Hydrochloric Acid → (R)-1-trichloromethyl-3-methyl-2-butenyl acetoacetate

HRID 127006Notes

Reaction equation

HRID 127006 reaction equation
C1([C@@H](N[C:14]([CH3:28])=[CH:15][C:16]([O:18][C@@H:19]([C:24]([Cl:27])([Cl:26])[Cl:25])[CH:20]=[C:21]([CH3:23])[CH3:22])=[O:17])C)C2C(=CC=CC=2)C=CC=1.Cl.[O:30]1CCCC1>>[C:16]([O:18][C@@H:19]([C:24]([Cl:27])([Cl:26])[Cl:25])[CH:20]=[C:21]([CH3:23])[CH3:22])(=[O:17])[CH2:15][C:14]([CH3:28])=[O:30]

Participants

4

Reactant 3

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 86737543(R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate

Product 1

HCID 12525204(R)-1-trichloromethyl-3-methyl-2-butenyl acetoacetateYield 85%

Procedure

To a solution of (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate (10 g, 0.023 mole) in tetrahydrofuran (200 ml) at room temperature was added, in one portion, 0.5 N aqueous hydrochloric acid (250 ml, 0.125 mole). Upon addition of the acid, a white precipitate formed immediately, then slowly disappeared. The mixture was stirred at room temperature for a total of 62 hours and then extracted three times with 200 ml of hexane, after which the combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. The pale yellow oily residue was distilled to yield (R)-1-trichloromethyl-3-methyl-2-butenyl acetoacetate (5.57 g, 85% yield); bp, 90°-92° C. (0.05 mmHg); [α]D25 =+13.00° (CHCl3).

Workup

  1. additionUpon addition of the acid
  2. customa white precipitate formed immediately
  3. extractionextracted three times with 200 ml of hexane
  4. dry with materialafter which the combined organic phases were dried over sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. distillationThe pale yellow oily residue was distilled

Sources & evidence

ORD record
ord-abb92c03ab26498bab6e952b3cedae93
Source dataset
uspto-grants-1981_03
Patent number
US04254279

Reaction notes

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