4-Bromo-1,1,2-trifluorobut-1-ene → HCID 23035376, compound

HRID 1710017Notes

Reaction equation

HRID 1710017 reaction equation
[Na].[N+:2]([C:5]1[CH:10]=[CH:9][C:8]([CH2:11][S:12][C:13]2[N:17]=[C:16]([SH:18])[S:15][N:14]=2)=[CH:7][CH:6]=1)([O-:4])=[O:3].Br[CH2:20][CH2:21][C:22]([F:26])=[C:23]([F:25])[F:24]>C(O)C.C(Cl)Cl>[N+:2]([C:5]1[CH:10]=[CH:9][C:8]([CH2:11][S:12][C:13]2[N:17]=[C:16]([S:18][CH2:20][CH2:21][C:22]([F:26])=[C:23]([F:25])[F:24])[S:15][N:14]=2)=[CH:7][CH:6]=1)([O-:4])=[O:3]

Participants

6

Reactant 3

HCID 663334-Bromo-1,1,2-trifluorobut-1-eneHCID 5360545SodiumHCID 178526642HCID 178526642, compound

Product 1

HCID 23035376HCID 23035376, compoundYield 62.8%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 0.25 gram (0.011 mole) of sodium in 35 ml of ethanol was stirred and 2.7 grams (0.0095 mole) of 3-(4-nitrophenylmethylthio)-5-mercapto-1,2,4-thiadiazole was added. Upon completion of addition the reaction mixture was stirred at ambient temperature for one hour. The ethanol solvent was removed under reduced pressure. The residue was dissolved in 35 ml of methyl ethyl ketone and 1.6 grams (0.0085 mole) of 4-bromo-1,1,2-trifluoro-1-butene was added. Upon completion of addition the reaction mixture was stirred for 16 hours, then was concentrated under reduced pressure to a residue. The residue was dissolved in 50 ml of toluene and washed with 25 ml of water, two 25 ml portions of aqueous 5% sodium hydroxide solution, and 25 ml of water. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield a residual oil. The oil was dissolved in methylene chloride and passed through a column of silica gel. The eluate was concentrated under reduced pressure to yield 2.1 grams of 3-(4-nitrophenylmethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-thiadiazole. The nmr spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of addition the reaction mixture
  2. customThe ethanol solvent was removed under reduced pressure
  3. dissolutionThe residue was dissolved in 35 ml of methyl ethyl ketone
  4. additionUpon completion of addition the reaction mixture
  5. stirringwas stirred for 16 hours
  6. concentrationwas concentrated under reduced pressure to a residue
  7. dissolutionThe residue was dissolved in 50 ml of toluene
  8. washwashed with 25 ml of water, two 25 ml portions of aqueous 5% sodium hydroxide solution, and 25 ml of water
  9. dry with materialThe organic layer was dried with sodium sulfate
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated under reduced pressure
  12. customto yield a residual oil
  13. concentrationThe eluate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-cb7a7e4fbd6548ba8a58fae3184962b9
Source dataset
uspto-grants-1990_08
Patent number
US04952580

Reaction notes

Loading…