Dimethylformamide → HCID 86622727, compound

HRID 1673250Notes

Reaction equation

HRID 1673250 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:13]=[C:12]3[O:14][C:15]([CH3:27])([CH3:26])[CH2:16][CH:17]([NH:18][C:19](=[O:25])[O:20][C:21]([CH3:24])([CH3:23])[CH3:22])[C:11]3=[CH:10][C:9]=2[C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][CH:29]=2)=[C:4]([Cl:35])[CH:3]=1.CN(C=O)C.CC1(C)C(C)(C)OB([C:49]2[CH:50]=[N:51][N:52](C(OC(C)(C)C)=O)[CH:53]=2)O1.C([O-])([O-])=O.[Na+].[Na+]>CCOC(C)=O.C1(P([Pd-4](P(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(P(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)P(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCO.O>[Cl:34][C:31]1[CH:30]=[CH:29][C:28]([C:9]2[CH:10]=[C:11]3[C@H:17]([NH:18][C:19](=[O:25])[O:20][C:21]([CH3:23])([CH3:22])[CH3:24])[CH2:16][C:15]([CH3:26])([CH3:27])[O:14][C:12]3=[N:13][C:8]=2[C:5]2[CH:6]=[CH:7][C:2]([C:49]3[CH:50]=[N:51][NH:52][CH:53]=3)=[CH:3][C:4]=2[Cl:35])=[CH:33][CH:32]=1

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 16217654tert-butyl 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylateHCID 71072739HCID 71072739, compound

Product 1

HCID 86622727HCID 86622727, compound

Reagents, catalysts & solvents 4

HCID 178420553HCID 178420553, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of Example 314 (1.5 g, 2.59 mmol) in a mixed solvent of 9.0 mL of DMF, 1.0 mL of H2O, and 2.0 mL of EtOH was added tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate (1.53 g, 5.19 mmol), Na2CO3 (830 mg, 7.78 mmol), and tetrakis(triphenylphosphino)palladium(0) (150 mg, 0.13 mmol). The mixture was stirred at 120° C. under microwave irradiation for 30 min. After cooling, the mixture was diluted with EtOAc (200 mL) and washed with H2O (50 mL) and brine (50 mL). The organic layer was separated, dried over MgSO4, and concentrated. Chromatography on a Biotage 40+M cartridge using 1:1 v/v EtOAc/hexanes as the eluant afforded the product: 1H NMR δ 1.49 (s, 3H), 1.52 (s, 9H), 1.58 (s, 3H), 1.84 (t, J=12.7, 1H), 2.33 (dd, J=6.2, 13.2, 1H), 4.78 (m, 1H), 5.15 (m, 1H), 7.09 (d, J=8.4, 2H), 7.20 (d, J=8.5, 2H), 7.26-7.41 (m, 3H), 7.74 (s, 1H), 7.85 (s, 2H).

Workup

  1. temperatureAfter cooling
  2. washwashed with H2O (50 mL) and brine (50 mL)
  3. customThe organic layer was separated
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customafforded the product

Sources & evidence

ORD record
ord-b98c937fe9fe410d992cb324e79ed861
Source dataset
uspto-grants-2011_08
Patent number
US07999107B2

Reaction notes

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