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

HRID 926812

Reaction equation

HRID 926812 reaction equation
[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]

Participants

6

Reactant 3

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

Product 1

HCID 866877953-Azidopropyl 4-cyano-4-thiobenzoylsulfanyl-pentanoateYield 84.6%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-1e56c85e082748f7a45e26c5df6939a1
Source dataset
uspto-grants-2016_03
Patent number
US09289510B2

Linked notes

Loading…