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5th March 2013 @ 00:01
Mnr: MNR101-110

See Also

Synthesis of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl)benzenesulfonamide (JRC 29-1)

Upscaled synthesis of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl)benzenesulfonamide (JRC 29-2)

Upscaled synthesis of (3-sulfamoylphenyl)boronic acid (JRC 29-3)

Synthesis of (3-sulfamoylphenyl)boronic acid (JRC 29-4)

Hazard Assessment

HIRAC MNR103.pdf

Procedure

3-bromobenzenesulfonamide (1.5 g, 6.35 mmol), potassium acetate (2.49 g, 25 .4 mmol) and bis(pinacolatodiborane) (2.42 g, 9.53 mmol) were dissolved in 1,4-dioxane (32 mL). Argon was bubbled through the suspension for ten minutes before [1,1-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.230g, 0.32 mmol) was added and the suspension heated at reflux with stirring for 22 h. The black solution was allowed to cool to room temperature and the filtered over celite being washed with MeOH (25 mL) and EtOAc (25 mL).  The filtrate was concentrated to yield a black sludge.  Recrystalisation was attempted using 50% EtOH/H2O (35 mL) but no crystals formed.  The mixture was contrantrated and ran through a coloumn.

 

TLC

TLC in 100% EtOAC, SM, RXN, co-spot, JRC29-4 - traces of SM but looks mainily like product, JRC28-4 looks to have decomposed a little.

 

2013-03-05 12.04.19.jpg

Column 40-100% EtOAc/Hex

 

Fracs 1-20    - 3.069 g - product and excess bis(pinacolatodiborane) as a pale yellow solid

Fracs 21-58  - 0.446 g - product and some other aromatic compound as a light brown solid

 

NMR

Starting Material

mnr103-1_sm_1H.pdf
mnr103-1_sm.zip

Frac 1-20

mnr103-1_frac1-20_1H.pdf
mnr103-1_frac1-20.zip

Frac21-58

mnr103-1_frac21-58_1H.pdf
mnr103-1_frac27-58.zip

Product - JRC29-4

jrc29-4_1H.pdf
mnr_jrc29-4.zip

Overlay of Aromatic Region

mnr103-1_overlay_1H.pdf

 

Post Column

Fracs 1-20 were triturated using petroleum benzine and filtered to give nice off white crystaline solid (1.036 g, 3.65 mmol, 58%) - more product in fracs 21-58 but not isolated at this stage.

 

mnr103-1_frac1-20_triturated_1H.pdf
mnr103-1_f1-20_trit.zip

Strings

Starting material

InChI=1S/C6H6BrNO2S/c7-5-2-1-3-6(4-5)11(8,9)10/h1-4H,(H2,8,9,10)

Product

InChI=1S/C12H18BNO4S/c1-11(2)12(3,4)18-13(17-11)9-6-5-7-10(8-9)19(14,15)16/h5-8H,1-4H3,(H2,14,15,16)

Linked Posts
Attached Files
MNR103-1_table.PNG
HIRAC MNR103.pdf
MNR103_scheme.png
2013-03-05 12.04.19.jpg
jrc29-4_1H.pdf
mnr103-1_frac1-20_1H.pdf
mnr103-1_frac21-58_1H.pdf
mnr103-1_sm_1H.pdf
mnr103-1_overlay_1H.pdf
mnr103-1_frac1-20.zip
mnr103-1_frac27-58.zip
mnr103-1_sm.zip
mnr_jrc29-4.zip
mnr103-1_frac1-20_triturated_1H.pdf
mnr103-1_f1-20_trit.zip
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