Ground State Complexes between 5-(4-Carboxyphenyl)-10,15,20-Tritolyl Porphyrin and Benzoquinones

The interactions of 5-(4-carboxyphenyl)-10,15,20-tritolyl porphyrin (TTPa)

1 Abbreviations: TTPa: 5-(4-carboxyphenyl)-10,15,20-tritolyl porphyrin; BQ: 1,4-benzoquinone; DQ: 2,3,5,6-tetramethyl 1,4-benzoquinone; CHLQ: 2,3,5,6-tetrachloro 1,4-benzoquinone; DMSO: dimethyl sulfoxide

with benzoquinones have been studied by spectrophotometry and steady state and transient fluorescent methods. TTPa forms a 1:1 molecular complex with 1,4-benzoquinone, 2,3,5,6-tetramethyl 1,4-benzoquinone and 2,3,5,6-tetrachloro 1,4-benzoquinone in dimethyl sulfoxide at room temperature. The equilibrium constants for the interaction of TTPa with the different quinones were evaluated.     

Polymerization initiation by N-p-tolylglycine: Free-radical reactions studied by pulse and steady-state radiolysis

The extensive use of N-p-tolylglycine (NTG) and analogous compounds in adhesive bonding technologies requires a better understanding of their role in initiating free-radical polymerization. The fast oxidation and reduction reactions of NTG proceed via the formation of various free radicals and radical cation and anion intermediates. These intermediates were identified and their reactivity with oxygen, to produce the corresponding peroxyl radicals, was measured. Hydroxyl radicals (?H) were used to initiate oxidation reactions of NTG, while the reduction reactions were initiated with hydrated electrons (e). OH radicals react with NTG predominately by addition to the aromatic ring followed by OHÞ elimination to produce NTG⁺· radical cations. In the presence of oxygen, the OH–NTG^? adduct also reacts with oxygen to produce peroxyl radicals. The reaction of NTG with e forms the radical anion, which subsequently protonates on the aromatic ring to produce cyclohexadienyl radicals, or undergoes an amine elimination to yield an acetic acid free radical and 4-methylaniline. Hydroperoxyl radicals (HO) abstract hydrogen from the α position of NTG to form the corresponding alkyl free radical. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Synthesis of Polyacrylonitrile Fiber‐Supported Poly(ammonium methanesulfonate)s as Active and Recyclable Heterogeneous Brønsted Acid Catalysts

A new polyacrylonitrile fiber‐supported Brønsted acid catalyst has been developed and verified to efficiently (high yield, 10 cycles) mediate Biginelli reactions in ethanol, Pechmann condensations in toluene, Friedel–Crafts alkylations of indoles in water and conversion of fructose in dimethyl sulfoxide (DMSO) and mixed‐aqueous system.

     

New copolymers from electrophilic trisubstituted ethylenes and electron-rich vinyl comonomers

Summary Ten new alternating, either 11 or 12, copolymers of electrophilic trisubstituted ethylenes with electron-rich vinyl monomers, were synthesized by free radical copolymerization.Thanks are also due to Dr. Anne Padias and Mr. Ashish Pandya of these Laboratories for the new synthesis of dimethyl cyanofumarate.     

二甲基亚砜捕获Fenton体系生成的·OH的研究

Fenton体系是H2O2与Fe（II）反应产生.OH的过程。本文主要研究了二甲基亚砜对Fenton体系产生的.OH的捕获,通过分析产物HCHO的浓度,确定.OH的生成量。同时,建立了DMSO捕获Fenton体系产.OH过程的化学反应模型,考察了DMSO初始浓度、pH值对Fenton体系的影响。结果表明DMSO浓度达到246 mmol/L时能够基本完全捕获Fenton体系所产生的.OH;pH值小于5时,Fenton体系受到H＋激发释放较多的.OH,pH值不大于5时,H＋对Fenton体系的激发能力不足。     

Inhibition of mild steel corrosion in hydrochloric acid medium by polymeric inhibitors containing residues of essential amino acid methionine

