2-Butenoic acid, 3-(acetylamino)-, methyl ester, (2Z)- → 3-(4-(di-n-butylamino)-3-fluorophenyl)-2,6-dimethylpyrimidin-4(3H)-one

HRID 56142Notes

Reaction equation

HRID 56142 reaction equation
[CH2:1]([N:5]([CH2:14][CH2:15][CH2:16][CH3:17])[C:6]1[CH:11]=[CH:10][C:9]([NH2:12])=[CH:8][C:7]=1[F:13])[CH2:2][CH2:3][CH3:4].C[Al](C)C.[NH:22](/[C:26](/[CH3:32])=[CH:27]\[C:28](OC)=[O:29])[C:23]([CH3:25])=O>C(Cl)Cl>[CH2:1]([N:5]([CH2:14][CH2:15][CH2:16][CH3:17])[C:6]1[CH:11]=[CH:10][C:9]([N:12]2[C:28](=[O:29])[CH:27]=[C:26]([CH3:32])[N:22]=[C:23]2[CH3:25])=[CH:8][C:7]=1[F:13])[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 3

HCID 57053602-Butenoic acid, 3-(acetylamino)-, methyl ester, (2Z)-HCID 16682925TrimethylaluminumHCID 28982364N1,N1-di-n-butyl-2-fluorobenzene-1,4-diamine

Product 1

HCID 729494823-(4-(di-n-butylamino)-3-fluorophenyl)-2,6-dimethylpyrimidin-4(3H)-oneYield 50.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of N1,N1-di-n-butyl-2-fluorobenzene-1,4-diamine (1.10 g, 4.62 mmol) in CH2Cl2 (20 mL) was added trimethylaluminum (23 mL, 23 mmol, 1 M in heptane) slowly at rt. The reaction mixture was stirred at rt for 0.5 h, followed by the addition of a solution of methyl 3-acetaminocrotonate (798 mg, 5.08 mmol) in CH2Cl2 (10 mL). The reaction was stirred at rt for 3 days, then quenched with saturated NH4Cl aqueous solution and extracted with CH2Cl2 (100 mL×3). The combined organic phases were dried over anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by a silica gel column chromatography (PE/EtOAc (V/V)=3:2) to give the title compound as pale yellow oil (800 mg, 50%). The compound was characterized by the following spectroscopic data:

Workup

  1. stirringThe reaction was stirred at rt for 3 days
  2. customquenched with saturated NH4Cl aqueous solution
  3. extractionextracted with CH2Cl2 (100 mL×3)
  4. dry with materialThe combined organic phases were dried over anhydrous Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by a silica gel column chromatography (PE/EtOAc (V/V)=3:2)

Sources & evidence

ORD record
ord-0687aad0d9f34981a92b40feb9fc1efa
Source dataset
uspto-grants-2016_09
Patent number
US09434695B2

Reaction notes

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