Triethylamine → benzyl N-(4-chloro-3-nitrophenyl)carbamate

HRID 431728

反応式

HRID 431728 の反応式
[Cl:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].C(N(CC)CC)C.Cl[C:20]([O:22][CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)=[O:21]>ClCCl.C(Cl)(Cl)Cl>[CH2:23]([O:22][C:20]([NH:6][C:5]1[CH:7]=[CH:8][C:2]([Cl:1])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1)=[O:21])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

参加物

6

反応物 3

HCID 8471TriethylamineHCID 10387Benzyl chloroformateHCID 124774-Chloro-3-nitroaniline

生成物 1

HCID 4935650benzyl N-(4-chloro-3-nitrophenyl)carbamate収率 90.5%

試薬・触媒・溶媒 2

HCID 6212Chloroform溶媒HCID 6344Dichloromethane溶媒

実験手順

Two equal batches of 4-chloro-3-nitroaniline (20.0 g each, 0.116 mol) were dissolved separately in freshly distilled dichloromethane (over P2O5) (150 mL each) and dry triethylamine (1.1 eq. each, 18 mL, 0.128 mol) under a drierite drying tube. Each of the reaction mixtures was chilled in an ice bath and benzyl chloroformate (50 mL each, 0.348 mol) was slowly added. The resulting solutions were heated to reflux for 4 days, and then they were combined and concentrated. The residue was further concentrated in vacuo using a kugelrohr apparatus (0.1 mm Hg, 60° C.) to give a thick oil. The oily material was dissolved in chloroform (300 mL) and washed with brine (100 mL). The organic layer was dried over sodium sulfate and concentrated in vacuo. The crude product was purified on a silica gel column, using a 2.5% methanol/chloroform as a solvent. A total yield of 32.2 g (46% yield) of N-benzyloxycarbonyl-4-chloro-3-nitroaniline was isolated as a yellow oil that solidified upon refrigeration. Rf320.61 (20% ethyl acetate/hexane). IR (neat) 3424, 3100, 3060, 3025, 2918, 2865, 1603, 1528, 1493, 1448, 1395, 1351, 1231, 1204, 1146, 1071, 1027, 960, 894, 841, 805, 734, 694. 1H-NMR (500 MHz, CDCl3) 7.28 (t, 9.0, 2H), 7.24 (s br, 1H), 7.22 (t, 9.0, 1H), 7.16 (d, 8.0, 1H), 7.13 (d, 9.0, 2H), 6.98 (d, 3.0, 1H), 6.73 (dd, 3.0, 8.0, 1H), 4.60 (s, 2H).

後処理

  1. customEach of the reaction mixtures
  2. temperaturewas chilled in an ice bath
  3. temperatureThe resulting solutions were heated
  4. temperatureto reflux for 4 days
  5. concentrationconcentrated
  6. concentrationThe residue was further concentrated in vacuo
  7. customa kugelrohr apparatus (0.1 mm Hg, 60° C.)
  8. customto give a thick oil
  9. washwashed with brine (100 mL)
  10. dry with materialThe organic layer was dried over sodium sulfate
  11. concentrationconcentrated in vacuo
  12. customThe crude product was purified on a silica gel column

出典と根拠

ORDレコード
ord-1c0eba72d70f4ebfbf26d195b88ee5d1
出典データセット
uspto-grants-2003_12
特許番号
US06660742B2

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