Allylic Sulfones Research Articles

Synthesis and Synthesis of High-Performance Water- Reducing Agent for Polyglycolic Acid

In this paper, using maleic anhydride (MA), allyl polyethylene glycol (AP), methyl allyl sulfonate (SM) as monomer and ammonia persulfate (KPA) as initiator, a polyether high-performance water-reducing agent for polyglycolic acid (PR) on good compatibility in sulphoaluminate cement (SAC) was synthesized by solution polymerization and orthogonal design. And the effects of various factors (reaction time, branched length and density of PR etc.) on the performance of PR were also studied. Results show that the optimum formula was as follows: the polymerization degree of AP was 56, the mass molar ratio of three monomers was n (MA): n (AP): n (SM) = 3:2:1, the amount of AP accounted for 9% of the total molar content of monomer, the reaction temperature was 65 °C, and the reaction time was 5 h.

Copper‐catalyzed Regioselective Hydroaminations of Allylic Sulfones With Aromatic Amines

The highly regioselective copper‐catalyzed hydroaminations of terminal or γ‐substituted allylic sulfones with aromatic amines is described. The combination of an N‐heterocyclic carbene‐copper complex and KOt‐Bu plays an important role in promoting selective amination under mild reaction conditions. This catalytic reaction tolerates a wide range of functional groups and enables the efficient syntheses of new and versatile functionalized β‐amino sulfones in high yields (up to 98%) with >98% regioselectivity.

Multi-functionalized self-floating microspheres for dyes capture: Amphoteric adsorption and rapid surface solid-liquid separation

With the rapidly increased discharges of various complex dyeing wastewaters, adsorbents are required to own more properties such as cost-effectiveness, amphoteric ability, and rapid solid-liquid separation ability, to treat dyeing wastewaters. A multi-functional adsorbent was synthesized by co-grafting m-phenylenediamine and sodium allyl sulfonate on the surface of a low-cost base-material: hollow glass microsphere (HGM). Characterization results indicated the surface roughness and –Si–OH groups of HGM were increased by NaOH corrosion; functional groups such as aromatic-rings, –NH2, and –HSO3− were grafted on the surface of HGM. The synthesized adsorbent showed amphoteric attraction abilities for anionic acid green 25 and cationic basic fuchsin dyes. Kinetics and isotherms studies suggested the PSO model and Langmuir model were most satisfactory for adsorption processes, the theoretical maximum adsorption capacities for acid green 25 and basic fuchsin reached 454.55 and 588.24 mg g−1, respectively. The mechanism investigations indicated the electrostatic attraction, π-π stacking, and hydrogen bonds were the potential interaction forces between dyes and adsorbents. The synthesized material owns self-floating ability due to the hollow structure of HGM, over 95.7% of adsorbents were collected at water surface via the self-floating process in 12 min, which was beneficial to the solid-liquid separation process and the reuse of adsorbents. The technologies developed by these research efforts can serve as templates for synthesizing multi-functional adsorbents for complex wastewaters decontaminations.

Controllable Activation of β-Alkyl Nitroalkenes: Regioselective Synthesis of Allyl and Vinyl Sulfones.

The regiospecific radical reactions of β-alkyl nitroalkenes with sulfonyl hydrazides depended to a great extent on the choice of a solvent and catalyst. In the presence of dimethylformamide (DMF), β-alkyl nitroalkenes more likely converted into electron-rich allyl nitro compounds, which reacted with sulfonyl hydrazides to afford allyl sulfones with high regioselectivity. While in acetonitrile (CH3CN), vinyl sulfones were obtained directly via sulfonation of electron-deficient β-alkyl nitroalkenes. The mechanism investigation revealed that the regioselectivity was controlled by the equilibrium of β-alkyl nitroalkenes and allyl nitro compounds.

