Small-scale screening of novel biobased monomers: the curious case of 1,3-cyclopentanediol

Noordzij, G. J.; Dietz, C.H.J.T.; Leoné, Nils; Wilsens, Carolus H. R. M.; Rastogi, Sanjay

doi:10.1039/c8ra08811j

Cited by 6 publications

(6 citation statements)

References 30 publications

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“…Therefore, the stability of this newly formed group can be promising to protect otherwise labile amine and/or acid functionalities. For example, as is reported in previous work, the potentially renewable cis / trans 1,3-cyclopentanediamines are prone to degrade (by oxidation and dehydration) at elevated temperatures, similar to their diol counterparts cis / trans 1,3-cyclopentanediols (Noordzij et al, 2018). This instability makes the use of these monomers via melt-polycondensation reactions challenging as the final products are heavily colored and either have low molecular weights or are cross-linked (Noordzij et al, 2018).…”

Section: State Of the Artsupporting

confidence: 67%

“…For example, as is reported in previous work, the potentially renewable cis / trans 1,3-cyclopentanediamines are prone to degrade (by oxidation and dehydration) at elevated temperatures, similar to their diol counterparts cis / trans 1,3-cyclopentanediols (Noordzij et al, 2018). This instability makes the use of these monomers via melt-polycondensation reactions challenging as the final products are heavily colored and either have low molecular weights or are cross-linked (Noordzij et al, 2018). Instead, when reacting these monomers with itaconic acid, thermally stable dicarboxylic acid monomers are obtained that can readily be used in melt-polycondensation reactions (Noordzij et al, 2019).…”

Section: State Of the Artsupporting

confidence: 67%

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Cascade aza-Michael Addition-Cyclizations; Toward Renewable and Multifunctional Carboxylic Acids for Melt-Polycondensation

Noordzij

Wilsens

2019

Front. Chem.

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Although the aza-Michael addition reaction on various unsaturated (di-)carboxylic acids and esters of, for example, itaconic acid, is well-known, the consecutive cyclization reaction has not received much attention in literature. The products of this aza-Michael cascade reaction, being mono- or di-carboxylic acid or ester functionalized N-alkyl-pyrrolidone structures, prove interesting for melt-polycondensation reactions as they exhibit excellent stability at elevated temperatures. In other words, this reaction is a toolbox for the generation of renewable monomers and, in turn, polymers with tunable physiological properties. Therefore, this work provides an overview of the state-of-the-art of the cascade aza-Michael addition-cyclization reactions on biobased unsaturated acids and esters, and their use in polymerization reactions. Furthermore, we extend this overview with the cascade aza-Michael addition-cyclization reaction of trans-trimethyl aconitate with di-amines to form a tetra-functional N-alkyl-bis-(pyrrolidone dimethylcarboxylate), which exhibits excellent thermal stability and could effectively be used as monomer in polycondensation reactions. Importantly, the aza-Michael addition reaction between primary amines and trans-trimethyl aconitate can be considered a click-reaction; it proceeds quantitatively within minutes under ambient conditions and follows the principles of green chemistry.

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Section: State Of the Artsupporting

confidence: 67%

Section: State Of the Artsupporting

confidence: 67%

Cascade aza-Michael Addition-Cyclizations; Toward Renewable and Multifunctional Carboxylic Acids for Melt-Polycondensation

Noordzij

Wilsens

2019

Front. Chem.

