HCID 12709236、化合物 → HCID 20426835、化合物

HRID 615668ノート

反応式

HRID 615668 の反応式
CC(C)([O-])C.[K+].[CH3:7][C:8]1[CH:16]=[CH:15][C:11]2[NH:12][N:13]=[N:14][C:10]=2[CH:9]=1.Cl[C:18]1([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][C:26]=2[N+:28]([O-:30])=[O:29])[C:20](=[O:21])[O:19]1>CN(C)C=O>[C:31]1([C:18]2([N:12]3[C:11]4[CH:15]=[CH:16][C:8]([CH3:7])=[CH:9][C:10]=4[N:14]=[N:13]3)[C:27]3[C:22](=[CH:23][CH:24]=[CH:25][C:26]=3[N+:28]([O-:30])=[O:29])[C:20](=[O:21])[O:19]2)[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1

参加物

5

反応物 3

HCID 12709236HCID 12709236、化合物HCID 23665647Potassium tert-butoxideHCID 178423511HCID 178423511、化合物

生成物 1

HCID 20426835HCID 20426835、化合物

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒2 回

実験手順

To 37 ml of thionyl chloride was added 40 g of 2-benzoyl-3-nitrobenzoic acid. The mixture was heated and stirred for 4 hours on an oil bath kept at a temperature of 50° to 60° C. Excess thionyl chloride was distilled away under reduced pressure, and 40.2 g of 3-chloro-3-phenyl-4-nitrophthalide was obtained as a brown oily substance. Separately, 9.0 g (0.08 mol.) of potassium tert-butoxide and 9.3 g (0.07 mol.) of 5-methylbenzotriazole were added to 300 ml of dried dimethylformamide, and stirred for 20 minutes at room temperature. The resulting mixture was cooled to 5° C. and thereto, was added dropwise gradually the previously prepared solution containing 20 g (0.07 mol.) of 3-chloro-3-phenyl-4-nitrophthalide in 100 ml of dried dimethylformamide as the mixture was kept at 5° C. After the dropwise addition, the cooling bath was removed, and the stirring was further continued for 5 hours at room temperature. Thereto, 300 ml of a saturated aqueous solution of ammonium chloride was added subsequently. The reaction mixture was extracted with ethyl acetate repeatedly, and the extract was washed with water. The rsulting organic layer was dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off with suction. The filtrate was concentrated to obtain 27.5 g of oily substance. This oily substance was separated and purified by flash column chromatography (silica gel: 1 Kg, eluate: hexane-ethyl acetate (2:1 by volume) mixture) to obtain the intended compound, 3-phenyl-3-(5-methyl-1-benzotriazolyl)-4-nitrophthalide, in the form of white crystals. Yield 6.9 g, Melting Point 240° to 248° C.

後処理

  1. temperatureThe resulting mixture was cooled to 5° C.
  2. additionwas added dropwise gradually the previously prepared solution
  3. customwas kept at 5° C
  4. additionAfter the dropwise addition
  5. customthe cooling bath was removed
  6. waitthe stirring was further continued for 5 hours at room temperature
  7. additionThereto, 300 ml of a saturated aqueous solution of ammonium chloride was added subsequently
  8. extractionThe reaction mixture was extracted with ethyl acetate repeatedly
  9. washthe extract was washed with water
  10. dry with materialThe rsulting organic layer was dried over anhydrous sodium sulfate
  11. filtrationthe sodium sulfate was filtered off with suction
  12. concentrationThe filtrate was concentrated
  13. customto obtain 27.5 g of oily substance
  14. customThis oily substance was separated
  15. custompurified by flash column chromatography (silica gel: 1 Kg, eluate: hexane-ethyl acetate (2:1 by volume) mixture)

出典と根拠

ORDレコード
ord-1bfd46287a3f4783b09ea0f3132f2d5e
出典データセット
uspto-grants-1985_02
特許番号
US04500636

反応ノート

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