Triethylamine → Carbamic acid, [2-[(2-amino-3-pyridinyl)amino]-2-oxoethyl]methyl-, phenylmethyl ester

HRID 1601069ノート

反応式

HRID 1601069 の反応式
[CH2:1]([O:8][C:9]([N:11]([CH2:13][C:14]([OH:16])=O)[CH3:12])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.C(OC(Cl)=O)C(C)C.[NH2:32][C:33]1[C:38]([NH2:39])=[CH:37][CH:36]=[CH:35][N:34]=1>C1COCC1>[NH2:32][C:33]1[C:38]([NH:39][C:14](=[O:16])[CH2:13][N:11]([C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[O:10])[CH3:12])=[CH:37][CH:36]=[CH:35][N:34]=1

参加物

6

反応物 4

HCID 8471TriethylamineHCID 99562,3-DiaminopyridineHCID 62365Isobutyl chloroformateHCID 97053N-Carbobenzoxysarcosine

生成物 1

HCID 21830410Carbamic acid, [2-[(2-amino-3-pyridinyl)amino]-2-oxoethyl]methyl-, phenylmethyl ester収率 19.4%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-20 °C

実験手順

N-(Benzyloxycarbonyl)sarcosine (4.1 g, 18.5 mmol) was dissolved in dry THF, and triethylamine (3 mL, 21.6 mmol) was added, followed by isobutylchloroformate (2.5 mL, 19.27 mmol). The solution was cooled to about -20° C. for 15 minutes, then a solution of 2,3-diaminopyridine (2.0767 g, 19.03 mmol) in dry THF was added slowly. The reaction was kept stirring between -10° C. to -20° C. for 15 minutes, then was allowed to warm to RT. After 3 d, the reaction was evaporated under vacuum, and the residue was partitioned between EtOAc and 1N NaHCO3. The EtOAc phase was dried (MgSO4) and evaporated under vacuum. The residue was dissolved in glacial AcOH and was stirred in a oil bath at 70° C. After 24 h, the reaction was removed from the oil bath, allowed to cool to RT, and concentrated under vacuum. The residue was evaporated with toluene, then was chromatographed on silica gel (CHCl3, then 3% MeOH/CHCl3, then 5% MeOH/CHCl3) to afford the title compound (1.13 g, 19%): 1H NMR (250 MHz, CDCl3) δ 3.05 (s, 3H), 3.99 (s, 2H), 4.82 (br s, 1H), 6.5-6.65 (m, 1H), 7.32 (s, 5H), 7.87 (d, 1H), 8.84 (br s, 1H); MS (ES) m/e 315.4 (M+H)+.

後処理

  1. temperatureto warm to RT
  2. waitAfter 3 d
  3. customthe reaction was evaporated under vacuum
  4. customthe residue was partitioned between EtOAc and 1N NaHCO3
  5. dry with materialThe EtOAc phase was dried (MgSO4)
  6. customevaporated under vacuum
  7. dissolutionThe residue was dissolved in glacial AcOH
  8. stirringwas stirred in a oil bath at 70° C
  9. waitAfter 24 h
  10. customthe reaction was removed from the oil bath
  11. temperatureto cool to RT
  12. concentrationconcentrated under vacuum
  13. customThe residue was evaporated with toluene
  14. customwas chromatographed on silica gel (CHCl3

出典と根拠

ORDレコード
ord-24bfde53b5b94a6a9100c87e686a2188
出典データセット
uspto-grants-1999_11
特許番号
US05977101

反応ノート

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