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Chemical Structure| 1276056-83-7 Chemical Structure| 1276056-83-7

Structure of 1276056-83-7

Chemical Structure| 1276056-83-7

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Product Details of [ 1276056-83-7 ]

CAS No. :1276056-83-7
Formula : C5H7BrN2O
M.W : 191.03
SMILES Code : OCC1=C(Br)C=NN1C
MDL No. :MFCD18793417
InChI Key :YLTQBUUGYXTAHV-UHFFFAOYSA-N
Pubchem ID :57415773

Safety of [ 1276056-83-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H332-H335
Precautionary Statements:P261-P280-P305+P351+P338

Application In Synthesis of [ 1276056-83-7 ]

* 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 [ 1276056-83-7 ]

[ 1276056-83-7 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 84547-84-2 ]
  • [ 1276056-83-7 ]
YieldReaction ConditionsOperation in experiment
92% With borane-THF; In tetrahydrofuran; at 80℃; for 12.0h;Inert atmosphere; A mixture of 4-bromo- 1 -methyl - 1 //-pyrazole-5-carboxylic acid (4.80 g, 23.4 mmol, CAS 84547-84-2) in THF (40.00 mL) was added BH3/THF (93.60 mL, 1 M). The mixture was stirred at 80 C for 12 hours under N2 atmosphere. To the mixture was added EtOAc (200 mL). The mixture was washed with saturated NaHCO, (200 mL x 3). The organic layer was dried over anhydrous Na2S04, filtered and concentrated to give a residue. The residue was purified by column chromatography (petroleum ether : ethyl acetate = 100 : 0 to 100 : 10) to give (4-bromo-l -methyl- li-pyrazol-5-yl)methanol (4.10 g, 92% yield) as a white solid. 1HNMR (400 MHz, DMSO-6): d 7.26 (s, 1H), 4.62 (s, 2H), 3.86 (s, 3H).
77% With borane-THF; In tetrahydrofuran; at 50℃; for 48.0h; A mixture of 4-bromo- 1 -methyl- 1 H-pyrazole-5-carboxylic acid (5.0 g, 24.4 mmol) and BH3.THF (36.6 mL of a 1 M solution in THF, 36.6 mmol) in THF (50 mL) was stirred at 50 C for 2 days; at this point LCMS showed the completion of the reaction. The reaction was cooled to RT and cautiously quenched with aq. 1N HC1 and stirred at RT for 1 h, after which the mixture was extracted with EtOAc (3 X 50 mL). The combined organic extracts were concentrated in vacuo. The residue was chromato graphed (80 g Si02; continuous gradient from 0% to 100% EtOAc in hexanes, 25 min) to give the title compound (3.60 g, 18.9 mmol, 77 % yield) as a white solid. LCMS, [M+H]+ = 193.0.
77% With borane-THF; In tetrahydrofuran; at 50℃; for 48.0h;Inert atmosphere; A mixture of 4-bromo- 1 -methyl- 1 H-pyrazole-5-carboxylic acid (5.0 g, 24.4 mmol) and BH3.THF (36.6 mL of a 1 M solution in THF, 36.6 mmol) in THF (50 mL) was stirred at 50 C for 2 days; at this point LCMS showed the completion of the reaction. The reaction was cooled to RT and cautiously quenched with aq. IN HC1 and stirred at RT for 1 h, after which the mixture was extracted with EtOAc (3 X 50 mL). The combined organic extracts were concentrated in vacuo. The residue was chromatographed (80 g Si02; continuous gradient from 0% to 100% EtOAc in hexanes, 25 min) to give the title compound (3.60 g, 18.9 mmol, 77 % yield) as a white solid. LCMS, [M+H]+ = 193.0.
77% With borane-THF; In tetrahydrofuran; at 50℃; for 48.0h; A mixture of 4-bromo-l-methyl-lH-pyrazole-5-carboxylic acid (5.0 g, 24.4 mmol) and BH3.THF (36.6 mL of a 1 M solution in THF, 36.6 mmol) in THF (50 mL) was stirred at 50 C for 2 days; at this point LCMS showed the completion of the reaction. The reaction was cooled to RT and cautiously quenched with aq. 1N F1C1 and stirred at RT for 1 h, after which the mixture was extracted with EtOAc (3 X 50 mL). The combined organic extracts were concentrated in vacuo. The residue was (0667) chromatographed (80 g S1O2; continuous gradient from 0% to 100% EtOAc in hexanes, 25 min) to give the title compound (3.60 g, 18.9 mmol, 77 % yield) as a white solid. LCMS, [M+H]+ = 193.0.
Example 44 (4-{3-[(1S)-1-(2-Chloro-3-fluoro-6-methoxyphenyl)ethyl]-1H-pyrrolo[2,3-b]pyridin-5-yl}-1-methyl-1H-pyrazol-5-yl)methanol To a solution of <strong>[84547-84-2]4-bromo-2-methyl-2H-pyrazole-3-carboxylic acid</strong> (20.0 mg, 0.0976 mmol) in THF (3 mL, 40 mmol) was added 1.0 M of BH3.THF in THF (0.49 mL, 0.49 mmol), and the resulting solution was heated to 60 C. overnight. The material was extracted with EtOAc, and washed with sat. NaHCO3 (3*) to remove carboxylic acid starting material. The organic layer was concentrated in vacuo. 3-[(S)-1-(2-Chloro-3-fluoro-6-methoxyphenyl)-ethyl]-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine (15.0 mg, 0.0348 mmol), (1,1'bis-(diphenylphosphino)-ferrocene) palladium dichloride (3.57 mg, 0.00488 mmol), K2CO3 (20.2 mg, 0.146 mmol) and 4:1 dioxane:H2O (1 mL, 10 mmol) were added, and the mixture was heated to 95 C. for 30 min. The solution was used directly for HPLC purification, and the fractions containing the pure product were concentrated in vacuo to afford the title compound as a white solid. 1H NMR (400 MHz, CD3OD): delta=1.80 (d, J=7.1 Hz, 3H), 3.67 (br. s., 3H), 3.96 (s, 3H), 4.55 (s, 2H), 5.08-5.17 (m, 1H), 6.90 (dd, J=9.1, 4.3 Hz, 1H), 7.08 (t, J=8.8 Hz, 1H), 7.34 (d, J=1.3 Hz, 1H), 7.46 (s, 1H), 7.53 (s, 1H), 8.15-8.22 (m, 1H). MS (ES+): m/z=415.13/417.13 (100/50) [MH+]. HPLC: tR=1.37 min (polar-3 min, UPLC-ACQUITY).
With borane-THF; In tetrahydrofuran; at 20 - 50℃; for 73.0h; To a RT solution of 4-bromo-l -methyl- lH-pyrazole-5-carboxylic acid (2.0 g, 9.8 mmol) in THF (24.4 ml) was added BH3.THF complex (19.5 mL of a 1M solution in TFIF, 19.5 mmol) and the reaction was stirred at RT for 1 h, then was heated to 50 C and stirred at 50 C for 3 days, then was cooled to RT. The reaction was quenched slowly by dropwise addition of 1M aq. HC1 (10 mL) at RT, then was partitioned between CH2Cl2 (30 mL) and water (30 mL). The aqueous phase was extracted with CFLCh (2 X 30 mL) and the combined organic extracts were dried (MgS04) and filtered through a pad of Si02 to give the crude title compound (1.86 g, 100 % yield) as a white solid. LCMS, [M + H]+ = 191.0, 193.0.

 

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