Diethyl Oxalate → HCID 14871092, compound

HRID 729171Notes

Reaction equation

HRID 729171 reaction equation
[Na].[Cl:2][C:3]1[CH:8]=[CH:7][C:6]([C:9](=O)[CH2:10][C:11](=O)[C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:5][CH:4]=1.CC(C1C=CC(Cl)=CC=1)=O.C(OC(=O)C(OCC)=O)C.C([N-]C(C)C)(C)C.[Li+].Cl.[CH3:48][O:49][C:50]1[CH:55]=[CH:54][C:53]([NH:56][NH2:57])=[CH:52][CH:51]=1.C1(N2C=CC(C3C=CC=CC=3)=N2)C=CC=CC=1>CCO>[Cl:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[N:56]([C:53]3[CH:54]=[CH:55][C:50]([O:49][CH3:48])=[CH:51][CH:52]=3)[N:57]=[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:10]=2)=[CH:5][CH:4]=1

Participants

8

Reactant 6

HCID 7268Diethyl OxalateHCID 7467P-ChloroacetophenoneHCID 6132841,3-Diphenyl-1H-pyrazoleHCID 27239044-Methoxyphenylhydrazine hydrochlorideHCID 2724682Lithium diisopropylamideHCID 67830464HCID 67830464, compound

Product 1

HCID 14871092HCID 14871092, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Ethyl 4-(4-chlorophenyl)-2,4-dioxobutanoate sodium salt (10.0 g, 36.1 mM), synthesized from 4-chloroacetophenone and diethyloxalate employing lithiumdiisopropylamide as base, and 4-methoxyphenylhydrazine hydrochloride (6.31 g, 36.1 mM) in cold absolute EtOH (360 ml) were stirred at 0° for 4hr., at rt for 18 hr and then at reflux for 5 hr. The resulting solution was evaporated in vacuo, H2O (100 ml) was added and the aqueous phase extracted with Et2O (3×100 ml). The combined ether layerwas washed (brine), dried (Na2SO4) and concentrated in vacuo to give a crude solid which by NMR was a 5:1 mixture of the title compound tothe corresponding 1,3-diphenyl pyrazole. Recrystallization from EtOAc:hexane (2×) afforded pure 1 (7.93 g, 61%) as a white solid, mp=107°-108° C., MS, (DCI) m/e 357 (M+1).

Workup

  1. temperatureat reflux for 5 hr
  2. customThe resulting solution was evaporated in vacuo, H2O (100 ml)
  3. additionwas added
  4. extractionthe aqueous phase extracted with Et2O (3×100 ml)
  5. washThe combined ether layerwas washed (brine)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customto give a crude solid which by NMR

Sources & evidence

ORD record
ord-529e242da2de486dbac2e1d29a04d345
Source dataset
uspto-grants-1991_09
Patent number
US05051518

Reaction notes

Loading…