Ethyl ester hydrochloride of amino acid l-methionine 1 was converted to cationic monomers N,N-diallyl methionine ethyl ester hydrochloride 2 and hydrochloride salt of N,N-diallylmethionine 3. Cationic monomers 2 and 3 underwent alternate copolymerization with SO₂ in dimethyl sulfoxide to give terpolymers 4 and 5, respectively, both having?≈?1:1 ratio of sulfide and sulfoxide motifs owing to O transfer from dimethyl sulfoxide to the S. The sulfide groups in 5 have been oxidized with H₂O₂ to give polymer sulfoxide 6. In the presence of a small concentration of 35.2 µM (~?11?±?1 ppm) of each of the polymers 4, 5 and 6, the inhibition efficiency against mild steel corrosion in 1.0 M HCl at 60 °C was determined to be 90.8, 98.7 and 93.0%, respectively. The inhibition efficiency obtained from gravimetric weight loss was corroborated by the findings of potentiodynamic polarization and electrochemical impedance spectroscopy methods. Adsorption of polymer compounds onto the mild steel surface followed a mixture of chemisorption and physisorption processes and obeyed Langmuir, Temkin and Freundlich adsorption isotherms. The X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy techniques further confirmed that the synthesized compounds formed a protective film onto the metal surface and prove it against further corrosion attack.     

The STOBBE Condensation with Pyrrolyl Aldehydes – a synthesis of indole derivatives

The condensation of pyrrolyl-2-aldehyde or 1-methyl-pyrrolyl-2-aldehyde with dimethyl succinate, using sodium hydride as condensing agent, gave predominantly the halfesters 1a and 1c respectively. Their structure and (E)-configuration

1 i. e., pyrrol ring and COOCH₃ group are in trans position. This nomenclature follows the IUPAC 1968 Tentative Rules, Section E, Fundamental Stereochemistry, J. org. Chemistry 35 , 2849 (1970).

were confirmed by their cyclisation to the corresponding indole derivatives 2a–h .     

An Efficient Synthesis of Polysubstituted Pyridines via C?H Oxidation and C?S Cleavage of Dimethyl Sulfoxide

An expedient cleavage of the C S bond of dimethyl sulfoxide (DMSO) has been developed for the preparation of substituted pyridines from ketones. In this transformation, the co‐product formic acid was formed from ammonium formate, which acted as an important catalyst for the reaction. Notably, this transformation exhibited a broad substrate scope towards a wide variety of different ketones to give the corresponding substituted pyridines in high yields. Mechanistic studies suggested that dimethyl sulfoxide delivered a methylene fragment, which was subsequently captured in situ to give a pyridine.

     

A Novel 3-D Nanoporous Ce(III) Metal-Organic Framework with Terephthalic Acid; Thermal,Topology, Porosity and Structural Studies

This study describes the synthesis, crystal structure, porosity, and thermal stability of a new three-dimensional nano-porous metal-organic framework, [Ce₂(tp)₃(DMF)₂(DMSO)₂]_n, 1, (H₂tp = terephthalic acid, DMF = dimethyl formamid, DMSO = dimethyl sulfoxide). Compound 1 was synthesized by the solvothermal reaction of Ce(NO₃)₃·6H₂O and H₂tp and was then characterized by single-crystal X-ray diffraction and infrared spectroscopy. Structural analysis of 1 showed that Ce(III) ion has coordination number nine in a distorted mono-capped square anti-prismatic geometry. Gas sorption studies revealed a relatively reversible type-I isotherm characteristic of a porous material with surface area, pore volume, and average pore size of 179.4 m² g^?1, 0.73 cm³ g^?1, and 3.8 Å, respectively.     

