HCID 9883579、化合物 → HCID 18784088、化合物

HRID 518907

反応式

HRID 518907 の反応式
[N:1]1([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])[CH2:5][CH2:4][CH2:3][NH:2]1.[C:13](C1CC(=O)NC1=O)([O:15][CH2:16][CH:17]1[C:29]2[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=2)[C:23]2[C:18]1=[CH:19][CH:20]=[CH:21][CH:22]=2)=[O:14]>ClCCl>[N:2]1([C:13]([O:15][CH2:16][CH:17]2[C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][C:23]=3[C:24]3[C:29]2=[CH:28][CH:27]=[CH:26][CH:25]=3)=[O:14])[CH2:3][CH2:4][CH2:5][N:1]1[C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7]

参加物

4

反応物 2

HCID 9883579HCID 9883579、化合物HCID 21857793tert-Butyl pyrazolidine-1-carboxylate

生成物 1

HCID 18784088HCID 18784088、化合物収率 94%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

Tert-butyl pyrazolidine-1-carboxylate (39) (1.39 g, 8.08 mmoles) was acylated with Fmoc succinimide (3.27 g, 9.69 mmoles, 1.2 eq.) in dry dichloromethane (20 mL). The reactive mixture was left stirring overnight. The volatiles were removed using a rotary evaporator and the residue was dissolved in EtOAc. The organic layer was extracted three times, respectively, with 5% citric acid, 5% NaHCO3 and brine, dried over Na2SO4, filtered and concentrated to a white foam which was purified by column chromatography using 7:3 EtOAc:Hexane as eluant. Evaporation of the collected fractions afforded 1-(9H-fluoren-9-yl)methyl 2-tert-butyl pyrazolidine-1,2-dicarboxylate as a white solid in a 94% yield. Pyrazolidine-1,2-dicarboxylate (1.34 g, 3.4 mmoles) was treated with 25 mL of a 1:1 TFA:DCM solution and stirred for one hour. Removal of the volatiles by rotary evaporation gave a residue that was dissolved in 1N HCl, stirred for 1 hour and freeze-dryed to yield hydrochloride (9H-fluoren-9-yl)methyl-1-carboxylate: mp (143.2-148.1° C.), 1H NMR (DMSO) δ 7.89 (d, J=7.32 Hz, 2H), 7.72 (d, J=7.33 Hz, 2H), 7.43 (ddd, J=7.36 Hz, 0.57 Hz, 2H), 7.33 (ddd, J=7.42 Hz, 1.14 Hz, 2H), 4.44 (d, J=6.90 Hz, 2H), 4.33 (t, J=6.56 Hz, 1H), 3.58 (t, J=6.96 Hz, 2H), 3.43 (t, J=6.96 Hz, 2H), 2.20 (m, 2H). 13C (DMSO) δ 154.57, 144.64, 142.11, 129.26, 126.54, 121.67, 69.89, 47.50, 25.50.

後処理

  1. waitThe reactive mixture was left
  2. customThe volatiles were removed
  3. customa rotary evaporator
  4. dissolutionthe residue was dissolved in EtOAc
  5. extractionThe organic layer was extracted three times
  6. dry with materialrespectively, with 5% citric acid, 5% NaHCO3 and brine, dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated to a white foam which
  9. customwas purified by column chromatography
  10. customEvaporation of the collected fractions

出典と根拠

ORDレコード
ord-a23971778b094d39911ac6125d674c38
出典データセット
uspto-grants-2015_08
特許番号
US09115171B2

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