Ethanol → HCID 58426411, compound

HRID 1468587Notes

Reaction equation

HRID 1468587 reaction equation
O.[NH2:2][NH2:3].C(O)C.[F:7][C:8]([F:15])([CH3:14])[C:9](OCC)=O.C(S[C:19]([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[N:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)C>C(O)CCC>[F:15][C:8]([C:9]1[N:20]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:19]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[N:3][N:2]=1)([F:7])[CH3:14]

Participants

6

Reactant 4

HCID 702EthanolHCID 24654Hydrazine hydrate (1:1)HCID 2761188Ethyl 2,2-difluoropropanoateHCID 13377974Ethyl N-phenylbenzenecarboximidothioate

Product 1

HCID 58426411HCID 58426411, compoundYield 27%

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent

Conditions

Temperature
-10 °C

Procedure

Next, 0.54 g (11 mmol) of hydrazine monohydrate and 10 mL of ethanol were put in a 100 mL three-neck flask and stirred at −10° C. for 15 minutes. Then, 1.5 g (11 mmol) of ethyl 2,2-difluoropropionate was dripped to this mixed solution at −10° C. little by little, and the solution was stirred for 48 hours while the temperature was increased to room temperature. Then, 2.6 g (11 mmol) of N-[(ethylsulfanyl)phenylmethylidene]aniline prepared in Step 1 and 20 mL of 1-butanol were added to this mixed solution, and the mixed solution was refluxed at 110° C. for 8 hours. After the reflux, the solvent was distilled off under a reduced pressure to give an oily substance. The given oily substance was purified by silica gel column chromatography. As developing solvents, first, toluene was used, and then ethyl acetate was used. The obtained fraction was concentrated to give a solid. This solid was recrystallized from a mixed solvent of ethanol and hexane, so that 3-(1,1-difluoroethyl)-4,5-diphenyl-4H-1,2,4-triazole (abbreviation: HMCF2ptz) was prepared (a white solid, yield: 27%). The synthesis scheme of Step 2 is shown by (b-1).

Workup

  1. customwas dripped to this mixed solution at −10° C.
  2. stirringwas stirred for 48 hours while the temperature
  3. temperaturewas increased to room temperature
  4. temperaturethe mixed solution was refluxed at 110° C. for 8 hours
  5. distillationAfter the reflux, the solvent was distilled off under a reduced pressure
  6. customto give an oily substance
  7. customThe given oily substance was purified by silica gel column chromatography
  8. concentrationThe obtained fraction was concentrated
  9. customto give a solid
  10. customThis solid was recrystallized from a mixed solvent of ethanol and hexane, so that 3-(1,1-difluoroethyl)-4,5-diphenyl-4H-1,2,4-triazole (abbreviation: HMCF2ptz)
  11. customwas prepared (a white solid, yield: 27%)
  12. customThe synthesis scheme of Step 2

Sources & evidence

ORD record
ord-8db695c882e246cf8e98a2525a299cfa
Source dataset
uspto-grants-2015_04
Patent number
US09005773B2

Reaction notes

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