Nitromethane → 5-(2-Nitroethenyl)-1,3-benzodioxole

HRID 3006

反応式

HRID 3006 の反応式
[CH:1]1[C:6]([CH:7]=O)=[CH:5][C:4]2[O:9][CH2:10][O:11][C:3]=2[CH:2]=1.[N+:12]([CH3:15])([O-:14])=[O:13].[OH-].[Na+]>CO.O>[CH2:10]1[O:11][C:3]2[CH:2]=[CH:1][C:6]([CH:7]=[CH:15][N+:12]([O-:14])=[O:13])=[CH:5][C:4]=2[O:9]1

参加物

6

反応物 3

HCID 6375NitromethaneHCID 8438PiperonalHCID 14798Sodium Hydroxide

生成物 1

HCID 949455-(2-Nitroethenyl)-1,3-benzodioxole

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 962Water溶媒2 回

反応条件

温度
4 °C

実験手順

In a 45-L cryogenic reactor with a contoured, anchor stirrer was dissolved 5.537 kg (36.9 moles) piperonal in 9 L methanol and 2.252 kg (36.9 moles) nitromethane at 15°-20° C. The jacket temperature was set to -5° C. and the reaction solution cooled to a temperature of +3.5° C. A 21° C. solution of 3.10 kg (38.8 moles) 50% (w:w) aquous sodium hydroxide diluted with 3.7 L water was pumped in. The reaction temperature was maintained between 10°-15° C. When addition was complete, the jacket temperature was reset to 1° C. and stirring continued for 30 minutes. A mixture of 7 kg ice in 19 L water was added to dissolve most of the solid. The reaction mixture was filtered through canvas and then a 27R10SV Honeycomb filter. The filtered solution was metered into a 21° C. mixture of 7.4 L concentrated hydrochloric acid in 11.1 L deionized water. The final reaction temperature was 26° C. The resulting product was centrifuged and washed until the wash pH rose to at least 6 (by pH indicating paper). The crude product was dissolved in 92 L dichloromethane and the layers separated. The aqueous layer was washed once with 8 L dichloromethane. The combined organics were dried over 1.32 kg magnesium sulfate and filtered through Whatman #1 paper. The volume was reduced to 20% and the solution cooled to 4° C. Filtration through Whatman #1 paper, followed by ambient temperature drying in vacuo with an air leak afforded 1.584 kg (22%) of a first crop Concentration of the MLS to 25% followed by similar cooling, filtration, and drying afforded 0.262 kg (4%) of a second crop. The yellow product darkened on standing in light and air.

後処理

  1. customwas set to -5° C.
  2. temperaturethe reaction solution cooled to a temperature of +3.5° C
  3. temperatureThe reaction temperature was maintained between 10°-15° C
  4. additionWhen addition
  5. customwas reset to 1° C.
  6. additionwas added
  7. dissolutionto dissolve most of the solid
  8. filtrationThe reaction mixture was filtered through canvas
  9. filtrationa 27R10SV Honeycomb filter
  10. customwas metered into a 21° C.
  11. additionmixture of 7.4 L concentrated hydrochloric acid in 11.1 L
  12. customThe final reaction temperature
  13. customwas 26° C
  14. washwashed until the
  15. washwash
  16. dissolutionThe crude product was dissolved in 92 L dichloromethane
  17. customthe layers separated
  18. washThe aqueous layer was washed once with 8 L dichloromethane
  19. dry with materialThe combined organics were dried over 1.32 kg magnesium sulfate
  20. filtrationfiltered through Whatman #1 paper
  21. filtrationFiltration through Whatman #1 paper
  22. customfollowed by ambient temperature
  23. customdrying in vacuo with an air leak
  24. customafforded 1.584 kg (22%) of a first crop Concentration of the MLS to 25%
  25. filtrationfollowed by similar cooling, filtration
  26. customdrying
  27. customafforded 0.262 kg (4%) of a second crop

出典と根拠

ORDレコード
ord-f03c70e534504a4d9fbd8ac5c0c335af
出典データセット
uspto-grants-1998_03
特許番号
US05731434

関連ノート

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