Hydrochloric Acid → (4-Nitrophenyl)methyl (2S,4S)-2-[[(aminosulfonyl)amino]methyl]-4-mercapto-1-pyrrolidinecarboxylate

HRID 1034489ノート

反応式

HRID 1034489 の反応式
[N+:1]([C:4]1[CH:21]=[CH:20][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([SH:17])[CH2:14][C@H:13]2[CH2:18][NH2:19])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].C(N(CC)CC)C.C[Si](C)(C)Cl.[S:34](Cl)(=[O:37])(=[O:36])[NH2:35].Cl>ClCCl>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([SH:17])[CH2:14][C@H:13]2[CH2:18][NH:19][S:34](=[O:37])(=[O:36])[NH2:35])=[O:11])=[CH:20][CH:21]=1)([O-:3])=[O:2]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 8471Triethylamine2 回HCID 24499Chlorosulfamic acidHCID 57083137(2s,4s)-1-p-Nitrobenzyloxycarbonyl-2-aminomethyl-4-mercaptopyrrolidine

生成物 1

HCID 10200398(4-Nitrophenyl)methyl (2S,4S)-2-[[(aminosulfonyl)amino]methyl]-4-mercapto-1-pyrrolidinecarboxylate収率 66.7%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

To a solution of crude (2S,4S)-1-p-nitrobenzyloxycarbonyl-2-aminomethyl-4-mercaptopyrrolidine (3.3 g: 10.18 mmole) in dichloromethane (100 ml) at -78° C., triethylamine (2.84 ml: 2.2 eq.) and trimethylchlorosilane (3.12 ml: 2.2 eq.) are dropwise added. After stirring for 20 minutes, triethylamine (4.25 ml: 3 eq.) and 1M-sulfamoyl chloride in dichloromethane (25 ml: 2.5 eq.) are dropwise added to the mixture. After 20 minutes stirring, the reaction mixture is acidified with hydrochloric acid, warmed to room temperature, and extracted with dichloromethane. The extract is washed with water, and 1N-hydrochloric acid (10 ml) and methanol (30 ml) are added thereto. The solution is stirred at room temperature for 30 minutes. The reaction mixture is washed with water, dried over magnesium sulfate, and concentrated in vacuo. The residue is purified by silica gel column chromatography (toluene: ethyl acetate) to give (2S,4S)-1-p-nitrobenzyloxycarbonyl-2-sulfamoylaminomethyl-4-mercaptopyrrolidine (2.65 g). Yield: 66.7%. NMR δ(CDCl3 -CD3OD) ppm: 1.42(t, J=7 Hz, 1H), 1.65 to 1.93(m, 1H), 2.48 to 2.70(m, 1H), 3.05 to 3.63(m, 4H), 3.93 to 4.16(m, 2H), 5.22(s, 2H), 7.53(d, J=8 Hz, 2H), 8.23(d, J=8 Hz, 2H). IR ν (CHCl3) cm-1 : 3276br, 1692, 1607.

後処理

  1. stirringAfter 20 minutes stirring
  2. extractionextracted with dichloromethane
  3. washThe extract is washed with water, and 1N-hydrochloric acid (10 ml) and methanol (30 ml)
  4. additionare added
  5. stirringThe solution is stirred at room temperature for 30 minutes
  6. washThe reaction mixture is washed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue is purified by silica gel column chromatography (toluene: ethyl acetate)

出典と根拠

ORDレコード
ord-2c68400fe4bb4a9da99b582f1c96665a
出典データセット
uspto-grants-1994_05
特許番号
US05317016

反応ノート

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