tert-Butanol → {2-[Benzenesulfonyl-(4-fluoro-3-trifluoromethyl-benzyl)-amino]-benzo[b]thiophen-3-yl}-carbamic acid t-butyl ester

HRID 57167Notes

Reaction equation

HRID 57167 reaction equation
[F:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][N:7]([C:17]2[S:21][C:20]3[CH:22]=[CH:23][CH:24]=[CH:25][C:19]=3[C:18]=2C(O)=O)[S:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)(=[O:10])=[O:9])=[CH:4][C:3]=1[C:31]([F:34])([F:33])[F:32].C([N:38]([CH:41](C)C)CC)(C)C.C1C=CC(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:51])=CC=1.[C:61]([OH:65])([CH3:64])([CH3:63])[CH3:62]>>[C:61]([O:65][C:41](=[O:51])[NH:38][C:18]1[C:19]2[CH:25]=[CH:24][CH:23]=[CH:22][C:20]=2[S:21][C:17]=1[N:7]([S:8]([C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1)(=[O:10])=[O:9])[CH2:6][C:5]1[CH:29]=[CH:30][C:2]([F:1])=[C:3]([C:31]([F:34])([F:33])[F:32])[CH:4]=1)([CH3:64])([CH3:63])[CH3:62]

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 81531DiisopropylethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 57920436HCID 57920436, compound

Product 1

HCID 57920407{2-[Benzenesulfonyl-(4-fluoro-3-trifluoromethyl-benzyl)-amino]-benzo[b]thiophen-3-yl}-carbamic acid t-butyl esterYield 45%

Procedure

A solution of compound 458-A (1.96 g, 3.85 mmol) and diisopropylethylamine (806 μL, 4.61 mmol) in t-butanol (30 mL) was treated with DPPA (1.0 mL, 4.61 mmol) and refluxed for 6 h. The solvent was evaporated in vacuo, and the crude residue purified by flash column chromatography (SiO2), eluting with an ethyl acetate (10-35%) in heptane gradient, to afford compound 509-A (1.0 g, 45%) as a yellow amorphous solid. 1H-NMR (CDCl3): δ 1.48 (br s, 9H), 4.74 (s, 2H), 6.92-7.14 (m, 2H), 7.29-7.39 (m, 2H), 7.43-7.58 (m, 5H), 7.62-7.77 (m, 4H); MS: m/z 603.0 (MNa+).

Workup

  1. temperaturerefluxed for 6 h
  2. customThe solvent was evaporated in vacuo
  3. customthe crude residue purified by flash column chromatography (SiO2)
  4. washeluting with an ethyl acetate (10-35%) in heptane gradient

Sources & evidence

ORD record
ord-1173518171cb42aa9cd362f0a68831d0
Source dataset
uspto-grants-2016_09
Patent number
US09434711B2

Reaction notes

Loading…