32082-74-9Relevant articles and documents
Carbonylative Polymerization of Epoxides Mediated by Tri-metallic Complexes: A Dual Catalysis Strategy for Synthesis of Biodegradable Polyhydroxyalkanoates
Li, Wen-Bing,Liu, Ye,Lu, Xiao-Bing,Yang, Jin-Chuang,Yang, Jun
supporting information, (2022/01/20)
Polyhydroxyalkanoates (PHAs) are a unique class of commercially manufactured biodegradable polyesters with properties suitable for partially substituting petroleum-based plastics. However, high costs and low volumes of production have restricted their application as commodity materials. In this study, tri-metallic complexes were developed for carbonylative polymerization via a dual catalysis strategy, and 17 products of novel PHAs with up to 38.2 kg mol?1 Mn values were discovered. The polymerization proceeds in a sequential fashion, which entails the carbonylative ring expansion of epoxide to β-lactone and its subsequent ring-opening polymerization that occurs selectively at the O-alkyl bond via carboxylate species. The wide availability and structural diversity of epoxide monomers provide PHAs with various structures, excellent functionalities, and tunable properties. This study represents a rare example of the preparation of PHAs using epoxides and carbon monoxide as raw materials.
Direct Heterogenization of Salphen Coordination Complexes to Porous Organic Polymers: Catalysts for Ring-Expansion Carbonylation of Epoxides
Ganesan, Vinothkumar,Yoon, Sungho
, (2020/02/27)
Salen and salphens are important ligands in coordination chemistry due to their ability to form various metal complexes that can be used for a variety of organic transformations. However, salen/salphen complexes are difficult to separate from the reaction mixture, thereby limiting their application to homogeneous systems. Accordingly, considerable effort has been spent to heterogenize the metallosalen/salphen complexes; however, this has resulted in compromised activities and selectivities. Direct heterogenization of metallosalens to form porous organic polymers (POPs) shows promise for heterogeneous catalysis, because it would allow easy separation while retaining catalytic function. Thus, a facile synthetic strategy for preparing metallosalen/salphen-based porous organic polymers through direct molecular knitting using a Friedel-Crafts reaction is presented herein for the first time. As representative candidates, salphenM(III)Cl (M = Al3+ and Cr3+) complexes are knitted by covalent cross-linking using this facile, scalable, one-pot method to synthesize highly POPs in high yields. When incorporated with [Co(CO)4]- anions, the resulting heterogeneous Lewis acidic metal (Al3+ and Cr3+) POPs exhibit propylene oxide ring-expansion carbonylation activity on par with those of their homogeneous counterparts.
Acrylonitrile Derivatives from Epoxide and Carbon Monoxide Reagents
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Paragraph 0223-0237, (2019/01/15)
The present invention is directed to reactor systems and processes for producing acrylonitrile and acrylonitrile derivatives. In preferred embodiments of the present invention, the processes comprise the following steps: introducing an epoxide reagent and carbon monoxide reagent to at least one reaction vessel through at least one feed stream inlet; contacting the epoxide reagent and carbon monoxide reagent with a carbonylation catalyst to produce a beta-lactone intermediate; polymerizing the beta-lactone intermediate with an initiator in the presence of a metal cation to produce a polylactone product; heating the polylactone product under thermolysis conditions to produce an organic acid product; optionally esterifying the organic acid product to produce one or more ester products; and reacting the organic acid product and/or ester product with an ammonia reagent under ammoxidation conditions to produce an acrylonitrile product.
An aluminum(III) picket fence phthalocyanine-based heterogeneous catalyst for ring-expansion carbonylation of epoxides
Jiang, Jianwei,Yoon, Sungho
, p. 6120 - 6125 (2019/03/19)
An effective heterogeneous catalyst for ring-expansion carbonylation of epoxides may have additional advantages over the homogeneous counterpart in terms of facile product separation and recyclability. A new Al(iii) picket fence phthalocyanine complex was synthesized and directly knitted using the Friedel-Crafts reaction to prepare a solid porous network, which was ultimately used to immobilize [Co(CO)4]- ions. The resulting heterogeneous catalyst, [Lewis acid]+[Co(CO)4]-, efficiently catalyzes the conversion of various epoxides into the corresponding β-lactones with high selectivity (99%) and stoichiometric conversion under mild reaction conditions, along with good functional group tolerance.
