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Chemical Structure| 693286-67-8 Chemical Structure| 693286-67-8

Structure of 693286-67-8

Chemical Structure| 693286-67-8

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Product Details of [ 693286-67-8 ]

CAS No. :693286-67-8
Formula : C9H10BNO2
M.W : 174.99
SMILES Code : CC1=C(B(O)O)C2=C(NC=C2)C=C1
MDL No. :MFCD12964847

Safety of [ 693286-67-8 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 693286-67-8 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 693286-67-8 ]

[ 693286-67-8 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 610794-15-5 ]
  • [ 693286-67-8 ]
YieldReaction ConditionsOperation in experiment
A solution of <strong>[610794-15-5]4-bromo-5-methylindole</strong> (800 mg, 3.8 mmol) in anhydrous ether (8 ML) is added with stirring to a suspension of potassium hydride (560 mg, 4.2 mmol, 30% dispersion in mineral oil) in anhydrous ether at 0 C under argon. The resulting mixture is cooled to-78 C and TERT-BUTYLLITHIUM (4.9 ML of 1.7 M in pentane, 8.4 mmol) is slowly added. The resulting cream-colored mixture is stirred at-78C for 1 hour. Tributylborate (3.1 mL, 11.4 mmol) is slowly added and the reaction mixture is stirred for 1 hour at-78C before being allowed to slowly warm to room temperature. More anhydrous ether is added to facilitate stirring. After stirring for 24 hours, the resulting sticky mixture is diluted with ether and transferred in portions with stirring to a precooled solution of 1 M phosphoric acid (50 mL). After stirring for 30 minutes, the acidic mixture is extracted with diethyl ether (75 mL * 3) and the combined extracts are extracted with 1 N sodium hydroxide (20 mL * 4). The combined base extracts are cooled with an ice bath, acidified with 1 M phosphoric acid and extracted with ethyl acetate (20 mL * 3). The combined extracts are washed with brine (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated to obtain a beige residue. The residue is triturated with hexane to obtain the desired 5-methylindole-4-boronic acid as a beige gum (230 mg).
To a suspension of potassium hydride (143 mg, 1.07 mmol) in anhydrous diethyl ether (2 mL) at 0 0C is added a solution of <strong>[610794-15-5]4-bromo-5-methylindole</strong> (186 mg, 0.89 mmol) in diethyl ether (2 mL). The reaction mixture is cooled to -78 0C prior to dropwise addition of tert-butyllithium (1.56 mL of a 1.7 M solution in hexane, 2.7 mmol). The resulting mixture is stirred for 40 min prior to slow addition of tributylborate (980 muL, 3.54 mmol) and the reaction mixture is allowed to slowly warm to ambient temperature. After stirring for 18 h the reaction is quenched by the addition of phosphoric acid (IM) and extraction with diethyl ether. The organic layer is back-extracted with aqueous sodium hydroxide (IM) and the resulting aqueous layer is acidified with phosphoric acid (IM) and extracted with ethyl acetate. The organic layer was washed with brine, dried (MgSO4), filtered and concentrated in vacuo. Trituration with hexane affords the desired 5- methylindole-4-boronic acid as a beige gum.
A solution of <strong>[610794-15-5]4-bromo-5-methylindole</strong> (800 mg, 3.8 mmol) in anhydrous ether (8 mL) is added with stirring to a suspension of potassium hydride (560 mg, 4.2 mmol, 30% dispersion in mineral oil) in anhydrous ether at 0 C under argon. The resulting mixture is cooled to -78 C and rert-butyllithium (4.9 mL of 1.7 M in pentane, 8.4 mmol) is slowly added. The resulting cream-colored mixture is stirred at -78 C for 1 h. Tributylborate (3.1 mL, 11.4 mmol) is slowly added and the reaction mixture is stirred for 1 h at -78 C before being allowed to slowly warm to room temperature. More anhydrous ether is added to facilitate stirring. After stirring for 24 h, the resulting sticky mixture is diluted with ether and transferred in portions with stirring to a precooled solution of 1 M phosphoric acid (50 mL). After stirring for 30 min, the acidic mixture is extracted with diethyl ether (75 mL x 3) and the combined extracts are extracted with 1 N sodium hydroxide (20 mL x 4). The combined base extracts are cooled with an ice bath, acidified with 1 M phosphoric acid and extracted with EtOAc (20 mL x 3). The combined extracts are washed with brine (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated to obtain a beige residue. The residue is triturated with hexane to obtain the desired 5-methylindole-4-boronic acid as a beige gum.
