Triethylamine → HCID 66939342, compound

HRID 1257330Notes

Reaction equation

HRID 1257330 reaction equation
Cl.[NH2:2][CH2:3][C:4]([C:6]1[CH:11]=[CH:10][C:9]([Cl:12])=[C:8]([Cl:13])[CH:7]=1)=O.[C:14]([O:17][CH2:18][C:19](Cl)=O)(=[O:16])[CH3:15].C(N(CC)CC)C.C(=O)([O-])O.[Na+].COC1C=CC(P2(=S)SP(=S)(C3C=CC(OC)=CC=3)[S:43]2)=CC=1>C(OCC)(=O)C.O1CCCC1>[C:14]([O:17][CH2:18][C:19]1[S:43][C:4]([C:6]2[CH:11]=[CH:10][C:9]([Cl:12])=[C:8]([Cl:13])[CH:7]=2)=[CH:3][N:2]=1)(=[O:16])[CH3:15]

Participants

8

Reactant 5

HCID 8471TriethylamineHCID 26297Acetoxyacetyl chlorideHCID 87949Lawesson's reagentHCID 516892Sodium Bicarbonate2×HCID 137240642-Amino-1-(3,4-dichlorophenyl)ethan-1-one--hydrogen chloride (1/1)

Product 1

HCID 66939342HCID 66939342, compoundYield 19%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 2-amino-1-(3,4-dichlorophenyl)ethanone hydrochloride (2.18 g, 9.06 mmol) in ethyl acetate (25 mL) was added 2-chloro-2-oxoethyl acetate (0.975 mL, 9.06 mmol), and triethylamine (3.8 mL, 27.2 mmol) was added dropwise under ice-cooling. The reaction mixture was stirred under ice-cooling for 30 min, and at room temperature for 1 hr. Saturated aqueous sodium hydrogen carbonate solution (20 mL) was added and the mixture was stirred overnight. The reaction mixture was extracted with ethyl acetate, washed successively with water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. Tetrahydrofuran (30 mL) and 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson reagent, 2.56 g, 6.34 mmol) was added to the residue, and the mixture was heated under reflux for 1 hr. To the reaction mixture was added saturated aqueous sodium hydrogen carbonate solution (15 mL) and the mixture was stirred for 1 hr, extracted with ethyl acetate, washed successively with water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, eluent: hexane-ethyl acetate) to give [5-(3,4-dichlorophenyl)-1,3-thiazol-2-yl]methyl acetate (364 mg, 13%) as a colorless oil. The present compound was reacted in the same manner as in Example 1 to give the title compound (260 mg, 83%) as colorless crystals.

Workup

  1. additionwas added dropwise under ice-
  2. temperaturecooling
  3. temperaturecooling for 30 min
  4. stirringthe mixture was stirred overnight
  5. extractionThe reaction mixture was extracted with ethyl acetate
  6. washwashed successively with water and saturated brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. temperaturethe mixture was heated
  10. temperatureunder reflux for 1 hr
  11. stirringthe mixture was stirred for 1 hr
  12. extractionextracted with ethyl acetate
  13. washwashed successively with water and saturated brine
  14. dry with materialdried over sodium sulfate
  15. concentrationconcentrated under reduced pressure
  16. customThe residue was purified by column chromatography (carrier: silica gel, eluent: hexane-ethyl acetate)

Sources & evidence

ORD record
ord-861eb0939b7a47d293173f184f2ac696
Source dataset
uspto-grants-2013_06
Patent number
US08461348B2

Reaction notes

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