Bisnitrone: New Starting Material for Heterocyclic Poly(1,2,4-oxadiazolidin-5-one) via Polycycloaddition with Diisocyanate and Urethane Prepolymer

Dickmeis, Marcus; Cinar, Hakan; Ritter, Helmut

doi:10.1021/ma300181g

Cited by 3 publications

(4 citation statements)

References 27 publications

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“…The known polymerization reactions, which use 1,3-dipolar cycloaddition, are based on the reactions of bis-oxaziridines, [ 11 ] nitryl oxides [ 12,13 ] and bisnitrones. [14][15][16][17] To our knowledge, no polymerization based on a 1,3-dipolar cycloaddition of azomethine ylides has been described to date, yet this reaction has a signifi cant potential for the synthesis of functional oligomers and…”

Section: Introductionmentioning

confidence: 99%

“…The most studied are polycycloadditions based on a 1,3‐dipolar cycloaddition of azides to alkynes, where several reviews and numerous research articles are available. The known polymerization reactions, which use 1,3‐dipolar cycloaddition, are based on the reactions of bis‐oxaziridines, nitryl oxides and bis‐nitrones . To our knowledge, no polymerization based on a 1,3‐dipolar cycloaddition of azomethine ylides has been described to date, yet this reaction has a significant potential for the synthesis of functional oligomers and polymers.…”

Section: Introductionmentioning

confidence: 99%

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The Implication of 1,3‐Dipolar Cycloaddition of Azomethine Ylides to the Synthesis of Main‐Chain Porphyrin Oligomers

Konev

Lukyanov

Vlasov

et al. 2014

Macro Chemistry & Physics

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The polycycloaddition of azomethine ylides to dipolarophiles is described for the first time. Use of (cis,cis)‐bis‐aziridines as a source of azomethine ylides allows selective polyaddition to be realized, which leads to oligomers exclusively with trans‐substituted pyrrolidine rings and modest molecular weights (ca. 5–10 kDa). The fluorescent, electrochemical, electrochromic, and non‐linear optical properties of the main‐chain free‐base porphyrin oligomer, synthesized by the developed procedure, are studied. An enhancement of the optical power limiting effect in a porphyrin oligomer solution is registered against that of the monomer.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Implication of 1,3‐Dipolar Cycloaddition of Azomethine Ylides to the Synthesis of Main‐Chain Porphyrin Oligomers

Konev

Lukyanov

Vlasov

et al. 2014

Macro Chemistry & Physics

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“…Using DSC, the glass transition temperature ( T g ) ranged from 46 to 91 °C, depending on the structure of the diisocyanate monomers. The decomposition temperatures ( T d5 ) measured for the aforementioned polymers were also dependent on structure and varied from 201 to 265 °C. , …”

Section: Resultsmentioning

confidence: 99%

Poly(2-imino-4-oxazolidinone)s via the Condensation of Diamidocarbenes with Bis(isocyanate)s

et al. 2015

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S Supporting Information ■ INTRODUCTIONPolycyclic polymers continue to attract interest as high performance materials on account of their high degrees of chemical and thermal stabilities. 1,2 In particular, spiro-and other ladder-like polymers comprised of bicyclic repeat units wherein the rings connect through a common atom have received increasing attention due to their restricted rotational freedom and utility in forming thermally robust materials. 3,4 In some cases (e.g., the poly(spirobifluorene)s), the polycycles have been shown to adopt twisted helical structures that effectively prevented aggregation and enhanced their optical properties. 5−12 Unfortunately, the synthesis of spiro-polycycles is challenging due to the need for an efficient polymerization reaction that forms cyclic linkages between the repeating units. 12 Toward this end, we recently demonstrated that readily available N,N′-diamidocarbenes (DACs) 13−15 rapidly and selectively afford 2-imino-4-oxazolidinones 16 upon exposure to 2 equiv of an isocyanate. The reactivity was remarkable as most NHCs catalyze the cyclotrimerization of isocyanates to isocyanurates rather than undergoing cycloaddition chemistry. 17 We envisioned condensing DACs with bifunctional isocyanates to access new classes of polycycles with functionally rich heterocyclic cores. Herein we report the synthesis and study of novel polyspiro(iminooxazolidinone)s via the formal [2 + 2 + 1] cycloaddition of a stable DAC with various diisocyanates. The chemistry presented herein overcomes many of the challenges associated with the synthesis of stable spirocenters in polymeric materials and provides a unique approach to rapidly access a new structural class of polyheterocycles. ■ RESULTS AND DISCUSSIONPreviously, we demonstrated that an oxazolidinone forms upon treatment of DAC 1 with two equivalents of 3-nitrophenylisocyanate. In order to use this chemistry to form high molecular weight polymers, we anticipated that less polarized and more solubilizing diisocyanates, such as methylene diphenyl diisocyanate (MDI), would be advantageous. Thus, initial experiments focused on probing the reactivity and product selectivity of 1 with phenylisocyanate, a nonpolymerizable model. As summarized in Scheme 1, adding two equivalents of phenylisocyanate to a solution of 1 in benzene resulted in the initial formation of a purple solution that became colorless after stirring for an additional 1 h at room temperature. The product of this reaction (2) was subsequently isolated in high yield (98%) as a white solid by recrystallization from benzene/pentane. Characterization using 1 H and 13 C NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis supported the formation of a 2:1 isocyanate/DAC adduct. The structure of this product was unambiguously elucidated using single crystal X-ray diffraction (XRD) analysis (Figure 1, left), which confirmed the formation of the oxazolidinone heterocycle 2, rather than the isomeric hydantoin 3. 16 We postulated that the formation of 2 originate...

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“…29,30 Aside from a vast range of ve membered heterocycles created using nitrone cycloaddition, there are fewer reports on the synthesis of polymeric compounds utilizing nitrones via this approach. [31][32][33] Furthermore, only a few studies report the synthesis of bis-nitrones and their usage as a dipole substrate to synthesize macro sized molecules. The use of nitrones in polymer synthesis dates back to 1971, when Manecke et al 34 for the rst time reported the synthesis of a-(p-maleinimidophenyl)-N-(phenylnitrone) that was subjected to dipolar cycloaddition with the maleinimido group in the same molecule and this upon repeated addition led to the formation of macromolecules.…”

Section: Introductionmentioning

confidence: 99%

Non-catalytic regioselective synthesis of trans bis-pyrrolo isoxazole cycloadducts in water

Majhool,

Khalaf,

Hasan

et al. 2024

RSC Sustain.

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Bisnitrone: New Starting Material for Heterocyclic Poly(1,2,4-oxadiazolidin-5-one) via Polycycloaddition with Diisocyanate and Urethane Prepolymer

Cited by 3 publications

References 27 publications

The Implication of 1,3‐Dipolar Cycloaddition of Azomethine Ylides to the Synthesis of Main‐Chain Porphyrin Oligomers

The Implication of 1,3‐Dipolar Cycloaddition of Azomethine Ylides to the Synthesis of Main‐Chain Porphyrin Oligomers

Poly(2-imino-4-oxazolidinone)s via the Condensation of Diamidocarbenes with Bis(isocyanate)s

Non-catalytic regioselective synthesis of trans bis-pyrrolo isoxazole cycloadducts in water

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