Methyl Vinyl Sulfone Research Articles

Construction of Sulfone‐Based Polymer Electrolyte Interface Enables the High Cyclic Stability of 4.6 V LiCoO2 Cathode by In Situ Polymerization

AbstractLithium cobalt oxide (LiCoO2) is considered an indispensable cathode material in the realm of consumer electronic batteries due to its high volumetric energy density. However, at a charging cut‐off voltage as high as 4.6 V, significant interfacial side reactions between LiCoO2 and the electrolyte occur, which adversely impact the battery's cycle performance. The surface‐related issues of LiCoO2 at high charge voltages not only constrain its utilization in conventional lithium‐ion batteries with liquid electrolytes but also limit its application in solid‐state batteries. Although traditional coating methods using inert inorganic compounds can partially alleviate this issue, their point‐like coatings fail to completely prevent the surface of LiCoO2 from direct contact with the electrolyte. The exploration of novel surface protection strategies for LiCoO2 remains imperative to address the associated challenges. Herein, introducing a sulfone‐based polymer electrolyte interface is proposed on the surface of LiCoO2 using methyl vinyl sulfone (MVS) through in situ polymerization. Remarkably, LiCoO2 with sulfone‐based polymer electrolyte interface exhibits a capacity retention rate of 83% after 500 cycles when employing a carbonate electrolyte without additives at a charge cut‐off voltage of 4.6 V. Furthermore, the LiCoO2 and polymer electrolyte interface exhibits exceptional cycle stability when paired with polyether solid electrolytes that do not possess high voltage tolerance. Moreover, the incorporation of a polymer electrolyte interface not only enhances the cycle stability of LiCoO2 but also improves its thermal stability. This work presents novel research perspectives for exploring high‐voltage stable LiCoO2.

Interfacial modulation of bifunctional electrolyte additive engineering for dendrite-free and robust lithium metal anode

Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential. Unfortunately, safety concerns related to dendrite formation on the anode surface caused by the uneven distribution of Li-ions during the discharge process interfere with the use of Li-metal in industrial batteries. In this study, methyl vinyl sulfone (MVS), a sulfone-based functional electrolyte additive, is used in an additive engineering strategy to control Li-electrolyte interactions and address the aforementioned problems. Li dendrite growth may be restricted, and transition metal degradation on the surface of the cathode can be reduced by the MVS-derived functional electrolyte additive interfacial layer. The electrochemical performance of an ethylene carbonate/dimethyl carbonate (EC/DMC) + 1 wt% MVS Li-metal anode of a Li||Li symmetric cell exhibits remarkable cycle stability, maintaining a low overvoltage for over 750 h at 1 mA cm−2, and capacity of 1 mA h cm−2. Additionally, LiNi0.8Co0.1Mn0.1O2 (NCM811) full cells with the MVS additive exhibit enhanced electrochemical stability for 250 cycles at a current density of 100 mA g−1. This study provides an innovative approach for stabilizing the metal-electrolyte interfacial layer that may be used for practical applications in metal-based rechargeable batteries.

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions.

The reactions of 2,4-di-tert-butyl-6-(diphenylphosphino)phenol and various Michael acceptors (acrylonitrile, acrylamide, methyl vinyl ketone, several acrylates, methyl vinyl sulfone) yield the respective phosphonium phenolate zwitterions at room temperature. Nine different zwitterions were synthesized and fully characterized. Zwitterions with the poor Michael acceptors methyl methacrylate and methyl crotonate formed, but could not be isolated in pure form. The solid-state structures of two phosphonium phenolate molecules were determined by single-crystal X-ray crystallography. The bonding situation in the solid state together with NMR data suggests an important contribution of an ylidic resonance structure in these molecules. The phosphonium phenolates are characterized by UV-vis absorptions peaking around 360 nm and exhibit a negative solvatochromism. An analysis of the kinetics of the zwitterion formation was performed for three Michael acceptors (acrylonitrile, methyl acrylate, and acrylamide) in two different solvents (chloroform and methanol). The results revealed the proton transfer step necessary to stabilize the initially formed carbanion as the rate-determining step. A preorganization of the carbonyl bearing Michael acceptors allowed for reasonable fast direct proton transfer from the phenol in aprotic solvents. In contrast, acrylonitrile, not capable of forming a similar preorganization, is hardly reactive in chloroform solution, while in methanol the corresponding phosphonium phenolate is formed.

A DFT Study of the Copolymerization of Methyl Vinyl Sulfone and Ethylene Catalyzed by Phosphine–Sulfonate and α-Diimine Palladium Complexes

Density functional theory (DFT) calculations were comparatively carried out to reveal the origins of different catalytic performances from phosphine–benzene sulfonate (A, [{P^O}PdMe(L)] (P^O = Κ2-P,O-Ar2PC6H4SO3 with Ar = 2-MeOC6H4)) and α-diimine (B, [{N^N}PdMe(Cl)] (N^N = (ArN=C(Me)-C(Me)=NAr) with Ar = 2,6-iPr2C6H3)) palladium complexes toward the copolymerization of ethylene and methyl vinyl sulfone (MVS). Having achieved agreement between theory and experiment, it was found that the favorable 2,1-selective insertion of MVS into phosphine–sulfonate palladium complex A was due to there being less structural deformations in the catalyst and monomer. Both the MVS and ethylene insertions were calculated, and the former was found to be more favorable for chain initiation and chain propagation. In the case of α-diimine palladium system B, the resulting product of the first MVS insertion was quite stable, and the stronger O-backbiting interaction hampered the insertion of the incoming ethylene molecule. These computational results are expected to provide some hints for the design of transition metal copolymerization catalysts.

