Diethyl Ether → HCID 86741649, compound

HRID 653401Notes

Reaction equation

HRID 653401 reaction equation
[C:1]1([Mg]Br)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:9][O:10][C:11]([C:13]1[CH:18](CCl)[C:17]([CH3:25])([C:21]([O:23][CH3:24])=[O:22])[CH2:16][NH:15][C:14]=1[CH3:26])=[O:12].[CH2:27](OCC)C>O1CCCC1>[CH3:24][O:23][C:21]([CH:17]1[CH:25]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH2:18][C:13]([C:11]([O:10][CH3:9])=[O:12])=[C:14]([CH3:26])[N:15]=[C:16]1[CH3:27])=[O:22]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 86741650HCID 86741650, compoundHCID 178418255HCID 178418255, compound

Product 1

HCID 86741649HCID 86741649, compoundYield 92%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-10 °C

Procedure

Phenyl magnesium bromide (2.68 mL) in diethylether (3.0M) was added dropwise to 1.00 gram of dimethyl-2,5-dimethyl-4-chloromethyl-1,4-dihydropyridine-3,5-dicarboxylate 11a (3.66 mm) [See; e.g., E. Benary, Chem. Ber., 44, 489 (1911)] in dry tetrahydrofuran under an argon atmosphere at -78° C. Stirring was continued at -78° for 15 minutes followed by warming to -10° C. for 1 hour. The excess Grignard reagent was quenched with saturated aqueous ammonium chloride. Extraction with ethyl acetate (3×75 mL), washing the organic portion with saturated aqueous NaCl, drying (MgSO4), filtering, and evaporation gave crude product. Crystallization from toluene/hexane (1/1) gave 1.10 gr (92%) of pure dimethyl-4-phenyl-4,5-dihydro-2,7-dimethylazepine-3,6-dicarboxylate (11).

Workup

  1. customThe excess Grignard reagent was quenched with saturated aqueous ammonium chloride
  2. extractionExtraction with ethyl acetate (3×75 mL)
  3. washwashing the organic portion with saturated aqueous NaCl
  4. dry with materialdrying (MgSO4)
  5. filtrationfiltering
  6. customevaporation
  7. customgave crude product
  8. customCrystallization from toluene/hexane (1/1)

Sources & evidence

ORD record
ord-51b71f2b6cd2401796b28952c776b684
Source dataset
uspto-grants-1987_06
Patent number
US04677101

Reaction notes

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