2-Cyano-N-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-6-yl)-4-nitrobenzenesulfonamide → 4-Amino-2-cyano-N-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-6-yl)benzenesulfonamide

HRID 1256072Notes

Reaction equation

HRID 1256072 reaction equation
[C:1]([C:3]1[CH:8]=[C:7]([N+:9]([O-])=O)[CH:6]=[CH:5][C:4]=1[S:12]([NH:15][C:16]1[CH:17]=[CH:18][C:19]2[CH2:23][O:22][B:21]([OH:24])[C:20]=2[CH:25]=1)(=[O:14])=[O:13])#[N:2]>CO.CS(C)=O.[Ni]>[NH2:9][C:7]1[CH:6]=[CH:5][C:4]([S:12]([NH:15][C:16]2[CH:17]=[CH:18][C:19]3[CH2:23][O:22][B:21]([OH:24])[C:20]=3[CH:25]=2)(=[O:13])=[O:14])=[C:3]([C:1]#[N:2])[CH:8]=1

Participants

4

Reactant 1

HCID 671740652-Cyano-N-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-6-yl)-4-nitrobenzenesulfonamide

Product 1

HCID 671751594-Amino-2-cyano-N-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-6-yl)benzenesulfonamideYield 27.62%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 22036561Dimethyl sulfoxide methanolSolvent

Procedure

To a solution of 2-cyano-N-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-6-yl)-4-nitrobenzenesulfonamide (400 mg, 1.1 mmol) in MeOH/DMSO (40 ml/1 ml) was added Raney Ni (100 mg) under nitrogen, then the solution was stirred under hydrogen atmosphere at room temperature for 2 hours. The mixture was filtered and the filtrate was concentrated. The residue was purified by prep. HPLC (column: YMC AQ 150×30.0 mm, 5 u; liquid phase: [A-H2O+0.075% TFA; B-MeCN+0.075% TFA] B %: 18%-48%, 10 min) to give the title compound (100 mg, 27.62%) as a yellow solid. 1H NMR: DMSO 400 MHz δ10.25 (s, 1H), 9.21 (s, 1H), 7.60 (d, J=9.6 Hz, 1H), 7.43 (s, 1H), 7.26 (d, J=8.4 Hz, 1H), 7.17 (d, J=9.2 Hz, 1H), 6.92 (s, 1H), 6.77 (d, J=10.4 Hz, 1H), 6.44 (brs, 2H), 4.89 (s, 2H). ESI-MS m/z 330 (M+H, positive); HPLC purity: 97.31% (MaxPlot 190-370 nm), 99.89% (220 nm).

Workup

  1. filtrationThe mixture was filtered
  2. concentrationthe filtrate was concentrated
  3. customThe residue was purified by prep

Sources & evidence

ORD record
ord-fc37c19b67a14e82a7fd6cda83966937
Source dataset
uspto-grants-2013_06
Patent number
US08461134B2

Reaction notes

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