Sodium Carbonate → HCID 178519821, compound

HRID 1497424Notes

Reaction equation

HRID 1497424 reaction equation
Br[C:2]1[S:3][C:4]([CH:7]=[O:8])=[CH:5][N:6]=1.CC1(C)C(C)(C)OB([C:17]2[CH:21]=[CH:20][N:19](C(OC(C)(C)C)=O)[N:18]=2)O1.C([O-])([O-])=O.[Na+].[Na+].CO.C(Cl)Cl>C1(C)C=CC=CC=1.CCO.C1C=CC([P]([Pd]([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)=CC=1>[NH:18]1[CH:17]=[CH:21][C:20]([C:2]2[S:3][C:4]([CH:7]=[O:8])=[CH:5][N:6]=2)=[N:19]1

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 27732592-Bromo-1,3-thiazole-5-carbaldehydeHCID 21226129Dichloromethane methanolHCID 46705337tert-Butyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate

Product 1

HCID 178519821HCID 178519821, compoundYield 33.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 2-bromothiazole-5-carbaldehyde (0.8 g, 4.16 mmol) in toluene (6 mL) and EtOH (5 mL), tert-butyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate (1.8 g, 6.2 mmol), 2M Na2CO3 (6.2 mL, 12.4 mmol) and Pd(PPh3)4 (0.45 mg, 0.4 mmol) were added under argon. The mixture was degassed, heated to 100° C., stirred for 1 h. After completion of the reaction, by monitoring with TLC (5% MeOH\DCM), the resulting mixture was filtered with Celite® reagent and the filtrate was separated. This filtrate was concentrated, extracted with EtOAc (2×100 mL), washed with water (100 mL), dried over Na2SO4 and concentrated in vacuo. The resulting residue was purified by Biotage Isolera® One column purifier (silica gel 100-200 microns) using 3% methanol in dichloromethane and isolated as yellow color solid (0.25 g, 33% yield). 1H NMR (400 MHz, DMSO-d6): δ 13.49 (brs, 1H), 10.03 (s, 1H), 8.60 (s, 1H), 8.55 (s, 1H), 8.09 (s, 1H); LC-MS m/z calcd for [M+H]+, 180.02. found, 180.1.

Workup

  1. customThe mixture was degassed
  2. customAfter completion of the reaction
  3. filtrationthe resulting mixture was filtered with Celite® reagent
  4. customthe filtrate was separated
  5. concentrationThis filtrate was concentrated
  6. extractionextracted with EtOAc (2×100 mL)
  7. washwashed with water (100 mL)
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated in vacuo
  10. customThe resulting residue was purified by Biotage Isolera® One column purifier (silica gel 100-200 microns)

Sources & evidence

ORD record
ord-0f4188d34bf145ec9db0044b665f787e
Source dataset
uspto-grants-2015_12
Patent number
US09199975B2

Reaction notes

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