1,2-Dichloroethane → HCID 68864647, compound

HRID 1454770Notes

Reaction equation

HRID 1454770 reaction equation
[CH3:1][C:2](=CC)[C:3](Cl)=[O:4].[CH3:8][C:9]1[CH:14]2[C:15]([CH3:17])([CH3:16])[CH:12]([CH2:13]2)[CH2:11][CH:10]=1.[CH2:18](Cl)[CH2:19]Cl>[Cl-].[Zn+2].[Cl-]>[C:15]([C:12]12[CH2:13][CH:14]([C:9]([CH3:8])=[CH:10][CH2:11]1)[C:3](=[O:4])[CH:2]([CH3:1])[CH:18]2[CH3:19])([CH3:16])=[CH2:17]

Participants

5

Reactant 3

HCID 111,2-Dichloroethane2×HCID 6654(+-)-alpha-PineneHCID 3015793HCID 3015793, compound

Product 1

HCID 68864647HCID 68864647, compoundYield 7.1%

Reagents, catalysts & solvents 1

HCID 3007855ZincchlorideCatalyst

Procedure

Method a) A mixture of 11.81 g 2-methyl-but-2-enoyl chloride (0.10 mol) and 1.36 g zinc chloride (0.01 mol, 0.1 eq.) in 100 ml ethylene chloride was treated with a soln. of 136 g α-pinene ((1S)-(−)/(1R)-(+) 90:10, 1 mol, 10 eq.) in 150 ml ethylene chloride and the resulting mixture was stirred 45 min. at 25° C., 2.5 h at 50° C., and 1 h at 80°. 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) filtered (SiO2, hexane/Et2O 200:6→200:13) and the residue (5.1 g) treated with 1 g LiOH.H2O in 75 ml MeOH at 25° C. for 48 h. The resulting mixture was poured into aq. sat. NaCl soln. and extracted with hexane. The combined org. phases were dried (Na2SO4), concentrated and purified by FC (SiO2, hexane/Et2O 100:3) gave 1.6 g (7.1%) of compound 11.

Workup

  1. additionwas treated with a soln
  2. custom1 h
  3. customat 80°
  4. temperatureAfter cooling
  5. washthe reaction mixture was washed with aq. sat. NaCl soln
  6. extractionThe aq. phases were extracted with Et2O
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated
  9. filtrationThe crude product (48 g) filtered (SiO2, hexane/Et2O 200:6→200:13)
  10. additionthe residue (5.1 g) treated with 1 g LiOH.H2O in 75 ml MeOH at 25° C. for 48 h
  11. additionThe resulting mixture was poured into aq. sat. NaCl soln
  12. extractionand extracted with hexane
  13. dry with materialphases were dried (Na2SO4)
  14. concentrationconcentrated
  15. custompurified by FC (SiO2, hexane/Et2O 100:3)

Sources & evidence

ORD record
ord-cf57c8374f6c41d8af043789165f1530
Source dataset
uspto-grants-2009_01
Patent number
US07482313B2

Reaction notes

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