Boron trifluoride etherate → HCID 21072805, compound

HRID 1867344Notes

Reaction equation

HRID 1867344 reaction equation
[CH3:1][C:2]1([CH3:17])[O:7][C:6](=[O:8])[N:5]([CH2:9][CH2:10][C:11]#[N:12])[C:4]2[CH:13]=[CH:14][CH:15]=[CH:16][C:3]1=2.[CH2:18]([Mg]Br)[CH3:19].B(F)(F)F.CCOCC.[OH-].[Na+]>C(OCC)C.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[NH2:12][C:11]1([CH2:10][CH2:9][N:5]2[C:4]3[CH:13]=[CH:14][CH:15]=[CH:16][C:3]=3[C:2]([CH3:17])([CH3:1])[O:7][C:6]2=[O:8])[CH2:19][CH2:18]1

Participants

7

Reactant 4

HCID 8000Boron trifluoride etherateHCID 14798Sodium HydroxideHCID 21072837HCID 21072837, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 21072805HCID 21072805, compound

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 3283Diethyl EtherSolvent3×

Procedure

A suspension of 6.0 g (26 mmol) of 3-(4,4-dimethyl-2-oxo-4H-benzo[d][1,3]oxazin-1-yl]propionitrile in 120 mL of diethyl ether is combined with 16.5 mL (56 mmol) of titanium tetraisopropoxide while being cooled with an ice bath. Then 18.5 mL of a 3 molar solution of ethylmagnesium bromide in diethyl ether is added dropwise such that the temperature does not climb past 20° C. The mixture is stirred for 30 minutes at ambient temperature and 7.0 mL (55 mmol) boron trifluoride-diethyl ether is added batchwise while cooling with an ice bath. The mixture is stirred for one hour at ambient temperature and 150 mL of a 1 molar sodium hydroxide solution is added dropwise while cooling. The reaction mixture is diluted with diethyl ether and the phases are separated. The aqueous phase is extracted with diethyl ether and the combined organic phases are extracted with sodium sulfite solution and repeatedly extracted with 1 molar hydrochloric acid. The hydrochloric acid phases are combined, extracted with diethyl ether, made alkaline with sodium hydroxide solution, and exhaustively extracted with dichloromethane. The dichloromethane phases are dried with sodium sulfate and evaporated down. Light yellow oil. Yield: 1.5 g (22%); mass spectroscopy: [M+H]+=261.

Workup

  1. temperaturewhile being cooled with an ice bath
  2. customdoes not climb past 20° C
  3. temperaturewhile cooling with an ice bath
  4. stirringThe mixture is stirred for one hour at ambient temperature
  5. temperaturewhile cooling
  6. customthe phases are separated
  7. extractionThe aqueous phase is extracted with diethyl ether
  8. extractionthe combined organic phases are extracted with sodium sulfite solution
  9. extractionrepeatedly extracted with 1 molar hydrochloric acid
  10. extractionextracted with diethyl ether
  11. extractionexhaustively extracted with dichloromethane
  12. dry with materialThe dichloromethane phases are dried with sodium sulfate
  13. customevaporated down

Sources & evidence

ORD record
ord-1e421e84535346df83a4dc0942fdaa40
Source dataset
uspto-grants-2009_12
Patent number
US07632834B2

Reaction notes

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