Chloroform → 4-Morpholinoacetophenone

HRID 1014783Notes

Reaction equation

HRID 1014783 reaction equation
[CH3:1][C:2]([C:4]1[CH:9]=[CH:8][C:7](Cl)=[CH:6][CH:5]=1)=[O:3].[NH:11]1[CH2:16][CH2:15][O:14][CH2:13][CH2:12]1.CC([O-])(C)C.[Na+].C(Cl)(Cl)Cl>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2[C-](N(C)C)C=CC=2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2]>[C:2]([C:4]1[CH:9]=[CH:8][C:7]([N:11]2[CH2:16][CH2:15][O:14][CH2:13][CH2:12]2)=[CH:6][CH:5]=1)(=[O:3])[CH3:1]

Participants

8

Reactant 4

HCID 6212ChloroformHCID 7467P-ChloroacetophenoneHCID 8083MorpholineHCID 23676156Sodium t-butoxide

Product 1

HCID 383624-MorpholinoacetophenoneYield 74.1%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1317290462-Diphenylphosphino-dimethylaminoferroceneCatalystHCID 1140TolueneSolvent

Procedure

According to General Procedure B, a mixture of 4-chloroacetophenone (65 μL, 0.50 mmol), morpholine (52 μL, 0.60 mmol), NaOt-Bu (67 mg, 0.70 mmol), Pd2(dba)3.CHCl3 (10 mg, 0.01 mmol) and 12f (8 mg, 0.02 mmol) in PhMe (2.5 mL) was heated, cooled and filtered. Evaporation of the solvent under reduced pressure and column chromatography of the pre-adsorbed crude material (83:2:15 to 78:2:20 hexane/Et3N/EtOAc, silica gel) gave 52b (76 mg, 74%) as a pale yellow solid. 1H NMR (300 MHz, CDCl3) δ 7.90 (d, 2H, J=9.0 Hz), 6.87 (d, 2H, J=9.0 Hz), 3.86 (t, 4H, J=4.8 Hz), 3.31 (t, 4H, J=5.1 Hz), 2.53 (s, 3H); 13C NMR (75.5 MHz, CDCl3) 196.4, 154.2, 130.3, 128.1, 113.2, 66.5, 47.5, 26.1.

Workup

  1. temperaturecooled
  2. filtrationfiltered
  3. customEvaporation of the solvent under reduced pressure and column chromatography of the pre-adsorbed crude material (83:2:15 to 78:2:20 hexane/Et3N/EtOAc, silica gel)

Sources & evidence

ORD record
ord-ff3a0367871143a09cee81ad28d69c51
Source dataset
uspto-grants-2011_07
Patent number
US07982064B2

Reaction notes

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