Anionic Polymerizations of N-Substituted Isomaleimide

Oishi, Tsutomu; Fujimoto, Minoru; Yoshimoto, Nobuko; Kimura, Tadashi

doi:10.1295/polymj.21.655

Cited by 9 publications

(3 citation statements)

References 15 publications

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“…This is consistent with the results of anionic oligomerization of RIMI only with n-BuLi, as reported previously. 4 Molecular weights (M,) for the oligomers were very low and the degrees of polymerization were 3 to 9. The poly(RIMI)s were oligomers.…”

Section: Nmr Ratios Ofrimi/([rimi] + [Rmi]) Werementioning

confidence: 99%

“…3 It has been reported that anionic polymerizations of N-substituted isomaleimide (RIMI) with n-BuLi give polymers consisting of both structures ofisomaleimide (35--45mol%) and maleimide (65-55 mol%). 4 The resulting polymers were oligomers, and the degrees of polymerization for the poly(RIMI)s were 3 to 7. The specific rotation of the oligo(RIMI) of * To whom all correspondence should be addressed.…”

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Asymmetric Oligomerization of N-Substituted Isomaleimide

Oishi

Kawamoto

Fujimoto

1993

Polym J

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Okamoto and co-workers 1 reported that anionic polymerizations of triphenylmethyl methacrylate (TrMA) were carried out with n-butyllithium (n-BuLi)/(-)-sparteine (Sp) as catalyst to obtain polymers with abnormally high specific rotation ([a] 0 > 300°). It was considered that chirality was due to helical conformation of the TrMA polymer main chain. Okamoto et al. 2 reported that the asymmetric polymerization of N-phenylmaleimide (PhMI) was performed with n-BuLi/(-)-Sp catalyst to yield the chiral PhMI polymer having 12o of specific rotation. We reported asymmetric polymerizations of eleven types of N-substituted maleimide (RMI) with nBuLi/(-)-Sp. 3 The specific rotations of the resulting poly(RMI)s were -40° to + 11.3°, and asymmetry was due to a threodiisotactic structure of the poly(RMI) main chain, i.e., helical structure and/or excess of chiral stereogenicity, (S, S) or (R, R). 3 It has been reported that anionic polymerizations of N-substituted isomaleimide (RIMI) with n-BuLi give polymers consisting of both structures ofisomaleimide (35--45mol%) and maleimide (65-55 mol%). 4 The resulting polymers were oligomers, and the degrees of polymerization for the poly(RIMI)s were 3 to 7. The specific rotation of the oligo(RIMI) of

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Section: Nmr Ratios Ofrimi/([rimi] + [Rmi]) Werementioning

confidence: 99%

mentioning

confidence: 99%

Asymmetric Oligomerization of N-Substituted Isomaleimide

Oishi

Kawamoto

Fujimoto

1993

Polym J

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“…IM are also compounds of wide interest. They are used in organic synthesis 9, as monomers in oligomers 10, 11, homopolymers 12, or copolymer synthesis 13, or as fungicides and defoliants 14. IM as derivatives of chromophores may be readily coupled to compounds of clinical or biological interest for the detection and measurement of biological compounds 15, 16.…”

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confidence: 99%

Computational study of maleamic acid cyclodehydration with acetic anhydride

Constantinescu

Ivanov

2005

Int J of Quantum Chemistry

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ABSTRACT:The reaction mechanisms of N-substituted maleamic acids (MA) cyclodehydration (CDH) to the corresponding maleimides (M) and isomaleimides (IM) and IM rearrangement to M were studied by the PM3 Hamiltonian with charge model 1 (CM1P) of the AMSOL computational method with solvation effect in order to establish the most probable pathways. CDH was considered in the presence of acetic anhydride in the presence of an acetate anion or triethylamine as the dehydrating agent in CH 2 Cl 2 as the solvent. In the first step, our computational results supported carboxylic proton losses, provided by a nucleophilic center on the dehydrating agent. In the next step, maleamic acid anion could either add a molecule of a dehydrating agent (path A) or cyclicize (path B). Our results indicate the path B to require more energy than path A, so path B is considered less likely to occur. The formation (path A) of an anion complex I2 between the anion of MA and the dehydration agent was supported as well as acetate anion loss to form the neutral mixed anhydride I3. The ring closure to M or IM occurs only after I3 amide proton loss, meaning that the dehydrating agent necessitate another nucleophilic center. The cyclization of I4 anion over amide nitrogen or oxygen to the reaction outcome depends on the electronic effect of amide nitrogen substituent. The same results were obtained studying CDH of N-substituted ophthalmic acids with acetic anhydride and for MA with N,NЈ-dicyclohexylcarbodiimide as dehydrating agent, in the same solvent. In such circumstances, one can consider them the common features of a general CDH reaction mechanism of MA. Our computational results found the IM to M rearrangement to correspond to the reversible final path of synthesis mechanism although the other investigators considered it to take place under a different reaction. They also supported the importance of the acetate anion in both cyclization and rearrangement mechanisms; the presence of tertiary amine blocks the acetic acid formed during reaction, determines I3 amide proton loss and prevents rearrangement. The theoretical conclusions are consistent with the experimental results.

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Synthesis of bio‐based poly(N‐phenylitaconimide) by atom transfer radical polymerization

Okada

Matyjaszewski

2014

J. Polym. Sci. Part A: Polym. Chem.

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Poly(N‐phenylitaconimide) (polyPhII) was prepared using initiators for continuous activator regeneration atom transfer radical polymerization of PhII using FeBr3 complexes as catalysts. Conversion reached 69% in 24 h, yielding polyPhII with a number average molecular weight Mn = 11,900 and a molecular weight distribution Mw/Mn = 1.52. Copolymerizations of PhII with styrene at various molar ratios were performed providing a range of polyPhII‐copolySt polymers. When the copolymerization was carried out with higher [St]0 > [PhII]0 ratio, a one‐pot synthesis of poly(St‐alt‐PhII)‐b‐polySt was achieved. The thermal properties of the obtained copolymers were studied by differential scanning calorimetry. PolyPhII prepared by ATRP showed high glass transition temperature (Tg) of 216 °C and the poly(St‐alt‐PhII)‐b‐polySt exhibited two Tgs, at 162 and 104 °C, corresponding to a poly(St‐alt‐PhII) and polySt segments, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 822–827

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Anionic Polymerizations of N-Substituted Isomaleimide

Cited by 9 publications

References 15 publications

Asymmetric Oligomerization of N-Substituted Isomaleimide

Asymmetric Oligomerization of N-Substituted Isomaleimide

Computational study of maleamic acid cyclodehydration with acetic anhydride

Synthesis of bio‐based poly(N‐phenylitaconimide) by atom transfer radical polymerization

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