Cesium carbonate → HCID 4435389, compound

HRID 2167332Notes

Reaction equation

HRID 2167332 reaction equation
I[C:2]1[CH:7]=[N:6][CH:5]=[CH:4][N:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[OH:14][C:15]1[CH:22]=[CH:21][C:18]([C:19]#[N:20])=[CH:17][CH:16]=1.Cl.CN(C)CC(O)=O>[Cu]I.O1CCOCC1>[N:3]1[CH:4]=[CH:5][N:6]=[CH:7][C:2]=1[O:14][C:15]1[CH:22]=[CH:21][C:18]([C:19]#[N:20])=[CH:17][CH:16]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 130194-CyanophenolHCID 75605N,N-Dimethylglycine hydrochlorideHCID 642841Iodopyrazine

Product 1

HCID 4435389HCID 4435389, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

2-Iodopyrazine (2.00 g, 9.42 mmol), copper(I) iodide (366 mg, 1.88 mmol), cesium carbonate (6.14 g, 18.84 mmol), 4-hydroxybenzonitrile (1.68 g, 14.13 mmol) and N,N-dimethylglycine hydrochloride (398 mg, 2.83 mmol) were dried and placed under nitrogen and then degassed 1,4-dioxane (25.0 mL) was added. The whole mixture was heated at 90° C. for 138 hours. The cooled mixture was partitioned between ethyl acetate (50 mL) and water (50 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (2×50 mL). The organic layers were combined and washed with brine (50 mL) and dried with Na2SO4 and concentrated in vacuo. The crude solid was placed on a silica gel column and purified (EtOAc/Hex 1:8) to give the product as an off white solid (1.61 g, 87%). 1H NMR (300 MHz, CDCL3) δ(ppm): 7.31 (2H, d, J=9.1 Hz), 7.74 (2H, d, J=9.1 Hz), 8.14 (1H, dd, J=2.4, 1.4 Hz), 8.37 (1H, d, J=2.4 Hz), 8.51 (1H, s). 13C NMR (75 MHz, CDCL3) δ(ppm): 109.0, 118.5, 122.0 (CH), 134.1 (CH), 136.4 (CH), 139.8 (CH), 141.1 (CH), 156.7, 159.1. MS (FAB+): 198 (MH+). HRMS for C11H7N3O (MH+): calculated: 198.0667; found 198.0661.

Workup

  1. customThe cooled mixture was partitioned between ethyl acetate (50 mL) and water (50 mL)
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted with ethyl acetate (2×50 mL)
  4. washwashed with brine (50 mL)
  5. dry with materialdried with Na2SO4
  6. concentrationconcentrated in vacuo
  7. custompurified (EtOAc/Hex 1:8)

Sources & evidence

ORD record
ord-0b7b3ea2c00b4d9485a9c6a7d8253ebd
Source dataset
uspto-grants-2015_06
Patent number
US09045442B2

Reaction notes

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