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Chemical Structure| 1220696-57-0 Chemical Structure| 1220696-57-0

Structure of 1220696-57-0

Chemical Structure| 1220696-57-0

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Product Details of [ 1220696-57-0 ]

CAS No. :1220696-57-0
Formula : C12H16BF2NO2
M.W : 255.07
SMILES Code : CC1(C)C(C)(C)OB(C2=CN=C(C(F)F)C=C2)O1
MDL No. :MFCD18733449
InChI Key :OTTJYNVKDDYWAP-UHFFFAOYSA-N
Pubchem ID :59535308

Safety of [ 1220696-57-0 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H315-H318-H335
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340+P312-P305+P351+P338-P310-P332+P313-P362-P403+P233-P405-P501
Class:8
UN#:1759
Packing Group:

Application In Synthesis of [ 1220696-57-0 ]

* 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 [ 1220696-57-0 ]

[ 1220696-57-0 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 845827-13-6 ]
  • [ 73183-34-3 ]
  • [ 1220696-57-0 ]
YieldReaction ConditionsOperation in experiment
89% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 20 - 100℃; for 1h;Inert atmosphere; To a solution of <strong>[845827-13-6]5-bromo-2-(difluoromethyl)pyridine</strong> (1.0 g, 4.8 mmol) and bis(pinacolato)diboron (1.34 g, 5.3 mmol) in dioxane (5 mL) was added potassium acetate (1.4 g, 14.4 mmol) at room temperature. Nitrogen gas was bubbled through the mixture for 5 mins and 1 ,1 '-bis(diphenylphosphino)ferrocenepalladium(ll) chloride (264 mg, 0.36 mmol) was then added. The mixture was heated at 100 C for 1 hour. The reaction mixture was then diluted with EtOAc (50 mL), filtered over Celite and washed with EtOAc (50 mL). The filtrate was concentrated at reduced pressure and the residue was purified by Biotage Isolera chromatography [SNAP Cartridge KP-Sil 50 g; 0-100% EtOAc in heptane, 16 column volumes]. The product containing fractions were combined and concentrated in vacuo to afford the title compound (1.15 g, 89% yield) as pale yellow crystalline solid.1H NMR (500 MHz, Chloroform-d) delta [ppm] 8.97 (s, 1 H), 8.21 (dd, J = 7.7, 1 .4 Hz, 1 H), 7.62 (d, J = 7.7 Hz, 1 H), 6.64 (t, J = 55.4 Hz, 1 H), 1.36 (s, 12H).LCMS (Analytical Method A): Rt = 0.78 mins, MS (ESIpos) m/z = 173.9 (Mass of boronic acid + H)
89% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100℃; for 1h;Inert atmosphere; To a solution of <strong>[845827-13-6]5-bromo-2-(difluoromethyl)pyridine</strong> (1 .0 g, 4.8 mmol) and bis(pinacolato)diboron (1 .34 g, 5.3 mmol) in dioxane (5 mL) at RT was added potassium acetate (1 .4 g, 14.4 mmol). Nitrogen gas was bubbled through the mixture for 5 mins and 1,1 '-bis(diphenylphosphino)ferrocenepalladium(ll) chloride (264 mg, 0.36 mmol) was added and the mixture heated at 100 C for 1 hour. The reaction mixture was then diluted with EtOAc (50 mL), filtered over Celite and washed with EtOAc (50 mL). The filtrate was concentrated at reduced pressure and the residue purified by Biotage Isolera chromatography (Biotage SNAP Cartridge KP-Sil 50 g; eluting with 0-100% EtOAc in heptane) to give the title compound (1 .15 g, 89% yield) as a pale yellow crystalline solid. 1H NMR (500 MHz, chloroform-d) delta [ppm] 8.97 (s, 1 H), 8.21 (dd, J = 7.7, 1.4 Hz, 1 H), 7.62 (d, J = 7.7 Hz, 1 H), 6.64 (t, J = 55.4 Hz, 1 H), 1 .36 (s, 12H). LCMS (Analytical Method A): Rt = 0.78 mins, MS (ESIPos) m/z = 173.9 (mass of boronic acid + H)
82% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100℃; for 0.75h; General procedure: Tributyl(thiazol-4-yl)stannane Synthesis of 3-Methyl-7 -(4,4,5, 5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 ,2,4,5-tetrahydro- 3-benzazepine 4.3100 mg of 7-bromo-3-methyl-1 ,2,4,5-tetrahydro-3-benzazepine, 127 mg bis-(pinacolato)- diboron, 20 mg 1 , -bis(diphenylphospino)ferrocenedichloropalladium(ll) and 123 mg potassium acetate were suspended in 2 mL dioxane and the mixture stirred at 100 C for 1 .25 h. The mixture was diluted after cooling with dioxane, filtered through Celite, washed with dioxane and the solvent was evaporated in vacuo to yield 220 mg (92 %, content 50 %) 3-methyl-7-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-1 ,2,4,5-tetrahydro-3-benzazepine 4.3 as solid, which was used in the next step without further purification.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 23 - 80℃; for 24h;Inert atmosphere; Sealed tube; Example 33 Preparation of 2-(difluoromethyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Dichloro[1,1'-bis(diphenylphosphino)ferrocene]-palladium(II) (42 mg, 0.058 mmol, 0.03 equiv), potassium acetate (570 mg, 5.8 mmol, 3.0 equiv), and diboron bis(pinocol) ester (490 mg, 1.9 mmol, 1.0 equiv) were sequentially added to a stirred solution of <strong>[845827-13-6]5-bromo-2-(difluoromethyl)pyridine</strong> (400 mg, 1.9 mmol, 1.0 equiv) in N,N-dimethylformamide (4.8 mL) at 23 C. The resulting dark brown mixture was sealed under nitrogen, heated to 80 C., and stirred for 24 h. The cooled reaction mixture was diluted with water (400 mL) and extracted with Et2O (4*100 mL). The combined organic layers were dried (MgSO4), gravity filtered, and concentrated by rotary evaporation to afford the title compound as a brown semisolid (500 mg, 99% crude yield): IR (neat film) 2996 (s), 2935 (w), 1668 (w), 1600 (m) cm-1; 1H NMR (300 MHz, CDCl3) delta 8.96 (br s, 1H), 8.21 (dd, J=8, 1.5 Hz, 1H), 7.62 (d, J=8 Hz, 1H), 6.64 (t, J=55 Hz, 1H), 1.36 (s, 9H).
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100℃; for 1h;Inert atmosphere; [00467] To a mixture of Example 82a (50 mg, 0.24 mmol), Example 82b (66 mg, 0.26 mmol), and KOAc (47 mg, 0.48 mmol) in Dioxane (2 mL) was added Pd(dppf)Cl2 (17 mg, 0.024 mmol). Then the mixture was degassed by bubbling N2 through the solution for 2 min using a syringe needle. After heated at 100C for 1 h, the mixture was cooled to r.t. and filtered. The filtrate Example 82c (2 mL) was used for next step directly. LCMS [M+l]+ = 256.0

 

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