Sodium Dithionite → Tert-butyl (3S,4S)-4-((3-amino-6-bromo-7-fluoroquinolin-4-YL)amino)-3-fluoropiperidine-1-carboxylate

HRID 588470Notes

Reaction equation

HRID 588470 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[F:12])[N:8]=[CH:7][C:6]([N+:13]([O-])=O)=[C:5]2[NH:16][C@H:17]1[CH2:22][CH2:21][N:20]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:19][C@@H:18]1[F:30].S(S([O-])=O)([O-])=O.[Na+].[Na+].CCOC(C)=O.CCCCCC>O1CCOCC1>[NH2:13][C:6]1[CH:7]=[N:8][C:9]2[C:4]([C:5]=1[NH:16][C@H:17]1[CH2:22][CH2:21][N:20]([C:23]([O:25][C:26]([CH3:29])([CH3:27])[CH3:28])=[O:24])[CH2:19][C@@H:18]1[F:30])=[CH:3][C:2]([Br:1])=[C:11]([F:12])[CH:10]=2

Participants

5

Reactant 3

HCID 24489Sodium DithioniteHCID 21226206Ethyl acetate hexaneHCID 117876247(3S,4S)-tert-butyl 4-((6-bromo-7-fluoro-3-nitroquinolin-4-yl)amino)-3-fluoropiperidine-1-carboxylate

Product 1

HCID 117876729Tert-butyl (3S,4S)-4-((3-amino-6-bromo-7-fluoroquinolin-4-YL)amino)-3-fluoropiperidine-1-carboxylateYield 107.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

(3S,4S)-tert-butyl 4-((6-bromo-7-fluoro-3-nitroquinolin-4-yl)amino)-3-fluoropiperidine-1-carboxylate (27 g, 0.055 mol) was taken in 1,4-dioxane (150 mL). Solution of sodium dithionite (29 g, 0.166 mol in 150 mL water) was added at RT and the resulting mixture was stirred for 5 h at RT. The reaction was monitored by TLC (50% EtOAc/hexane), after completion of reaction the reaction mixture was poured into ice water and extracted with EtOAc (3×200 mL). The combined organic layers were washed with brine and water, dried over sodium sulphate. The organic layer was evaporated under vacuum, to afford the (3S,4S)-tert-butyl 4-((3-amino-6-bromo-7-fluoroquinolin-4-yl)amino)-3-fluoropiperidine-1-carboxylate, 2 (27 g). This material used directly in next step without purification. LCMS: 99.5%, m/z=456.7 (M+).

Workup

  1. customafter completion of reaction the reaction mixture
  2. extractionextracted with EtOAc (3×200 mL)
  3. washThe combined organic layers were washed with brine and water
  4. dry with materialdried over sodium sulphate
  5. customThe organic layer was evaporated under vacuum

Sources & evidence

ORD record
ord-cb50426b13234454917e926df17254ab
Source dataset
uspto-grants-2016_01
Patent number
US09227969B2

Reaction notes

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