A cascade reaction of cinnamyl azides with vinyl sulfones directly generates dihydro-pyrrolo-pyrazole heterocycles

This report describes the direct synthesis of dihydro-pyrrolo-pyrazole heterocycles from allylic azides and methyl vinyl sulfone. The product results from a complex cascade reaction that is operationally straightforward, with aromatization being the result of a concomitant elimination step. A variety of azides could participate in this reaction (12 examples) and the isolated yields of the desired product ranged from 51%−72%. Lastly the ethylene sulfone group could be removed by heating the product in pyrrolidine.

Reaction of Methyl Vinyl Sulfone with Schiff Bases Derived from α-Alanine Methyl Ester and Aromatic Aldehydes

Schiff bases derived from α-alanine methyl ester and aromatic aldehydes reacted with methyl vinyl sulfone in toluene at 20°C in the presence of silver acetate and 1.5 equiv of triethylamine to give the corresponding 1,3-dipolar cycloaddition products, methyl (2S*,4S*,5S*)-5-aryl-4-methanesuffonylpyrrolidine-2-carboxylates containing a small impurity (8–25%) of diastereoisomeric (2S*,4R*,5S*)-5-aryl-4-methanesulfonylpyrrolidine-2-carboxylates. The same compounds were formed when the reaction was carried out in boiling toluene, but in this case the (4S*)-diastereoisomer was the minor product. The stereoselectivity of the cycloaddition reactions was interpreted by DFT/PBE calculations of the energies of the final products and transition states.

Thiol-Michael addition in polar aprotic solvents: nucleophilic initiation or base catalysis?

The thiol-Michael addition of ethanethiol to ethyl acrylate, methyl vinylsulfone and maleimide initiated by ethyl-, diethyl-, triethylamine and triethylphosphine in tetrahydrofuran (THF) is investigated at room temperature.

Short-Chain Branched Polar-Functionalized Linear Polyethylene via “Tandem Catalysis”

Cationic PdII complex 1 chelated by an N-fixed phosphine sultam has been synthesized and structurally characterized. Exposure of 1 to ethylene resulted in the formation of short-chain olefins (1-butene: 2-butene: 1-hexene: 1-octene = 86:7:6:1) with a high catalytic activity of 105 molE molPd–1 h–1. By combination of 1 and one of the well-known phosphinesulfonato PdII catalyst precursors 2–5, linear polyethylenes containing methyl, ethyl, and n-butyl branches of up to 100 per 1000 C were generated from the polymerization of ethylene alone in a “tandem catalysis” one-pot approach. In further exploitation of this concept, linear polyethylenes with both various short-chain branches and a choice of different polar functional groups incorporated into the main chain were obtained for the first time from the copolymerization of ethylene and polar vinyl monomers (methyl acrylate, N-isopropylacrylamide, methyl vinyl sulfone, acrylonitrile, ethyl vinyl ether, vinyl acetate, and allyl bromide). All these apolar and p...

Vinyl sulfones as SEI-forming additives in propylene carbonate based electrolytes for lithium-ion batteries

The electrochemical performance of propylene carbonate (PC) based electrolytes with methyl vinyl sulfone (MVS) and ethyl vinyl sulfone (EVS) as film-forming additives on graphite electrode was studied. The results indicate that already small amount of these additives is able to form a stable SEI and thus successfully prevent exfoliation of the graphite. Moreover, the tested additives showed slight impact on the cathode performance as well as on the safety characteristics.

ChemInform Abstract: Poly(N‐vinylimidazole) as Efficient Recyclable Catalyst for the Michael Addition of CH‐Acids to Electron Deficient Alkenes in Water.

Efficiency of poly(N-vinylimidazole) as the basic recyclable catalyst for the Michael addition of CH-acids to acrylonitrile, methyl acrylate, methyl vinyl ketone and methyl vinyl sulfone in water at ambient temperature was studied. In these reactions, formation of both 1: 1 and 1: 2 adducts is possible.

Synthesis, crystal structure, and in vitro antiprotozoal activity of some 5-phenyl(methyl)sulfonyl-substituted dihydroisoxazoles

4,5-Dihydroisoxazole derivatives are interesting synthetic targets that exhibit various biological activities, including anti-infective. Taking account of the principle of bioisosterism, a number of 4,5-dihydroisoxazoles carrying a phenyl- (or methyl-)sulfonyl group at position 5 were designed and synthesized by 1,3-dipolar cycloaddition of nitrolic acid-generated nitrile oxides with electron-deficient phenyl (or methyl) vinyl sulfones. The structures of all the cycloadducts were elucidated by means of spectroscopic methods (NMR, MS), X-ray diffraction, and physical characteristics. The in vitro antiprotozoal and cytotoxic activities of these heterocyclic compounds were investigated.

