Ethylenediamine → HCID 66616721, compound

HRID 2172140Notes

Reaction equation

HRID 2172140 reaction equation
[NH:1]1[CH:5]=[CH:4][C:3]([C:6]2[CH:15]=[CH:14][C:9](C(OC)=O)=[CH:8][CH:7]=2)=[CH:2]1.I[C:17]1[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][CH:18]=1.C(N)CN.P([O-])([O-])([O-])=[O:32].[K+].[K+].[K+].O1C[CH2:43][O:42][CH2:41]C1>O>[F:24][C:23]([F:26])([F:25])[C:20]1[CH:21]=[CH:22][C:17]([N:1]2[CH:5]=[CH:4][C:3]([C:6]3[CH:7]=[C:8]([CH:9]=[CH:14][CH:15]=3)[C:43]([O:42][CH3:41])=[O:32])=[CH:2]2)=[CH:18][CH:19]=1

Participants

7

Reactant 5

HCID 3301EthylenediamineHCID 312751,4-DioxaneHCID 62657Potassium Phosphate, TribasicHCID 67993Benzene, 1-iodo-4-(trifluoromethyl)-HCID 66616139HCID 66616139, compound

Product 1

HCID 66616721HCID 66616721, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a solution of methyl 4-(1H-pyrrol-3-yl)-benzoate in anhydrous dioxane (67 mL) is added 4-iodobenzotrifluoride (4.39 g, 16.1 mmol), cuprous iodide (0.255 g, 1.34 mmol), ethylenediamine (81 mg, 1.35 mmol) and potassium phosphate (10.16 g, 44.1 mmol). The reaction mixture is heated at reflux for 20 h. under a nitrogen atmosphere, then cooled to room temperature. The solid is filtered, washed with ethyl acetate and discarded. The filtrate is concentrated to give a dark solid which is diluted with water (50 mL) and extracted with ethyl acetate (3×20 mL). The extracts are washed with water (2×20 mL), combined, dried over MgSO4 and concentrated to give the crude product. The crude product is purified by silica gel chromatography (5-20% ethyl acetate) to give 2.00 g of methyl 3-[1-(4-trifluoromethyl-phenyl)-1H-pyrrol-3-yl]-benzoate as a white solid (73% yield). 1H NMR (300 MHz, DMSO-d6): δ 3.93 (s, 3H), 6.75 (m, 1H), 7.19 (in, 1H), 7.50 (m, 1H), 7.55 (d, 2H, J=8.7 Hz), 7.63 (d, 2H, J=6.6 Hz), 7.73 (d, 2H, J=8.4 Hz), 8.04 (d, 2H, J=6.6 Hz).

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureat reflux for 20 h. under a nitrogen atmosphere
  3. filtrationThe solid is filtered
  4. washwashed with ethyl acetate
  5. concentrationThe filtrate is concentrated
  6. customto give a dark solid which
  7. extractionextracted with ethyl acetate (3×20 mL)
  8. washThe extracts are washed with water (2×20 mL)
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated
  11. customto give the crude product
  12. customThe crude product is purified by silica gel chromatography (5-20% ethyl acetate)

Sources & evidence

ORD record
ord-698f6bf855a2411682f88c377d47c9cc
Source dataset
uspto-grants-2015_06
Patent number
US09051342B2

Reaction notes

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