Chloromethyl Methyl Ether → HCID 57792036, compound

HRID 421987Notes

Reaction equation

HRID 421987 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([NH:8][C:9]2[S:10][CH:11]=[CH:12][N:13]=2)[N:5]=[C:4]([C:14]([O:16][CH3:17])=[O:15])[CH:3]=1.[H-].[Na+].Cl[CH2:21][O:22][CH3:23].C(=O)(O)[O-].[Na+]>C(N(CC)C(C)C)(C)C>[Br:1][C:2]1[CH:7]=[C:6]([N:8]([CH2:21][O:22][CH3:23])[C:9]2[S:10][CH:11]=[CH:12][N:13]=2)[N:5]=[C:4]([C:14]([O:16][CH3:17])=[O:15])[CH:3]=1

Participants

6

Reactant 4

HCID 7864Chloromethyl Methyl Ether2×HCID 24758Sodium hydride2×HCID 516892Sodium BicarbonateHCID 46941893Methyl 4-bromo-6-(2-thiazolylamino)-2-pyridinecarboxylate

Product 1

HCID 57792036HCID 57792036, compound

Reagents, catalysts & solvents 1

HCID 81531DiisopropylethylamineSolvent

Procedure

To a mixture of 34.3 g of methyl 4-bromo-6-(1,3-thiazol-2-ylamino)pyridine-2-carboxylate and 440 ml of N,N-diisopropylethylamine was added 5.29 g of sodium hydride (60%, in oil) under an ice bath followed by stirring at the ambient temperature for 30 minutes. To the reaction mixture was added 9.9 ml of chloromethylmethyl ether followed by stirring at the ambient temperature for 4 hours. To the reaction mixture was added 4.52 g of sodium hydride (60%, in oil) and 8.3 ml of chloromethylmethyl ether, followed by further stirring for three hours. After warming to room temperature, to the reaction mixture was added saturated aqueous sodium bicarbonate. The precipitate was filtered off and washed with water. The filtrate was extracted with ethyl acetate and then the organic layer was washed with water and saturated brine. The resulting organic layer was dried over anhydrous sodium sulfate, filtered and the filtrate was concentrated in vacuo. The resulting residue was purified by a silica gel column chromatography (eluent: hexane/ethyl acetate=9/1 to 3/1) to give the title compound as a pale yellow solid.

Workup

  1. stirringby stirring at the ambient temperature for 4 hours
  2. stirringby further stirring for three hours
  3. temperatureAfter warming to room temperature, to the reaction mixture
  4. filtrationThe precipitate was filtered off
  5. washwashed with water
  6. extractionThe filtrate was extracted with ethyl acetate
  7. washthe organic layer was washed with water and saturated brine
  8. dry with materialThe resulting organic layer was dried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated in vacuo
  11. customThe resulting residue was purified by a silica gel column chromatography (eluent: hexane/ethyl acetate=9/1 to 3/1)

Sources & evidence

ORD record
ord-9d3ee685942d4650abdba35bc1349b02
Source dataset
uspto-grants-2012_01
Patent number
US08101621B2

Reaction notes

Loading…