Ethyl 2-chloroacetoacetate → AC1N4D2J

HRID 1761531Notes

Reaction equation

HRID 1761531 reaction equation
[C:1]1([NH:7][C:8](=S)[NH:9][NH2:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl[CH:13]([C:19]([CH3:21])=O)[C:14]([O:16][CH2:17][CH3:18])=[O:15].NNC(N)=S>C(O)C>[CH3:21][C:19]1[NH:10][N:9]=[C:8]([NH:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C:13]=1[C:14]([O:16][CH2:17][CH3:18])=[O:15]

Participants

5

Reactant 3

HCID 11858Ethyl 2-chloroacetoacetateHCID 730679Hydrazinecarbothioamide, N-phenyl-HCID 2723789Thiosemicarbazide

Product 1

HCID 4153579AC1N4D2J

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A suspension of 16.7 g (0.1 mole) of 4-phenyl-3-thiosemicarbazide in 60 mL of absolute ethanol was treated with 16.5 g (0.1 mole) of ethyl 2-chloroacetoacetate and the mixture stirred for 1 hr at room temperature. As the thiosemicarbazide began to dissolve the reaction mixture became exothermic and a reddish-brown solid precipitated. Alcoholic hydrogen chloride (2N, 50 mL) was added, and the reaction mixture heated at reflux for 1.0 hr. The solution was filtered while hot and the filtrate was evaporated under reduced pressure. The solid residue was triturated in cold absolute ethanol and a red solid collected by filtration. The solid was warmed in 2N hydrochloric acid (100 mL) and the suspended sulfur removed by filtration. An orange-red solid precipitated from the filtrate, was collected by filtration and air dried for ~16 hr (14.6 g, mp 160°-40° C.). Recrystallization from benzene left 10.5 g of product, mp 165°-6° C. The material was air dried and submitted for elemental analysis.

Workup

  1. dissolutionto dissolve the reaction mixture
  2. customa reddish-brown solid precipitated
  3. additionAlcoholic hydrogen chloride (2N, 50 mL) was added
  4. temperaturethe reaction mixture heated
  5. temperatureat reflux for 1.0 hr
  6. filtrationThe solution was filtered while hot and the filtrate
  7. customwas evaporated under reduced pressure
  8. customThe solid residue was triturated in cold absolute ethanol
  9. filtrationa red solid collected by filtration
  10. temperatureThe solid was warmed in 2N hydrochloric acid (100 mL)
  11. customthe suspended sulfur removed by filtration
  12. customAn orange-red solid precipitated from the filtrate
  13. filtrationwas collected by filtration and air
  14. customdried for ~16 hr (14.6 g, mp 160°-40° C.)
  15. customRecrystallization from benzene
  16. waitleft 10.5 g of product, mp 165°-6° C
  17. customdried

Sources & evidence

ORD record
ord-d0b271f3f49e43d5868b34e462459e90
Source dataset
uspto-grants-1989_05
Patent number
US04826866

Reaction notes

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