Tetrahydrofuran → 2,2,5,5-Tetramethylcyclopentanamine

HRID 648348Notes

Reaction equation

HRID 648348 reaction equation
[Na].C[C:3]([CH3:13])([CH2:6][CH2:7][C:8]([CH3:12])([CH3:11])[C:9]#[N:10])[C:4]#N.O1CCCC1.[Cl-].[NH4+]>C(O)C>[CH3:13][C:3]1([CH3:4])[CH2:6][CH2:7][C:8]([CH3:11])([CH3:12])[CH:9]1[NH2:10]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 2642332,2,5,5-tetramethylhexanedinitrileHCID 5360545Sodium4×

Product 1

HCID 132479392,2,5,5-Tetramethylcyclopentanamine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

A flask was charged with 35 g. (0.61 mole) of 40% sodium dispersion in mineral oil. The oil was removed by washing with ethyl ether and decantation. The sodium was then mixed with 400 ml. of ether and a mixture of 32.8 g. (0.20 mole) 2,2,5,5-tetramethyladiponitrile, prepared by the method of Coffman et al., J. Am. Chem. Soc., 80, 2868 (1957), and 400 ml. of tetrahydrofuran was added slowly. The resulting mixture was stirred at room temperature for 4 hours, the excess sodium decomposed by dropwise addition of saturated aqueous ammonium chloride, the organic layer washed with water, dried (Na2SO4) and evaporated to afford 25.1 g. of crude 2,2,5,5-tetramethylcyclopentylimine. The imine was dissolved in 75 ml. of ethanol and added dropwise to a flask containing 23.3 g. (1 mole) sodium shot. An additional 75 ml. ethanol was added and the mixture heated at reflux until the remaining sodium metal was consumed. The reaction mixture was diluted with water, acidified to pH 1 with concentrated hydrochloric acid, the aqueous phase washed with ether then made strongly basic by addition of sodium hydroxide. The organic layer was extracted with ether, washed with brine, dried (Na2SO4) and evaporated to dryness. The residue was distilled in vacuo to afford 6.6 g. (23%) of the desired amine, B.P. 60-61° C. (20 mm.).

Workup

  1. additionA flask was charged with 35 g
  2. customThe oil was removed
  3. washby washing with ethyl ether and decantation
  4. additionThe sodium was then mixed with 400 ml
  5. additionof ether and a mixture of 32.8 g
  6. washthe organic layer washed with water
  7. dry with materialdried (Na2SO4)
  8. customevaporated
  9. customto afford 25.1 g
  10. additioncontaining 23.3 g
  11. temperaturethe mixture heated
  12. customwas consumed
  13. additionThe reaction mixture was diluted with water
  14. washthe aqueous phase washed with ether
  15. additionthen made strongly basic by addition of sodium hydroxide
  16. extractionThe organic layer was extracted with ether
  17. washwashed with brine
  18. dry with materialdried (Na2SO4)
  19. customevaporated to dryness
  20. distillationThe residue was distilled in vacuo
  21. customto afford 6.6 g

Sources & evidence

ORD record
ord-79c23426c042413f9660fdc16f3ca9f6
Source dataset
uspto-grants-1983_10
Patent number
US04411925

Reaction notes

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