A solution of <strong>[610794-15-5]4-bromo-5-methylindole</strong> (800 mg, 3.8 mmol) in anhydrous ether (8 mL) is added with stirring to a suspension of potassium hydride (560 mg, 4.2 mmol, 30% dispersion in mineral oil) in anhydrous ether at 0 C under argon. The resulting mixture is cooled to-78 C and tert-butyllithium (4.9 mL of 1.7 M in pentane, 8.4 mmol) is slowly added. The resulting cream- colored mixture is stirred at-78 C for 1 hour. Tributylborate (3.1 mL, 11.4 mmol) is slowly added and the reaction mixture is stirred for 1 hour at-78 C before being allowed to slowly warm to room temperature. More anhydrous ether is added to facilitate stirring. After stirring for 24 h, the resulting sticky mixture is diluted with ether and transferred in portions with stirring to a precooled solution of 1 M phosphoric acid (50 mL). After stirring for 30 min, the acidic mixture is extracted with diethyl ether (75 mL x 3) and the combined extracts are extracted with 1 N sodium hydroxide (20 mL x 4). The combined base extracts are cooled with an ice bath, acidified with 1 M phosphoric acid and extracted with EtOAc (20 mL x 3). The combined extracts are washed with brine (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated to obtain a beige residue. The residue is triturated with hexane to obtain the desired 5-methylindole-4-boronic acid as a beige gum.
Fuming nitric acid (>90% yellow fuming HN03) is slowly added to a solution of 2-bromo-m-xylene (20 g, 150 mmol) in acetic acid (100 mL) cooled in an ice bath (above freezing point). The resulting mixture is allowed to warm to room temperature, stirred for 1 h, and heated at 80 C for 2 h or until the reaction is complete by GC/MS analysis following micro-scale base work-up. The reaction mixture is cooled to room temperature and poured into ice/water with stirring. The resulting yellow precipitates are collected by suction filtration and air dried to obtain 2,6-dimethyl-3-nitrobromobenzene. Bredereck's reagent (tert-butoxybis(dimethylamino)methane (16 g, 91 mmol) is added to a solution of 2,6-dimethyl-3-nitrobromobenzene (20 g, 87 mmol) in anhydrous DMF (120 mL) at room temperature. The reaction mixture is heated at 120-125 C under N2 for 5 h or until starting material is mostly consumed according to TLC. The reaction mixture is allowed to cool to room temperature, poured into water (300 mL), and extracted with dichloromethane (100 mL x 3). The combined extracts are dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a mixture of enamines as a dark brown oil. This material is used in the next step without purification. The crude mixture is dissolved in acetic acid/water (250 mL of 4 : 1), cooled to 0 C and treated with zinc dust (57 g, 870 mmol) added slowly in portions. After complete addition, the reaction mixture is heated at 110 C for 4 h. Zinc is removed by filtration through a celite pad and the filtrate is extracted with dichloromethane (100 mL x 3). The combined extracts are dried over anhydrous sodium sulfate, concentrated, and purified by flash chromatography on silica gel (EtOAc/Hexane 1:20) to obtain <strong>[610794-15-5]4-bromo-5-methylindole</strong> as a light purple oil. A solution of <strong>[610794-15-5]4-bromo-5-methylindole</strong> (800 mg, 3.8 mmol) in anhydrous ether (8 mL) is added with stirring to a suspension of potassium hydride (560 mg, 4.2 mmol, 30% dispersion in mineral oil) in anhydrous ether at 0 C under argon. The resulting mixture is cooled to-78 C and tert-butyllithium (4.9 mL of 1.7 M in pentane, 8.4 mmol) is slowly added. The resulting cream- colored mixture is stirred at -78 C for 1 h. Tributylborate (3.1 mL, 11.4 mmol) is slowly added and the reaction mixture is stirred for 1 h at -78 C before being allowed to slowly warm to room temperature. More anhydrous ether is added to facilitate stirring. After stirring for 24 h, the resulting sticky mixture is diluted with ether and transferred in portions with stirring to a precooled solution of 1 M phosphoric acid (50 mL). After stirring for 30 min, the acidic mixture is extracted with diethyl ether (75 mL x 3) and the combined extracts are extracted with 1 N sodium hydroxide (20 mL x 4). The combined base extracts are cooled with an ice bath, acidified with 1 M phosphoric acid and extracted with ethyl acetate (20 mL x 3). The combined extracts are washed with brine (20 mL), dried over anhydrous sodium sulfate, filtered and concentrated to obtain a beige residue. The residue is triturated with hexane to obtain the desired 5-methylindole-4-boronic acid as a beige gum.

 

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