Potassium Carbonate → Ethyl 2-(6-(5-cyano-1,3,4-thiadiazol-2-yloxy)-1-hydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetate

HRID 1798300Notes

Reaction equation

HRID 1798300 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].Br[C:20]1[S:24][C:23]([C:25]#[N:26])=[N:22][N:21]=1.C(=O)([O-])[O-].[K+].[K+]>C(#N)C.O>[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:20]3[S:24][C:23]([C:25]#[N:26])=[N:22][N:21]=3)[CH:14]=[C:15]([CH3:16])[C:7]1=2)[CH3:2]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 533885265-Bromo-1,3,4-thiadiazole-2-carbonitrileHCID 58292549Ethyl 2-(1,6-dihydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetate

Product 1

HCID 67252448Ethyl 2-(6-(5-cyano-1,3,4-thiadiazol-2-yloxy)-1-hydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetateYield 72%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of (1,6-dihydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl)-acetic acid ethyl ester (0.44 g, 1.75 mmol) in acetonitrile (30 mL) was added 5-bromo-[1,3,4]thiadiazole-2-carbonitrile (0.6 g, 3.16 mmol) and potassium carbonate (0.73 g, 5.25 mmol). The suspension was heated at 60° C. for 6 hours. The mixture was cooled to 0° C., diluted with water and extracted with EtOAc (2×50 mL). The organic extracts were combined, dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel flash column chromatography (30-60% EtOAc/hexane) to give [6-(5-cyano-[1,3,4]thiadiazol-2-yloxy)-1-hydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl]-acetic acid ethyl ester (0.44 g, 72%). 1H NMR (400 MHz, DMSO-d6) δ ppm 9.41 (s, 1H), 7.55 (d, J=2.21 Hz, 1H), 7.43 (d, J=1.62 Hz, 1H), 5.59 (dd, J=8.72, 2.73 Hz, 1H), 4.04 (q, J=6.92 Hz, 2H), 3.16 (dd, J=15.56, 2.94 Hz, 1H), 2.37-2.43 (m, 1H), 2.35 (s, 3H), 1.14 (t, J=7.17 Hz, 3H).

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. extractionextracted with EtOAc (2×50 mL)
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel flash column chromatography (30-60% EtOAc/hexane)

Sources & evidence

ORD record
ord-8854b670f1f84ffaaa2bd22a73e353c0
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

Loading…