Bromide ion → Ether phthalimide

HRID 483938Notes

Reaction equation

HRID 483938 reaction equation
C(N([CH2:6][CH3:7])CC)C.[Br-].[I-].[K+].O[N:12]1[C:16](=[O:17])[C:15]2=[CH:18][CH:19]=[CH:20][CH:21]=[C:14]2[C:13]1=[O:22].[OH-].[Na+]>CN1CCCC1=O>[C:16]1(=[O:17])[NH:12][C:13](=[O:22])[C:14]2=[CH:21][CH:20]=[CH:19][CH:18]=[C:15]12.[CH3:15][CH2:16][O:17][CH2:6][CH3:7]

Participants

7

Reactant 5

HCID 259Bromide ionHCID 4875Potassium IodideHCID 8471TriethylamineHCID 10665N-HydroxyphthalimideHCID 14798Sodium Hydroxide

Product 1

HCID 18959638Ether phthalimideYield 78.6%

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

At 20° to 25° C., 190 ml (1.37 mol) of triethylamine was dripped over a period of 2.5 hours into a mixture of 283 g (1.30 mol) of the bromide prepared above, 1300 ml of N-methyl-2-pyrrolidone, 10 g of potassium iodide and 212 g (1.30 mol) of N-hydroxyphthalimide. After the mixture had been kept for 4 hours at 20° to 25° C., it was poured into 4000 ml of ice water, and 500 ml of 10% strength sodium hydroxide solution was added in portions. The mixture was extracted four times, each time with 500 ml of ethyl acetate. The combined ethyl acetate phases were washed neutral with dilute sodium hydroxide solution and water, dried over magnesium sulfate and evaporated down under reduced pressure. The crude product was purified chromatographically using 1000 g of silica gel/column 30×15 cm (developer: n-hexane/dichloromethane 7:3). There was obtained 113 g (29%) of phthalimide ether of melting point 69°-71° C. (isopropanol). 1H-NMR (250 MHz, d6 -DMSO): δ=2.55-2.70 (m, 2H), 4.28 (t, 2H), 6.00-6.20 (m, 1H), 6.77 (d, 1H), 7.00 (m, 2H), 7.35 (m, 1H), 7.87 (s, 4H).

Workup

  1. additionwas added in portions
  2. extractionThe mixture was extracted four times
  3. washThe combined ethyl acetate phases were washed neutral with dilute sodium hydroxide solution and water
  4. dry with materialdried over magnesium sulfate
  5. customevaporated down under reduced pressure
  6. customThe crude product was purified chromatographically

Sources & evidence

ORD record
ord-049c69a62dcd4b82a378771b9ee21a01
Source dataset
uspto-grants-1993_07
Patent number
US05228896

Reaction notes

Loading…