Sodium Carbonate → HCID 19375609, compound

HRID 2361022Notes

Reaction equation

HRID 2361022 reaction equation
Cl[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([Cl:12])=[N:4][N:3]=1.[CH3:13][C:14]1[CH:15]=[C:16](B(O)O)[S:17][CH:18]=1.C(=O)([O-])[O-].[Na+].[Na+].O1CCOCC1>C1C=CC(P([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC(P([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Fe]>[Cl:12][C:5]1[C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[C:2]([C:16]2[S:17][CH:18]=[C:14]([CH3:13])[CH:15]=2)=[N:3][N:4]=1

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 784901,4-Dichlorophthalazine2×HCID 27343734-Methylthiophene-2-boronic acid

Product 1

HCID 19375609HCID 19375609, compound

Reagents, catalysts & solvents 1

HCID 178477754HCID 178477754, compoundCatalyst

Procedure

1,4-Dichlorophthalazine (1.40 g, 7.03 mmol), 4-methylthiophen-2-ylboronic acid (999 mg, 7.03 mmol), and PdCl2(DPPF) (721 mg, 985 μmol) were added into a sealed tube. The tube was purged with Argon. Then sodium carbonate (2.0 M in water) (7.74 ml, 15.5 mmol) and 1,4-dioxane (35.2 ml, 7.03 mmol) were added. The tube was sealed, stirred at rt for 5 min, and placed in a preheated oil bath at 110° C. After 1 h, LC-MS showed product and byproduct (double coupling), and SM dichlorophthalazine. The reaction was cooled to rt, filtered through a pad of celite with an aid of EtOAc, concentrated, and loaded onto column. The product was purified by column chromatography using Hex to remove the top spot, then 80:20 Hex:EtOAc to collect the product. The product, 1-chloro-4-(4-methylthiophen-2-yl)phthalazine was obtained as yellow solid. LC-MS showed that the product was contaminated with a small amount of SM dichlorophthalazine and biscoupling byproduct. MS m/z=261 [M+1]+. Calcd for C13H9ClN2S: 260.12.

Workup

  1. customThe tube was purged with Argon
  2. customThe tube was sealed
  3. customplaced in a preheated oil bath at 110° C
  4. waitAfter 1 h
  5. temperatureThe reaction was cooled to rt
  6. filtrationfiltered through a pad of celite with an aid of EtOAc
  7. concentrationconcentrated
  8. customThe product was purified by column chromatography
  9. customto remove the top spot
  10. custom80:20 Hex:EtOAc to collect the product

Sources & evidence

ORD record
ord-ac798da71f814e5aa9690435de7cbafa
Source dataset
uspto-grants-2014_04
Patent number
US08686155B2

Reaction notes

Loading…