 5.5 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 4:1) gave the title compound as an orange oil (1.09 g, 59%).

 

General Procedure A:

A solution of the appropriate sulfonamide (1 eq.) and the appropriate bromide (1.1 eq.) in DMF (35 mL) was added to K2CO3 (2 eq.), CuSO4.5H2O (0.1 eq.) and 1,10-phenanthroline (0.2 eq.).  The reaction mixture was stirred at 65 °C for 16 h.  The reaction mixture was poured into water (200 mL) and extracted with ether (3 × 50 mL).  The organic extracts were combined, washed with water (2 × 100 mL), dried (MgSO4), filtered and the solvent removed in vacuo to give the crude product, which was purified as described.

*Authors Comments  
Lead Reference A. Henderson, 2010, "Organozirconium approaches to small molecule synthesis",PhD thesis, University of Southampton
Other References  
Multimedia Content  
*Data 1H NMR (300 MHz, CDCl3); 13C NMR (75 MHz, CDCl3)
#Data file 1  
HNMR_117i.pdf
#Data file 2  
CNMR_117i.pdf
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
Scheme_117i.cdx
 
*#Image file (GIF or PNG)  
Scheme_117i.gif

Keywords

Compounds Keywords alkynes, aromatics
Reactions Keywords addition, substitution
Other Keywords  
Attached Files
31st July 2013 @ 16:48

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Compound

ChemSpider ID  29272437
*#Name of Compound mol file
Structure_117i.mol
 

Description and Tags

Description Compound 117i in A.Henderson's thesis
Tags (separated by comma)  

Identifiers

*Chemical Name 4-Methyl-N-(4-(trimethylsilyl)but-3-yn-1-yl)-N-((trimethylsilyl)ethynyl)benzenesulfonamide
Common Name  
Synonym  

Spectra

  *#Spectrum jcamp file *Spectrum Type Comments OpenData Image or PDF
Spectrum 1  
HNMR_117i.jdx
HNMR  

1H NMR: dH (400 MHz, CDCl3) 7.79 (2H, d, J 8.5 Hz, H-17), 7.33 (2H, d, J 8.5 Hz, H‑18), 3.37 (2H, t, J 7.0 Hz, H-7), 2.45 (3H, s, H-20), 2.26 (2H, t, J 7.0 Hz, H-9), 2.22–2.09 (4H, m, H-3,12), 1.80 (2H, quin, J 7.0 Hz, H-8), 1.54–1.31 (8H, m, H‑4,5,13,14), 0.91 (3H, t, J 7.3 Hz, H-6 or H-15), 0.90 (3H, t, J 7.5 Hz, H-6 or H-15)

AH Thesis_2011_pp176-223.pdf
Y  
HNMR_117i.pdf
Spectrum 2  
CNMR_117i.jdx
CNMR  

13C NMR: dC(100 MHz, CDCl3) 144.18 (C, C-19), 134.64 (C, C-16), 129.53 (2 × CH), 127.64 (2 × CH), 81.21 (C), 78.33 (C), 72.89 (C), 70.22 (C), 50.50 (CH2, C-7), 31.10 (CH2), 30.98 (CH2), 27.43 (CH2), 21.89 (CH2), 21.81 (CH2), 21.59 (CH3, C-20), 18.37 (CH2), 18.11 (CH2), 15.90 (CH2), 13.58 (CH3), 13.55 (CH3)

Y  
CNMR_117i.pdf
Spectrum 3  
CDEPT135NMR_117i.jdx
CNMR   Y  
CDEPT135NMR_117i.pdf
Spectrum 4   ESI+ mass spectrum  

LRMS: (ES+) m/z 396.3 ([M+Na]+)

Y  
LRMS.gif
Spectrum 5   ESI+ mass spectrum  

HRMS: (ES+) Calculated for C22H31NNaO2S: 396.1968 Da, found: 396.1974 Da

Y  
HRMS.gif
Spectrum 6   Infrared  

IR: nmax (neat)/cm−1 2956 (w), 2930 (w), 2871 (w), 1597 (w), 1166 (s), 544 (s)

Y  
IR.gif
Spectrum 7          
Spectrum 8          
Spectrum 9          
Spectrum 10          

Properties

Experimental Physico-chemical Properties

Property Value Unit Comments
Experimental Boiling Point      
Experimental Flash Point      
Experimental Freezing Point      
Experimental Gravity      
Experimental Ionization Potent      
Experimental LogP      
Experimental Melting Point      
Experimental Optical Rotation      
Experimental Refraction Index      
Experimental Solubility      
Experimental Vapor Pressure      
Non Water Solubility      
Non Water Solubility      

