1,9-Dichloro-3-methyl-7-phenyl-5H-pyrimido[4,5-d][2]benzazepine → 9-Chloro-1,3-dimethyl-7-phenyl-5H-pyrimido[4,5-d][2]benzazepine

HRID 464585Notes

Reaction equation

HRID 464585 reaction equation
[CH3:1][Li].Cl[C:4]1[C:14]2[C:13]3[CH:15]=[CH:16][C:17]([Cl:19])=[CH:18][C:12]=3[C:11]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)=[N:10][CH2:9][C:8]=2[N:7]=[C:6]([CH3:26])[N:5]=1>CCOCC.O.S>[Cl:19][C:17]1[CH:16]=[CH:15][C:13]2[C:14]3[C:4]([CH3:1])=[N:5][C:6]([CH3:26])=[N:7][C:8]=3[CH2:9][N:10]=[C:11]([C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:12]=2[CH:18]=1

Participants

6

Reactant 2

HCID 132717911,9-Dichloro-3-methyl-7-phenyl-5H-pyrimido[4,5-d][2]benzazepineHCID 178418348HCID 178418348, compound

Product 1

HCID 132717909-Chloro-1,3-dimethyl-7-phenyl-5H-pyrimido[4,5-d][2]benzazepine

Reagents, catalysts & solvents 3

HCID 402Hydrogen SulfideSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent4×

Procedure

Dropwise 13.2 ml (18.5 mmol) of a 1.4M ether solution of methyl lithium was added to a suspension of 1.7 g (8.9 mmol) of cuprous iodide in 50 mL of ether which was cooled to 0°. A solution of 0.8 g (2.2 mmol) of 1,9-dichloro-3-methyl-7-phenyl-5H-pyrimido[4,5-d][2]benzazepine in 30 mL of ether was added dropwise to the ether solution of lithium dimethylcuprate which was further cooled to -25°. The mixture was stirred at -25° for 1 hr, warmed to room temperature, diluted with water and saturated with hydrogen sulfide. The resulting precipitate was removed by filtration over celite and the filtrate was concentrated at reduced pressure. Purification of the residue by column chromatography (silica gel, 10 g; eluent, 20% ether in methylene chloride) gave an oil which was crystallized from a mixture of ether and petroleum ether to give off-white needles, mp 121°-124°.

Workup

  1. temperaturewas cooled to 0°
  2. temperaturewas further cooled to -25°
  3. customThe resulting precipitate was removed by filtration over celite
  4. concentrationthe filtrate was concentrated at reduced pressure
  5. customPurification of the residue by column chromatography (silica gel, 10 g; eluent, 20% ether in methylene chloride)
  6. customgave an oil which
  7. customwas crystallized from a mixture of ether and petroleum ether
  8. customto give off-white needles, mp 121°-124°

Sources & evidence

ORD record
ord-1d5c4670b7cf444eaf5f2e83d07d8944
Source dataset
uspto-grants-1985_10
Patent number
US04548750

Reaction notes

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