Ammonium Chloride → Ethyl 4,5-dichloro-6-((1-ethoxymethyl-pyrazol-5-yl)-hydroxymethyl)-1,3-benzodioxole-2-carboxylate

HRID 1089160Notes

Reaction equation

HRID 1089160 reaction equation
C([Li])CCC.[CH2:6]([O:8][CH2:9][N:10]1[CH:14]=[CH:13][CH:12]=[N:11]1)[CH3:7].[Cl:15][C:16]1[C:24]2[O:23][CH:22]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[O:21][C:20]=2[CH:19]=[C:18]([CH:30]=[O:31])[C:17]=1[Cl:32].[Cl-].[NH4+]>CCCCCC.O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[Cl:15][C:16]1[C:24]2[O:23][CH:22]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[O:21][C:20]=2[CH:19]=[C:18]([CH:30]([C:14]2[N:10]([CH2:9][O:8][CH2:6][CH3:7])[N:11]=[CH:12][CH:13]=2)[OH:31])[C:17]=1[Cl:32]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 14748638Ethyl 4,5-dichloro-6-formyl-1,3-benzodioxole-2-carboxylateHCID 157143991-(ethoxymethyl)-1H-pyrazoleHCID 178418339Butyllithium

Product 1

HCID 15052557Ethyl 4,5-dichloro-6-((1-ethoxymethyl-pyrazol-5-yl)-hydroxymethyl)-1,3-benzodioxole-2-carboxylateYield 28.8%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

1.25 ml of 1.6M n-butyl lithium in n-hexane is added dropwise to a solution of 252 mg of 1-ethoxymethyl-pyrazole in 5 ml of tetrahydrofuran at -60° to -50° C. 0.4 ml of hexamethylphosphoric triamide is added to the mixture and the mixture is stirred at the same temperature for 1 hour. The mixture is added to a solution of 582 mg of ethyl 4,5-dichloro-6-formyl-1,3-benzodioxole-2-carboxylate in 10 ml of tetrahydrofuran at -60° to -50° C. and the mixture is stirred at the same temperature for 5 minutes. An aqueous saturated ammonium chloride solution is added to the mixture and the mixture is extracted with ethyl acetate. The extract is washed, dried and evaporated to remove solvent. The residue is purified by silica gel column chromatography (solvent; chloroform-acetone-ethanol) to give 240 mg of ethyl 4,5-dichloro-6-((1-ethoxymethyl-pyrazol-5-yl)-hydroxymethyl)-1,3-benzodioxole-2-carboxylate.

Workup

  1. stirringthe mixture is stirred at the same temperature for 5 minutes
  2. extractionthe mixture is extracted with ethyl acetate
  3. washThe extract is washed
  4. customdried
  5. customevaporated
  6. customto remove solvent
  7. customThe residue is purified by silica gel column chromatography (solvent; chloroform-acetone-ethanol)

Sources & evidence

ORD record
ord-a75fc72dc67148f3b861b8a003a4ad17
Source dataset
uspto-grants-1990_10
Patent number
US04965282

Reaction notes

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