scholarly journals Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1651
Author(s):  
Felipe de la Cruz-Martínez ◽  
Marc Martínez de Sarasa Buchaca ◽  
Almudena del Campo-Balguerías ◽  
Juan Fernández-Baeza ◽  
Luis F. Sánchez-Barba ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Reaction Mechanism ◽  
Catalytic System ◽  
Phthalic Anhydride ◽  
Ring Opening ◽  
High Selectivity ◽  
Zinc Complexes ◽  
Cyclohexene Oxide ◽  
Reaction Conditions ◽  
Cyclic Anhydrides

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

Novel catalytic system: N-hydroxyphthalimide/hydrotalcite-like compounds catalysing allylic carbonylation of cyclic olefins

2016 ◽  
Vol 70 (7) ◽  
Author(s):  
Yin Zhou ◽  
Rui-Ren Tang ◽  
Dan Song
Keyword(s):  
Catalytic Activity ◽  
Reaction Mechanism ◽  
Catalytic System ◽  
Catalytic Reaction ◽  
Model Reaction ◽  
Reaction Conditions ◽  
Cyclic Olefins ◽  
Tert Butyl Hydroperoxide ◽  
Optimal Reaction ◽  
Catalytic Reaction Mechanism

Abstract-hydroxyphthalimide (NHPI) combined with stable and recoverable transition metal–aluminium binary hydrotalcite-like compounds (M-Al HTLcs, M = Cu, Ni, Co) as an unprecedented catalytic system was demonstrated for the allylic carbonylation, as the model reaction, of cyclic olefins with tert-butyl hydroperoxide (TBHP), using isophorone (IP) to ketoisophorone (KIP). The results showed NHPI combined with Cu-Al HTLcs to be an efficient catalytic system and the influences of various reaction conditions of the catalytic reaction were optimised. A maximum IP conversion of 68.0 % with 81.8 % selectivity to KIP was afforded under the optimal reaction conditions. Experiments of repeatability and restorability showed Cu-Al HTLcs to be stable for at least five cycles without noticeable loss of catalytic activity. Expanding substrates could also be efficiently converted to the corresponding ketones under the optimised reaction conditions with appreciable yields. A plausible catalytic reaction mechanism was proposed.

scholarly journals LiHSO4/SiO2as a New, Efficient and Reusable Catalytic System for the Chemoselective Conversion of Aldehydes to Acylals under Solvent-Free Conditions

2009 ◽  
Vol 6 (s1) ◽  
pp. S390-S396 ◽  
Author(s):  
Abdolkarim Zare ◽  
Alireza Hasaninejad ◽  
Esmael Rostami ◽  
Ahmad Reza Moosavi-Zare ◽  
Maria Merajoddin ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Acetic Anhydride ◽  
Catalytic System ◽  
Catalytic Amount ◽  
Significant Loss ◽  
Solvent Free ◽  
Reaction Conditions ◽  
Highly Efficient ◽  
Solvent Free Conditions

A highly efficient, green and expeditious solvent-free method is described for the chemoselective conversion of aldehydes to the corresponding acylals in excellent yields, using acetic anhydride in the presence of catalytic amount (20 mol%) of silica-supported LiHSO4. Ketones does not react under these reaction conditions. LiHSO4/SiO2can be recovered and reused without any significant loss of its catalytic activity.

scholarly journals Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2

2019 ◽  
Vol 48 (15) ◽  
pp. 4887-4893 ◽  
Author(s):  
James R. Pankhurst ◽  
Shyeni Paul ◽  
Yunqing Zhu ◽  
Charlotte K. Williams ◽  
Jason B. Love
Keyword(s):  
Carbon Dioxide ◽  
Ring Opening ◽  
Zinc Complexes ◽  
Cyclohexene Oxide

Tri- and tetranuclear macrocyclic zinc alkoxides act as catalysts for the ring-opening polymerisation of epoxides and carbon dioxide.

