Sodium Carbonate → HCID 67438394, compound

HRID 1665448Notes

Reaction equation

HRID 1665448 reaction equation
[CH:1]([NH:3][C:4]1[C:9]([CH2:10][CH3:11])=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:12][CH3:13])=O.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:15].[Cl:28][CH2:29][CH2:30][C:31](=O)[CH3:32].C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.O>[Cl-:28].[CH2:12]([C:5]1[CH:6]=[CH:7][CH:8]=[C:9]([CH2:10][CH3:11])[C:4]=1[N+:3]1[C:30]([CH3:29])=[C:31]([CH3:32])[S:15][CH:1]=1)[CH3:13]

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 14817Phosphorus sulfide (P2S5)HCID 806084-Chloro-2-butanoneHCID 13494842HCID 13494842, compound

Product 1

HCID 67438394HCID 67438394, compoundYield 98.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 8d (3.545 g, 20 mmol) and phosphorus pentasulfide (0.900 g, 2.02 mmol) in dry 1,4-dioxane (5 mL) was stirred at room temperature for 15 min under an argon atmosphere. 4-Chloro-2-butanone (1.422 g, 20 mmol) was added and the resulting slurry was heated at 100° C. The reaction mixture was refluxed for 50 min, initially becoming clear yellow and finally deep red. After cooling at room temperature, the crude mixture was diluted with H2O (20 mL). Na2CO3 was added to the reaction mixture until pH≈7. The solvent was evaporated under reduced pressure and the resulting solid was suspended in CH2Cl2 and purified by column chromatography (column packed with silica gel) eluting with EtOH/CH2Cl2 (15/85). Upon concentration of the last band, a viscous brownish oil was obtained. This was solidified when washed under vigorous stirring with diethyl ether (3×2 mL) to afford 9d as a tan solid (560 mg, 10%). 1H NMR (CDCl3. 300 MHz): δ=10.97 (s, 1H), 7.52 (t, J=8 Hz, 1H), 7.30 (d, J=8 Hz, 2H), 2.63 (s, 3H), 2.16 (q, J=8 Hz, 4H), 2.06 (s, 3H), 1.14 (t, J=8 Hz, 6H); 13C{1H} NMR (CDCl3, 75 MHz): δ=161.92, 141.63, 139.62, 135.04, 134.20, 132.30, 127.65, 23.97, 14.18, 13.16, 11.82; HRMS (FAB+) calculated for C15H20NS [M]+ 246.1316, observed 246.1326.

Workup

  1. temperaturethe resulting slurry was heated at 100° C
  2. temperatureThe reaction mixture was refluxed for 50 min
  3. temperatureAfter cooling at room temperature
  4. customThe solvent was evaporated under reduced pressure
  5. custompurified by column chromatography (column packed with silica gel)
  6. washeluting with EtOH/CH2Cl2 (15/85)
  7. customUpon concentration of the last band, a viscous brownish oil was obtained
  8. washwashed
  9. stirringunder vigorous stirring with diethyl ether (3×2 mL)

Sources & evidence

ORD record
ord-d1aa8719059a47c184d088a743427cd1
Source dataset
uspto-grants-2011_10
Patent number
US08039566B2

Reaction notes

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