Hydrochloric Acid → 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 1798297Notes

Reaction equation

HRID 1798297 reaction equation
Cl.O.[OH:3][B:4]1[C:8]2[CH:9]=[C:10]([O:14][C:15]3[S:16][C:17]([N+:20]([O-])=O)=[N:18][N:19]=3)[CH:11]=[C:12]([CH3:13])[C:7]=2[CH:6]([CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[O:5]1>C(O)C.[Fe]>[NH2:20][C:17]1[S:16][C:15]([O:14][C:10]2[CH:11]=[C:12]([CH3:13])[C:7]3[CH:6]([CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[O:5][B:4]([OH:3])[C:8]=3[CH:9]=2)=[N:19][N:18]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 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 63.6%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Conditions

Temperature
85 °C

Procedure

Concentrated aq. HCl (50 mL) and water (1000 mL) were added to a mixture of ethyl 2-(1-hydroxy-4-methyl-6-(5-nitro-1,3,4-thiadiazol-2-yloxy)-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetate (70 g, 0.18 mol) and iron powder (51 g, 0.9 mol) in ethanol (3000 mL) at room temperature. The resulting mixture was stirred at 85° C. for 2 hrs, cooled to room temperature and filtered through a pad of celite. The filtrate was evaporated and the residue dissolved in EtOAc, washed with brine, dried over Na2SO4 and concentrated to give compound 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 (40 g, 63% yield) which was used without further purification. 1H NMR (400 MHz, DMSO-d6) δ 9.30 (1H, s), 7.32 (1H, m), 7.16 (1H, m), 7.15 (2H, s), 5.50 (1H, m), 4.03 (2H, m), 3.08 (1H, m), 2.32 (4H, m), 1.10 (3H, m).

Workup

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

Sources & evidence

ORD record
ord-a04804ec6e1643a5bf55b9fbb1852015
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

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