Ethyl 2-chloroacetoacetate → HCID 14500732, compound

HRID 2350903Notes

Reaction equation

HRID 2350903 reaction equation
[CH3:1][CH:2]([NH:4][C:5](=S)[NH:6][NH2:7])[CH3:3].[Cl:9][CH:10]([C:16]([CH3:18])=O)[C:11]([O:13][CH2:14][CH3:15])=[O:12]>O1CCCC1>[ClH:9].[CH3:18][C:16]1[NH:7][N:6]=[C:5]([NH:4][CH:2]([CH3:3])[CH3:1])[C:10]=1[C:11]([O:13][CH2:14][CH3:15])=[O:12]

Participants

4

Reactant 2

HCID 11858Ethyl 2-chloroacetoacetateHCID 18093764-Isopropyl-3-thiosemicarbazide

Product 1

HCID 14500732HCID 14500732, compoundYield 33.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A stirred slurry of 10.5 g (0.079 mole) of 4-(2-propanyl)-3-thiosemicarbazide in 100 mL of tetrahydrofuran under nitrogen atmosphere was treated with 13 g (0.079 mole) of ethyl 2-chloroacetoacetate. After 30 minutes the reaction mixture became suddenly exothermic, turning green-yellow and amorphous sulfur separated. The reaction mixture was stirred at ambient temperature for 2 hr, diluted with water, made acidic with 3N hydrochloric acid and filtered to remove the insoluble sulfur. The filtrate was adjusted to pH 8 with sodium carbonate and extracted with 3×50 mL of methylene chloride. The extracts were combined, washed with water, dried over magnesium sulfate and the filtrate concentrated in vacuo. The oily residue in acetone was treated with ethereal hydrogen chloride and diluted with an equal volume of isopropyl ether to five the crude product. Recrystallization from acetone gave 6.6 g of large beige crystals, mp 158°-159° C., as the hydrochloride salt.

Workup

  1. customamorphous sulfur separated
  2. additiondiluted with water
  3. filtrationfiltered
  4. customto remove the insoluble sulfur
  5. extractionextracted with 3×50 mL of methylene chloride
  6. washwashed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationthe filtrate concentrated in vacuo
  9. additionThe oily residue in acetone was treated with ethereal hydrogen chloride
  10. additiondiluted with an equal volume of isopropyl ether to five the crude product
  11. customRecrystallization from acetone

Sources & evidence

ORD record
ord-f412f252888e490bb1a9afe0b8fd593c
Source dataset
uspto-grants-1989_10
Patent number
US04871737

Reaction notes

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