Boron trifluoride etherate → Allyl 4-[1-oxo-3-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)-2-propynyl]benzoate

HRID 840446Notes

Reaction equation

HRID 840446 reaction equation
[CH3:1][C:2]1([CH3:16])[CH2:11][CH2:10][C:9]([CH3:13])([CH3:12])[C:8]2[CH:7]=[C:6]([C:14]#[CH:15])[CH:5]=[CH:4][C:3]1=2.C([Li])CCC.B(F)(F)F.CCOCC.CN(C)[C:33]([C:35]1[CH:46]=[CH:45][C:38]([C:39]([O:41][CH2:42][CH:43]=[CH2:44])=[O:40])=[CH:37][CH:36]=1)=[O:34].[Cl-].[NH4+]>C1COCC1.C(OCC)C>[O:34]=[C:33]([C:35]1[CH:36]=[CH:37][C:38]([C:39]([O:41][CH2:42][CH:43]=[CH2:44])=[O:40])=[CH:45][CH:46]=1)[C:15]#[C:14][C:6]1[CH:5]=[CH:4][C:3]2[C:2]([CH3:16])([CH3:1])[CH2:11][CH2:10][C:9]([CH3:12])([CH3:13])[C:8]=2[CH:7]=1

Participants

8

Reactant 5

HCID 8000Boron trifluoride etherateHCID 25517Ammonium ChlorideHCID 147265491,1,4,4-Tetramethyl-6-ethynyl-1,2,3,4-tetrahydronaphthaleneHCID 22619405allyl 4-(N,N'-dimethylcarbamoyl)benzoateHCID 178418339Butyllithium

Product 1

HCID 22619466Allyl 4-[1-oxo-3-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)-2-propynyl]benzoate

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

4.3 g (20 mmol) of 5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-ethynylnaphthalene and 20 ml of THF were introduced into a three-necked flask under a stream of nitrogen. 12.5 ml (20 mmol) of an n-butyllithium solution (1.6M in hexane) were added dropwise at −78° C. and the reaction mixture was stirred for 10 minutes. 2.7 ml of BF3—Et2O were then added at this same temperature and the reaction mixture was stirred for 30 minutes. A solution of 2.5 g (10 mmol) of allyl 4-(N,N′-dimethylcarbamoyl)benzoate in 10 ml of THF was added, while maintained at −78° C., to the solution and stirring was carried out for 1 hour. The reaction mixture was poured into an aqueous ammonium chloride solution and extraction was carried out with ethyl ether. The organic phase was separated by settling, dried over magnesium sulfate and evaporated. The residue obtained was purified by chromatography on a silica column eluted with a mixture of dichloromethane and hexane (10/90). After evaporation of the solvents, 4.2 g (52%) of the expected ester were recovered in the form of an oil.

Workup

  1. stirringthe reaction mixture was stirred for 30 minutes
  2. stirringstirring
  3. waitwas carried out for 1 hour
  4. customThe organic phase was separated
  5. dry with materialdried over magnesium sulfate
  6. customevaporated
  7. customThe residue obtained
  8. customwas purified by chromatography on a silica column
  9. washeluted with a mixture of dichloromethane and hexane (10/90)
  10. customAfter evaporation of the solvents, 4.2 g (52%) of the expected ester
  11. customwere recovered in the form of an oil

Sources & evidence

ORD record
ord-38fe4fb837f24c13aecfc1d35a7e7c2a
Source dataset
uspto-grants-2002_04
Patent number
US06368608B1

Reaction notes

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