Hydrochloric Acid → HCID 14500682, compound

HRID 2350877Notes

Reaction equation

HRID 2350877 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9](=S)[NH:10][NH2:11].Cl[CH:14]([C:20]([CH3:22])=O)[C:15]([O:17][CH2:18][CH3:19])=[O:16].Cl.O>C(O)C.CC(C)=O.CO>[CH3:22][C:20]1[NH:11][N:10]=[C:9]([NH:8][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[CH3:1])[C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 11858Ethyl 2-chloroacetoacetateHCID 737133N-(2-Methylphenyl)hydrazinecarboximidothioic acid

Product 1

HCID 14500682HCID 14500682, compound

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 702EthanolSolventHCID 887MethanolSolvent

Procedure

A stirred slurry of 4-(2-methylphenyl)-3-thiosemicarbazide, 15.3 g (0.08 mole), in 100 mL of absolute ethanol was treated under nitrogen atmosphere with ethyl 2-chloroacetoacetate, 13.61 g (0.08 mole). After stirring for 1 hr the slurry had turned from white to yellow with most of the material going into solution. The reaction mixture was treated with 50 mL of 2N ethanolic hydrogen chloride and stirred for 18 hr., after which the reaction mixture was heated at reflux for 2 hours. A clear orange solution was decanted from some residual material. The hot solution was filtered through a sintered glass filter and the filtrate concentrated in vacuo to give a yellow solid residue. This residue was dissolved in 500 mL of acetone and 50 mL methanol. After filtering, the volume of the filtrate was concentrated to 125 mL under nitrogen atmosphere. The product was allowed to crystallize at ~7-10° C. for ~72 hr. Some sulfur crystals separated and were removed by filtration. The filtrate was again concentrated in vacuo to a solid. The solid was dissolved in hot acetone and upon cooling at ~7-10° C., long needle-like crystals formed and redissolved on warming to room temperature. The solution was treated with water and overnight gave pale, yellow needle-like crystals which, after drying, weighed 15 g, mp 156°-160° C. After 3 recrystallizations from benzene/ligroin a fine white crystalline solid was obtained (8.6 g, mp 160°-161° C.).

Workup

  1. stirringstirred for 18 hr
  2. temperature, after which the reaction mixture was heated
  3. temperatureat reflux for 2 hours
  4. customA clear orange solution was decanted from some residual material
  5. filtrationThe hot solution was filtered through a sintered glass
  6. filtrationfilter
  7. concentrationthe filtrate concentrated in vacuo
  8. customto give a yellow solid residue
  9. filtrationAfter filtering
  10. concentrationthe volume of the filtrate was concentrated to 125 mL under nitrogen atmosphere
  11. customto crystallize at ~7-10° C. for ~72 hr
  12. customSome sulfur crystals separated
  13. customwere removed by filtration
  14. concentrationThe filtrate was again concentrated in vacuo to a solid
  15. dissolutionThe solid was dissolved in hot acetone
  16. temperatureupon cooling at ~7-10° C.
  17. customlong needle-like crystals formed
  18. dissolutionredissolved
  19. customgave pale
  20. customyellow needle-like crystals which, after drying
  21. customAfter 3 recrystallizations from benzene/ligroin a fine white crystalline solid
  22. customwas obtained (8.6 g, mp 160°-161° C.)

Sources & evidence

ORD record
ord-39950f4d0d1442b3ac3cc76e8a0edfcf
Source dataset
uspto-grants-1989_10
Patent number
US04871737

Reaction notes

Loading…