Effect of an Ionic Liquid on the Catalytic Performance of Thiocyanatodioxomolybdenum(VI) Complexes for the Oxidation of Cyclooctene and Benzyl Alcohol

The complexes (PPh₄)₂[Mo^VIO₂(NCS)₄] (1), Mo^VIO₂(NCS)₂(di-tBu-bipy) (2) and Mo ₂ ^VI O₅(NCS)₂(di-tBu-bipy)₂ (3) (di-tBu-bipy = 4,4′-di-tert-butyl-2,2′-bipyridine) were studied as catalyst precursors for the oxidation of cyclooctene (Cy8) and benzyl alcohol (BzOH), using either dimethyl sulfoxide (DMSO) or tert-butyl hydroperoxide (TBHP) as oxidant. By dissolving complex 2 in the room temperature ionic liquid 1-butyl-3-methylpyridinium tetrafluoroborate, the catalytic performance with TBHP was improved (higher selectivity to the aldehyde and higher Cy8 conversions). For Cy8 oxidation, the unreacted substrate and products were easily extracted with n-hexane, and the ionic phase containing the catalyst could be reused without loss of catalytic performance.     

A high molecular weight acrylonitrile copolymer prepared by mixed solvents polymerization: II. effect of DMSO/water ratios on polymerization and stabilization

A bifunctional comonomer β-methylhydrogen itaconate was synthesized to prepare high molecular weight poly [acrylonitrile-co-(β-methylhydrogen itaconate)] [P (AN-co-MHI)] by mixed solvents polymerization, which was used as carbon fiber precursor instead of acrylonitrile terpolymers. The effect of dimethyl sulfoxide (DMSO)/deionized water ratios on the polymerization, structure and stabilization of P (AN-co-MHI) was studied by elemental analysis, UV-Visible Spectroscopy, fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The highest viscosity-average molecular weight (76.72 × 10⁴ g/mol) of P(AN-co-MHI) was obtained in the mixed solvents of DMSO/deionized water = 10/90 (wt/wt) due to the zero chain transfer constant of deionized water for radical ~ ~ ~AN·, which is 10 times larger than that of P(AN-co-MHI) copolymers prepared in DMSO solution polymerization under the same conditions and is beneficial to improving the tensile strength of resulting carbon fiber. The composition of P(AN-co-MHI) was controlled by the ratio of DMSO/deionized water in the mixed solvents, it is attributed to the changes of AN/MHI ratio taking part in the polymerization reactions, which is caused by the different solubility of AN in the mixed solvents. From elemental analysis and FTIR studies, it can be found out that the content of MHI in P(AN-co-MHI) copolymer becomes larger with the increase of DMSO content in the mixed solvents. The FTIR, XRD and DSC results show that the stabilization of P(AN-co-MHI) copolymer was significantly improved by MHI compared with PAN homopolymer and poly (acrlonitrile-methyl acrylate-acrylic acid) terpolymer, such as larger extent of stabilization, lower initiation temperature and smaller E _a of cyclization, which is beneficial to preparing high performance carbon fiber.     

An old kinetic method for a new polymerization mechanism: Toward photochemically mediated ATRP

With the idea of “an old method for a new mechanism,” a detailed kinetic insight into photochemically mediated atom‐transfer radical polymerization (photo ATRP) was presented through a validated comprehensive model. The simulation mimics the experimental results of the model system using optimized photochemically mediated radical generation rate coefficients. The activator and radical (re)generated from the photo mediated reactions endow the photo ATRP with unique features, such as rapid ATRP equilibrium and quick consumption of initiator with a small amount of residual. The effect of the reaction parameters on ATRP behaviors was also investigated. Results showed that the acceleration of polymerization rate follows the square root law in the following three cases: the overall photochemically mediated radical generation rate coefficients (k_r), the free ligand concentration, and the initiator concentration. However, the independence of the apparent propagation rate coefficient ( ) on the square root of catalyst concentration might be attributed to the result of the synergy between the activators regenerated by electron‐transfer ATRP and the initiators for continuous activator regeneration ATRP mechanism. The photo ATRP is able to design and prepare various polymers by carefully tuning the conditions using the model‐based optimization approach. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1947–1958, 2015     

Electrochemiluminescence of luminol in dimethyl sulfoxide at a polycrystalline gold electrode

