Azobisisobutyronitrile → Tert-butyl 5-norbornene-2-carboxylate 2-hydroxyethyl 5-norbornene-2-carboxylate mono-methyl cis-5-norbornene-endo-2, 3-dicarboxylate maleic anhydride

HRID 841001Notes

Reaction equation

HRID 841001 reaction equation
[C:1]1(=[O:7])[O:6][C:4](=[O:5])[CH:3]=[CH:2]1.[CH:8]12[CH2:14][CH:11]([CH:12]=[CH:13]1)[CH2:10][CH:9]2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16].[CH:22]12[CH2:28][CH:25]([CH:26]=[CH:27]1)[CH2:24][CH:23]2[C:29]([O:31][CH2:32][CH2:33][OH:34])=[O:30].[CH3:35][O:36][C:37]([CH:39]1[CH:43]([C:44]([OH:46])=[O:45])[CH:42]2[CH:47]=[CH:48][CH:40]1[CH2:41]2)=[O:38].N(C(C)(C)C#N)=NC(C)(C)C#N>O1CCCC1.C1(C)C=CC=CC=1>[CH:8]12[CH2:14][CH:11]([CH:12]=[CH:13]1)[CH2:10][CH:9]2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16].[CH:22]12[CH2:28][CH:25]([CH:26]=[CH:27]1)[CH2:24][CH:23]2[C:29]([O:31][CH2:32][CH2:33][OH:34])=[O:30].[CH3:35][O:36][C:37]([CH:39]1[CH:43]([C:44]([OH:46])=[O:45])[CH:42]2[CH:47]=[CH:48][CH:40]1[CH2:41]2)=[O:38].[C:4]1(=[O:5])[O:6][C:1](=[O:7])[CH:2]=[CH:3]1

Participants

8

Reactant 5

HCID 6547AzobisisobutyronitrileHCID 7923Maleic AnhydrideHCID 984652-Methyl bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylateHCID 120338232-Hydroxyethyl bicyclo[2.2.1]hept-5-ene-2-carboxylateHCID 15607334Bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, 1,1-dimethylethyl ester

Product 1

HCID 131723174Tert-butyl 5-norbornene-2-carboxylate 2-hydroxyethyl 5-norbornene-2-carboxylate mono-methyl cis-5-norbornene-endo-2, 3-dicarboxylate maleic anhydrideYield 63%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

In tetrahydrofuran or toluene, dissolved were maleic anhydride (1 mol), tert-butyl 5-norbornene-2-carboxylate (0.5-0.9 mol) prepared according to Preparation Example I, 2-hydroxyethyl 5-norbornene-2-carboxylate (0.05-0.8 mol) prepared according to Example II, and mono-methyl cis-5-norbornene-endo-2, 3-dicarboxylate (0.01-0.5 mol) prepared according to Preparation Example VI. then, 2,2′-azobisisobutyronitrile (AIBN) (0.5-10 g), as a polymerization initiator, was added thereto, and the reaction was performed at a temperature between 65° C. and 70° C. under nitrogen or argon atmosphere for 4-24 hours. Crude product thus obtained was precipitated from ethyl ether or hexane, and the precipitate was dried to give the title copolymer resin (Formula IV) having a molecular weight of 3,000-100,000 (yield: 63%). The copolymer resin thus prepared has high transparency to ArF light, increased etching resistance and excellent adhesiveness, and is developable by 2.38 wt % aqueous TMAH solution.

Workup

  1. customprepared
  2. customprepared
  3. customprepared
  4. customaccording to Preparation Example VI
  5. customwas performed at a temperature between 65° C. and 70° C. under nitrogen
  6. customCrude product thus obtained
  7. customwas precipitated from ethyl ether or hexane
  8. customthe precipitate was dried

Sources & evidence

ORD record
ord-886652f081804e3d87db71a2ecf943cf
Source dataset
uspto-grants-2002_04
Patent number
US06369181B1

Reaction notes

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