(+-)-alpha-Pinene → HCID 68865026, compound

HRID 1454769Notes

Reaction equation

HRID 1454769 reaction equation
[C:1](Cl)(=[O:4])[CH:2]=[CH2:3].[CH3:6][C:7]1[CH:12]2[C:13]([CH3:15])([CH3:14])[CH:10]([CH2:11]2)[CH2:9][CH:8]=1>C(Cl)CCl.[Cl-].[Zn+2].[Cl-]>[C:13]([C:10]12[CH2:11][CH:12]([C:7]([CH3:6])=[CH:8][CH2:9]1)[C:1](=[O:4])[CH2:2][CH2:3]2)([CH3:15])=[CH2:14]

Participants

5

Reactant 2

HCID 6654(+-)-alpha-PineneHCID 13140Acryloyl chloride

Product 1

HCID 68865026HCID 68865026, compoundYield 0.8%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 111,2-DichloroethaneSolvent2×

Procedure

A mixture of 20.0 g acryloyl chloride (0.22 mol) and 3.01 g zinc chloride (0.02 ml, 0.1 eq.) in 150 ml ethylene chloride was treated with a soln. of 350 ml α-pinene ((1S-(−)/(1R)-(+) 90:10, 2.20 mol, 10 eq.) in 250 ml ethylene chloride and the resulting mixture was stirred 1 h at 25° C. and 4 h at 50° C. After cooling, the reaction mixture was washed with aq. sat. NaCl soln. and aq. sat. NaHCO3 soln. The aq. phases were extracted with Et2O, dried (Na2SO4), and concentrated. The crude product (48 g) was filtered (SiO2, hexane/Et2O 200:6→200:10) and the residue (1.42 g) treated with 300 mg LiOH.H2O in 15 ml MeOH at 25° C. for 7 h. The resulting mixture was poured into aq. sat. NaCl soln., extracted with hexane and the org. phases dried with Na2SO4, FC (SiO2, hexane/Et2O 30:1) gave 347 mg (0.8%) of compound 10. Boiling point: 80° C. at 0.07 torr (0.09 mbar).

Workup

  1. additionwas treated with a soln
  2. temperatureAfter cooling
  3. washthe reaction mixture was washed with aq. sat. NaCl soln
  4. extractionThe aq. phases were extracted with Et2O
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. filtrationThe crude product (48 g) was filtered (SiO2, hexane/Et2O 200:6→200:10)
  8. additionthe residue (1.42 g) treated with 300 mg LiOH.H2O in 15 ml MeOH at 25° C. for 7 h
  9. additionThe resulting mixture was poured into aq. sat. NaCl soln
  10. extraction, extracted with hexane
  11. dry with materialphases dried with Na2SO4, FC (SiO2, hexane/Et2O 30:1)

Sources & evidence

ORD record
ord-0734dae2d9654b4fb3f1e8a96472cec0
Source dataset
uspto-grants-2009_01
Patent number
US07482313B2

Reaction notes

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