Sodium Carbonate → Methyl 5-chloro-4-(1-ethyl-4-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylate

HRID 2392260Notes

Reaction equation

HRID 2392260 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[O:9])[S:5][C:6]=1[Cl:7].[CH2:12]([N:14]1[C:18](B2OC(C)(C)C(C)(C)O2)=[C:17]([CH3:28])[CH:16]=[N:15]1)[CH3:13].C(=O)([O-])[O-].[Na+].[Na+]>C1COCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:7][C:6]1[S:5][C:4]([C:8]([O:10][CH3:11])=[O:9])=[CH:3][C:2]=1[C:18]1[N:14]([CH2:12][CH3:13])[N:15]=[CH:16][C:17]=1[CH3:28]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 57826388Methyl 4-bromo-5-chlorothiophene-2-carboxylateHCID 578269151-ethyl-4-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole

Product 1

HCID 57826796Methyl 5-chloro-4-(1-ethyl-4-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylateYield 94%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of methyl 4-bromo-5-chloro-2-thiophenecarboxylate (230 mg, 0.9 mmol), 1-ethyl-4-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (425 mg, 1.8 mmol), PdCl2(dppf) (65.9 mg, 0.09 mmol), and sodium carbonate (2N aq, 1.35 mL, 2.7 mmol) in THF (5 mL) was heated to 70° C. in a sealed tube. After 5 h, the reaction mixture was concentrated under vacuum and purified on silica (EtOAc/Hex, 40-60%) to afford the title compound (241 mg, 92%) as a light yellow solid: LC-MS (ES) m/z=285 (M+H)+.

Workup

  1. concentrationthe reaction mixture was concentrated under vacuum
  2. custompurified on silica (EtOAc/Hex, 40-60%)

Sources & evidence

ORD record
ord-9d48b3181a064705b83508b7806f8de1
Source dataset
uspto-grants-2012_09
Patent number
US08273782B2

Reaction notes

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