Nitrogen mustard hydrochloride → 1-Methyl-4-(3-nitrophenyl)piperazine

HRID 53263ノート

反応式

HRID 53263 の反応式
Cl.[CH3:2][N:3]([CH2:7][CH2:8]Cl)[CH2:4][CH2:5]Cl.[N+:10]([C:13]1[CH:14]=[C:15]([CH:17]=[CH:18][CH:19]=1)[NH2:16])([O-:12])=[O:11].C(=O)([O-])[O-].[Na+].[Na+]>C(O)CCC>[CH3:2][N:3]1[CH2:7][CH2:8][N:16]([C:15]2[CH:14]=[C:13]([N+:10]([O-:12])=[O:11])[CH:19]=[CH:18][CH:17]=2)[CH2:5][CH2:4]1

参加物

5

反応物 3

HCID 5935Nitrogen mustard hydrochlorideHCID 74233-NitroanilineHCID 10340Sodium Carbonate

生成物 1

HCID 121521611-Methyl-4-(3-nitrophenyl)piperazine収率 50.3%

試薬・触媒・溶媒 1

HCID 2631-Butanol溶媒

実験手順

A mixture of N-methylbis (2-chloroethyl)amine hydrochloride (9.8 g) and 3-nitroaniline (7.0 g) in 1-butanol (100 ml) was heated at reflux for 60 h then cooled to room temperature. Sodium carbonate (2.8 g) was then added and the mixture heated at reflux for a further 18 h, then cooled to 0° C. and filtered. The solid was collected, washed with anhydrous ether then partitioned between dichloromethane (200 ml) and sodium hydroxide solution (1M, 150 ml). The organic layer was separated and the aqueous phase washed once more with dichloromethane (200 ml). The combined organic layers were dried (K2CO3) and evaporated in vacuo. The resultant residue was chromatographed on silica gel, using dichloromethane:methanol (96:4) as the eluant, to afford an orange oil. The oil crystallised on standing and the resultant solid was triturated with petrol (60/80) to give the desired piperazine (5.64 g). 1H NMR (360 MHz, CDCl3) δ2.37 (3H, s), 2.58 (4H, t, J=5 Hz), 3.30 (4H, t, J=5 Hz), 7.18 (1H, dd, J=9 and 3 Hz), 7.35 (1H, t, J=8 Hz), 7.64 (1H, dd, J=9 and 2 Hz), 7.71 (1H, d, J=2 Hz). MS (CI, NH3) 222 (M+1).

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 60 h
  3. temperaturethe mixture heated
  4. temperatureat reflux for a further 18 h
  5. temperaturecooled to 0° C.
  6. filtrationfiltered
  7. customThe solid was collected
  8. washwashed with anhydrous ether
  9. customthen partitioned between dichloromethane (200 ml) and sodium hydroxide solution (1M, 150 ml)
  10. customThe organic layer was separated
  11. washthe aqueous phase washed once more with dichloromethane (200 ml)
  12. dry with materialThe combined organic layers were dried (K2CO3)
  13. customevaporated in vacuo
  14. customThe resultant residue was chromatographed on silica gel
  15. customto afford an orange oil
  16. customThe oil crystallised
  17. customthe resultant solid was triturated with petrol (60/80)

出典と根拠

ORDレコード
ord-8c00a7cd75684bf6beee7bc795341495
出典データセット
uspto-grants-1997_04
特許番号
US05618812

反応ノート

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