Hydrochloric Acid → HCID 58292574, compound

HRID 1798270Notes

Reaction equation

HRID 1798270 reaction equation
[CH2:1]([O:3][C:4](=[O:18])[CH2:5][CH:6]1[O:10][B:9]([OH:11])[C:8]2[CH:12]=[C:13]([OH:17])[CH:14]=[C:15]([CH3:16])[C:7]1=2)[CH3:2].[Cl:19][C:20]1[N:21]=[N:22][C:23](Cl)=[CH:24][CH:25]=1.[H-].[Na+].[NH4+].[Cl-].Cl>CN(C=O)C>[CH2:1]([O:3][C:4](=[O:18])[CH2:5][CH:6]1[O:10][B:9]([OH:11])[C:8]2[CH:12]=[C:13]([O:17][C:23]3[N:22]=[N:21][C:20]([Cl:19])=[CH:25][CH:24]=3)[CH:14]=[C:15]([CH3:16])[C:7]1=2)[CH3:2]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 673313,6-DichloropyridazineHCID 58292549Ethyl 2-(1,6-dihydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetate

Product 1

HCID 58292574HCID 58292574, compoundYield 42%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of (1,6-dihydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl)-acetic acid ethyl ester (0.2 g, 0.8 mmol) and 3,6-dichloro-pyridazine (0.24 g, 1.6 mmol) in DMF (15 mL) at 0° C. was added NaH (0.1 g, 2.4 mmol) in portions. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. Saturated NH4Cl (10 mL) was added at 0° C. and the solution acidified to pH˜4 with dilute HCl. The mixture was extracted with EtOAc (2×10 mL) and the organic extracts washed with water (10 mL), dried and concentrated in vacuo. The residue was purified by silica gel flash column chromatography (DCM:MeOH 95:5) to give [6-(6-chloro-pyridazin-3-yloxy)-1-hydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl]-acetic acid ethyl ester (0.12 g, 42%). 1H NMR (400 MHz, CDCl3): δ 7.49 (d, J=8.8 Hz, 1H), 7.33 (d, J=2.0 Hz, 1H), 7.16 (d, J=9.6 Hz, 1H), 7.11 (s, 1H), 5.66 (dd, J=2.4, 9.6 Hz, 1H), 4.20 (q, J=7.2 Hz, 2H), 3.10 (dd, J=2.0, 15.6 Hz, 1H), 2.44-2.38 (m, 1H), 2.35 (s, 3H), 1.26 (t, J=7.2 Hz, 3H). MS (ESI) m/z=363 [M+H]+.

Workup

  1. extractionThe mixture was extracted with EtOAc (2×10 mL)
  2. washthe organic extracts washed with water (10 mL)
  3. customdried
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel flash column chromatography (DCM:MeOH 95:5)

Sources & evidence

ORD record
ord-830dea672aaa4d98b3476937233b0a5e
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

Loading…