Phthalic Acid → N-Hydroxyphthalimide

HRID 1181671Notes

Reaction equation

HRID 1181671 reaction equation
C1CCCCC1.C1(O)CCCCC1.C1(=O)CCCCC1.C1(=O)NC(=O)C2=CC=CC=C12.C1([O:38][N:39]2[C:43](=[O:44])[C:42]3=[CH:45][CH:46]=[CH:47][CH:48]=[C:41]3[C:40]2=[O:49])CCCCC1.C(O)(=O)C1C(=CC=CC=1)C(O)=O>N1C=CC=CC=1>[OH:38][N:39]1[C:40](=[O:49])[C:41]2=[CH:48][CH:47]=[CH:46][CH:45]=[C:42]2[C:43]1=[O:44]

Participants

8

Reactant 6

HCID 1017Phthalic AcidHCID 6809PhthalimideHCID 7966CyclohexanolHCID 7967CyclohexanoneHCID 8078CyclohexaneHCID 10467039N-cyclohexyloxyphthalimide

Product 1

HCID 10665N-HydroxyphthalimideYield 260%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
97 °C

Procedure

A mixture of 1500 g (17.82 mol) of cyclohexane, 3.16 g (0.019 mol) of N-hydroxyphthalimide, and 0.045 g (0.18 mmol) of cobalt acetate was reacted at 160° C. and 40 kgf/cm2 (3.92 MPa) in atmosphere of oxygen for 2 hours to obtain a mixture containing 1334 g (15.84 mol) of cyclohexane, 83.89 g (0.84 mol) of cyclohexanol, 59.47 g (0.61 mol) of cyclohexanone, 1.77 g (0.012 mol) of phthalimide, and 1.30 g (0.005 mol) of N-cyclohexyloxyphthalimide. From the reaction mixture, cyclohexane was distilled off, 2N (2 mol/L) of sodium hydroxide aqueous solution (30 mL) was added thereto, completely mixed for 2 hours at 97° C. and stood for 1 hour to be liquid-separated into an aqueous layer and an organic layer. Phthalimide and N-cyclohexyloxyphthalimide were distributed into the aqueous layer by converting into sodium salt of phthalic acid. To the aqueous layer was added diluted hydrochloric acid to convert into phthalic acid, and phthalic acid was recovered by condensation and filtration. After hydroxylamine hydrochloride NH2OH.HCl (1.39 g, 40 mmol) was dissolved in 50 mL of pyridine, the recovered phthalic acid was added thereto, and stirred at 97° C. for 4 hours. The mixture was condensed, filtrated and washed with hexane to form N-hydroxyphthalimide (2.05 g, 0.013 mol). The regeneration ratio of N-hydroxyphthalimide (a ratio of N-hydroxyphthalimide regenerated relative to N-hydroxyphthalimide used in the reaction) was 65%.

Workup

  1. distillationFrom the reaction mixture, cyclohexane was distilled off
  2. addition2N (2 mol/L) of sodium hydroxide aqueous solution (30 mL) was added
  3. additioncompletely mixed for 2 hours at 97° C.
  4. customto be liquid-separated into an aqueous layer
  5. additionTo the aqueous layer was added diluted hydrochloric acid
  6. filtrationwas recovered by condensation and filtration
  7. customcondensed
  8. filtrationfiltrated
  9. washwashed with hexane

Sources & evidence

ORD record
ord-02353954a34143e19730614db61f05ac
Source dataset
uspto-grants-2007_10
Patent number
US07285684B2

Reaction notes

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