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

HRID 1798293Notes

Reaction equation

HRID 1798293 reaction equation
O.[CH2:2]([O:4][C:5](=[O:27])[CH2:6][CH:7]1[O:11][B:10]([OH:12])[C:9]2[CH:13]=[C:14]([O:18][C:19]3[S:20][C:21]([N+:24]([O-])=O)=[N:22][N:23]=3)[CH:15]=[C:16]([CH3:17])[C:8]1=2)[CH3:3]>Cl.C(O)C.[Fe]>[CH2:2]([O:4][C:5](=[O:27])[CH2:6][CH:7]1[O:11][B:10]([OH:12])[C:9]2[CH:13]=[C:14]([O:18][C:19]3[S:20][C:21]([NH2:24])=[N:22][N:23]=3)[CH:15]=[C:16]([CH3:17])[C:8]1=2)[CH3:3]

Participants

6

Reactant 2

HCID 962WaterHCID 58292621Ethyl 2-(1-hydroxy-4-methyl-6-(5-nitro-1,3,4-thiadiazol-2-yloxy)-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetate

Product 1

HCID 58292641Ethyl 2-(6-(5-amino-1,3,4-thiadiazol-2-yloxy)-1-hydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetateYield 108.9%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidCatalystHCID 23925IronCatalystHCID 702EthanolSolvent

Conditions

Temperature
85 °C

Procedure

Concentrated HCl (10 drops) and water (12 ml) were added to a mixture of [6-(5-nitro-[1,3,4]thiadiazol-2-yloxy)-1-hydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl]-acetic acid ethyl ester (0.65 g, 1.71 mmol) and iron powder (0.479 g; 8.55 mmol) in ethanol (30 mL) at room temperature. The resulting mixture was stirred at 85° C. for 1.5 hours, cooled to room temperature and filtered through a pad of celite. The filtrate was evaporated and the residue dissolved in EtOAc (300 mL), washed with brine, dried over Na2SO4 and concentrated to give [6-(5-amino-[1,3,4]thiadiazol-2-yloxy)-1-hydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl]-acetic acid ethyl ester (0.650 g, 100%) which was used without further purification. 1HNMR (400 MHz, DMSO-d6) δ 9.33 (s, 1H), 7.33 (d, J=12.4 Hz, 1H), 7.18 (d, J=16.8 Hz, 1H), 5.51 (d, J=6.0 Hz, 1H), 4.02 (q, J=7.2 Hz, 2H), 3.10 (d, J=14.4 Hz, 1H), 2.33-2.31 (m, 1H), 2.30 (s, 3H), 1.10 (t, J=7.6 Hz, 3H). MS (ESI) m/z=350 [M+H]+.

Workup

  1. temperaturecooled to room temperature
  2. filtrationfiltered through a pad of celite
  3. customThe filtrate was evaporated
  4. dissolutionthe residue dissolved in EtOAc (300 mL)
  5. washwashed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-9bfbf87d5f784bf6a3c4fbcfb8796ab7
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

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