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“…Cycloaliphatic diols such as 4b are interesting building blocks for novel jet fuels, 15 surfactants, 16 and particularly specialized polymers. 13 , 17 Their molecular structure is moderately rigid and consists of at least two diastereoisomers, namely, cis and trans (as primary classification). For related polyesters, it has been shown that the incorporation of larger relative portions of the cyclic trans -monomer generally leads to polymeric materials with higher crystallinity and glass-transition temperatures ( T g ).…”

Section: Introductionmentioning

confidence: 99%

“… 17 , 19 For these polyesters made from 4b , the cis – trans ratio of the cyclopentane ring units also affects the degradation temperature as the ester groups of cis -units are more susceptible to dehydrative decomposition than those of trans -units. 17 …”

Section: Introductionmentioning

confidence: 99%

Hydrogenation of Cyclic 1,3-Diones to Their 1,3-Diols Using Heterogeneous Catalysts: Toward a Facile, Robust, Scalable, and Potentially Bio-Based Route

Slagmaat

Verzijl²,

Quaedflieg³

et al. 2021

ACS Omega

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Cyclopentane-1,3-diol ( 4b ) has gained renewed attention as a potential building block for polymers and fuels because its synthesis from hemicellulose-derived 4-hydroxycyclopent-2-enone ( 3 ) was recently disclosed. However, cyclopentane-1,3-dione ( 4 ), which is a constitutional isomer of 3 , possesses a higher chemical stability and can therefore afford higher carbon mass balances and higher yields of 4b in the hydrogenation reaction under more concentrated conditions. In this work, the hydrogenation of 4 into 4b over a commercial Ru/C catalyst was systematically investigated on a bench scale through kinetic studies and variation of reaction conditions. Herein, the temperature, H 2 -pressure, and the solvent choice were found to have significant effects on the reaction rate and suppression of undesired dehydration of 4 . The cis – trans ratio of 4b is naturally generated as 7:3 in these reactions. However, at elevated reaction temperatures, 4b epimerizes, yielding more trans products. This effect was also studied and rationalized from a thermodynamic perspective using DFT. The combined optimized reaction conditions provided 78% yield for 4b , and successful applications to 8-fold scaled up reactions (40 g) and a substrate scope of several 1,3-diones demonstrate the general applicability of this catalytic approach.

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“…To this end, we designed, and 3D-printed linear and circular vial holders for 10 and 20 vials respectively. The circular vial holder is expected to ensure identical stirring conditions and thus, maximize the reproducibility and reliability of small-scale screening experiments, [31][32][33][34][35] where small differences may attract significant attention. In addition, the vial holders can be scaled up or down easily (using the software corresponding to the 3D printer of choice) to handle larger or smaller reaction vials.…”

Section: Introductionmentioning

confidence: 99%

Standardized Stirring for Small Scale Surveys**

2021

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Stirring rates in heterogeneous catalytic reactions have an effect on reaction rates. When conducting small-scale surveys using a single central stir plate, reaction vessels in different positions experience slightly different levels and patterns of agitation. We probed this effect by running the same reaction 40 times, varying the stir rate (fast/slow) and the vial position using two 3D-printed vial holders. We found variability of conversion (measured mass spectrometrically) to be approximately two times higher for vials placed somewhat randomly in comparison to when vials are consistently placed at a fixed distance from the centre of the stir plate, but the effect was relatively small and could be minimized by using a high stir rate. For those experimenters wishing to completely eliminate differential stirring as a cause for variation in results, the 3D-printed circular array we designed is recommended over a conventional rectangular array.

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Small-scale screening of novel biobased monomers: the curious case of 1,3-cyclopentanediol

Abstract: In this work, we report on the small scale polycondensation and consecutive analysis of novel polyesters based on the potentially renewable 1,3-cyclopentanediol (CPdiol).

Cited by 6 publications

References 30 publications

Cascade aza-Michael Addition-Cyclizations; Toward Renewable and Multifunctional Carboxylic Acids for Melt-Polycondensation

Cascade aza-Michael Addition-Cyclizations; Toward Renewable and Multifunctional Carboxylic Acids for Melt-Polycondensation

Hydrogenation of Cyclic 1,3-Diones to Their 1,3-Diols Using Heterogeneous Catalysts: Toward a Facile, Robust, Scalable, and Potentially Bio-Based Route

Standardized Stirring for Small Scale Surveys**

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