Ethyl bromoacetate → HCID 91376496, compound

HRID 1925191Notes

Reaction equation

HRID 1925191 reaction equation
C(=O)([O-])[O-].[K+].[K+].Br[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].C(OC(=O)C[N:19]1[C:23]([C:24]2[CH:29]=[CH:28][N:27]=[CH:26][CH:25]=2)=[N:22][C:21]([C:30]2[CH:35]=[C:34]([Cl:36])[CH:33]=[C:32]([Cl:37])[CH:31]=2)=[N:20]1)C>O>[CH2:12]([O:11][C:9](=[O:10])[CH2:8][N:20]1[C:21]([C:30]2[CH:35]=[C:34]([Cl:36])[CH:33]=[C:32]([Cl:37])[CH:31]=2)=[N:22][C:23]([C:24]2[CH:29]=[CH:28][N:27]=[CH:26][CH:25]=2)=[N:19]1)[CH3:13]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 91594767HCID 91594767, compound

Product 1

HCID 91376496HCID 91376496, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Iso-nicotinic hydrazide (1.0 g, 7.3 mmol), 3,5-dichlorobenzonitrile (1.5 g, 8.8 mmol), and sodium ethoxide (1.5 g, 22 mmol) were transferred to a pressure tube. Ethanol (4 mL) was added and the reaction was stirred at 120° C. overnight. The reaction was monitored by LCMS. Upon completion, the ethanol was removed in vacuo to afford the triazole as a solid and carried on to the next step without purification. This material was dissolved in DMF (10 mL), and potassium carbonate (1.5 g, 11 mmol) and ethyl bromoacetate (1.2 mL, 11 mmol) were added. The reaction was stirred at room temperature overnight. The reaction was monitored by LCMS. Upon completion, the reaction mixture was diluted with water. The precipitate was collected via vacuum filtration and the filtrate was discarded. The crude product was purified by silica gel chromatography (3:2 hexanes/ethyl acetate) to afford two regioisomers as solids. 1H NMR (400 MHz, d6-DMSO): δ 8.7 (d, 21, 7.95 (s, 2H), 7.9 (d, 1H), 7.8 (d, 2H), 5.5 (s, 2H), 4.1 (q, 2H), 1.1 (t, 3H). MS (EI) for C17H14N4O2Cl2: 377 (MH+). Ethyl[3-(3,5-dichlorophenyl)-5-pyridin-4-yl-1H-1,2,4-triazol-1-yl]acetate: 1H NMR (400 MHz, d6-DMSO): δ 8.8 (d, 2H), 8.0 (s, 2H), 7.8 (m, 3H), 5.5 (s, 2H), 4.1 (q, 2H), 1.2 (t, 3H). MS (EI) for C17H14N4O2Cl2: 377 (MH+).

Workup

  1. customcarried on to the next step without purification
  2. dissolutionThis material was dissolved in DMF (10 mL)
  3. filtrationThe precipitate was collected via vacuum filtration
  4. customThe crude product was purified by silica gel chromatography (3:2 hexanes/ethyl acetate)
  5. customto afford two regioisomers as solids

Sources & evidence

ORD record
ord-da35fdebcf164a17820c39697b187a8e
Source dataset
uspto-grants-2012_05
Patent number
US08178570B2

Reaction notes

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