Hydroesterification of ethylene oxide catalyzed by 1-butyl-3-methylimidazolium cobalt tetracarbonyl ionic liquid

Abstract

In this paper, functional ionic liquid 1-butyl-3-methylimidazolium cobalt tetracarbonyl [Bmim][Co(CO) 4 ] is prepared in a metathesis reaction between [Bmim]Cl and KCo(CO) 4 . The structure of [Bmim] ? is illustrated by 1 H NMR, while [Co(CO) 4 ] -is confirmed by IR(m CO ) spectrum. Methyl 3-hydroxypropionate(3-HPM), an intermediate to 1,3-propanediol (1,3-PDO), can be prepared in high yield by hydroesterification of ethylene oxide in the presence of a [Bmim][Co(CO) 4 ] catalyst. Under a pressure of 3.7 MPa and at a temperature of 75°C, the yield of 3-HPM can reach 90.8% in 10 h. Even after the catalyst is recycled three times, a yield of more than 80% can be obtained. A possible reaction mechanism has also been proposed.

Ionic-Liquid-Based Heterogeneous Covalent Triazine Framework Cobalt Catalyst for the Direct Synthesis of Methyl 3-Hydroxybutyrate from Propylene Oxide

“…Here, on the basis of our understanding and the available literature, , we propose a plausible mechanism for conversion of PO to MHB, including the formation of the side products catalyzed by 5 (Figure ). The imidazolium acidic proton activates the PO followed by the nucleophilic attack of [Co­(CO) 4 ] − at the less-hindered carbon atom to form the cobalt–alkyl bond a .…”

Cobalt carbonyl ionic liquids based on the 1,1,3,3-tetra-alkylguanidine cation: Novel, highly efficient, and reusable catalysts for the carbonylation of epoxides

“…It is apparent that the catalytic activity of 3a was better than that of Co2(CO)8. The existence of 1,1-dimethyl-3,3-diethylguanidinium + appeared to assist the ring-opening process of the PO [23,28,[30][31][32], and the introduction of the guanidinium ILs pattern to the catalyst not only prevented catalyst leaching but also increased the stability of the catalyst.…”

“…Recently, among the vast research related to ILs, organometallic ILs [8][9][10][11][12] based on transition metals have received increasing attention, especially in catalysis [5,13], because of their potential catalytic activity and considerable reusability [11,14]. Notably, Co(CO)4  as a widely used catalytic active species has been used in organometallic ILs [11,[15][16][17][18][19][20][21] [11,[22][23][24][25][26]. According to the previous reports, [CnPy][Co(CO)4] and [bmim][Co(CO)4] organometallic ILs have been applied in the carbonylation of epoxides.…”

“…Therefore, the C atom connected with the three N atoms presents an electron-deficient state. Thus, the cationic part can be regarded as a Lewis acid [29], which can assist the ring-opening process of the epoxides [23,[30][31][32]. It is expected that cobalt carbonyl ILs based on 1,1,3,3-tetraalkylguanidine can play the dual role of stabilizing Co(CO)4  anions and activating epoxy compounds.…”

Chemical kinetics and promoted Co-immobilization for efficient catalytic carbonylation of ethylene oxide into methyl 3-hydroxypropionate

“…Among the most commonly used epoxides, ethylene oxide (EO) could be obtained as a petrochemical product in excess capacity by industrial production. It also becomes a promising raw material to produce methyl 3-hydroxypropionate (3-HPM) through carbonylative conversion, with the subsequent hydrogenation product 1,3-propanediol (1,3-PDO) as one of the most expected industrial products for new polyester (PTT) and medical intermediates (Lv et al, 2010;Rajendiran et al, 2018;Wen et al, 2018;Xu and Wu, 2019). No matter how, the industrial path for perspective 3-HPM and 1,3-PDO required the key carbonylative transformation of EO with high efficiency and selectivity, which was, however, greatly challenging until current days.…”