Spectroscopy

Property Value Unit Comments
Lambda Max      

Miscellaneous

Property Value Unit Comments
Appearance orange oil    
Bio Activity      
Chemical Class      
Compound Source      
Drug Status      
Exposure Limits      
Exposure Limits Niosh Rel      
Exposure Routes      
First-Aid      
Incompatability      
Personal Protection      
Safety      
Stability      
Symptoms      
Target Organs      
Therapeutical Effect      
Toxicity      
Attached Files
31st July 2013 @ 16:42

This post is compatible for submission to ChemSpider SyntheticPages.

See ChemSpider SyntheticPages style reaction template - help and further information for help when using it.

SOURCE

Author 1 is the author of this LabTrove post (and has contributor role of "Abstracter").

  *First name *Last name Email Organization Role
Author 2 Alan Henderson   University of Southampton Doer
Author 3 Richard Whitby   University of Southampton Conceiver
Author 4          

TEXT

*Procedure or Transformation Zirconocene mediated cocyclisations of ynamides
*Compound(s) being made 4-Methyl-N-(4-phenylbut-3-yn-1-yl)-N-((trimethylsilyl)ethynyl)benzenesulfonamide
*Chemicals used (delimited by semicolons ;)

4-Methyl-N-(4-phenylbut-3-yn-1-yl)benzenesulfonamide;  (Bromoethynyl)trimethylsilaneDMFK2CO3CuSO4.5H2O1,10-phenanthrolineetherMgSO4 

*Procedure  

General procedure B (see below) with 4-Methyl-N-(4-phenylbut-3-yn-1-yl)benzenesulfonamide  (1.50 g, 5.0 mmol) and (Bromoethynyl)trimethylsilane (886 mg, 5.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 4:1) gave the title compound as a yellow solid (930 mg, 47%).

 

 

General procedure B:

A solution of the appropriate bromide (1 eq.) and N,N‑dimethylethylenediamine (0.2 eq.) in dry toluene (20 mL) was added to the appropriate sulfonamide (1 eq.), K3PO4 (2 eq.) and CuI (0.05 eq.) in toluene (10.0 mL).  The reaction mixture was heated to reflux for 16 h.  The reaction mixture was filtered through a plug of silica using ether to elute and the solvent removed in vacuo to give the crude product, which was purified as described.

*Authors Comments  
Lead Reference A. Henderson, 2010, "Organozirconium approaches to small molecule synthesis",PhD thesis, University of Southampton
Other References  
Multimedia Content  
*Data 1H NMR (300 MHz, CDCl3); 13C NMR (75 MHz, CDCl3)
#Data file 1
HNMR_117h.pdf
#Data file 2
CNMR_117h.pdf
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
Scheme_117h.cdx
 
*#Image file (GIF or PNG)  
Scheme_117h.gif

Keywords

Compounds Keywords alkynes, aromatics
Reactions Keywords addition, substitution
Other Keywords  
Attached Files
31st July 2013 @ 16:37

This post is compatible for submission to ChemSpider.

See ChemSpider compound and associated data template - help and further information for help when using it.

Compound

ChemSpider ID  29272432
*#Name of Compound mol file  
Structure_117h.mol

Description and Tags

Description Compound 117h in A.Henderson's thesis
Tags (separated by comma)  

Identifiers

*Chemical Name 4-Methyl-N-(4-phenylbut-3-yn-1-yl)-N-((trimethylsilyl)ethynyl)benzenesulfonamide
Common Name  
Synonym  

Spectra

  *#Spectrum jcamp file *Spectrum Type Comments OpenData Image or PDF
Spectrum 1  
HNMR_117h.jdx
HNMR  

1H NMR: dH(300 MHz, CDCl3) 7.81 (2H, d, J 8.1 Hz, H-13), 7.42–7.21 (7H, m, H‑9,10,11,14), 3.58 (2H, t, J 7.6 Hz, H-4), 2.74 (2H, t, J 7.6 Hz, H-5), 2.43 (3H, s, H-16), 0.16 (9H, s, H-3)

AH Thesis_2011_pp176-223.pdf
Y  
HNMR_117h.pdf
Spectrum 2  
CNMR_117h.jdx
CNMR  

13C NMR: dC (75 MHz, CDCl3) 144.73 (C, C-15), 134.51 (C, C-12), 131.61 (2 × CH), 129.65 (2 × CH), 128.18 (2 × CH), 127.97 (CH, C-11), 127.77 (2 × CH), 123.17 (C, C-8), 94.41 (C, C-1), 85.19 (C), 82.55 (C), 73.75 (C), 50.11 (CH2, C-4), 21.62 (CH3, C-16), 19.30 (CH2, C-5), 0.05 (CH3, C-3)