Ni-rich LiNi0.8Co0.1Mn0.1O2 oxide functionalized by allyl phenyl sulfone as high-performance cathode material for lithium-ion batteries

• Surface stability of Ni-rich Cathode is improved by using APS additive. • Electrochemical reaction of APS makes stable CEI layer on Ni-rich NCM surface. • APS-based CEI layer effectively suppresses decomposition of electrolytes. • The cell cycled with APS shows improved cycling performance at 45 °C. • NMR result exhibits APS effectively scavenge F – to prevent transition metal dissolution. Nickel-rich layered lithium metal oxides have been on the spotlight for their being advanced cathode materials for lithium-ion batteries; however, their poor cycling performance at high temperature is a critical bottleneck in their application. To improve the interfacial stability of Ni-rich layered lithium metal oxides, we propose the use of a functional electrolyte additive, allyl phenyl sulfone (APS), which is modified by allyl and sulfone functional groups. The sulfone functional group introduced into cathode–electrolyte interphases (CEI) is anticipated to effectively suppress electrolyte decomposition during cycling, whereas the allyl functional group renders the CEI more durable as its desirable chemical reactivity promotes additional crosslinking reaction between CEI. Additionally, the allyl functional group selectively scavenges fluoride (F − ) species in a cell and is thus is expected to reduce F − concentration, leading to the improved overall electrochemical performance of a cell. Results of ex-situ nuclear magnetic resonance spectroscopy confirmed that the APS additive effectively reduced the F − species via a chemical scavenging reaction. As regards the cycling performance of a half-cell, the cell cycled with the APS additive exhibited a considerably improved cycling retention at high temperature (78.9%), whereas the cell cycled with standard electrolyte suffered from continuous fading of retention (64.3%).

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.

Photoredox/cobaloxime co-catalyzed allylation of amines and sulfonyl hydrazines with olefins to access α-allylic amines and allylic sulfones.

Herein, we reported a dual-catalytic platform for the allylation of amines and sulfonyl hydrazines with olefins to selectively access α-allylic amines and allylic sulfones in good yields by combining photoredox catalysis and cobaloxime catalysis. This strategy avoided the use of a stoichiometric amount of terminal oxidant and the use of pre-functionalized allylic precursors, representing a green and ideal atom- & step-economical process. Good substrate scope and gram-scale synthesis demonstrated the utility of this protocol. Mechanistic studies revealed that a radical process is probably involved in this reaction.

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds.

This review highlights the preparation of sodium sulfinates (RSO2Na) and their multifaceted synthetic applications. Substantial progress has been made over the last decade in the utilization of sodium sulfinates emerging as sulfonylating, sulfenylating or sulfinylating reagents, depending on reaction conditions. Sodium sulfinates act as versatile building blocks for preparing many valuable organosulfur compounds through S–S, N–S, and C–S bond-forming reactions. Remarkable advancement has been made in synthesizing thiosulfonates, sulfonamides, sulfides, and sulfones, including vinyl sulfones, allyl sulfones, and β-keto sulfones. The significant achievement of developing sulfonyl radical-triggered ring-closing sulfonylation and multicomponent reactions is also thoroughly discussed. Of note, the most promising site-selective C–H sulfonylation, photoredox catalytic transformations and electrochemical synthesis of sodium sulfinates are also demonstrated. Holistically, this review provides a unique and comprehensive overview of sodium sulfinates, which summarizes 355 core references up to March 2020. The chemistry of sodium sulfinate salts is divided into several sections based on the classes of sulfur-containing compounds with some critical mechanistic insights that are also disclosed.

