N,N'-Dimethylethylenediamine → HCID 22348000, compound

HRID 897242Notes

Reaction equation

HRID 897242 reaction equation
Br[C:2]1[CH:3]=[C:4]([Cl:30])[CH:5]=[C:6]2[C:11]=1[O:10][C:9](=[O:12])[CH:8]=[C:7]2[NH:13][CH:14]1[CH2:19][CH2:18][N:17]([CH2:20][C:21]2[CH:29]=[CH:28][C:24]3[O:25][CH2:26][O:27][C:23]=3[CH:22]=2)[CH2:16][CH2:15]1.C([O-])([O-])=O.[K+].[K+].[NH:37]1[CH2:41][CH2:40][CH2:39][C:38]1=O.CNCCNC>C1(C)C=CC=CC=1.C(Cl)Cl.[Cu]I>[N:37]1([C:2]2[CH:3]=[C:4]([Cl:30])[CH:5]=[C:6]3[C:11]=2[O:10][C:9](=[O:12])[CH:8]=[C:7]3[NH:13][CH:14]2[CH2:19][CH2:18][N:17]([CH2:20][C:21]3[CH:29]=[CH:28][C:24]4[O:25][CH2:26][O:27][C:23]=4[CH:22]=3)[CH2:16][CH2:15]2)[CH2:41][CH2:40][CH2:39][CH2:38]1

Participants

8

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 120252-PyrrolidoneHCID 10051310HCID 10051310, compound

Product 1

HCID 22348000HCID 22348000, compoundYield 20.4%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 8-Bromo-6-chloro-4-[1-benzo[1,3]dioxol-5-ylmethyl-piperidin-4-ylamino]chromen-2-one (30 mg, 0.061 mmol) in 0.3 mL toluene under nitrogen was treated with K2CO3 (20 mg, 0.13 mmol), about 3 mg CuI (0.016 mmol), 2-pyrrolidinone (10 uL, 0.13 mmol), followed by N,N′-dimethylethylenediamine (3 uL, 0.025 mmol) and heated to reflux. After 16 hours, the reaction was allowed to cool to room temperature, diluted with CH2Cl2, washed with distilled water, dried (Na2SO4) and concentrated. Purification by reverse phase HPLC (Zorbax C18, 21.2×250 mm column, 15 mL/min, 0 to 60% acetonitrile:water with 0.1% trifluoroacetic acid) followed by extraction into CH2Cl2 after basification with 1 M K2CO3, dried (Na2SO4) and concentrated to give the title compound (6 mg, 20%). 1H NMR (300 MHz, ppm, DMSO-d6) δ 1.6 (m, 2H), 1.8 (m, 2H), 2.1 (m, 4H), 2.7 (m, 2H), 3.4-3.5 (m, 3H), 3.72 (t, J=7 Hz, 2H) 5.23 (s, 1H), 5.92 (s, 2H), 6.68-6.80 (m, 3H), 7.27 (m, 1H), 7.62 (d, J=2.3 Hz, 1H), 8.20 (d, J=2.4 Hz, 1H). MS(ESI) 496 (M+H), 494 (M−H).

Workup

  1. temperatureheated to reflux
  2. washwashed with distilled water
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customPurification by reverse phase HPLC (Zorbax C18, 21.2×250 mm column, 15 mL/min, 0 to 60% acetonitrile:water with 0.1% trifluoroacetic acid)
  6. extractionfollowed by extraction into CH2Cl2 after basification with 1 M K2CO3
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-442000488109470faa5ee0d6dc8a0b61
Source dataset
uspto-grants-2005_07
Patent number
US06921821B2

Reaction notes

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