Y  
CNMR_117h.pdf
Spectrum 3  
CDEPT135NMR_117h.jdx
CNMR   Y  
CDEPT135NMR_117h.pdf
Spectrum 4   ESI+ mass spectrum  

LRMS: (ES+) m/z 418.2 ([M+Na]+)

Y  
LRMS.gif
Spectrum 5   Infrared  

IR: nmax (neat)/cm−1 2958 (w), 2156 (m), 1597 (w), 1168 (s), 838 (s), 659 (s), 542 (s)

Y  
IR.gif
Spectrum 6          
Spectrum 7          
Spectrum 8          
Spectrum 9          
Spectrum 10          

Properties

Experimental Physico-chemical Properties

Property Value Unit Comments
Experimental Boiling Point      
Experimental Flash Point      
Experimental Freezing Point      
Experimental Gravity      
Experimental Ionization Potent      
Experimental LogP      
Experimental Melting Point 89  °C MP range: 87-89
Experimental Optical Rotation      
Experimental Refraction Index      
Experimental Solubility      
Experimental Vapor Pressure      
Non Water Solubility      
Non Water Solubility      

Spectroscopy

Property Value Unit Comments
Lambda Max      

Miscellaneous

Property Value Unit Comments
Appearance Yellow solid    
Bio Activity      
Chemical Class      
Compound Source      
Drug Status      
Exposure Limits      
Exposure Limits Niosh Rel      
Exposure Routes      
First-Aid      
Incompatability      
Personal Protection      
Safety      
Stability      
Symptoms      
Target Organs      
Therapeutical Effect      
Toxicity      
Attached Files
31st July 2013 @ 16:30

This post is compatible for submission to ChemSpider SyntheticPages.

See ChemSpider SyntheticPages style reaction template - help and further information for help when using it.

SOURCE

Author 1 is the author of this LabTrove post (and has contributor role of "Abstracter").

  *First name *Last name Email Organization Role
Author 2 Alan Henderson   University of Southampton Doer
Author 3 Richard Whitby   University of Southampton Conceiver
Author 4          

TEXT

*Procedure or Transformation Zirconocene mediated cocyclisations of ynamides
*Compound(s) being made 4-Methyl-N-(oct-3-yn-1-yl)-N-((trimethylsilyl)ethynyl)benzenesulfonamide
*Chemicals used (delimited by semicolons ;)  4-Methyl-N-(oct-3-yn-1-yl)benzenesulfonamide; (Bromoethynyl)trimethylsilaneDMFK2CO3CuSO4.5H2O1,10-phenanthrolineetherMgSO4 
*Procedure

General procedure B with 4-Methyl-N-(oct-3-yn-1-yl)benzenesulfonamide (1.40 g, 5.0 mmol) and (Bromoethynyl)trimethylsilane  (886 mg, 5.0 mmol).  Purification by column chromatography (SiO2, hexane/Et2O 4:1) gave the title compound as an orange oil (445 mg, 30%).

  

 

General procedure B:

A solution of the appropriate bromide (1 eq.) and N,N‑dimethylethylenediamine (0.2 eq.) in dry toluene (20 mL) was added to the appropriate sulfonamide (1 eq.), K3PO4 (2 eq.) and CuI (0.05 eq.) in toluene (10.0 mL).  The reaction mixture was heated to reflux for 16 h.  The reaction mixture was filtered through a plug of silica using ether to elute and the solvent removed in vacuo to give the crude product, which was purified as described.

*Authors Comments  
Lead Reference A. Henderson, 2010, "Organozirconium approaches to small molecule synthesis",PhD thesis, University of Southampton
Other References  
Multimedia Content  
*Data 1H NMR (300 MHz, CDCl3); 13C NMR (75 MHz, CDCl3)
#Data file 1
HNMR_117g.pdf
#Data file 2
CNMR_117g.pdf
#Data file 3  
#Data file 4  
#Data file 5  

SCHEME

*#Structure file (ChemDraw, ChemSketch or RXN file)
Scheme_117g.cdx
 
*#Image file (GIF or PNG)  
Scheme_117g.gif

Keywords

Compounds Keywords alkynes, aromatics
Reactions Keywords addition, substitution
Other Keywords  
Attached Files