Gamma-Butyrolactone → 5,5'-Carbonyldi(2-benzofuran-1,3-dione)--1-(4-aminophenyl)-1,3,3-trimethyl-2,3-dihydro-1H-inden-5-amine (1/1)

HRID 1443024Notes

Reaction equation

HRID 1443024 reaction equation
N[C:2]1C=C[C:5](C([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([CH3:24])([CH3:23])[C:16]3[CH:21]=[CH:20][C:19]([NH2:22])=[CH:18][CH:17]=3)[CH:10]=2)(C)C)=[CH:4][CH:3]=1.[C:27]1(=[O:32])[O:31][CH2:30][CH2:29][CH2:28]1.[CH2:33]1[CH:38]2[C:39]([O:41][C:42](=[O:43])[CH:37]2[CH2:36][CH:35]2C(O[C:47](=[O:48])[CH:34]12)=O)=[O:40].C([N:51](CC)CC)C.CN(C)C(=[O:60])C>>[CH3:27][C:28]1([CH3:29])[C:10]2[CH:9]=[C:14]([NH2:51])[CH:13]=[CH:12][C:11]=2[C:15]([C:16]2[CH:21]=[CH:20][C:19]([NH2:22])=[CH:18][CH:17]=2)([CH3:24])[CH2:23]1.[CH:35]1[C:34]([C:47]([C:3]2[CH:4]=[CH:5][C:28]3[C:27]([O:31][C:30](=[O:60])[C:29]=3[CH:2]=2)=[O:32])=[O:48])=[CH:33][C:38]2[C:39]([O:41][C:42](=[O:43])[C:37]=2[CH:36]=1)=[O:40]

Participants

6

Reactant 5

HCID 7302Gamma-ButyrolactoneHCID 8471TriethylamineHCID 31374Dimethylacetamide2×HCID 32921011,3-Bis[2-(4-aminophenyl)-2-propyl]benzeneHCID 144536671,2,4,5-Cyclohexanetetracarboxylic dianhydride

Product 1

HCID 64544855,5'-Carbonyldi(2-benzofuran-1,3-dione)--1-(4-aminophenyl)-1,3,3-trimethyl-2,3-dihydro-1H-inden-5-amine (1/1)

Conditions

Temperature
5 °C

Procedure

In a 500-mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube with a fractionating device, 34.58 g (0.1 mol) of 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene (4,4′-(m-phenylenediisopropylidene)dianiline also known as BisA-M) was dissolved in a solvent (68.65 g of γ-butyrolactone and 17.16 g of N,N-dimethylacetamide) in a nitrogen atmosphere. The obtained solution was cooled to 5° C. in an ice-water bath. While maintaining the temperature at 5° C., 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g (0.005 mol) of triethylamine as an imidation catalyst were added at one time. After the addition, the temperature was raised to 180° C. to continue the reflux for 8 h while removing the distillate from time to time. After the completion of the reaction, the inside temperature was lowered to 100° C. by air cooling. Thereafter, the reaction solution was diluted by adding 143.6 g of N,N-dimethylacetamide and cooled while stirring, thereby obtaining a polyimide resin solution having a solid content of 20% by weight. The weight of the polyimide resin solution was 262.47 g and the total amount of the distillate was 4.86 g. A part of the polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and then dried at 100° C. for 24 h in a vacuum dryer, thereby obtaining a white powder. In the IR spectrum thereof, the absorptions at 1702 cm−1 and 1772 cm−1 which were characteristic of imido group were found. The logarithmic viscosity of the polyimide was 0.94.

Workup

  1. temperatureWhile maintaining the temperature at 5° C.
  2. additionAfter the addition
  3. temperaturethe temperature was raised to 180° C.
  4. temperaturereflux for 8 h
  5. customwhile removing the distillate from time to time
  6. customAfter the completion of the reaction
  7. customwas lowered to 100° C. by air
  8. temperaturecooling
  9. additionThereafter, the reaction solution was diluted
  10. temperaturecooled

Sources & evidence

ORD record
ord-a402ff1a3a5b4ecfa2930f36375a2606
Source dataset
uspto-grants-2010_02
Patent number
US07659360B2

Reaction notes

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