Acetic Acid → Maleimide, N-allyl-

HRID 1649259Notes

Reaction equation

HRID 1649259 reaction equation
[C:1]([OH:4])(=O)[CH3:2].[CH2:5]([NH2:8])[CH:6]=[CH2:7].C([C:13]1C=C(C)C=C(C(C)(C)C)[C:14]=1[OH:24])(C)(C)C>O>[CH2:5]([N:8]1[C:1](=[O:4])[CH:2]=[CH:13][C:14]1=[O:24])[CH:6]=[CH2:7]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 7853AllylamineHCID 314042,6-Di-tert-butyl-4-methylphenol

Product 1

HCID 18098Maleimide, N-allyl-

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of 25 g of a commercial styrene/maleic anhydride copolymer (1/1 molar ratio, Mn 1600) and 250 mL of glacial acetic acid was stirred under nitrogen while 7.1 g of allylamine was added dropwise over a period of 10 min. The mixture was then heated at 114° for 2 hours. The clear solution was cooled, treated with 0.125 g of 2,6-di-tert-butyl-4-methylphenol, and added with stirring to about 2500 mL of water. The precipitated polymer was filtered, washed, re-dissolved in about 700 mL of acetone and again precipitated in excess water acidified with 10 mL of concentrated hydrochloric acid/liter. The resultant polymer was dried to constant weight under vacuum. The N-allylmaleimide copolymer was obtained as a white powder; weight 25.4 g. The infrared spectrum showed imide absorption at 1705 cm-1 and 1775 cm-1, and essentially no anhydride or amide absorption was seen. The nmr spectrum was also consistent with the styrene/N-allylmaleimide structure. The nitrogen analysis and nmr spectrum indicated about 75% conversion of anhydride groups to N-allylmaleimide groups, and complete hydrolysis was indicated for the remainder of the anhydride units. Found, N 4.38%.

Workup

  1. additionwas added dropwise over a period of 10 min
  2. temperatureThe mixture was then heated at 114° for 2 hours
  3. temperatureThe clear solution was cooled
  4. additionadded
  5. filtrationThe precipitated polymer was filtered
  6. washwashed
  7. dissolutionre-dissolved in about 700 mL of acetone
  8. customagain precipitated in excess water
  9. dry with materialThe resultant polymer was dried to constant weight under vacuum

Sources & evidence

ORD record
ord-12ede8497a10458f99ebe1c85455d66a
Source dataset
uspto-grants-1983_11
Patent number
US04415652

Reaction notes

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