Phenothiazine → 2-(Trifluoromethylsulfonamido)ethyl methacrylate

HRID 1817984Notes

Reaction equation

HRID 1817984 reaction equation
C(N(CC)CC)C.Cl.[CH3:9][C:10](=[CH2:17])[C:11]([O:13][CH2:14][CH2:15][NH2:16])=[O:12].C1C2NC3C(=CC=CC=3)SC=2C=CC=1.[F:32][C:33]([F:39])([F:38])[S:34](Cl)(=[O:36])=[O:35]>C(#N)C>[CH3:17][C:10](=[CH2:9])[C:11]([O:13][CH2:14][CH2:15][NH:16][S:34]([C:33]([F:39])([F:38])[F:32])(=[O:36])=[O:35])=[O:12]

Participants

6

Reactant 4

HCID 7108PhenothiazineHCID 8471TriethylamineHCID 75495Aminoethyl methacrylate hydrochlorideHCID 79000Trifluoromethanesulfonyl chloride2×

Product 1

HCID 119842502-(Trifluoromethylsulfonamido)ethyl methacrylate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

In a 1-liter three-neck flask equipped with a thermometer, a reflex condenser and a calcium chloride tube were placed 350 g of acetonitrile, 70.7 g (0.699 mol) of triethylamine, 33.1 g (0.200 mol) of 2-aminoethyl 2-methylacrylate hydrochloride and 0.2 g of phenothiazine, followed by cooling to −30o C with stirring. After the inside temperature of the flask reached −30° C., 40.3 g (0.239 mol) of trifluoromethanesulfonyl chloride was introduced as a gas into the slurry over 1 hour. Upon completion of the gas introduction, the reaction solution was stirred for 1 hour and then warmed to room temperature. The solvent (acetonitrile) and the unreacted reaction substrate (trifluoromethanesulfonyl chloride) were evaporated from the reaction solution under a reduced pressure. To the solution was added 1 liter of diisopropyl ether. The resulting slurry was subjected to filtration to filter out a precipitate of triethylamine hydrochloride. The filtrate was washed three times with 200 g of 10% aqueous sodium chloride solution, and then, dried with 40 g of magnesium sulfate. The magnesium sulfate was removed by filtration. After that, 0.2 g of phenothiazine was added to the organic phase. The solvent was evaporated to obtain 22.5 g of a crude reaction product. The crude reaction product was subjected to distillation under a reduced pressure, thereby yielding 9.9 g of target 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-methylacrylate as an organic fraction at 105-115° C. /13Pa. The purity of the 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-methylacrylate was determined by gas chromatography to be 98.0%. The yield of the 2-{[(trifluoromethyl)sulfonyl]amino}ethyl 2-methylacrylate was 19%.

Workup

  1. customIn a 1-liter three-neck flask equipped with a thermometer, a reflex condenser and a calcium chloride tube
  2. temperatureby cooling to −30o C
  3. customreached −30° C.
  4. stirringUpon completion of the gas introduction, the reaction solution was stirred for 1 hour
  5. customwere evaporated from the reaction solution under a reduced pressure
  6. additionTo the solution was added 1 liter of diisopropyl ether
  7. filtrationThe resulting slurry was subjected to filtration
  8. filtrationto filter out a precipitate of triethylamine hydrochloride
  9. washThe filtrate was washed three times with 200 g of 10% aqueous sodium chloride solution
  10. dry with materialdried with 40 g of magnesium sulfate
  11. customThe magnesium sulfate was removed by filtration
  12. additionAfter that, 0.2 g of phenothiazine was added to the organic phase
  13. customThe solvent was evaporated
  14. customto obtain 22.5 g of a crude
  15. customreaction product
  16. customThe crude reaction product
  17. distillationwas subjected to distillation under a reduced pressure

Sources & evidence

ORD record
ord-031bf6467a954ba39ef3cb5f3007546b
Source dataset
uspto-grants-2009_10
Patent number
US07598413B2

Reaction notes

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