Phthalic Anhydride → HCID 10708017, compound

HRID 1977923Notes

Reaction equation

HRID 1977923 reaction equation
[CH2:1]([O:4][C:5]1[CH:6]=[C:7](Br)[CH:8]=[CH:9][CH:10]=1)[CH:2]=[CH2:3].C([Li])CCC.[C:17]1(=[O:27])[O:22][C:20](=[O:21])[C:19]2=[CH:23][CH:24]=[CH:25][CH:26]=[C:18]12>O1CCCC1.[Cl-].[NH4+]>[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH:8]=[CH:9][CH:10]=1)[C:17]([C:18]1[CH:26]=[CH:25][CH:24]=[CH:23][C:19]=1[C:20]([OH:22])=[O:21])=[O:27])[CH:2]=[CH2:3]

Participants

6

Reactant 3

HCID 6811Phthalic AnhydrideHCID 257945Allyl m-bromophenyl etherHCID 178418339Butyllithium

Product 1

HCID 10708017HCID 10708017, compoundYield 52%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Procedure

To a solution of 3-(allyloxy)bromobenzene (15.0 g, 70.5 mmol) in tetrahydrofuran (750 mL) at −70° C. was added 1.6M n-butyllithium (44.1 mL, 70.5 mmol). After stirring for 1 hour, a solution of phthalic anhydride (11.4 g, 77.0 mmol) in tetrahydrofuran (100 mL, previously cooled to −70° C.) was added over 1 hour. The mixture was allowed to warm to room temperature and stirred for 3 hours. The mixture was diluted with saturated ammonium chloride solution and extracted with diethyl ether. The organic layer was washed three times with 1N sodium hydroxide solution and the combined aqueous layers were back-extracted with a fresh portion of diethyl ether. The aqueous layer was adjusted to pH˜3 with aqueous hydrochloric acid and extracted three times with fresh diethyl ether. The combined organic layers were washed once with water, once with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated in vacuo to reveal an off-white solid. Recrystallization from ether/hexane provided 10.3 g (52%) of the title intermediate as a white crystalline material: mp 109° C.; NMR (CDCl3) 8.20 (d, J=8 Hz, 1H), 7.65 (t, J=8 Hz, 1H), 7.60 (t, J=8 Hz, 1H), 7.30-7.45 (m, 3H), 7.28 (d, J=8 Hz, 1H), 7.20 (d, J=8 Hz, 1H), 6.02 (m, 1H), 5.35 (d, J=16 Hz, 1H), 5.30 (d, J=11 Hz, 1H), 4.55 (d, J=6 Hz, 2H); MS-FD m/e 283 (p+1, 27), 282 (p, 100).

Workup

  1. additionwas added over 1 hour
  2. stirringstirred for 3 hours
  3. extractionextracted with diethyl ether
  4. washThe organic layer was washed three times with 1N sodium hydroxide solution
  5. extractionthe combined aqueous layers were back-extracted with a fresh portion of diethyl ether
  6. extractionextracted three times with fresh diethyl ether
  7. washThe combined organic layers were washed once with water, once with saturated sodium chloride solution
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customRecrystallization from ether/hexane

Sources & evidence

ORD record
ord-686e074a84984b32b9499eb45a3972bc
Source dataset
uspto-grants-2001_05
Patent number
US06235785B1

Reaction notes

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