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Chemical Structure| 1126320-24-8

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Product Details of [ 1126320-24-8 ]

CAS No. :1126320-24-8
Formula : C12H14BClF2O2
M.W : 274.50
SMILES Code : CC1(C)C(C)(C)OB(C2=CC(F)=C(Cl)C=C2F)O1
MDL No. :MFCD22418270

Safety of [ 1126320-24-8 ]

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

Application In Synthesis of [ 1126320-24-8 ]

* 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 [ 1126320-24-8 ]

[ 1126320-24-8 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 61676-62-8 ]
  • [ 172921-33-4 ]
  • [ 1126320-24-8 ]
YieldReaction ConditionsOperation in experiment
72.3% <strong>[172921-33-4]1-Bromo-4-chloro-2,5-difluorobenzene</strong> (1.11 g, 4.9 mmol) was dissolved in tetrahydrofuran (THF; 15 mL) and cooled to -10° C. A 2.0M solution of isopropyl-magnesium chloride (2.7 mL, 5.4 mmol) in THF was added dropwise via syringe. The reaction mixture was stirred at -10° C. for 1 h, allowed to warm toward 0° C. for 1 h, then cooled again to -10° C. A solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.0 g, 5.4 mmol) in THF (1.0 mL) was then added dropwise and the reaction mixture was allowed to warm to ambient temperature. The reaction mixture was then added to diethyl ether and extracted with 1N sodium hydroxide twice. The aqueous phases were combined, acidified to pH 3 with concentrated HCl, and extracted with dichloromethane twice. The organic phases were combined, dried, filtered and concentrated to give the title compound (0.97 g, 72.3percent yield) that was used without further purification: 1H NMR (CDCl3) delta 7.45 (dd, 1H), 7.09 dd, 1H), 1.36 (s, 12H).
62% To a solution of l-bromo-4-chloro-2,5-difluorobenzene (200 mg, 0.879 mmol) in THF (10 mL) cooled to -10 0 C was added isopropylmagnesium bromide (1M in THF, 1.055 mL, 1.055 mmol) dropwise and the reaction mixture was stirred at this temperature for 1 h. The reaction mixture was then warmed to 0 °C and stirred for another 1 h. The resultant mixture was again cooled to -10 °C and treated dropwise with a solution of 2-isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (196 mg, 1.055 mmol). The reaction mixture was allowed to warm up to room temperature and treated with a saturated solution of ammonium chloride (3 mL). The layers were separated and aqueous layer was extracted with dichloromethane (2 x 2 mL). The combined organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to afford crude compound which was purified by column chromatography on a silica (7:3 - Ethyl acetate :hexane) to afford 2-(4- chloro-2,5-difluorophenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (150 mg, 0.546 mmol, 62percent yield) as an oil. 1H NMR (400 MHz, DMSO-d6) delta ppm 7.46 - 7.49 (m, 1H), 7.09 - 7.13 (m, 1 H), 1.35 (s, 12H).
62% To a solution of <strong>[172921-33-4]1-bromo-4-chloro-2,5-difluorobenzene</strong> (200 mg, 0.879 mmol) in THF (10 mL) cooled to -10°C was added isopropylmagnesium bromide (1M in THF, 1.055 mL, 1.055 mmol) dropwise and the reaction mixture was stirred at this temperature for 1 h. The reaction mixture was then warmed to 0 °C and stirred for another 1 h. The resultant mixture was again cooled to -10 °C and treated dropwise with a solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (196 mg, 1.055 mmol). The reaction mixture was allowed to warm up to room temperature and treated with a saturated solution of ammonium chloride (3 mL). The layers were separated and aqueous layer was extracted with dichloromethane (2x2 mL). The combined organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to afford crude compound which was purified by column chromatography on a silica (7:3 - Ethyl acetate:hexane) to afford 2-(4-chloro-2,5-difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (150 mg, 0.546 mmol, 62percent yield) as an oil.
3. Preparation of 2-(4-Chloro-2,5-difluorophenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane <strong>[172921-33-4]1-Bromo-4-chloro-2,5-difluorobenzene</strong> (1.11 g, 4.9 mmol) was dissolved in tetrahydrofuran (THF; 15 mL) and cooled to -10° C. A 2.0M solution of isopropyl-magnesium chloride (2.7 mL, 5.4 mmol) in THF was added dropwise via a syringe. The reaction mixture was stirred at -10° C. for 1 hour, allowed to warm toward 0° C. for 1 hour, then cooled to -10° C. again. A solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.0 g, 5.4 mmol) in THF (1.0 mL) was then added dropwise and the reaction was allowed to warm to ambient temperature. The reaction mixture was then added to diethyl ether and extracted with 1N sodium hydroxide twice. The aqueous phases were combined, acidified to pH 3 with concentrated HCl, and extracted with dichloromethane twice. The organic phases were combined, dried, filtered and concentrated to give the title compound (0.97 g, 72.3percent yield) that was used without further purification: 1H NMR (CDCl3): delta 7.45 (dd, 1H), 7.09 dd, 1H), 1.36 (s, 12H).

  • 2
  • [ 172921-33-4 ]
  • [ 73183-34-3 ]
  • [ 1126320-24-8 ]
YieldReaction ConditionsOperation in experiment
56% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100℃; for 18.0h;Inert atmosphere; A mixture of 1 -bromo-4-chloro-2,5-difluorobenzene (9.00 g, 39.6 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi-1 ,3,2-dioxaborolane (15.1 g, 59.5 mmol), and potassium acetate (7.8 g, 80 mmol) in 1 ,4-dioxane (80 mL) was degassed via sparging with nitrogen for 2 minutes. [1 , 1 '-Bis(diphenylphosphino)ferrocene]dichloropalladium(l l) (1 .5 g, 2.0 mmol) was then added, and the reaction mixture was stirred at 100 °C for 18 hours. It was then filtered; the filtrate was concentrated in vacuo and subjected to silica gel chromatography (Gradient: 0percent to 10percent ethyl acetate in petroleum ether), affording the product as a yellow solid. Yield: 6.1 g, 2.2 mmol, 56percent. 1H NMR (400 MHz, CDCI3) delta 7.48 (dd, J=8.8, 4.9 Hz, 1 H), 7.12 (dd, J=8.0, 5.6 Hz, 1 H), 1 .36 (s, 12H).
 

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