2-(Chloromethyl)-2,3-dihydro-1,4-benzodioxin → 2-Aminomethyl-1,4-benzodioxane

HRID 374669

反応式

HRID 374669 の反応式
Cl[CH2:2][CH:3]1[O:8][C:7]2[CH:9]=[CH:10][CH:11]=[CH:12][C:6]=2[O:5][CH2:4]1.[K].C1(=O)[NH:18]C(=O)C2=CC=CC=C12>CN(C)C=O>[NH2:18][CH2:2][CH:3]1[O:8][C:7]2[CH:9]=[CH:10][CH:11]=[CH:12][C:6]=2[O:5][CH2:4]1

参加物

4

反応物 2

HCID 953202-(Chloromethyl)-2,3-dihydro-1,4-benzodioxinHCID 24194345Phthalimide potassium salt

生成物 1

HCID 150532-Aminomethyl-1,4-benzodioxane

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

Commercial grade of 2-chloromethyl-1,4-benzodioxane (10.0 g, 54.7 mmol) and phthalimide potassium salt (12.0 g, 65.0 mmol) were added to N,N-dimethylformamide (350 ml) and subjected to reaction overnight under reflux; thereafter, N,N-dlmethylformamide was distilled off under vacuum. Water (250 ml) was added to the residue and the mixture was stirred well, with the floating solids being subsequently recovered by filtration. The solids were dried, then recrystallized from methanol/methylene chloride, thereby yielding (1,4-benzodioxan-2-ylmethyl)phthalimide as a colorless tabular crystal in an amount of 8.43 g. The thus obtained crystal was dissolved in ethanol (500 ml); to the solution, hydrazine hydrate (4.3 g) was added, followed by refluxing under heating for 3 h. The resulting solids were filtered off and ethanol was distilled off under vacuum, followed by addition of water (300 ml). Thereafter, an aqueous solution of 6N sodium hydroxide was added to adjust pH to 12 and the mixture was subjected to 3 cycles of extraction with methylene chloride. The methylene chloride layers were dried with anhydrous sodium sulfate, and concentrated under vacuum, thereby yielding a crude product of 2-aminomethyl-1,4-benzodioxane as a colorless oil (crude product, 4.3 g).

後処理

  1. customsubjected to reaction overnight
  2. temperatureunder reflux
  3. distillationthereafter, N,N-dlmethylformamide was distilled off under vacuum
  4. additionWater (250 ml) was added to the residue
  5. filtrationbeing subsequently recovered by filtration
  6. customThe solids were dried
  7. customrecrystallized from methanol/methylene chloride
  8. dissolutionThe thus obtained crystal was dissolved in ethanol (500 ml)
  9. additionto the solution, hydrazine hydrate (4.3 g) was added
  10. temperatureby refluxing
  11. temperatureunder heating for 3 h
  12. filtrationThe resulting solids were filtered off
  13. distillationethanol was distilled off under vacuum
  14. additionfollowed by addition of water (300 ml)
  15. additionThereafter, an aqueous solution of 6N sodium hydroxide was added
  16. extractionthe mixture was subjected to 3 cycles of extraction with methylene chloride
  17. dry with materialThe methylene chloride layers were dried with anhydrous sodium sulfate
  18. concentrationconcentrated under vacuum

出典と根拠

ORDレコード
ord-4e049f7f95094f20b49b427909f24510
出典データセット
uspto-grants-1996_01
特許番号
US05480905

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