1,8-Diazabicyclo(5.4.0)undec-7-ene → (E)-But-2-en-1-yl 2-(2,2,2-trifluoroacetamido)acetate

HRID 636022

Reaction equation

HRID 636022 reaction equation
[F:1][C:2]([F:11])([F:10])[C:3]([NH:5][CH2:6][C:7]([OH:9])=[O:8])=[O:4].[CH2:12](Br)/[CH:13]=[CH:14]/[CH3:15].C1CCN2C(=NCCC2)CC1>CN(C=O)C>[F:1][C:2]([F:10])([F:11])[C:3]([NH:5][CH2:6][C:7]([O:9][CH2:12]/[CH:13]=[CH:14]/[CH3:15])=[O:8])=[O:4]

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene2×HCID 136227N-(trifluoroacetyl)aminoacetic acidHCID 6375322-Butene, 1-bromo-, (2E)-

Product 1

HCID 10944121(E)-But-2-en-1-yl 2-(2,2,2-trifluoroacetamido)acetateYield 26.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
25 °C

Procedure

A mixture of 143.1 g (836 mmol) of N-trifluoroacetylglycine in 1 L of DMF is chilled to −8° C. as 100 mL (844 mmol) of E-crotyl bromide is added dropwise, followed by addition of 140 mL (937 mmol) of DBU at −5° C. After 1.5 h at −5° C. and 2 h at −2° C. the mixture is allowed to warm to 25° C. The mixture is cooled to 0° C. and 40 mL more DBU is added. After warming to 25° C. the mixture is concentrated in vacuo. 1 L of 1:1 ether-water is added. The organic layer is separated, washed with water, 1 N HCl, saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride. Drying and concentration in vacuo is followed by trituration of the oil with hexanes-EtOAC to provide a solid. Chromatography on silica gel (elution with 3:1 hexanes-EtOAc) affords 49.96 g of (2E)-2-buten-1-yl N-trifluoroacetylglycinate as an oil.

Workup

  1. additionis added dropwise
  2. custom2 h
  3. customat −2° C.
  4. temperatureThe mixture is cooled to 0° C.
  5. temperatureAfter warming to 25° C. the mixture
  6. concentrationis concentrated in vacuo
  7. addition1 L of 1:1 ether-water is added
  8. customThe organic layer is separated
  9. washwashed with water, 1 N HCl, saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride
  10. customDrying
  11. concentrationconcentration in vacuo
  12. customto provide a solid

Sources & evidence

ORD record
ord-9a9831f3deea4e5991318b7765dc614e
Source dataset
uspto-grants-2001_02
Patent number
US06191150B1

Linked notes

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