Synthesis and Evaluation of a Water-Swelling Polymer Plugging Agent SWL-1

In this paper, to solve the problems of low water absorption and weak pressure bearing capacity of current plugging materials, acrylic acid (AA), acrylamide (AM), and sodium allyl sulfonate (SAS) are used as monomers, and soluble starch is used as grafting. Material, the use of free radical aqueous solution method to synthesize the plugging agent SWL-1 with good water absorption and strong salt resistance. The monomer ratio is set as n (AA):n (AM):n (SAS) = 5:2:1, the experimental synthesis temperature is 70°C, and the orthogonal experiment is used to determine the experimental synthesis conditions as AA neutralization degree 80%, The amount of initiator is 0.60%, the amount of crosslinking agent is 0.50%, the ratio of monomer to starch is 7:1, and the amount of calcium carbonate is 13%. The comprehensive evaluation of the performance of the plugging agent SWL-1 shows that the water absorption performance at 60°C is the best 268.78 g/g, and the water absorption performance in 8% NaCl, 0.9% CaCl2 and composite brine is 21.5 g/g, 12.5 g/g and 24.9 g/g, indicating good resistance to sodium and calcium, the water retention rate is still higher than 30% after 15 days at 160°C. The sand bed plugging test found that the maximum pressure of SWL-1 was 7 MPa, and the crack plugging test found that when the crack width was 1 mm, 2 mm, and 3 mm, the maximum compressive strength of SWL-1 was 10 MPa. The acid solubility test showed that the maximum pressure was 10 MPa. The highest rate is 86.38%.

Anticorrosion allyl sulfonate graft chitosan/graphene oxide nanocomposite material

A novel organic/inorganic hybrid allyl sulfonate graft chitosan/graphene oxide nanocomposite material is synthesized, characterized and utilized as a corrosion inhibitor for an X70 pipeline steel substrate in CO2saturated brine at 60 °C.

Visible-light-driven radical 1,3-addition of selenosulfonates to vinyldiazo compounds

A visible-light driven 1,3-selenosulfonylation of vinyldiazo compounds with selenosulfonates provided γ-seleno allylic sulfones in good yields. Control experiments showed that the 1,3-addition proceededviaa radical-chain propagation process.

Simple and Efficient Synthesis of Allyl Sulfones through Cs2CO3-Mediated Radical Sulfonylation of Morita–Baylis–Hillman Adducts with Thiosulfonates

AbstractA highly efficient and eco-friendly method has been developed for the synthesis of allyl sulfones using Morita–Baylis–Hillman (MBH) adducts and thiosulfonates under mild conditions. The Cs2CO3-promoted radical sulfonylation provided a series of allyl sulfones in good to high yields with high stereoselectivities. A wide variety of MBH bromides/acetates as well as thiosulfonates were tolerated and reliable in scaled-up synthesis. A plausible mechanism is proposed to rationalize the radical sulfonylation.

Synergistic photoredox and tertiary amine catalysis: generation of allylic sulfones from Morita–Baylis–Hillman acetates and sulfur dioxide

The first example of the synthesis of allylic sulfones through synergistic photoredox and tertiary amine catalysis, starting from MBH acetates, DABCO·(SO2)2 and 4-substituted Hantzsch esters or potassium alkyltrifluoroborates via a radical pathway, is reported.

Visible-light-induced sulfonylation of Baylis–Hillman acetates under metal- and oxidant-free conditions

A visible-light-driven metal- and oxidant-free procedure for the sulfonylation of Baylis–Hillman acetates with sulfonyl hydrazides under open-air conditions at room temperature is reported. The methods provide a green and facile synthetic route to access allylic sulfones.

Effect of sulfonation modification of polycarboxylate superplasticizer on tolerance enhancement in sulfate

