HCID 66693554, compound → HCID 56944657, compound

HRID 2368001Notes

Reaction equation

HRID 2368001 reaction equation
[Cl:1][C:2]1[CH:15]=[C:14]([O:16][CH2:17][CH2:18][CH2:19][OH:20])[C:5]2[B:6]([OH:13])[O:7][CH:8]([CH2:9][N+:10]([O-])=O)[C:4]=2[CH:3]=1.[H][H]>N.[Ni]>[ClH:1].[NH2:10][CH2:9][CH:8]1[O:7][B:6]([OH:13])[C:5]2[C:14]([O:16][CH2:17][CH2:18][CH2:19][OH:20])=[CH:15][C:2]([Cl:1])=[CH:3][C:4]1=2

Participants

5

Reactant 2

HCID 66693554HCID 66693554, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 56944657HCID 56944657, compoundYield 190%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 222AmmoniaSolvent

Procedure

To a 5-chloro-7-(3-hydroxy-propoxy)-3-nitromethyl-3H-benzo[c][1,2]oxaborol-1-ol 7 (80 mg, 0.27 mmol) in methanolic ammonia solution (2 M, 20 mL) was added Ra/Ni (˜0.1 g, 2800 Nickel slurry in water) and the reaction vessel was pressurized to 40 psi with hydrogen overnight at room temperature. The mixture was filtered through a pad of Celite® and washed with EtOAc. The filtrate was concentrated in vacuo and to the resulting residue was added water (1 mL), followed by conc HCl to pH 1. The heterogeneous mixture was lyophilized providing the title compound as a hygroscopic ivory solid (79 mg, quantitative). 1H NMR (400 MHz, DMSO-d6) δ ppm 7.20 (s, 1H), 6.99 (s, 1H), 5.28 (dd, J=8.0, 2.5 Hz, 1H), 4.13 (t, J=6.0 Hz, 2H), 3.59 (t, J=6.0 Hz, 2H), 3.47 (dd, J=13.0, 2.5 Hz, 1H), 2.89 (dd, J=13.2, 8.6 Hz, 1H), 1.89 (t, J=6.0 Hz, 2H); MS (ESI) m/z=272 (M+1, positive); HPLC purity: 96.83% (MaxPlot 200-400 nm), 95.40% (220 nm).

Workup

  1. filtrationThe mixture was filtered through a pad of Celite®
  2. washwashed with EtOAc
  3. concentrationThe filtrate was concentrated in vacuo and to the resulting residue
  4. additionwas added water (1 mL)

Sources & evidence

ORD record
ord-2bf7558bc03e4be9810751f2f4d92560
Source dataset
uspto-grants-2014_04
Patent number
US08703742B2

Reaction notes

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