36747-96-3

Usage

Synthesis Reference(s)

Synthetic Communications, 20, p. 2789, 1990 DOI: 10.1080/00397919008051491

Upstream product

• 96-09-3 styrene oxide 
• 64-17-5 ethanol 
• 79309-63-0 ethyl α-ethoxy-α-phenylacetate 
• 65792-30-5 methyl α-ethoxy-α-phenylacetate 
• 4358-87-6 (RS)-methyl mandelate 
• 2882-19-1 ethyl 2-phenyl-2-bromoacetate 
• 100-42-5 styrene 
• 62-53-3 aniline 
• 611-71-2 (R)-Mandelic Acid 
• 75-03-6 ethyl iodide 
• 17199-29-0 (S)-Mandelic acid 

Downstream Products

• 89423-15-4 2-phenyl-2-ethoxyethyl-p-toluene sulphonate 
• 53574-79-1 Benzoic acid 2-ethoxy-2-phenyl-ethyl ester 
• 314754-16-0 2-ethoxy-2-phenylethyl methanesulfonate 
• 314754-71-7 2-ethoxy-2-phenyl-1-(2,3,4,6-tetra-O-benzyl-1-deoxy-β-D-glucopyranosylthio)ethane 
• 65885-18-9 phenyl (2-phenyl-2-ethoxy ethyl)sulphone 
• 89457-03-4 phenyl (β-ethoxy-β-phenylethyl)sulphide 

Relevant academic research and scientific papers

Oxidomolybdenum complexes for acid catalysis using alcohols as solvents and reactants

The application field of dichloridodioxidomolybdenum(vi) chelate complexes, which have been intensively investigated as catalysts for liquid-phase olefin epoxidation, is broadened to encompass acid catalysis, in particular, alcoholysis and acetalisation reactions. Complex [MoO2Cl2(L)] (1) with L = 4,4′-di-tert-butyl-2,2′-bipyridine was chosen as (pre)catalyst. Depending on the reaction conditions, 1 either remained structurally intact or was transformed into different metal species, the structures of which were determined on the basis of single-crystal X-ray diffraction, spectroscopic techniques (FT-IR and 1H NMR), and elemental analysis. The first example of a mixed-ligand complex of the type [MoO2X(OR)(L)] (X = halide) is disclosed. This complex is one of only a handful of complexes known to date that exhibit an all-cis configuration instead of the usual cis-oxido, trans-X, cis-L configuration (X = anionic ligand). Mechanistic considerations of the formation of the metal species are made.

Rational design of a flu -type heterometallic cluster-based Zr-MOF

Following the HSAB principle, the cooperative assembly of tetrahedral [Cu4I4(Ina)4]4- metalloligands and 8-connecting [Zr6(μ3-OH)8(OH)8]8+ building units leads to the first heterometallic cluster-based Zr-MOF (1). The results provide a successful strategy for rational design of heterometallic cluster-based Zr-MOFs.

Polyoxometalate-modified reduced graphene oxide foam as a monolith reactor for efficient flow catalysis of epoxide ring-opening reactions

Continuous flow catalysis has been attracting significant interest due to its remarkable advantages over traditional batch reactions. In this work, a facile and broad-spectrum hydrothermal approach has been developed to construct polyoxometalate-modified reduced graphene oxide (POM@rGO) foam, which worked as a monolith reactor for efficient continuous flow catalysis of epoxide ring-opening reactions. The porous structures of rGO foam allow the high dispersion of the POM catalyst onto the substrate through electrostatic interactions. Specifically, a phosphotungstic acid (H3PW12O40, denoted as PW12)-modified rGO (PW12@rGO) monolith reactor exhibits remarkable catalytic activity and durability towards epoxide ring-opening reactions with alcohols, achieving 99% conversion and 92% selectivity for the methanolysis product in 10 min under ambient conditions without stirring. Notably, while coupling with a micro-injection pump, such PW12@rGO foam can work as an efficient continuous flow reactor towards methanolysis of styrene oxide for 38 h with 99% conversion and over 90% selectivity, reaching a turnover number (TON) as high as 28?044.

