Cesium carbonate → HCID 12164493, compound

HRID 2167319Notes

Reaction equation

HRID 2167319 reaction equation
[F:1][C:2]([F:11])([F:10])[C:3]1[CH:4]=[CH:5][C:6]([OH:9])=[CH:7][CH:8]=1.C(=O)([O-])[O-].[Cs+].[Cs+].I[C:19]1[CH:26]=[CH:25][C:22]([C:23]#[N:24])=[CH:21][CH:20]=1.Cl.CN(C)CC(O)=O>[Cu]I>[F:1][C:2]([F:10])([F:11])[C:3]1[CH:4]=[CH:5][C:6]([O:9][C:19]2[CH:26]=[CH:25][C:22]([C:23]#[N:24])=[CH:21][CH:20]=2)=[CH:7][CH:8]=1

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 678744-(Trifluoromethyl)phenolHCID 75605N,N-Dimethylglycine hydrochlorideHCID 764674-Iodobenzonitrile

Product 1

HCID 12164493HCID 12164493, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Conditions

Temperature
90 °C

Procedure

To dried trifluoro-p-cresol (531 mg, 3.27 mmol), copper(I) iodide (83 mg, 0.4 mmol), cesium carbonate (1.42 g, 4.36 mmol), 4-iodobenzonitrile (500 mg, 2.18 mmol) and N,N-dimethylglycine hydrochloride (91 mg, 0.65 mmol) under nitrogen was added degassed 1,4-dioxane (10.0 mL). The whole mixture was heated at 90° C. for 140 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 (100 mL) and dried with Na2SO4 and concentrated in vacuo. The crude liquid was placed on a silica gel column and purified CH2Cl2/Hex (1:8→1:4) and then was recrystallized with hot hexane to give the product as white crystals (286 mg, 50%). 1H NMR (500 MHz, CDCL3) δ(ppm): 7.08 (1H, d, J=8.4 Hz), 7.15 (1H, d, J=8.8 Hz), 7.66 (1H, d, J=8.4 Hz), 7.67 (1H, d, J=8.8 Hz). 13C NMR (125 MHz, CDCL3) δ(ppm): 107.4, 118.7, 119.1 (CH), 120.0 (CH), 122.9, 125.1, 127.0 (1C, q, J=32.5 Hz), 127.3, 127.8 (2CH, q, J=3.8 Hz), 134.5 (CH), 158.2, 160.4. 19F (282 MHz, CDCL3) δ(ppm): −62.05 (3F, s). MS (FAB+): 264 (MH+). HRMS for C14H8F3NO (MH+): calculated: 264.0636; found 264.0621.

Workup

  1. customdegassed 1,4-dioxane (10.0 mL)
  2. customThe cooled mixture was partitioned between ethyl acetate (50 mL) and water (50 mL)
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with ethyl acetate (2×50 mL)
  5. washwashed with brine (100 mL)
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated in vacuo
  8. custompurified CH2Cl2/Hex (1:8→1:4)
  9. customwas recrystallized with hot hexane

Sources & evidence

ORD record
ord-164d7b02dcc142a589f2c1cf72d279f3
Source dataset
uspto-grants-2015_06
Patent number
US09045442B2

Reaction notes

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