Hydrochloric Acid → HCID 14500676, compound

HRID 1761532Notes

Reaction equation

HRID 1761532 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=S)[NH:10][NH2:11])=[CH:4][CH:3]=1.Cl[CH:14]([C:20]([CH3:22])=O)[C:15]([O:17][CH2:18][CH3:19])=[O:16].Cl.C(=O)(O)[O-].[Na+]>C(O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]2[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[C:20]([CH3:22])[NH:11][N:10]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11858Ethyl 2-chloroacetoacetateHCID 516892Sodium BicarbonateHCID 7069884-(4-Chlorophenyl)-3-thiosemicarbazide

Product 1

HCID 14500676HCID 14500676, compoundYield 13.6%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A suspension of 20.1 g (0.10 mole) of 4-(4-chlorophenyl)-3-thiosemicarbazide in 80 mL of absolute ethanol was treated with 16.5 g (0.10 mole) of ethyl 2-chloroacetoacetate and the mixture stirred for 1.0 hr at room temperature. Alcoholic hydrogen chloride (2N, 60 mL) was added and the dark precipitate dissolved while heating the mixture at reflux for 1.0 hr. The solution was filtered while hot, and the filter cake washed with absolute ethanol. The filtrate was evaporated under reduced pressure and the residue triturated in cold absolute ethanol and filtered. Both filter cakes were found to be the same compound by TLC (10% methanol in benzene on silica gel). The two were combined, dissolved in hot absolute ethanol (the hydrochloride salt was water insoluble), partially neutralized with saturated aqueous sodium bicarbonate, and the solid filtered (10.4 g, mp 212°-226° C.). A second crop was obtained by treating the filtrate with saturated aqueous sodium bicarbonate (11.5 g, mp 220°-225° C.). The second crop was recrystallized from absolute ethanol to give 3.8 g of product, mp 223°-225° C. This solid was dried at 100° C./0.1 mmHg/3 hr; then for ~16 hr at RT/0.1 mmHg.

Workup

  1. dissolutionthe dark precipitate dissolved
  2. temperaturewhile heating the mixture
  3. temperatureat reflux for 1.0 hr
  4. filtrationThe solution was filtered while hot, and the filter cake
  5. washwashed with absolute ethanol
  6. customThe filtrate was evaporated under reduced pressure
  7. customthe residue triturated in cold absolute ethanol
  8. filtrationfiltered
  9. dissolutiondissolved in hot absolute ethanol (the hydrochloride salt
  10. filtrationthe solid filtered (10.4 g, mp 212°-226° C.)
  11. customA second crop was obtained
  12. customThe second crop was recrystallized from absolute ethanol

Sources & evidence

ORD record
ord-c7e37893e5134933b31110d964a1f104
Source dataset
uspto-grants-1989_05
Patent number
US04826866

Reaction notes

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