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

HRID 2295977Notes

Reaction equation

HRID 2295977 reaction equation
[Cl:1][C:2]1[CH:24]=[CH:23][C:5]2[C:6]3[C:20](=O)[NH:19][C:18]([CH3:22])=[N:17][C:7]=3[CH2:8][N:9]=[C:10]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1.P(Cl)(Cl)([Cl:27])=O>C(Cl)Cl>[Cl:27][C:20]1[C:6]2[C:5]3[CH:23]=[CH:24][C:2]([Cl:1])=[CH:3][C:4]=3[C:10]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)=[N:9][CH2:8][C:7]=2[N:17]=[C:18]([CH3:22])[N:19]=1

Participants

4

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 135759068HCID 135759068, compound

Product 1

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

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 3.5 g (10.4 mmol) of 9-chloro-3-methyl-7-phenyl-5H-pyrimido[4,5-d][2]benzazepin-1(2H)-one and 22 mL of phosphorous oxychloride in 100 mL of methylene chloride was stirred at room temperature for 18 hr. The reaction mixture was concentrated at reduced pressure to a solid residue. The residue was partitioned between ice cold saturated aqueous sodium bicarbonate and methylene chloride. The methylene chloride solution was dried over anhydrous sodium sulfate and concentrated at reduced pressure to a yellow residue. Purification by column chromatography (silica gel, 40.0 g; eluent:methylene chloride ether, 10:1) gave a pale yellow solid, mp 190°-192°. A portion was recrystallized from a mixture of ether and petroleum ether to yield colorless prisms, mp 191°-193°.

Workup

  1. concentrationThe reaction mixture was concentrated at reduced pressure to a solid residue
  2. customThe residue was partitioned between ice cold saturated aqueous sodium bicarbonate and methylene chloride
  3. dry with materialThe methylene chloride solution was dried over anhydrous sodium sulfate
  4. concentrationconcentrated at reduced pressure to a yellow residue
  5. customPurification by column chromatography (silica gel, 40.0 g; eluent:methylene chloride ether, 10:1)
  6. customgave a pale yellow solid, mp 190°-192°
  7. customA portion was recrystallized from a mixture of ether and petroleum ether
  8. customto yield colorless prisms, mp 191°-193°

Sources & evidence

ORD record
ord-28623c4fe1ea44ce8aee4597754d648d
Source dataset
uspto-grants-1984_01
Patent number
US04427589

Reaction notes

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