Hydrochloric Acid → HCID 14500717, compound

HRID 2350893Notes

Reaction equation

HRID 2350893 reaction equation
[CH3:1][CH:2]([NH:5][C:6](=S)[NH:7][NH2:8])[CH2:3][CH3:4].[Cl:10][CH:11]([C:17]([CH3:19])=O)[C:12]([O:14][CH2:15][CH3:16])=[O:13].Cl>C(O)C>[ClH:10].[CH3:19][C:17]1[NH:8][N:7]=[C:6]([NH:5][CH:2]([CH3:1])[CH2:3][CH3:4])[C:11]=1[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

5

Reactant 3

HCID 313Hydrochloric Acid2×HCID 11858Ethyl 2-chloroacetoacetate2×HCID 3962768N-(Butan-2-yl)hydrazinecarbothioamide

Product 1

HCID 14500717HCID 14500717, compoundYield 43.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

A stirred solution of 5.1 g (0.035 mole) of 4-(2-butyl)-3-thiosemicarbazide in 40 mL of absolute ethanol was treated with 5.7 g (0.035 mole) of ethyl 2-chloroacetoacetate and stirred at ambient temperature for 3 hr. The mixture was treated with 20 mL of 2N ethanolic hydrogen chloride, heated at reflux for 1 hr and stirred for ~16 hr at ambient temperature. The reaction mixture after filtering and concentrating in vacuo gave a crude orange solid. A second reaction mixture was prepared with 8.0 g (0.054 mole) of crude 4-(2-buytl)-3-thiosemicarbazide, 50 mL of absolute ethanol, 8.9 g (0.054 mole) of ethyl 2-chloroacetoacetate, and 25 mL of 2N ethanolic hydrogen chloride as described above and gave a crude orange solid. The TLC of both crude products (10% methanol/benzene; silica gel) were identical. Recrystallization of the first batch from acetone/isopropyl ether gave 4 g of fine white crystals, mp 147°-148.5° C. Recrystallization of the second batch from benzene/ligroin gave 2.5 g of pale yellow crystalline product, mp 146°-148.5° C. The 2 solids were combined (6.5 g) and recrystallized from 200 mL of acetone/isopropyl ester (3:1) to give 3.6 g of white fluffy crystals, mp 147°-149° C.

Workup

  1. temperatureheated
  2. temperatureat reflux for 1 hr
  3. stirringstirred for ~16 hr at ambient temperature
  4. filtrationThe reaction mixture after filtering
  5. concentrationconcentrating in vacuo
  6. customgave a crude orange solid
  7. customA second reaction mixture
  8. customgave a crude orange solid
  9. customRecrystallization of the first batch from acetone/isopropyl ether

Sources & evidence

ORD record
ord-e4837c1ebfee4763b4286cc6406229b1
Source dataset
uspto-grants-1989_10
Patent number
US04871737

Reaction notes

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