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Chemical Structure| 16628-26-5 Chemical Structure| 16628-26-5

Structure of 16628-26-5

Chemical Structure| 16628-26-5

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Product Details of [ 16628-26-5 ]

CAS No. :16628-26-5
Formula : C9H7BrN2OS
M.W : 271.13
SMILES Code : CC(NC1=NC2=CC=C(Br)C=C2S1)=O
MDL No. :MFCD00608268

Safety of [ 16628-26-5 ]

Application In Synthesis of [ 16628-26-5 ]

* 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 [ 16628-26-5 ]

[ 16628-26-5 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 16628-26-5 ]
  • [ 73183-34-3 ]
  • [ 885069-14-7 ]
YieldReaction ConditionsOperation in experiment
97% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 90℃; for 8h;Inert atmosphere; A mixture of N-(6-bromobenzo[d]thiazol-2-yl)acetamide (2.10 g, 7.75 mmol), bis(pinacolato)diboron (3.00 g, 11.8 mmol), Pd(dppf)Cl2 (560 mg, 0.77 mmol), KOAc (3.00 g, 30.6 mmol) and DMSO (50 mL) was stirred at 90 C under N2 atmosphere for 8 h. After cooling to room temperature, the mixture was filtered. The filtrate was diluted with ethyl acetate (200 mL), washed with brine (20 mL * 3), dried overNa2SO4, and concentrated. The resulting residue was washed with petroleum ether (50 mL) to give a pale brown solid (2.40 g, 97%).
97% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 90℃; for 8h;Inert atmosphere; A 100 mL flask was charged with A42-1 (2.10 g, 7.75 mmol), bis(pinacolato)diboron (3.00 g, 11.8 mmol), KOAc (3.00 g, 30.6 mmol) and Pd(dppf)Cl2 (560 mg, 0.765 mmol) followed by addition of 50 mL DMSO. The equipment was evacuated and refilled with N2 three times. The reaction was carried out at 90 C for 8 h. After cooled to r.t., the mixture was filtered. The filtrate was diluted with ethyl acetate. The organic phase was washed with brine. The organic phase was dried with Na2S04 and the solvent was removed by vacuum. The residue was recrystallized in petroleum ether to give A42-2 as a brown solid (2.40 g, 97%). FontWeight="Bold" FontSize="10" H NMR(300 MHz, CDC13) delta 8.30 (s, 1H), 7.87 (d, / = 8.0 Hz, 1H), 7.72 (d, / = 8.0 Hz, 1H), 2.30 (s, 3H), 1.37 (s, 12H).
97% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 90℃; for 8h;Inert atmosphere; In a 100 mL round bottom flask,I-1 (2.10 g, 7.75 mmol) was added in sequence.Riboponic boron ester (3.00 g, 11.8 mmol),KOAc (3.00 g, 30.6 mmol)And Pd(dppf)Cl2(560mg, 0.765mmol)Soluble in 50mL DMSO,After reacting at 90C for 8h under nitrogen protection,Filtration, the filtrate was diluted with ethyl acetate, the organic phase was washed with saturated brine, and the organic phase was dried and evaporated. The solvent was derotated and the solute was recrystallized from petroleum ether to give a pale yellow solid (2.40 g, 97%).
93% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 110℃; for 2h; To a stirred mixture of N-(6-bromobenzo[d]thiazol-2-yl) acetamide (I-3) (32.5 g, 120 mmol) and 4,4,4?,4?,5,5,5?,5?-octamethyl-2,2?-bi(1,3,2-dioxaborolane) (I-4) (36.5 g, 144 mmol) in 1,4-dioxane (1000 mL), dppf(PdCl2) (10 g, 12 mmol) and KOAc (70 g, 720 mmol) were added sequentially. The resulting mixture was degassed and back-filled with argon three times and then stirred at 110 C. for 2 h. The mixture was allowed to cool to RT, filtered through silica gel (10 g) and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (10-50% ethyl acetate/petroether) to afford the desired product, N-(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[d]thiazol-2-yl)acetamide (I-5) (35 g, 93% yield) as a white solid. ESI-MS (M+H)+ m/z: 317.05.
75% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 5h; Intermediate 2: Formation of Lambda/-[6-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)- 1 ,3-benzothiazol-2-yl]acetamide A mixture of Lambda/-(6-bromo-1 ,3-benzothiazol-2-yl)acetamide (2.0 g, 7.38 mmol), bis(pinacolato)diboron (3.75 g, 14.75 mmol), 1 ,1'- bis(diphenylphosphino)ferrocenedichloro palladium(ll) (325 mg, 0.44 mmol) and potassium acetate (3.62 g, 36.88 mmol) in DMSO (24 ml) was prepared and the resulting mixture was heated at 800C for 5 hours. The reaction mixture was cooled at RT and poured into water (80 ml_), then extracted with EtOAc (2x50 ml_). The organic layers were combined, dried (MgSO4) and the solvents were concentrated under reduced pressure to give a brown oil. Purification by precipitation from methanol gave the title compound as an off-white powder (1.75 g, 75%). UPLC/MS, M+(ESI): 319.2,M-(ESI): 317.3. 1 H-NMR (DMSO-d6): delta 12.44 (s, 1 H), 8.26 (brs, 1 H), 7.71 (brs, 2H), 2.21 (s, 3H), 1.31 (s, 12H).
75% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 2h;Inert atmosphere; Step 2: n-[6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzothiazol-2-yl]-acetamide A mixture of n-(6-bromo-benzothiazol-2-yl)-acetamide (1.35 g, 5 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (2.51 g, 10 mmol), Pd(dppf)Cl2 (0.25 g, 0.3 mmol) and potassium acetate CH3COOK (2.45 g, 25 mmol)in DMSO (20 mL) was stirred at 80 for 2 hrs under N2. Then the mixture was cooled to room temperature, added H2O (100 mL) and extracted with EtOAc (40 mL×3). The combined organic layers were concentrated in vacuo. The residue was purified by column chromatography on silica gel (PE:EtOAc=3:1) to give n-[6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzothiazol-2-yl]-acetamide (1.2 g, yield 75%) as a yellow solid.
75% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 5h; A mixture of lambda/-(6-bromo-1 ,3-benzothiazol-2-yl)acetamide (2.0 g, 7.38 mmol), bis(pinacolato)diboron (3.75 g, 14.75 mmol), 1 ,1 '- bis(diphenylphosphino)ferrocenedichloro palladium(ll) (325 mg, 0.44 mmol) and potassium acetate (3.62 g, 36.88 mmol) in DMSO (24 ml) was prepared and the resulting mixture was heated at 800C for 5 hours. The reaction mixture was cooled at RT and poured into water (80 ml_), then extracted with EtOAc (2x50 ml_). The organic layers were combined, dried (MgSO4) and the solvents were concentrated under reduced pressure to give a brown oil. Purification by precipitation from methanol gave the title compound as an off- white powder (1.75 g, 75%). UPLC/MS, M+(ESI): 319.2, M-(ESI): 317.3. 1 H- NMR (DMSO-d6): delta 12.44 (s, 1 H), 8.26 (brs, 1 H), 7.71 (brs, 2H), 2.21 (s, 3H), 1.31 (s, 12H).
72% With potassium acetate;tetrakis(triphenylphosphine) palladium(0); In dimethyl sulfoxide; at 90℃; for 7h;Inert atmosphere; Sealed vessel; As shown in step 2-ii of Scheme 2, lambda/-(6-bromobenzo[
70% With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 100℃; Step 7; To a solution of 50 (5 g, 0.019 mol) in DMSO (100 mL), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (9.7 g), potassium acetate (7.5 g), and Pd(dppf)Cl2 (1.5 g) were added. The solution was stirred at 100C overnight. The reaction mixture was cooled, and then partitioned between ethyl acetate and water. The organic layer was washed sequentially with water and brine, and then dried over sodium sulfate. The solvent was evaporated off to yield target compound 51 as a white solid (4.2 g, y. 70%). 1H-NMR (DMSO-D6): 8.32 (s, 1H), 7.88 (d, 1H, J = 8.1), 7.76 (d, 1H, J = 8.1), 2.27 (s, 3H), 1.37 (s, 12H).
With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 100℃; Step 2. N-(6-(4,4,5,5-tetramethyl-l .3.2-dioxaborolan-2-yl)benzordlthiazol-2-yl)acetamide; N-(6-Bromobenzo[d]thiazol-2-yl)acetamide (10.29 g, 38.0 mmol), 4,4,5,5-tetramethyl-2-(4,4,5,5- tetramethyl-1 ,3,2-dioxaborolan-2-yl)-l ,3,2-dioxaborolane (13.34 g, 52.53 mmol), and potassium acetate (14.9 g, 152 mmol) were suspended in DMSO (140 mL) to which 1,1'- bis(diphenylphosphino)ferrocene]dichloride palladium(ii) (2.81 g, 3.84 mmol) (a 1 : 1 complex with DCM, 3.44 mmol) was added. Argon was bubbled through the suspension for about 1 minute, and the reaction flask was placed in a preheated oil bath (100 C) and heated while stirring under argon overnight. The reaction was then cooled to RT and filtered through Celite (diatomaceous earth), which was washed with MeOH. The filtrate was partially concentrated, and poured into water (500 mL), and extracted repeatedly with DCM. The organic extracts were combined, concentrated, and purified on a silica gel filter (~ 3 inches; DCM to 50: 1 to 30: 1 DCM / MeOH). The fractions containing product were collected, concentrated, and dried under vacuum to afford the desired boronic ester (14.22 g). MS (ESI pos. ion) m/z: 319. Calculated exact mass for C15Hi9BN2O3S: 318.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; A compound of Formula P-1 is treated with, for example, potassium thiocyanate and bromine in acetic acid to produce a compound of Formula P-2. The compound of Formula P-2 is treated with an acetylating reagent such as acetyl chloride to produce a compound of Formula P-3. The compound of P-3 is reacted with, for example, bis(pinacolato)diboron (compound P-4) in the presence of a catalyst such as palladium chloride to produce a compound of Formula P-5.
6 mg With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 100℃; for 5h;Inert atmosphere; To a solution of compound 14 (20 mg, 0.078 mmol) and bis(pinacolato)diboron (39.8 mg, 0.156 mmol) in DMSO (0.5mL) was added Pd(dppf)C12 (300 mg) and AcOK (38 g, 0.392 mmol) under N2 protection. The resulting mixture was stirred at 100 C for 5 hours. The mixture was dissolved in DCM and filtrated over celite. The orgatmc phase was washed w1th H20 and brine. After dried over Na2SO4, filtered and concentrated, the crude product was purified by Pre-TLC (PE / EA = 1 : 1) to give compound 15 (6 mg, yield: 25.3%) as solid. ?H-NIVIR (CDC13, 400 MHz) oe 7.89 (s, 1H), 7.77 (d, 1H, J 7.6 Hz), 7.57 (d, 1H, J 7.2 Hz), 2.52 (s, 3H), 1.36 (s, 12H).

 

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