Ethyl benzoylformate → HCID 54747357, compound

HRID 2046246Notes

Reaction equation

HRID 2046246 reaction equation
C(O[C:4](=[O:29])[C:5](=[N:12][N:13]([C:21](=[O:28])[CH2:22][C:23]([O:25]CC)=O)[CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)C.O=[C:31](C1C=CC=CC=1)[C:32]([O:34]CC)=[O:33].Cl.Cl.C([NH:52]N)C1C=CC=CC=1.C(N(C(C)C)CC)(C)C.S([O-])([O-])(=O)=O.[Mg+2].N12CCCN=C1CCCCC2.ClC(=O)CC(OCC)=O>O.ClCCl>[OH:29][C:4]1[C:5]([C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=2)=[N:12][N:13]([CH2:14][C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)[C:21](=[O:28])[C:22]=1[C:23]([NH:52][CH2:31][C:32]([OH:34])=[O:33])=[O:25]

Participants

10

Reactant 7

HCID 15349Ethyl benzoylformateHCID 24083Sulfuric acid magnesium salt (1:1)HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 81531DiisopropylethylamineHCID 118931Ethyl 3-chloro-3-oxopropionateHCID 146540Benzylhydrazine dihydrochlorideHCID 86623015HCID 86623015, compound

Product 1

HCID 54747357HCID 54747357, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Ethyl 3-[2-[2-(ethyloxy)-2-oxo-l-phenylethylidene]-1-(phenylmethyl)hydrazino]-3-oxopropanoate. A mixture of ethyl oxo(phenyl)acetate (0.315 g, 1.77 mmol), benzylhydrazine dihydrochloride (0.334 g, 1.71 mmol), diisopropylethylamine (0.596 mL, 3.42 mmol), dichloromethane (10 mL) and excess magnesium sulfate was stirred for 18 h, then filtered through a plug of silica gel and the cake washed with 50% ethyl acetate/hexane. The solvent was removed under reduced pressure and the crude hydrazone dissolved in tetrahydrofuran (5 mL) and placed under nitrogen. 1,8-Diazabicyclo[5.4.0]undec-7-ene (0.212 mL, 1.42 mmol) was added, followed by ethyl 3-chloro-3-oxopropionate (0.182 mL, 1.42 mmol) dropwise. The mixture was stirred at room temperature for 2 h, then poured into water (50 mL) and extracted with ethyl acetate. The extracts were dried (MgSO4), evaporated under reduced pressure and the residue chromatographed (silica gel, 10-50% ethyl acetate/hexane) to give the title compound (0.117 g) as a gum, sufficiently pure to use in the next reaction. LCMS (ES+) m/z 397 (MH+).

Workup

  1. filtrationfiltered through a plug of silica gel
  2. washthe cake washed with 50% ethyl acetate/hexane
  3. customThe solvent was removed under reduced pressure
  4. dissolutionthe crude hydrazone dissolved in tetrahydrofuran (5 mL)
  5. stirringThe mixture was stirred at room temperature for 2 h
  6. extractionextracted with ethyl acetate
  7. dry with materialThe extracts were dried (MgSO4)
  8. customevaporated under reduced pressure
  9. customthe residue chromatographed (silica gel, 10-50% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-80b9d0b257ee4140ba201363c0e8bfa3
Source dataset
uspto-grants-2013_11
Patent number
USRE044613E1

Reaction notes

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