Ethyl chloroformate → HCID 69217764, compound

HRID 2221809Notes

Reaction equation

HRID 2221809 reaction equation
[O:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[O:7][C:8]([CH3:39])=[C:9]([CH2:11][O:12][C:13]2[CH:36]=[CH:35][C:16]([CH2:17][O:18][C:19]3[C:23]([CH:24]=[CH:25][C:26]([OH:28])=O)=[CH:22][N:21]([C:29]4[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=4)[N:20]=3)=[CH:15][C:14]=2[O:37][CH3:38])[N:10]=1.C(Cl)(=O)OCC.Cl.[NH2:47][CH2:48][CH2:49]Cl>O.O1CCCC1.C(N(CC)CC)C>[O:28]1[CH2:49][CH2:48][N:47]=[C:26]1/[CH:25]=[CH:24]/[C:23]1[C:19]([O:18][CH2:17][C:16]2[CH:35]=[CH:36][C:13]([O:12][CH2:11][C:9]3[N:10]=[C:6]([C:2]4[O:1][CH:5]=[CH:4][CH:3]=4)[O:7][C:8]=3[CH3:39])=[C:14]([O:37][CH3:38])[CH:15]=2)=[N:20][N:21]([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[CH:22]=1

Participants

7

Reactant 3

HCID 10928Ethyl chloroformateHCID 97937372-Chloroethylamine hydrochlorideHCID 69215040HCID 69215040, compound

Product 1

HCID 69217764HCID 69217764, compoundYield 35%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8471TriethylamineSolvent2×

Procedure

To a mixture of (2E)-{3-{3-[(4-([2-(2-furyl)-5-methyl-4-oxazolyl]methoxy}-3-methoxybenzyl)oxy]-1-phenyl-1H-pyrazol-4-yl}-2-propenoic acid (0.60 g), triethylamine (0.14 g) and tetrahydrofuran (30 mL) was added ethyl chlorocarbonate (0.15 g) at −30° C. The reaction mixture was stirred at the same temperature for 40 min and added to a mixture of 1-amino-2-chloroethane hydrochloride (0.66 g), triethylamine (0.58 g) and tetrahydrofuran (20 mL) at −30° C. After stirring the reaction mixture at room temperature for 1 hr, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. A mixture of the obtained residue, potassium carbonate (0.19 g) and N,N-dimethylformamide (20 mL) was stirred at 90° C. for 2 hrs. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 4-({4-[({4-[(E)-2-(4,5-dihydro-1,3-oxazol-2-yl)ethenyl]-1-phenyl-1H-pyrazol-3-yl}oxy)methyl]-2-methoxyphenoxy}methyl)-2-(2-furyl)-5-methyl-1,3-oxazole as pale-yellow crystals (0.22 g, yield 35%) from a fraction eluted with ethyl acetate-methanol (50:1, v/v). Recrystallization from ethyl acetate-hexane gave pale-yellow prism crystals. melting point: 162-163° C.

Workup

  1. stirringAfter stirring the reaction mixture at room temperature for 1 hr
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. additionA mixture of the obtained residue, potassium carbonate (0.19 g) and N,N-dimethylformamide (20 mL)
  7. stirringwas stirred at 90° C. for 2 hrs
  8. additionWater was poured into the reaction mixture
  9. extractionthe mixture was extracted with ethyl acetate
  10. washThe organic layer was washed with saturated brine
  11. dry with materialdried over anhydrous magnesium sulfate
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-b3c238841b094bb79e2f6448820b2372
Source dataset
uspto-grants-2008_05
Patent number
US07368578B2

Reaction notes

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