The electrochemiluminescence (ECL) behavior of luminol in oxygen-saturated dimethyl sulfoxide (DMSO) solution at a polycrystalline gold electrode was studied under conventional cyclic voltammetric (CV) conditions. Corresponding to the reduction processes of oxygen, one ECL peak (ECL-1 at −1.40 V versus SCE) with two shoulders (S_1-1 at −0.55 V and S_1-2 at −0.90 V) was observed on the curve of ECL intensity versus potential. Corresponding to the subsequent oxidation processes of oxygen-containing species generated by the reduction of oxygen, one ECL peak (ECL-2 at −0.34 V) with a shoulder (S₂ at −0.67 V) was found. Among them, ECL-2 was strongest; it was 10 times stronger than ECL in pH 13.0 aqueous alkaline solution under the same conditions. These ECL peaks and shoulders were found to depend on the presence of N₂ and O₂, potential scan range, water concentration, supporting electrolyte, and the concentration of luminol. The emitter of both ECL peaks was identified as 3-aminophthalate (AP²⁻) by analyzing the ECL spectra. The origin for these ECL peaks is proposed to be related to the reactions of luminol with various oxygen-containing species such as O₂⁻, H₂O₂, OH⁻ and O₂ electrogenerated by the redox reactions of dissolved oxygen at different potentials. The results indicate that the ECL of luminol was correlated to the redox behavior of oxygen in DMSO. The present work reveals that the solvent plays an important role in the ECL behavior of luminol.     

Synthesis of phosphorus-containing polymers with potential bioactivity

Phosphorylation of poly(N-vinyl pyrrolidone-co-vinyl amine) and poly(N-vinyl pyrrolidone-co-glycidylcrotonate

1 Systematic name: (2,3-Epoxypropyl)crotonate.

) is realized by Atherton-Todd and Fields-Kabachnik reactions and by the means of direct interaction with phosphorus trichloride and phosphorus trichloride oxide. The composition and structure of the isolated final products was proved by NMR (¹H and ³¹P), IR spectroscopy and elemental analysis.     

One‐Pot Synthesis of 2‐Arylquinazolines and Tetracyclic Isoindolo[1,2‐a]quinazolines via Cyanation Followed by Rearrangement of ortho‐Substituted 2‐Halo‐N‐arylbenzamides

The one‐pot synthesis of substituted 2‐arylquinazoline derivatives and tetracylic isoindolo[1,2‐a]quinazoline via cyanation followed by rearrangement of ortho‐substituted 2‐halo‐N‐arylbenzamides is described. Using dimethyl sulfoxide (DMSO) as the solvent, the cleavage of the tetracyclic isoindole fused quinazoline leads to the formation of 2‐arylquinazoline derivatives. When 1,4‐dioxane is used as the solvent, tetracyclic isoindole fused quinazolines are produced in good yield. A wide range of products, including 2‐phenylquinazolin‐4‐amine, 4‐methyl‐2‐phenylquinazoline and long‐chain 2‐phenyl‐4‐styrylquinazoline derivatives were produced in moderate to good yields using DMSO as the solvent. However, various tetracyclic isoindole fused quinazoline derivatives were obtained in good yields when 1,4‐dioxane was used as the solvent.

     

Dimethyl Sulfoxide/Potassium Hydroxide: A Superbase for the Transition Metal‐Free Preparation of Cross‐Coupling Products

Potassium hydroxide (KOH) in dimethyl sulfoxide (DMSO) forms a superbasic medium that allows one to access cross‐coupling products from reactions between aryl halides with various sulfur‐, oxygen‐ and nitrogen‐based nucleophiles under transition metal‐free conditions.     

Anodic oxidation of dimethyl sulfoxide based electrolyte solutions: Anin situ FTIR study

Anodic oxidation of dimethyl sulfoxide (DMSO) based electrolyte solutions, containing LiClO₄, LiBF₄ and KPF₆, on platinum (Pt), glassy carbon (GC) andn-TiO₂ (anatase), electrodes was studied usingin situ Fourier transform infrared spectroscopy (FTIR). All solutions contained small amounts of H₂O. Regardless of the supporting electrolyte all systems were unstable at potentials above 1.0 V vs SCE. The major oxidation product is dimethyl sulfone, formation of which is initiated by the trace water breakdown. In contrast to acetonitrile based solutions there is no evidence of electrolyte involvement in the breakdown process. Photoanodic decomposition of dimethyl sulfoxide based solutions proceeds in the same way as the anodic oxidation in the dark. In the presence of nucleophilic agent (iodides) the prevailing redox process is iodide oxidation. Small amounts of, probably, methylsulfinyliodide are also formed. The irreversible consumption of charge mediator significantly restricts the possible practical use of DMSO in photoelectrochemical devices.     

