Phthalic Anhydride → HCID 14478552, compound

HRID 1199319Notes

Reaction equation

HRID 1199319 reaction equation
[C:1]([O:4][C:5]1[C:10]([CH3:11])=[C:9]([CH3:12])[C:8]([O:13][C:14](=[O:16])[CH3:15])=[C:7]([CH3:17])[C:6]=1[CH2:18][CH2:19][C:20]([CH3:24])([OH:23])[C:21]#[CH:22])(=[O:3])[CH3:2].C(N(CC)CC)C.[C:32]1(=[O:42])[O:37][C:35](=[O:36])[C:34]2=[CH:38][CH:39]=[CH:40][CH:41]=[C:33]12>CN(C)C1C=CN=CC=1.ClCCl.C(OCC)C>[C:1]([O:4][C:5]1[C:10]([CH3:11])=[C:9]([CH3:12])[C:8]([O:13][C:14](=[O:16])[CH3:15])=[C:7]([CH3:17])[C:6]=1[CH2:18][CH2:19][C:20]([O:23][C:32]([C:33]1[C:34]([C:35]([OH:37])=[O:36])=[CH:38][CH:39]=[CH:40][CH:41]=1)=[O:42])([C:21]#[CH:22])[CH3:24])(=[O:3])[CH3:2]

Participants

7

Reactant 3

HCID 6811Phthalic AnhydrideHCID 8471TriethylamineHCID 14478549HCID 14478549, compound

Product 1

HCID 14478552HCID 14478552, compoundYield 100.8%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

A mixture of 21.25 g (0.064 mol) of (rac.-5-[2,5-bis(acetyloxy)-3,4,6-trimethylphenyl]-3-methyl-1-pentyn-3-ol), 12.12 g (0.12 mol) of triethylamine, 2.44 g (0.02 mol) of 4-dimethylaminopyridine, and 11.84 g (0.08 mol) of phthalic anhydride in 100 mL of dichloromethane was stirred at 25° C. for 3.0 h, then heated under reflux for 10 h. The reaction mixture was cooled to 25° C. and diluted with 200 mL of diethylether. The solution was washed with 3×150 mL of 1.0N HCl. The aqueous phase was further extracted with 2×200 mL of diethylether. The organic phases were combined and extracted with 3×100 mL of 1.0N ammonium hydroxide. The basic aqueous extracts were combined, cooled in an ice-bath, and acidified carefully to pH 5.0 with approximately 60 mL of cold 6.0N HCl. It was then extracted with 4×200 mL of dichloromethane. The combined extracts were dried over MgSO4. Filtration and solvent removal on a rotary evaporator (35° C., 40 mm) gave a light yellow oily residue. This material was transferred to a flask with about 100 mL of diethylether, and the solvent was evaporated as described above to give a foam, which was further dried at 25° C./0.5 mm for 18 h to yield 31 g of rac.-benzenedicarboxylic acid [3-[2,5-bis (acetyloxy)-3,4,6-trimethylphenyl]-1-ethynyl-1-methylpropyl] ester as a pale yellow foam.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 10 h
  3. temperatureThe reaction mixture was cooled to 25° C.
  4. washThe solution was washed with 3×150 mL of 1.0N HCl
  5. extractionThe aqueous phase was further extracted with 2×200 mL of diethylether
  6. extractionextracted with 3×100 mL of 1.0N ammonium hydroxide
  7. temperaturecooled in an ice-bath
  8. extractionIt was then extracted with 4×200 mL of dichloromethane
  9. dry with materialThe combined extracts were dried over MgSO4
  10. filtrationFiltration and solvent removal
  11. customon a rotary evaporator (35° C., 40 mm)
  12. customgave a light yellow oily residue
  13. customthe solvent was evaporated
  14. customto give a foam, which
  15. customwas further dried at 25° C./0.5 mm for 18 h

Sources & evidence

ORD record
ord-962249844c1c4960ba42236fd6ee7f5e
Source dataset
uspto-grants-1990_02
Patent number
US04900476

Reaction notes

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