Dichloromethane → HCID 178519325, compound

HRID 707466Notes

Reaction equation

HRID 707466 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:10]=[O:11])[S:5][C:6]=1[N+:7]([O-:9])=[O:8].[NH:12]1[C:16](B(O)O)=[CH:15][CH:14]=[N:13]1.COCCOC.ClCCl>C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O.C(N(CC)CC)C>[N+:7]([C:6]1[S:5][C:4]([CH:10]=[O:11])=[CH:3][C:2]=1[C:16]1[CH:15]=[CH:14][NH:13][N:12]=1)([O-:9])=[O:8]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 80711,2-DimethoxyethaneHCID 112519791H-Pyrazole-5-boronic acidHCID 218862814-Bromo-5-nitrothiophene-2-carbaldehyde

Product 1

HCID 178519325HCID 178519325, compoundYield 100.4%

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 962WaterSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

A flask containing 4-bromo-5-nitrothiophene-2-carbaldehyde (1.00 g, 4.24 mmol), (1H-pyrazol-5-yl)boronic acid (510 mg, 4.56 mmol), ethyleneglycol dimethyl ether (20 mL), triethylamine (1.80 mL), water (2.00 mL) and bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (340 mg, 0.42 mmol) was evacuated and purged with nitrogen twice, then heated at 80° C. under nitrogen for 4 h. The reaction was cooled to room temperature, poured into a saturated solution of ammonium chloride (20 mL), extracted with ethyl acetate (3×10 mL), combined organics washed with a saturated solution of ammonium chloride (30 mL), dried (Na2SO4) and concentrated under reduced pressure. The crude product was purified by flash chromatography, eluting with ethyl acetate in hexanes, to yield 5-nitro-4-(1H-pyrazol-3-yl)thiophene-2-carbaldehyde as a yellow oil (950 mg, 28%). 1H NMR (400 MHZ, DMSO-d6) δ 6.99 (s, 1H), 7.94 (s, 1H), 8.42 (s, 1H), 10.07 (s, 1H).

Workup

  1. customwas evacuated
  2. custompurged with nitrogen twice
  3. temperatureThe reaction was cooled to room temperature
  4. additionpoured into a saturated solution of ammonium chloride (20 mL)
  5. extractionextracted with ethyl acetate (3×10 mL)
  6. washcombined organics washed with a saturated solution of ammonium chloride (30 mL)
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated under reduced pressure
  9. customThe crude product was purified by flash chromatography
  10. washeluting with ethyl acetate in hexanes

Sources & evidence

ORD record
ord-ceebab437e3f454a9bd99cf7b5456914
Source dataset
uspto-grants-2015_11
Patent number
US09175010B2

Reaction notes

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