Cellulose sulfate: An efficient heterogeneous catalyst for the ring-opening of epoxides with alcohols and anilines

Cellulose sulfate was synthesized by esterification of α-cellulose with concentrated sulfuric acid at ?10°C in ethanol. Cellulose is mainly sulfated on 3-, 6- and 3, 6-positions of the cellulose. It acts as a heterogeneous catalyst for the ring-opening of epoxides with alcohols or anilines and the Friedel-Crafts reaction between N-benzylindole and crotonaldehyde at room temperature. Methanolysis of cyclic epoxides, styrene oxide, terminal aliphatic epoxides, and glycidyl ethers were carried out using the catalyst (0.4–6.8 mg/mmol of epoxide) and afforded the corresponding products in 53–97% isolated yields after 10 min–24 h. Cellulose sulfate was successfully recycled and reused up to 3 catalytic cycles for the ring-opening of styrene oxide with methanol.

Cross-linked poly(N-vinylpyrrolidone)-titanium tetrachloride complex: A novel stable solid TiCl4 equivalent as a recyclable polymeric Lewis acid catalyst for regioselective ring-opening alcoholysis of epoxides

Cross-linked poly(N-vinylpyrrolidone) resin beads were prepared as macromolecular ligand precursors by suspension copolymerization of N-vinyl-2-pyrrolidone and N,N′-methylenebisacrylamide (MBA) as a crosslinking agent in water. Subsequently, the resulting polymer carrier precursor was readily combined with titanium tetrachloride to form a stable polymeric coordination complex (PNVP/TiCl4), and this novel stable TiCl4 equivalent evaluated as a heterogeneous and reusable solid Lewis acid catalyst for the regio-and stereoselective nucleophilic ring opening of various epoxides with various alcohols to prepare β-alkoxy alcohols in excellent yields without generating any waste. The MBA-cross-linked PNVP and resultant catalyst were characterized by Fourier transform infrared spectroscopy (FT–IR), field-emission scanning electron microscope (FE–SEM), energy dispersive X-ray (EDX), inductively coupled plasma (ICP), and thermogravimetric analysis (TGA) techniques. Moreover, the catalyst is very stable, easily separated, and reused at least five times without significant loss of activity. In terms of scope, yields, the amount of catalyst used, and reaction time, the PNVP-TiCl4 complex catalyst is an improvement over previously reported heterogeneous catalysts for ring opening of epoxides methods. Further, the experimental outcome revealed that using the copolymer beads as carriers with a high percentage of crosslinking and the high mesh size leads had an adverse effect on the reaction rate.

Synergistic Peptide and Gold Catalysis: Enantioselective Addition of Branched Aldehydes to Allenamides

The combination of a peptide catalyst and a gold catalyst is presented for enantioselective addition reactions between branched aldehydes and allenamides. The two catalysts act in concert to provide γ,δ-enamide aldehydes bearing a fully substituted, benzylic stereogenic center – a structural motif common in many natural products and therapeutically active compounds – with good yields and enantioselectivities. The reaction tolerates a variety of alkyl and alkoxy substituted aldehydes and the products can be elaborated into several chiral building blocks bearing either 1,4- or 1,5- functional group relationships. Mechanistic studies showed that the conformational features of the peptide are important for both the catalytic efficiency and stereochemistry, while a balance of acid/base additives is key for ensuring formation of the desired product over undesired side reactions.

Ship-in-bottle preparation of multi-SO3H functionalized ionic liquid@MIL-100(Fe) for acid-catalyzed ring-opening of epoxides

The fact that the homogeneous acid catalysts are usually separated difficulty than heterogeneous catalysts from the reaction media, the opportunity to combine the advantages of both homogeneous and heterogeneous catalytic systems by immobilizing ILs within the pores of a porous solid support host is an alternative method. In this research, a multi-SO3H functionalized ionic liquid derived from hexamethylenetetramine (HMTA) and 1,3-propane sultone was entrapped inside the pores of MIL-100(Fe) through the ship-in-bottle method and utilized for heterogeneous acid-catalyzed ring-opening of epoxides under solvent-free conditions. The physicochemical properties of prepared catalyst were fully elucidated by various methods. FT-IR spectroscopy and elemental analysis approved the successful incorporation of modified groups within the MIL-100(Fe) cavities. The concentration of acid sites was measured via the acid–base titration which exhibited the 0.9?mmol/g H+ in the catalyst structure. Also, thermogravimetric analysis (TGA) profile showed the loosing of modified groups at 300–600°C. Moreover, X-ray diffraction (XRD) analysis showed that the MIL-100(Fe) structure was retained after modification and nitrogen adsorption–desorption analysis (BET method) manifested the decrease in surface area caused by incorporation of ionic liquid. The fabricated catalyst exhibited high catalytic efficiency in methanolysis of styrene oxide (99% conversion in 3?h) under ambient conditions and used without a substantial drop in product yield in further rounds.

