Water → 1,7,7-Trimethyltricyclo[2.2.1.02,6]heptane

HRID 1600391Notes

Reaction equation

HRID 1600391 reaction equation
S(=O)(=O)(O)O.[CH2:6](C(CN)O)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.O.[CH:18](O)([CH3:20])[CH3:19]>C1(C)C=CC=CC=1.[Pd]>[CH3:19][C:18]1([CH3:20])[C:7]2([CH3:6])[CH:8]3[CH2:9][CH:10]1[CH2:11][CH:12]23

Participants

7

Reactant 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 3776IsopropanolHCID 37580461-Amino-3-phenylpropan-2-ol

Product 1

HCID 790351,7,7-Trimethyltricyclo[2.2.1.02,6]heptaneYield 55%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
20 °C

Procedure

53 ml of concentrated sulfuric acid is added to a solution of 95 ml of benzylethanolamine in 690 ml of toluene. The suspension that is produced is heated to boiling for 2 hours. The water that is produced in this case (14 ml) is separated with the aid of a water separator. After cooling to 20° C., the reaction mixture is mixed with 1300 ml of water and absorptively precipitated for 10 minutes, and the organic phase is separated. Then, the aqueous phase is quickly added to a solution of 92.2 g of NaOH in 95 ml of water that is introduced in a second reaction vessel. The reaction mixture is heated to boiling. 880 g of water-N-benzylaziridine emulsion in a third reaction vessel is distilled off through a distillation bridge. The emulsion is mixed with 880 ml of ethanol and heated to 60° C. To this end, a solution of 38.0 g of p-TsOH in 19 ml of water is added within 8 hours via a metering pump. After the addition is completed, it is refluxed for two hours. Then, the reaction mixture is mixed with a solution of 12.0 g of NaOH in 20 ml of water. The precipitated product is filtered and recrystallized from 600 mlof 2:1 ethanol-THF mixture. The tetrabenzylcyclene (53 g) thus obtained is dissolved in 500 ml of isopropanol and hydrogenated with 10 g of Pd/C (10%) at 80° C. and 20 bar of H2 pressure. After the catalyst is filtered off, the reaction solution is concentrated by evaporation, andthe product is recrystallized from toluene. 15.9 g (55% of theory) of cyclene is obtained as colorless crystals. Melting point 110°-112° C.

Workup

  1. customThe suspension that is produced
  2. temperatureis heated
  3. customis separated with the aid of a water separator
  4. additionthe reaction mixture is mixed with 1300 ml of water
  5. customabsorptively precipitated for 10 minutes
  6. customthe organic phase is separated
  7. additionThen, the aqueous phase is quickly added to a solution of 92.2 g of NaOH in 95 ml of water that
  8. additionis introduced in a second reaction vessel
  9. temperatureThe reaction mixture is heated to boiling
  10. custom880 g of water-N-benzylaziridine emulsion in a third reaction vessel
  11. distillationis distilled off through a distillation bridge
  12. additionThe emulsion is mixed with 880 ml of ethanol
  13. temperatureheated to 60° C
  14. additionTo this end, a solution of 38.0 g of p-TsOH in 19 ml of water is added within 8 hours via a metering pump
  15. additionAfter the addition
  16. temperatureit is refluxed for two hours
  17. additionThen, the reaction mixture is mixed with a solution of 12.0 g of NaOH in 20 ml of water
  18. filtrationThe precipitated product is filtered
  19. customrecrystallized from 600 mlof 2:1 ethanol-THF mixture
  20. customThe tetrabenzylcyclene (53 g) thus obtained
  21. filtrationAfter the catalyst is filtered off
  22. concentrationthe reaction solution is concentrated by evaporation
  23. customandthe product is recrystallized from toluene

Sources & evidence

ORD record
ord-60f6e5e5a2de4ab699600427021a7d37
Source dataset
uspto-grants-1998_04
Patent number
US05744616

Reaction notes

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