Diethyl Ether → HCID 10035154, compound

HRID 1464635Notes

Reaction equation

HRID 1464635 reaction equation
O.O.O.O.O.O.O.[Cl-].[Ce+3].[Cl-].[Cl-].C[Li].[CH3:14]COCC.[C:19](=[NH:30])([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH2:20][CH2:21][CH2:22][CH3:23].[OH-].[NH4+]>O1CCCC1>[CH3:14][C:19]([NH2:30])([CH2:20][CH2:21][CH2:22][CH3:23])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

7

Reactant 5

HCID 3283Diethyl EtherHCID 14923Ammonium HydroxideHCID 12734728HCID 12734728, compoundHCID 21585214Cerium trichloride heptahydrateHCID 178418348HCID 178418348, compound

Product 1

HCID 10035154HCID 10035154, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A suspension of MeCeCl2 was prepared as described in Example 1 from 7.5 g (20 mmol) of cerium chloride heptahydrate, 40 mL of tetrahydrofuran, and 14 mL of 1.4M methyllithium in ether (20 mmol). To this was added below -60° a solution of 1.35 g (8.4 mmol) of valerophenone imine in 5 mL of tetrahydrofuran. The mixture was stirred in a dry ice-acetone bath for 3 hours, treated below -40° slowly with 12 mL of conc. ammonium hydroxide solution, and allowed to come to room temperature. Celite™ was added, the mixture was filtered, and the solids were washed several times with methylene chloride. The dried organic layer of the filtrates was concentrated. The crude product (1.39 g) still contained ca. 10% unreacted imine as shown by 1H NMR spectroscopy. The product was dissolved in toluene and stirred with 3% phosphoric acid for 2 hours. The toluene layer was washed twice with water, and the combined aqueous phases were washed once with toluene and made basic with conc. ammonium hydroxide solution. Extraction with methylene chloride and short-path distillation of the crude product gave 0.83 g (56%) of the title compound., distilling at a bath temperature of 110° (0.005 mm). 1H NMR (in CDCl3) ∂ 0.8 (t, J=7 Hz, 3H), 1.0-1.3 (m, 4H); 1.4 (s, 3H), 1.5 (br, 2H), 1.6-1.8 (m, 2H), 7.2-7.5 (m, 5H). The hydrochloride had mp 153°-156° after crystallization from acetonitrile.

Workup

  1. additionA suspension of MeCeCl2
  2. customwas prepared
  3. customto come to room temperature
  4. additionCelite™ was added
  5. filtrationthe mixture was filtered
  6. washthe solids were washed several times with methylene chloride
  7. concentrationThe dried organic layer of the filtrates was concentrated
  8. dissolutionThe product was dissolved in toluene
  9. stirringstirred with 3% phosphoric acid for 2 hours
  10. washThe toluene layer was washed twice with water
  11. washthe combined aqueous phases were washed once with toluene
  12. extractionExtraction
  13. distillationwith methylene chloride and short-path distillation of the crude product

Sources & evidence

ORD record
ord-5911f3cf845643699664df4289b02345
Source dataset
uspto-grants-1994_04
Patent number
US05306821

Reaction notes

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