MBA-cross-linked poly(N-vinyl-2-pyrrolidone)/ferric chloride macromolecular coordination complex as a novel and recyclable Lewis acid catalyst: Synthesis, characterization, and performance toward for regioselective ring-opening alcoholysis of epoxides

A novel macromolecular-metal coordination complex, MBA-cross-linked PNVP/FeCl3 material was fabricated by immobilization of water intolerant ferric chloride onto the porous cross-linked poly(N-vinyl-2-pyrrolidone) carrier beads as a macromolecular ligand or carrier which was prepared by suspension free-radical copolymerization of N-vinyl-2-pyrrolidone (NVP) and N,N′-methylene bis-acrylamide (MBA) as a crosslinking agent in water. The obtained PNVP/FeCl3 was characterized by UV/vis and FT-IR spectroscopies, TGA, FE-SEM, EDX, and ICP techniques. This heterogenized version of ferric chloride is a convenient and safe alternative to highly water intolerant ferric chloride. The catalytic performance of (PNVP/FeCl3) as an efficient and recyclable polymeric Lewis acid catalyst was appropriately probed in the regio-and stereoselective nucleophilic ring opening of various epoxides with various alcohols in excellent yields with TOF up to 182.48 h?1 without generating any waste. The activity data indicate that this heterogeneous catalyst is very active and could be easily recovered, and reused at least six times without appreciable loss of activity indicating its stability under experimental conditions.

Metalation of Catechol-Functionalized Defective Covalent Organic Frameworks for Lewis Acid Catalysis

Covalent organic frameworks (COFs) have emerged as a fascinating crystalline porous material and are widely used in the field of catalysis. However, developing simple approaches to fabricate conjugated COFs with specific functional groups remains a significant challenge. In this study, the construction of defective COF-LZU1 with Lewis acid sites embedded into the frameworks is fulfilled by a facile solvent-assisted ligand exchange method. A monodentate ligand, protocatechualdehyde, is successfully introduced into the skeleton of COF-LZU1, which endows the defects in the structure of COF-LZU1 via replacement of the original coordinated benzene-1,3,5-tricarbaldehyde ligand. As-synthesized defective COF-LZU1 decorated with protocatechualdehyde is rich of free hydroxy groups for chelating with active metal ions. Specifically, after combining with Fe3+, the defective COF-LZU1 shows excellent activity in catalytic alcoholysis of epoxides under mild conditions. The method reported here will open up the opportunity to incorporate different functional groups into COFs and enrich the strategies for creating new types of porous catalysts.

Influence of Hydrogen Bond Donating Sites in UiO-66 Metal-Organic Framework for Highly Regioselective Methanolysis of Epoxides

A Zr(IV)-based UiO-66 metal-organic framework (MOF) (named 1) was synthesized by employing 1-(aminomethyl)naphthalene-2-ol appended terephthalate linker and Zr(IV) salt via solvothermal method and subsequently characterized. Furthermore, the potential efficiency of activated (named 1′) form of as-synthesized MOF was investigated as an organocatalyst for the ring-opening of epoxide by methanol. The catalytic performance of 1 and 1′ was studied in the methanolysis of styrene oxide as a model substrate and the activity of 1′ was also examined with various alcohols. Under the optimized reaction conditions, the catalytic performance of 1′ reached 96 % conversion of styrene oxide to its corresponding product with 98 % regioselectivity. The reusability and stability of the catalyst were proved by recycling up to four runs in the methanolysis of styrene oxide. The Lewis acidity originating from metal nodes and hydrogen bond donating (HBD) sites in the linker is distributed homogeneously throughout the framework, thus playing crucial role in the activation of epoxide with easy accessibility.