Kinetics of diffusion in polyacrylonitrile fiber formation

A H₂O/dimethyl sulfoxide (DMSO) mixture was used as the coagulation bath of the wet‐spun process for polyacrylonitrile fibers. Diffusion behaviors of coagulate and solvent of the protofibers were studied. Diffusion coefficients of H₂O and DMSO of the protofibers, prepared by acrylonitrile (AN) homopolymers, were also determined. It was found that diffusion coefficients of H₂O and DMSO in the protofibers prepared by AN homopolymers, synthesized by DMSO solution polymerization, are highest compared with those of AN homopolymers synthesized by H₂O/DMSO mixture suspension polymerization and aqueous suspension polymerization. With increasing polyacrylonitrile concentration in the dope, diffusion coefficients of H₂O and DMSO decreased continuously. Diffusion coefficients of H₂O and DMSO increased concomitantly with increasing bath temperature, but the changes of diffusion coefficient values were less prominent when the temperature increased beyond 60°C. When DMSO concentration in the coagulation bath was 55 wt %, the values of diffusion coefficients of H₂O and DMSO were minimal. Diffusion coefficients increased with increasing jet stretch minus ratio. When the protofiber radius was increased, there was a corresponding increase of diffusion coefficients of H₂O and DMSO. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1529–1533, 2005     

Iodine‐Mediated Copper‐Catalyzed Efficient α‐C(sp2)‐Thiomethylation of α‐Oxoketene Dithioacetals with Dimethyl Sulfoxide in One Pot

The direct α‐Csp² H functionalization and thiomethylation of α‐oxoketene dithioacetals (DTAs) has been accomplished with dimethyl sulfoxide (DMSO) in the presence of iodine and a copper(I) salt for the first time. A prerequisite is the in situ iodination of the α‐Csp² atom of dithioacetals that could offer other reaction channels. The operationally simple one‐pot protocol includes region‐defined consecutive iodination and sulfenylation of the challenging α‐Csp² H bond of dithioacetals employing cheap and readily available reagents. DMSO here plays a dual role as thiomethyl source and solvent.

     

Characteristic rheological features of PVA solutions in water-containing solvents with different hydration states

Two organic solvent systems containing equimolar ratio of water but different association strenght, 8/2 by wt mixture of dimethyl sulfoxide (DMSO) and water and 86.7/13.3 by wt mixture of N-methyl morpholine N-oxide and water (NMMO monohydrate), were chosen and the rheological properties of polyvinyl alcohol (PVA) solutions in the solvents were investigated and compared. The associated state of water in the solvent systems had a significant effect on the rheological properties of the solutions. In dilute concentration regime, NMMO monohydrate gave higher intrinsic viscosity than DMSO/water although two solvents gave similar values of the Mark-Houwink exponent. More noticeable difference was observed on the viscosity curve in high concentration regime. DMSO/water exhibited near a Bingham behavior and gave much lower power-law index than NMMO monohydrate. On the logarithmic plot of storage modulus (G′) against loss modulus (G″), both solutions exhibited slight decrease in slope with increasing concentration. Of two solvent systems DMSO/water gave lower values of slope than NMMO monohydrate. In addition, NMMO monohydrate gave greater than one at low frequency whereas DMSO/water gave much less than one over the entire frequency range examined. Further, the frequency to cause gelation was decreased with increasing concentration in the case of NMMO monohydrate. This indicates that PVA/DMSO/water system is more heterogeneous because weakly bonded water molecules produce hydrogel structure.