O2-Sulfonylethyl Protected Isopropylamine Diazen-1-ium-1,2-diolates as Nitroxyl (HNO) Donors: Synthesis, β-Elimination Fragmentation, HNO Release, Positive Inotropic Properties, and Blood Pressure Lowering Studies

New types of nonexplosive O(2)-sulfonylethyl protected (-CH(2)CH(2)SO(2)R; R = OMe, NHOMe, NHOBn, Me) derivatives of isopropylamine diazen-1-ium-1,2-diolate (IPA/NO) (2-5) were developed that are designed to act as novel HNO donors. These compounds, with suitable half-lives (6.6-17.1 h) at pH 7.4, undergo a base-induced β-elimination reaction that releases a methyl vinyl sulfone product and the parent IPA/NO anion which subsequently preferentially releases HNO (46-61% range). Importantly, the O(2)-methylsulfonylethyl compound 5 exhibited a significant in vitro inotropic effect up to 283% of the baseline value and increased the rates of contraction and relaxation but did not induce a chronotropic effect. Furthermore, compound 5 (22.5 mg/kg po dose) provided a significant reduction in blood pressure up to 6 h after drug administration. All these data suggest that O(2)-sulfonylethyl protected derivatives of IPA/NO, which are efficient HNO donors, could have potential applications to treat cardiovascular disease(s) such as congestive heart failure.

Poly(N-vinylimidazole) as efficient recyclable catalyst for the Michael addition of CH-acids to electron deficient alkenes in water

Efficiency of poly(N-vinylimidazole) as the basic recyclable catalyst for the Michael addition of CH-acids to acrylonitrile, methyl acrylate, methyl vinyl ketone and methyl vinyl sulfone in water at ambient temperature was studied. In these reactions, formation of both 1: 1 and 1: 2 adducts is possible.

ChemInform Abstract: Poly(N‐vinylimidazole) as an Efficient and Recyclable Catalyst of the Aza‐Michael Reaction in Water.

Poly(N-vinylimidazole) effectively catalyzed Michael addition of 1H-1,2,4-triazole, 3,5-dimethyl-1H-1,2,4-triazole, uracil, oxazolidin-2-one, and succinimide to but-3-en-2-one, cyclohex-2-en-1-one, methyl acrylate, and methyl vinyl sulfone in water at room temperature. The catalyst can readily be regenerated and repeatedly used at least five times without loss in activity, as shown in the reaction of 1H-1,2,4-triazole with but-3-en-2-one as an example.

Poly(N-vinylimidazole) as an efficient and recyclable catalyst of the aza-Michael reaction in water

Poly(N-vinylimidazole) effectively catalyzed Michael addition of 1H-1,2,4-triazole, 3,5-dimethyl-1H-1,2,4-triazole, uracil, oxazolidin-2-one, and succinimide to but-3-en-2-one, cyclohex-2-en-1-one, methyl acrylate, and methyl vinyl sulfone in water at room temperature. The catalyst can readily be regenerated and repeatedly used at least five times without loss in activity, as shown in the reaction of 1H-1,2,4-triazole with but-3-en-2-one as an example.

ChemInform Abstract: Condensation Products of Mono‐ and Dibromo‐Substituted Methyl Vinyl Sulfones with CH‐Acids Enolates.

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Condensation products of mono-and dibromo-substituted methyl vinyl sulfones with CH-acids enolates

Bromomethyl (E)-2-phenylethenyl and bromomethyl (Z)-1-bromo-2-phenylethenyl sulfones undergo condensation with enolates generated from malononitrile, dimethyl malonate, methyl and ethyl acetoacetate using NaH in THF to give tetrahydrothiophene S,S-dioxides. Methyl (E)-1-bromo-2-phenylethenyl and methyl (E)-2-bromo-2-phenylethenyl sulfones react with sodium malononitrile to give 2-[2-(methylsulfonyl)-1-phenylethylidene]malononitrile. The bromomethyl-(E)-2-bromo-2-phenyl ethenyl sulfone reacts with sodium malononitrile to give 2-[2-(bromomethylsulfonyl)-1-phenylethylidene]malononitrile exclusively.

Aza-Michael reactions with vinyl sulfones and Amberlyst-15 as catalyst

Vinyl p-aminophenylsulfone and methyl vinyl sulfone were shown to react, as Michael acceptors, with a broad range of secondary and primary amines using Amberlyst as catalyst. The reactions occurred, generally, with high yields and in a short time.

An Economical and Convenient Synthesis of Vinyl Sulfones.

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An Economical and Convenient Synthesis of Vinyl Sulfones

A general process for the efficient synthesis of vinyl sulfones has been developed using commercially available sulfinic acid sodium salts and dibromides. A variety of phenyl and methyl vinyl sulfones have been formed in good yields, in the absence of any catalyst.