Hexane → 2-Methoxycarbonylmethyl-4,5-bis-phenylthiazole

HRID 544644Notes

Reaction equation

HRID 544644 reaction equation
[C:1]1([C:7]2[CH:11]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[S:10][C:9](=S)[N:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Na+].CCCCCC.[CH3:27][O:28][C:29](=[O:32])[CH2:30]Br>CN(C)P(=O)(N(C)C)N(C)C>[CH3:27][O:28][C:29]([CH2:30][C:9]1[S:10][C:11]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[N:8]=1)=[O:32]

Participants

6

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 60984Methyl bromoacetateHCID 132096534,5-Bis-phenylthiazoline-2-thione

Product 1

HCID 204583882-Methoxycarbonylmethyl-4,5-bis-phenylthiazole

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Procedure

The starting material can be produced, for example, in the following manner: 6 g of 4,5-bis-phenylthiazoline-2-thione are dissolved in 50 ml of hexamethylphosphoric acid triamide, the solution is cooled to 5° and, while stirring, sodium hydride (0.89 g of a 50% strength suspension in mineral oil, de-oiled with hexane) is added. The mixture is stirred for 30 minutes at room temperature, 3.57 g of bromoacetic acid methyl ester are slowly added dropwise, the mixture is then stirred for 1 hour at room temperature, poured into 500 ml of ice-water, extracted by shaking twice with 300 ml of ethyl acetate each time, washed with water, dried over magnesium sulphate and concentrated to dryness by evaporation under reduced pressure. The remaining oil is dissolved in toluene and purified by chromatography over 50 g of silica gel. The eluate with toluene/ethyl acetate (95:5) is concentrated by evaporation under reduced pressure. 2-Methoxycarbonylmethyl-4,5-bis-phenylthiazole having a melting point of 65°-67° is obtained.

Workup

  1. temperaturethe solution is cooled to 5°
  2. stirringThe mixture is stirred for 30 minutes at room temperature
  3. stirringthe mixture is then stirred for 1 hour at room temperature
  4. extractionextracted
  5. stirringby shaking twice with 300 ml of ethyl acetate each time
  6. washwashed with water
  7. dry with materialdried over magnesium sulphate
  8. concentrationconcentrated to dryness by evaporation under reduced pressure
  9. dissolutionThe remaining oil is dissolved in toluene
  10. custompurified by chromatography over 50 g of silica gel
  11. concentrationThe eluate with toluene/ethyl acetate (95:5) is concentrated by evaporation under reduced pressure

Sources & evidence

ORD record
ord-a8addc3646994d0d9ac4a838efb52014
Source dataset
uspto-grants-1984_05
Patent number
US04451471

Reaction notes

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