Tributylamine → HCID 86618521, compound

HRID 2239887Notes

Reaction equation

HRID 2239887 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:8](=O)[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:5]=[CH:6][CH:7]=1.C(OC(=O)C)(=[O:17])C.C(N(CCCC)CCCC)CCC.[Cl-].[NH4+]>ClCCCl.[Ti](Cl)(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[C:9](=[O:10])[O:11][C:12](=[O:17])[CH:13]=2)[CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 7622TributylamineHCID 7918Acetic AnhydrideHCID 25517Ammonium ChlorideHCID 2758814ethyl 2-(3-chlorophenyl)-2-oxoacetate

Product 1

HCID 86618521HCID 86618521, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 111,2-DichloroethaneSolvent

Procedure

To a flask was added ethyl 2-(3-chlorophenyl)-2-oxoacetate (1.8 g, 8.47 mmol) and acetic anhydride (1.60 ml, 16.93 mmol) in DCE (5 ml) at RT. To the resulting solution was added titanium(IV) chloride (16.93 ml, 16.93 mmol) and tributylamine (2.42 ml, 10.16 mmol). The solution was heated to reflux for 12 hours. The solution was then cooled in ice, and a solution of ammonium chloride was added. The mixture was stirred for 30 min. LC/MS indicated all starting material was gone. The solution was washed with 1×NH4Cl, 1N HCl, water, dried and concentrated in vacuo to provide 3-(3-chlorophenyl)furan-2,5-dione which was used as is in the next reaction. LC/MS, m/e 209 (M+1). HPLC Rt, 2.89 min. Waters Sunfire C18 column (4.6×50 mm). 0%-100% B. Solvent B: (90% MeOH, 10% H2O, 0.1% TFA). Solvent A: (10% MeOH, 90% H2O, 0.1% TFA). Gradient, start % B=0, final % B=100, gradient time 4 min. hold at 100% B 1 min, flow rate 4 mL/min.

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 12 hours
  3. temperatureThe solution was then cooled in ice
  4. washThe solution was washed with 1×NH4Cl, 1N HCl, water
  5. customdried
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-bcc4d356e4914ac38c1ce5bab8aa2622
Source dataset
uspto-grants-2010_05
Patent number
US07723336B2

Reaction notes

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