Magnesium → 512-61-8

HRID 1974008Notes

Reaction equation

HRID 1974008 reaction equation
[Mg].[C:2]1([CH3:18])[CH:7]=[C:6](C)[CH:5]=[C:4]([CH3:9])[C:3]=1[C:10](OCC=C(C)C)=O>C(OCC)C>[CH3:7][C:2]([CH3:18])=[CH:3][CH2:4][CH2:5][C:4]1([CH3:9])[C:3]2([CH3:10])[CH:2]3[CH2:18][CH:5]1[CH2:6][CH:7]23

Participants

4

Reactant 2

HCID 5462224MagnesiumHCID 131710581HCID 131710581, compound

Product 1

HCID 94164512-61-8Yield 30.3%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

10 grams (0.046 moles) of π-bromotricyclene having the structure: ##STR61## prepared according to the process of Corey et al., J. Am. Chem. Soc. 79, 5773 (1957) in 500 ml of absolute diethyl ether is added to 70 g (2.9 moles) of magnesium in 100 ml of ether during 7 hours. The mixture is heated at reflux for an additional 1.5 hours. The Grignard reagent is filtered through a glass-wood plug into γ,γ -dimethylallyl mesitoate (12.8 g., 0.055 mole, b.p. 95°-100° (0.1 mm.)) in 50 ml of ether. The time required for the addition was 2 hours. The excess magnesium is rinsed with 100 ml of ether and the washing is also added to the ester. The mixture is allowed to stand at room temperature for 96 hours. At the end of this time, a fine white percipitate appears in considerable quantity. To the ether solution is added with stirring a saturated ammonium chloride solution, and stirring is continued until both aqueous and ether layers are clear. The ether solution is washed with 10% sodium hydroxide, water and dried over sodium sulfate. The crude oil (12 g) after evaporation of ether is dissolved in pentane and chromatographed on alumina. The product is eluted with pentane and distilled to give two fractions: no. 1, 1.29 g., b.p. 56°-130° (15-20 mm.), N25D 1.4496; no. 2 2.81 g, b.p. 130°-140° (15-20 mm), n25D 1.4820. The residue from the distillation which solidified is largely bi-π-tricyclyl. Fraction 2 is redistilled, dissolved in pentane and chromatographed on alumina. The eluate is distilled and yields 1.7 g of oil, b.p. 116°-120° (8 ± 2 mm.), n25D 1.4822; infrared absorption at 1670, 858 and 840 cm,- 1 ; alpha26D + 18.4° , +17.2° (pure liquid).

Workup

  1. custom##STR61## prepared
  2. temperatureThe mixture is heated
  3. temperatureat reflux for an additional 1.5 hours
  4. additionThe time required for the addition
  5. washThe excess magnesium is rinsed with 100 ml of ether
  6. additionthe washing is also added to the ester
  7. waitto stand at room temperature for 96 hours
  8. additionTo the ether solution is added
  9. stirringstirring
  10. washThe ether solution is washed with 10% sodium hydroxide, water
  11. dry with materialdried over sodium sulfate
  12. customThe crude oil (12 g) after evaporation of ether
  13. dissolutionis dissolved in pentane
  14. customchromatographed on alumina
  15. washThe product is eluted with pentane
  16. distillationdistilled
  17. customto give two fractions
  18. distillationThe residue from the distillation which
  19. distillationFraction 2 is redistilled
  20. dissolutiondissolved in pentane
  21. customchromatographed on alumina
  22. distillationThe eluate is distilled

Sources & evidence

ORD record
ord-0077ab6e7a1e411d9886a65a2150fffc
Source dataset
uspto-grants-1976_12
Patent number
US04000050

Reaction notes

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