A novel polycarboxylate superplasticizer (PCE) was synthesized by graft copolymerization between acrylic acid (AA) and end-functionalized poly (allyl sulfonate) (PALS) to produce comb polymer, i.e. PAA-g-PALS. The molecular structure was confirmed by Infrared Spectroscopy (IR) and 1H Nuclear Magnetic Resonance (1H NMR), and the molecular properties were characterized by Gel Permeation Chromatography (GPC). The conventional PCE with comb structure using isobutenyl polyethylene glycol (IPEG) as side chains (i.e. PAA-g-IPEG) was also synthesized to explore the effect of the side chain on the PCE performances. The fluidity and its retention, rheological properties, hydrodynamic radii (Rh), adsorption behavior and zeta potential of the cement pastes containing PAA-g-PALS or PAA-g-IPEG were comparatively tested. It was found that this designed “sulfonate modified PCE” exhibited stronger dispersing stability and sulfate tolerance to cement paste and less sensitive to the sulfate competitive adsorption and the increase in ionic strength. Based on the above results, the evaluation method (the sulfate resistance index of PAA-g-PALS was increased by 24% as compared to that of PAA-g-IPEG) was innovatively established and the mechanism of sulfate resistance was clarified in detail. The purpose of this research is to offer an avenue with great potentials to synthesize a novel PCE with excellent workability retention and sulfate tolerance in fresh cement pastes. This sulfonate-modified polycarboxylate superplasticizer has great potentials as a viable alternative to conventional PCE, especially in some harsh cement systems.

Palladium‐Catalyzed Asymmetric Hydrosulfonylation of 1,3‐Dienes with Sulfonyl Hydrazides

AbstractA highly enantio‐ and regioselective hydrosulfonylation of 1,3‐dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity‐determining step.

Palladium‐Catalyzed Asymmetric Hydrosulfonylation of 1,3‐Dienes with Sulfonyl Hydrazides

A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity-determining step.

KOt‐Bu‐Catalyzed Chemo‐ and Regioselective Hydroamination of Allylic Sulfones with Indoles

AbstractA highly chemo‐ and regioselective KOt‐Bu‐catalyzed addition of substituted indoles to terminal or disubstituted allylic sulfones at the indole N‐position is reported. The catalytic protocol allows for the efficient and mild synthesis of a broad range of new and versatile sulfonyl‐substituted indoles and azoles bearing various functional groups from readily available starting materials in good to excellent yields with complete regioselectivity.

Incorporation of poly(sodium allyl sulfonate) branches on corn starch chains for enhancing its sizing properties: Viscosity stability, adhesion, film properties and desizability

The purpose of this work was to examine the influence of poly(sodium allyl sulfonate) (PSAS) branches on sizing properties of biological macromolecule (corn starch) for exploring a new anionic starch graft copolymer size (S-g-PSAS). Successful synthesis of S-g-PSAS samples was confirmed by energy dispersive X-ray spectrometer. Viscosity stability, adhesion, film properties and desizability of the samples were also investigated. Compared with HS, improved adhesion to cotton and viscose fibers, viscosity stability and desizability for S-g-PSAS as well as enhanced breaking elongation and bending endurance for S-g-PSAS film were exhibited. With the rise in grafting ratio, bonding forces to both fibers, viscosity stability and desizability of S-g-PSAS and its film properties such as breaking elongation and bending endurance, were gradually enhanced. These results indicated that S-g-PSAS showed potential for the use as a new starch-based size in the sizing of cotton and viscose warps.

Water‐Promoted Dehydrative Tsuji–Trost Reaction of Non‐Derivatized Allylic Alcohols with Sulfinic Acids

A mild, green and extra activator‐free synthesis of allylic sulfones from non‐derivatized allylic alcohols and sulfinic acids was developed and only the easily‐available Pd(PPh3)4 was used as the catalyst. This new method could be easily scaled up to gram scale, affording the target allylic sulfones in a nearly quantitative yield with water as the sole by‐product. Mechanism studies both by various NMR techniques and by theoretical calculations suggested two reaction pathways may be involved in the reaction, which are dependent on the reaction media, that is, an eight‐membered ring binding species may be formed in aqueous media between allylic alcohol, sulfinic acid and water, while a six‐membered ring binding species may be formed in common aprotic organic solvent between allylic alcohol and sulfinic acid. Both binding species may be accounted for the efficient activation of allylic alcohols via hydrogen bonding.