1-Ethyl-3-(3'-dimethylaminopropyl)carbodiimide → 3-Azidopropyl 4-cyano-4-thiobenzoylsulfanyl-pentanoate

HRID 926812ノート

反応式

HRID 926812 の反応式
[C:1]([C:3]([S:10][C:11](=[S:18])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([CH3:9])[CH2:4][CH2:5][C:6]([OH:8])=[O:7])#[N:2].CCN=C=NCCCN(C)C.[N:30]([CH2:33][CH2:34][CH2:35]O)=[N+:31]=[N-:32]>CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:1]([C:3]([S:10][C:11](=[S:18])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)([CH3:9])[CH2:4][CH2:5][C:6]([O:8][CH2:35][CH2:34][CH2:33][N:30]=[N+:31]=[N-:32])=[O:7])#[N:2]

参加物

6

反応物 3

HCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 99217634-Cyano-4-[(phenylcarbonothioyl)thio]pentanoic AcidHCID 109969743-Azidopropan-1-ol

生成物 1

HCID 866877953-Azidopropyl 4-cyano-4-thiobenzoylsulfanyl-pentanoate収率 84.6%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒

実験手順

4-cyano-4-thiobenzoylsulfanyl-pentanoic acid (CTP, 1.0 g, 3.6 mmol) and DMAP (439.8 mg, 3.6 mmol) were dissolved in anhydrous DCM (50 mL). The solution was stirred for 5 min in ice bath, and EDCI (690.1 mg, 3.6 mmol) was added and stirred for 30 min. 3-Azidopropanol (364 mg, 3.6 mmol) was added and the solution was stirred in ice bath for 30 min and at room temperature for another 8 h. After reaction, the solution was washed with NaHCO3 aq. (satd.) and then H2O. The organic layer was dried (Na2SO4), solvent removed by rotary evaporation and the crude product was purified by column chromatography (silicagel 60 Å, 200-400 mesh, ethyl acetate:hexane, 1:4) to give rose-red oil in 84.6% yield. The structure of this compound was confirmed by 1H NMR and 13C NMR spectroscopy. 1H NMR (300 MHz, CDCl3, δ in ppm): 1.90-1.93 (m, 5 H, —CH2CH2N3, —CH3), 2.45-2.60 (m, 2 H, C(CN)CH2—), 2.68 (m, 2 H, C(CN)CH2CH2—), 3.40 (t, 2 H, —CH2N3), 4.21 (t, 4 H, —OCH2CH2—), 7.39 (m, 2 H, PH-2H), 7.57 (m, 1 H, PH-4H), 7.89 (m, 2 H, PH-3H). 13C NMR (75 MHz, CDCl3, δ in ppm): 222.40, 171.43, 144.74, 133.29, 128.82, 126.91, 118.68, 62.22, 48.34, 45.93, 33.60, 29.98, 28.27, 24.41.

後処理

  1. stirringstirred for 30 min
  2. stirringthe solution was stirred in ice bath for 30 min
  3. waitat room temperature for another 8 h
  4. customAfter reaction
  5. washthe solution was washed with NaHCO3 aq. (satd.)
  6. dry with materialThe organic layer was dried (Na2SO4), solvent
  7. customremoved by rotary evaporation
  8. customthe crude product was purified by column chromatography (silicagel 60 Å, 200-400 mesh, ethyl acetate:hexane, 1:4)
  9. customto give rose-red oil in 84.6% yield

出典と根拠

ORDレコード
ord-1e56c85e082748f7a45e26c5df6939a1
出典データセット
uspto-grants-2016_03
特許番号
US09289510B2

反応ノート

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