The design of efficient carbonate interchange reactions with catechol carbonate

Tabanelli, Tommaso; Monti, Enrico; Cavani, Fabrizio; Selva, Maurizio

doi:10.1039/c6gc03466g

Cited by 29 publications

(23 citation statements)

References 51 publications

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“…However, no reaction occurred with such carbonates and the starting material was recovered unaltered (entries 3–4). Finally, catechol carbonate 8 , prepared following a reported method, [35] proved to be a good candidate as it gave vinylene carbonate 3 with 71% yield (entry 5), but it is not competing with diphenyl carbonate (entry 6). The success of the reaction when diphenyl carbonate 2 , or catechol carbonate 8 to a lesser extent, was used probably lies in the leaving group ability of the phenolate ion by comparison with other alcoholates.…”

Section: Resultsmentioning

confidence: 99%

Organocatalytic Synthesis of Substituted Vinylene Carbonates

et al. 2021

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The organocatalytic synthesis of substituted vinylene carbonates from benzoins and acyloins was studied using diphenyl carbonate as a carbonyl source. A range of N‐Heterocyclic Carbene (NHC) precursors were screened and it was found that imidazolium salts were the most active for this transformation. The reaction occurs at 90 °C under solvent‐free conditions. A wide range of substituted vinylene carbonates (symmetrical and unsymmetrical, aromatic or aliphatic), including some derived from natural products, were prepared with 20–99% isolated yields (24 examples). The reaction was also developed using thermomorphic polyethylene‐supported organocatalysts as recoverable and recyclable species. The use of such species facilitates the workup and allows the synthesis of vinylene carbonates on the preparative scale (>30 g after 5 runs).

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Section: Resultsmentioning

confidence: 99%

Organocatalytic Synthesis of Substituted Vinylene Carbonates

et al. 2021

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“…Hence, 3 chloro-1,2-propylenecarbonate remains underutilized and needs to be upgraded to value added chemical entities considering the value of the active form of CO2 in the molecule The concept of the transesterification of 3-chloro-1,2-propylenecarbonate under alkalin conditions was designed based on the previous reports where the cyclic carbonates suc as ethylene carbonates, catechol carbonate, etc. were used to synthesize various aliphati carbonates [13,29]. As shown in Scheme 4, the reaction of the alkaline transesterification involved the interaction of methanol with 3-chloro-1,2-propylenecarbonate and results i the formation of the DMC and 3-Chloro-1, 2-propanediol.…”

Section: Resultsmentioning

confidence: 99%

Integrated and Metal Free Synthesis of Dimethyl Carbonate and Glycidol from Glycerol Derived 1,3-Dichloro-2-propanol via CO2 Capture

2021

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Dimethyl carbonate (DMC) and glycidol are considered industrially important chemical entities and there is a great benefit if these moieties can be synthesized from biomass-derived feedstocks such as glycerol or its derivatives. In this report, both DMC and glycidol were synthesized in an integrated process from glycerol derived 1,3-dichloro-2-propanol and CO2 through a metal-free reaction approach and at mild reaction conditions. Initially, the chlorinated cyclic carbonate, i.e., 3-chloro-1,2-propylenecarbonate was synthesized using the equivalent interaction of organic superbase 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,3-dichloro-2-propanol with CO2 at room temperature. Further, DMC and glycidol were synthesized by the base-catalyzed transesterification of 3-chloro-1,2-propylenecarbonate using DBU in methanol. The synthesis of 3-chloro-1,2-propylenecarbonate was performed in different solvents such as dimethyl sulfoxide (DMSO) and 2-methyltetrahydrofuran (2-Me-THF). In this case, 2-Me-THF further facilitated an easy separation of the product where a 97% recovery of the 3-chloro-1,2-propylenecarbonate was obtained compared to 63% with DMSO. The use of DBU as the base in the transformation of 3-chloro-1,2-propylenecarbonate further facilitates the conversion of the 3-chloro-1,2 propandiol that forms in situ during the transesterification process. Hence, in this synthetic approach, DBU not only eased the CO2 capture and served as a base catalyst in the transesterification process, but it also performed as a reservoir for chloride ions, which further facilitates the synthesis of 3-chloro-1,2-propylenecarbonate and glycidol in the overall process. The separation of the reaction components proceeded through the solvent extraction technique where a 93 and 89% recovery of the DMC and glycidol, respectively, were obtained. The DBU superbase was recovered from its chlorinated salt, [DBUH][Cl], via a neutralization technique. The progress of the reactions as well as the purity of the recovered chemical species was confirmed by means of the NMR analysis technique. Hence, a single base, as well as a renewable solvent comprising an integrated process approach was carried out under mild reaction conditions where CO2 sequestration along with industrially important chemicals such as dimethyl carbonate and glycidol were synthesized.

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“…Finally, catechol carbonate 8, prepared following a reported method, 29 proved to be a good candidate as it gave vinylene carbonate 3 with 71% yield (entry 5), but it is not competing with diphenyl carbonate (entry 6). The success of the reaction when diphenyl carbonate 2, or catechol carbonate 8 to a lesser extent, was used probably lies in the leaving group ability of the phenolate ion by comparison with other alcoholates.…”

Section: Pc12mentioning

confidence: 99%

Organocatalytic synthesis of vinylene carbonates

Onida

Haddleton

Norsic

et al. 2021

Preprint

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The organocatalytic synthesis of vinylene carbonates from benzoins and acyloins was studied using diphenyl carbonate as a carbonyl source. A range of N-Heterocyclic Carbene (NHC) precursors were screened and it was found that imidazolium salts were the most active for this transformation. The reaction occurs at 90°C under solvent-free conditions. A wide range of vinylene carbonates (symmetrical and unsymmetrical, aromatic or aliphatic), including some derived from natural products, were prepared with 20-99% isolated yields (24 examples). The reaction was also developed using thermomorphic polyethylene-supported organocatalysts as recoverable and recyclable species. The use of such species facilitates the workup and allows the synthesis of vinylene carbonates on the preparative scale (> 30 g after 5 runs).

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The design of efficient carbonate interchange reactions with catechol carbonate

Abstract: Catechol carbonate (CC) has been investigated as an innovative and highly active reactant for carbonate interchange reactions (CIRs).

Cited by 29 publications

References 51 publications

Organocatalytic Synthesis of Substituted Vinylene Carbonates

Organocatalytic Synthesis of Substituted Vinylene Carbonates

Integrated and Metal Free Synthesis of Dimethyl Carbonate and Glycidol from Glycerol Derived 1,3-Dichloro-2-propanol via CO2 Capture

Organocatalytic synthesis of vinylene carbonates

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