Ethyl chloroformate → HCID 14424358, compound

HRID 1165126Notes

Reaction equation

HRID 1165126 reaction equation
C([Li])CCC.[F:6][C:7]([F:25])([F:24])[C:8]1[CH:13]=[CH:12][C:11]([C:14]2[S:15][C:16]([C:19]3[S:20][CH:21]=[CH:22][CH:23]=3)=[CH:17][N:18]=2)=[CH:10][CH:9]=1.[CH2:26]([O:28][C:29](Cl)=[O:30])[CH3:27]>CCCCCC.O1CCCC1.C(OCC)C>[CH2:26]([O:28][C:29]([C:21]1[S:20][C:19]([C:16]2[S:15][C:14]([C:11]3[CH:10]=[CH:9][C:8]([C:7]([F:6])([F:24])[F:25])=[CH:13][CH:12]=3)=[N:18][CH:17]=2)=[CH:23][CH:22]=1)=[O:30])[CH3:27]

Participants

7

Reactant 3

HCID 10928Ethyl chloroformateHCID 14424293HCID 14424293, compoundHCID 178418339Butyllithium

Product 1

HCID 14424358HCID 14424358, compoundYield 45.6%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

Under a dry nitrogen atmosphere, 1.6 ml of a 2.5 M solution of n-butyllithium in n-hexane was added dropwise to a stirred, cold (-78° C.) solution of 1.0 g (0.0032 mole) of 2-(4-trifluoromethylphenyl)-5-thien-2-ylthiazole in 15 ml of tetrahydrofuran. This mixture was stirred at -78° C. for two hours and then was added to a stirred, cold (-78° C.) solution of 0.70 g (0.0064 mole) of ethylchloroformate in 20 ml of tetrahydrofuran. After complete addition the mixture was allowed to warm to room temperature and was stirred for approximately 18 hours. The mixture was diluted with 100 ml of diethyl ether and was washed in succession with an aqueous, saturated ammonium chloride solution, water, and an aqueous, saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure, leaving a solid. This solid was purified by column chromatography on silica gel, eluting with methylene chloride:n-hexane (60:40) to yield 0.56 g of 5-(5-ethoxycarbonylthien-2-yl)-2-(4-trifluoromethylphenyl)thiazole as a solid, compound 1 of Table 1.

Workup

  1. additionAfter complete addition the mixture
  2. temperatureto warm to room temperature
  3. stirringwas stirred for approximately 18 hours
  4. washwas washed in succession with an aqueous, saturated ammonium chloride solution, water
  5. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  6. filtrationwas filtered
  7. customThe filtrate was evaporated under reduced pressure
  8. customleaving a solid
  9. customThis solid was purified by column chromatography on silica gel
  10. washeluting with methylene chloride:n-hexane (60:40)

Sources & evidence

ORD record
ord-c33cb29dbb7c44f6b65b9178554f8a2a
Source dataset
uspto-grants-1990_03
Patent number
US04908357

Reaction notes

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