Balancing between Heterogeneity and Reactivity in Porphyrin Chromium-Cobaltate Catalyzed Ring Expansion Carbonylation of Epoxide into β-Lactone
Rajendiran, Senkuttuvan,Ganesan, Vinothkumar,Yoon, Sungho
supporting information, p. 3283 - 3289 (2019/05/15)
The synthesis of a unique heterogeneous catalyst that combines the functionality of a homogeneous catalyst and the advantages of a heterogeneous catalytic process is a continuing goal in various industrially applicable reactions. Here, we report heterogenization of homogeneous catalyst for lactone production from epoxide carbonylation through a facile polymerization using Friedel-Crafts reaction. A correlation between reactivity and degree of heterogeneity has been deduced by synthesizing different sized polymeric catalysts. The partially polymerized catalyst showed a remarkable initial turnover frequency of 400 h-1, and the fully polymerized catalyst displayed excellent selectivity during recycling with a total turnover number of 4100.
PROCESSES FOR PRODUCING BETA-LACTONE AND BETA-LACTONE DERIVATIVES WITH HETEROGENOUS CATALYSTS
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Paragraph 0193-0195, (2019/02/24)
The present invention is directed to processes from producing beta-lactone and beta-lactone derivatives using heterogenous catalysts. In preferred embodiments of the present invention, the processes comprise the steps: passing a feed stream comprising an epoxide reagent and a carbon monoxide reagent to a reaction zone; contacting the epoxide reagent and the carbon monoxide reagent with a heterogenous catalyst to produce a beta-lactone product in the reaction zone; and removing the beta-lactone product from the reaction zone. In preferred embodiments, the heterogenous catalyst comprises a solid support containing a cationic Lewis acid functional group and a metal carbonyl compound comprising at least one of anionic metal carbonyl compound or a neutral metal carbonyl compound. In certain preferred embodiments, the epoxide reagent and carbon monoxide reagent have a biobased content.
Efficient synthesis of the ketone body ester (R)-3-hydroxybutyryl-(R)-3-hydroxybutyrate and its (S,S) enantiomer
Budin, Noah,Higgins, Erin,DiBernardo, Anthony,Raab, Cassidy,Li, Chun,Ulrich, Scott
, p. 560 - 564 (2018/07/25)
The ketone body ester (R)-3-hydroxybutyryl-(R)-3-hydroxybutyrate and its (S,S) enantiomer were prepared in a short, operationally simple synthetic sequence from racemic β-butyrolactone. Enantioselective hydrolysis of β-butyrolactone with immobilized Candida antarctica lipase-B (CAL-B) results in (R)-β-butyrolactone and (S)-β-hydroxybutyric acid, which are easily converted to (R) or (S)-ethyl-3-hydroxybutyrate and reduced to (R) or (S)-1,3 butanediol. Either enantiomer of ethyl-3-hydroxybutyrate and 1,3 butanediol are then coupled, again using CAL-B, to produce the ketone body ester product. This is an efficient, scalable, atom-economic, chromatography-free, and low cost synthetic method to produce the ketone body esters.
METHODS FOR PRODUCTION OF TEREPHTHALIC ACID FROM ETHYLENE OXIDE
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Page/Page column 26-28, (2017/01/23)
The present invention provides methods for the production of terephthalic acid and derivatives thereof using ethylene oxide, carbon monoxide and furan as feedstocks. The process is characterized by high yields and high carbon efficiency. The process can utilize 100% biobased feedstocks (EO via ethanol, CO via biomass gasification, and furan via known processes from cellulosic feedstocks).
A covalent triazine framework-based heterogenized Al-Co bimetallic catalyst for the ring-expansion carbonylation of epoxide to β-lactone
Rajendiran, Senkuttuvan,Natarajan, Prakash,Yoon, Sungho
, p. 4635 - 4638 (2017/01/29)
Difficulties in product separation and ineffective recycling of the homogenous catalyst deter the mass production of β-lactones via carbonylation of epoxides. Herein, we address these issues, for the first time, using a recyclable heterogenized catalyst [bpy-CTF-Al(OTf)2][Co(CO)4] that efficiently converts propylene oxide (PO) to β-butyrolactone with high selectivity.
Acceptorless dehydrogenative lactonization of diols by Pt-loaded SnO2 catalysts
Touchy, Abeda Sultana,Shimizu, Ken-Ichi
, p. 29072 - 29075 (2015/04/14)
We report herein a new heterogeneous catalytic system for dehydrogenative lactonization of various diols under solvent-free and acceptor-free conditions using 1 mol% of Pt-loaded SnO2, providing the first successful example of acceptorless lactonization of 1,6-hexanediol to ε-caprolactone by a heterogeneous catalyst. This journal is