Strategies for Tuning the Catalytic Activity of Zinc Complexes in the Solvent-Free Coupling Reaction of CO2 and Cyclohexene Oxide

2021 ◽  
pp. 120753
Author(s):  
Paolo Biagini ◽  
Carlo Perego ◽  
Riccardo Pò ◽  
Laura Boggioni ◽  
Mariachiara Cozzolino ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Coupling Reaction ◽  
Zinc Complexes ◽  
Solvent Free ◽  
Cyclohexene Oxide

Alternating ring-opening copolymerization of cyclohexene oxide with phthalic anhydride catalyzed by iron(III) salen complexes

2015 ◽  
Vol 23 (2) ◽  
pp. 161-166 ◽  
Author(s):  
Robert Mundil ◽  
Zdeněk Hošt’álek ◽  
Ivana Šeděnková ◽  
Jan Merna
Keyword(s):  
Phthalic Anhydride ◽  
Ring Opening ◽  
Cyclohexene Oxide ◽  
Salen Complexes

Alternating ring-opening copolymerization of phthalic anhydride with epoxides catalysed by salophen chromium(iii) complexes. An effect of substituents in salophen ligands

2018 ◽  
Vol 9 (16) ◽  
pp. 2147-2156 ◽  
Author(s):  
K. Bester ◽  
A. Bukowska ◽  
B. Myśliwiec ◽  
K. Hus ◽  
D. Tomczyk ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Phthalic Anhydride ◽  
Ring Opening ◽  
Effect Of Substituents ◽  
Ligand Structure

The effect of a ligand structure on the catalytic activity of salophen chromium(iii) complexes in the ring-opening copolymerization of phthalic anhydride with a series of epoxides was studied.

Ring-opening of hindered cyclic epoxides with potassium carboxylates in the presence of conjugate acids

2013 ◽  
Vol 91 (12) ◽  
pp. 1179-1185 ◽  
Author(s):  
John F. Trant ◽  
Tomas Hudlicky
Keyword(s):  
Carboxylic Acids ◽  
Ring Opening ◽  
Wide Spectrum ◽  
Acid Catalyst ◽  
Solvent Mixture ◽  
Cyclohexene Oxide ◽  
Reaction Conditions ◽  
Systematic Analysis ◽  
Conjugate Acid ◽  
Ring Open

During attempts to ring-open a highly hindered epoxide, traditional methods were found to be ineffective. An alternative strategy for opening epoxides was implemented that employed a potassium carboxylate in the presence of its conjugate acid in a solvent mixture containing polar and potassium-sequestering components. A systematic analysis of the components of the reaction mixture indicated that the addition of the conjugate acid was the most important feature for providing good conversion. This reaction appears to be general for most classes of carboxylic acids including cinnamic, aromatic, and highly hindered carboxylic acids (30%–79% yield) and only fails with weak carboxylate nucleophiles. Three highly substituted and hindered cyclohexene oxide derivatives were examined for reactivity and the reaction conditions appear to tolerate a variety of functional groups to provide the ring-opened species. This pH-moderate system proved useful for hindered cyclic epoxides when all other techniques failed and should prove general to a wide spectrum of epoxide and carboxylic acid partners in those cases where the use of a strong Lewis or protic acid catalyst, or a strong basic nucleophile, is inappropriate.

scholarly journals Application of Diethylzinc/propyl Gallate Catalytic System for Ring-Opening Copolymerization of rac-Lactide and ε-Caprolactone

Molecules ◽  
2019 ◽  
Vol 24 (22) ◽  
pp. 4168 ◽  
Author(s):  
Wyrębiak ◽  
Oledzka ◽  
Figat ◽  
Sobczak
Keyword(s):  
Catalytic System ◽  
Propyl Gallate ◽  
Ring Opening ◽  
Reaction Conditions ◽  
Catalytic Systems ◽  
Cyclic Esters ◽  
Biomedical Polymers ◽  
Low Toxicity ◽  
High Yields ◽  
Polymerization Method

Biodegradable polyesters gain significant attention because of their wide potential biomedical applications. The ring-opening polymerization method is widely used to obtain such polymers, due to high yields and advantageous properties of the obtained material. The preparation of new, effective, and bio-safe catalytic systems for the synthesis of biomedical polymers is one of the main directions of the research in modern medical chemistry. The new diethylzinc/propyl gallate catalytic system was first used in the copolymerization of ε-caprolactone and rac-lactide. In this paper, the activity of the new zinc-based catalytic system in the copolymerization of cyclic esters depending on the reaction conditions was described. The microstructure analysis of the obtained copolyesters and their toxicity studies were performed. Resulted copolyesters were characterized by low toxicity, moderate dispersity (1.19–1.71), varying randomness degree (0.18–0.83), and average molar mass (5300–9800 Da).

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