p-Chlorothiophenol → HCID 15050275, compound

HRID 2284378Notes

Reaction equation

HRID 2284378 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([SH:8])=[CH:4][CH:3]=1.Cl[CH2:10][C:11](=[O:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14].C(N(CC)CC)C.NN>C(Cl)Cl.C(O)C.O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][CH2:10][C:11](=[O:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 7815p-ChlorothiophenolHCID 8471TriethylamineHCID 9321HydrazineHCID 69484Ethyl 4-chloroacetoacetate

Product 1

HCID 15050275HCID 15050275, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

4-Chlorothiophenol (1.1 g, 7.61 mmol) was mixed with ethyl 4-chloro-acetoacetate (0.95 mL, 7.00 mmol) in CH2Cl2 (100 mL) at 0° C. Triethyl amine (1.5 mL, 10.8 mmol) was then added drop wise. After the resulting suspension was stirred at 0° C. for another 30 min, the reaction mixture was poured into water, and the aqueous layer was extracted with EtOAc. The combined organic layer was washed by saturated NaHCO3, HCl (0.25 N), brine, concentrated in vacuo, and purified by flash column chromatography (ethyl acetate/hexanes=1/9) to afford TC-I-164 (1.82 g, 96%) as light yellow oil. Exposure to hydrazine in refluxing ethanol, generated TC-II-165.

Workup

  1. extractionthe aqueous layer was extracted with EtOAc
  2. washThe combined organic layer was washed by saturated NaHCO3, HCl (0.25 N), brine
  3. concentrationconcentrated in vacuo
  4. custompurified by flash column chromatography (ethyl acetate/hexanes=1/9)
  5. customto afford TC-I-164 (1.82 g, 96%) as light yellow oil

Sources & evidence

ORD record
ord-dae7ba4a706048dd9bb525dbd170b47e
Source dataset
uspto-grants-2015_09
Patent number
US09145424B2

Reaction notes

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