Iodoethane → HCID 13423965, compound

HRID 1980251Notes

Reaction equation

HRID 1980251 reaction equation
[CH2:1]([N:8]1[CH2:12][CH2:11][C:10]([CH2:14][O:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[O:22][CH2:23][CH3:24])([OH:13])[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H][H].[CH2:27](I)[CH3:28].O.O.[C:32]([OH:37])(=[O:36])[C:33]([OH:35])=[O:34]>O.C(O)(C)C.CN(C)C=O>[C:32]([OH:37])(=[O:36])[C:33]([OH:35])=[O:34].[CH2:27]([O:13][C:10]1([CH2:14][O:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[O:22][CH2:23][CH3:24])[CH2:11][CH2:12][N:8]([CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[CH2:9]1)[CH3:28]

Participants

8

Reactant 4

HCID 6340IodoethaneHCID 61373Oxalic acid dihydrateHCID 13423950HCID 13423950, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 13423965HCID 13423965, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 3776IsopropanolSolventHCID 6228DimethylformamideSolvent2×

Procedure

Sodium hydride, 3.44 g (0.0816 mole) in 57% mineral oil suspension was washed three times with petroleum ether (30°-60° C.) under nitrogen atmosphere, suspended in 60 ml of freshly distilled anhydrous dimethylformamide and treated slowly with a solution of 24.3 g (0.0742 mole) of 1-benzyl-3-(2-ethoxyphenoxy)methyl-3-pyrrolidinol in 60 ml of freshly distilled anhydrous dimethylformamide. After hydrogen evolution had ceased, a solution of 11.6 g (0.0742 mole) of ethyl iodide in 60 ml of freshly distilled anhydrous dimethylformamide was added dropwise under a nitrogen atmosphere. The reaction mixture was stirred at room temperature for 16 hours (overnight), then cautiously diluted with 50 ml of water and poured into 1500 ml of water. The suspension was extracted with chloroform (3×200 ml) and the combined chloroform extracts washed with water (3×200 ml), dried over magnesium sulfate and evaporated under reduced pressure (26.1 g). The crude product which contained starting material was dissolved in benzene and chromatographed on a 500 g column of florisil packed in benzene. The column was eluted with benzene and methanol-benzene solvent mixtures. The fractions containing product were combined and evaporated under reduced pressure. Weight of residue was 15.0 g (57%). A mixture of 3.0 g (0.0084 mole) of the product and 1.06 g (0.0084 mole) of oxalic acid dihydrate in isopropanol was warmed to solution, filtered, and the filtrate seeded. The oxalate salt, 3.4 g, was collected by filtration, m.p. 125°-127° C. The material was recrystallized twice from isopropanol-isopropyl ether leaving 0.8 g of salt, m.p. 127°-129° C., which did not analyze as expected. The filtrate gave a second crop, 1.0 g, m.p. 125°-127° C. which was dried at 62° C. and 0.01 mm pressure for 4 hours and at room temperature and 0.01 mm pressure overnight.

Workup

  1. washSodium hydride, 3.44 g (0.0816 mole) in 57% mineral oil suspension was washed three times with petroleum ether (30°-60° C.) under nitrogen atmosphere
  2. extractionThe suspension was extracted with chloroform (3×200 ml)
  3. washthe combined chloroform extracts washed with water (3×200 ml)
  4. dry with materialdried over magnesium sulfate
  5. customevaporated under reduced pressure (26.1 g)
  6. dissolutionwas dissolved in benzene
  7. customchromatographed on a 500 g column of florisil
  8. washThe column was eluted with benzene and methanol-benzene solvent mixtures
  9. additionThe fractions containing product
  10. customevaporated under reduced pressure
  11. temperaturewas warmed to solution
  12. filtrationfiltered
  13. filtrationThe oxalate salt, 3.4 g, was collected by filtration, m.p. 125°-127° C
  14. customThe material was recrystallized twice from isopropanol-isopropyl ether leaving 0.8 g of salt, m.p. 127°-129° C., which
  15. customThe filtrate gave a second crop, 1.0 g, m.p. 125°-127° C. which
  16. customwas dried at 62° C.
  17. wait0.01 mm pressure for 4 hours
  18. customat room temperature
  19. custom0.01 mm pressure overnight

Sources & evidence

ORD record
ord-48ed37c8901a457db908b619afb35192
Source dataset
uspto-grants-1985_04
Patent number
US04508724

Reaction notes

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