1H-Isoindole-1,3(2H)-dione, 2-(2-bromoethyl)- → Diallyl 2-[2-(1,3-dioxoisoindolin-2-yl)ethyl]propanedioate

HRID 481574

Reaction equation

HRID 481574 reaction equation
[H-].[Na+].[C:3]([O:12][CH2:13][CH:14]=[CH2:15])(=[O:11])[CH2:4][C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6].Br[CH2:17][CH2:18][N:19]1[C:23](=[O:24])[C:22]2=[CH:25][CH:26]=[CH:27][CH:28]=[C:21]2[C:20]1=[O:29]>C1COCC1>[C:20]1(=[O:29])[N:19]([CH2:18][CH2:17][CH:4]([C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6])[C:3]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])[C:23](=[O:24])[C:22]2=[CH:25][CH:26]=[CH:27][CH:28]=[C:21]12

Participants

5

Reactant 3

HCID 113251H-Isoindole-1,3(2H)-dione, 2-(2-bromoethyl)-HCID 24758Sodium hydrideHCID 228227Diallyl malonate

Product 1

HCID 22116402Diallyl 2-[2-(1,3-dioxoisoindolin-2-yl)ethyl]propanedioateYield 67.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of sodium hydride (4.35 g, 0.18 mol) in freshly distilled THF (100 mL) was cooled to 0° C. and treated with diallyl malonate (35 g, 0.19 mol) over 40 min via a dropping funnel. After stirring at room temperature for 30 min, N-(2-bromoethyl)phthalimide (43.9 g, 0.17 mol) was added to the solution in one portion and the mixture was heated to reflux. After 48 h the solution was cooled to 0° C., quenched with 2N HCl and concentrated to about 20% of its original volume. The concentrate was diluted with ethyl acetate (300 mL) and washed successively with satd. aq. K2CO3 and NaCl. The organic layer was dried over MgSO4, filtered and concentrated under reduced pressure. Purification by flash column chromatography (5-25% ethyl acetate:hexanes) provided diallyl 2-phthalimidoethylmalonate (41.2 g, 67%) as a colorless oil. 1H NMR (300 MHz, CDCl3) d 7.82 (m, 2H), 7.72 (m, 2H), 5.85 (m, 2H), 5.30 (m, 2H), 5.22 (m, 2H), 4.60 (m, 4H), 3.80 (t, J=6.6 Hz, 2H), 3.46 (t, J=7.2 Hz, 1H), 2.30 (dd, J=13.8, 6.9 Hz, 2H). ##STR222## Step 3

Workup

  1. temperaturethe mixture was heated to reflux
  2. temperatureAfter 48 h the solution was cooled to 0° C.
  3. customquenched with 2N HCl
  4. concentrationconcentrated to about 20% of its original volume
  5. additionThe concentrate was diluted with ethyl acetate (300 mL)
  6. washwashed successively with satd
  7. dry with materialThe organic layer was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customPurification by flash column chromatography (5-25% ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-ae22c7efff774adc8f67872dc72ce28c
Source dataset
uspto-grants-1998_08
Patent number
US05789434

Linked notes

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