Highly Efficient and Metal‐Free Aerobic Hydrocarbons Oxidation Process by an o‐Phenanthroline‐Mediated Organocatalytic System

A highly efficient o‐phenanthroline‐mediated, metal‐free catalytic system has been developed for oxidation of hydrocarbons with dioxygen in the presence of N‐hydroxyphthalimide; various hydrocarbons were efficiently and high selectively oxidized, e.g., ethylbenzene to acetophenone in 97% selectivity and 76% conversion, under mild conditions.     

Synthesis of Ag/g‐C3N4 Composite as Highly Efficient Visible‐Light Photocatalyst for Oxidative Amidation of Aromatic Aldehydes

In this contribution, an Ag/g‐C₃N₄ nanocomposite was synthesized and utilized as highly efficient and green photocatalyst for organic reactions under visible light irradiation. A layered, porous g‐C₃N₄ was synthesized following a modified solvothermal‐roasting process by using melamine and cyanuric chloride as precursor. Silver nanoparticles (NPs) were well anchored on g‐C₃N₄ nanosheets, which were prepared by a facile impregnation–roasting method. The inexpensive, stable g‐C₃N₄ coupled with the localized surface plasmon resonance (LSPR) effect of Ag NPs exhibited high photocatalytic activities toward aerobic oxidative amidation of aromatic aldehydes under visible light irradiation. Good to excellent yields were achieved for various substrates under the light of a 25 W compact fluorescent light (CFL) bulb in air. The operationally easy procedure provides an economical, green, and mild alternative for the formation of amide bonds.

     

A Facile Method for the Synthesis of a MoS2/g‐C3N4 Photocatalyst

A MoS₂/g‐C₃N₄ composite was synthesized by a significantly simple method using Na₂MoO₄ and thiourea as precursors, without the need for a hydrothermal or an ultrasound step. The photocatalytic activity of the synthesized material was evaluated by the degradation of rhodamine B (RhB) in aqueous solution under blue light. The composites with low content of MoS₂ performed better than pure g‐C₃N₄. Using a low‐power light‐emitting diode light source, an improvement of two orders of magnitude in the photochemical space‐time yield was achieved, proving enhanced energy efficiency and productivity compared to earlier studies. The degradation pathway of organic pollutants was confirmed by the effects of selective scavengers.     

Ag decorated G‐C3N4/black titanium oxides composite for the destruction of environmental pollutant under solar irradiation

Research on the synthesis of advanced composite materials is an important area of research on the visible‐active photodegradation of environmental pollutants. Novel hybridized structures of graphitic carbon nitride (g‐C₃N₄) are synthesized by a facile one‐step in‐situ method. Black titanium oxides, TiO, Ti₂O ₃, a mixture of TiO + Ti₂O₃, and a reference material, white TiO₂ P25, are used for the synthesis of the hybridized g‐C₃N₄ and further decorated with Ag nanoparticles. Physicochemical and optical properties of the obtained materials are characterized by various techniques. XRD patterns revealed that the structural regularity of g‐C₃N₄ and titanium oxide(s) is maintained in the composites. However, the main diffraction peak for g‐C₃N₄ is prominently shifted to a lower 2‐theta along with a decrease in the intensity, indicating the formation of g‐C₃N₄ nanosheet heterojunction. Vibrational spectra of the composites showed signature IR peaks for g‐C₃N₄ and demonstrated an enhancement in the vibrations after modifications, and further supported the XRD results. A distinct red‐shift in the optical spectra of g‐C₃N₄ upon modifications with black titanium oxide(s) demonstrated an enhanced absorbance of visible light, yet on the contrast white TiO₂ P25 showed a blue‐shift. Under the experimental conditions of simulated solar light, pristine g‐C₃N₄, and its composites g‐C₃N₄/TiO and g‐C₃N₄/Ti₂O₃ showed moderate activity for the photodegradation of an organic pollutant, rhodamine B. Interestingly, a synergistic enhancement in the photoactivity is demonstrated by the g‐C₃N₄ modified with a mixture of black titanium oxides (g‐C₃N₄/TiO + Ti₂O₃). On the other hand, the composite synthesized by a post‐synthesis method is found less effective in photodegradation reaction.     

Carbon Nitride‐Catalyzed Photoredox C?C Bond Formation with N‐Aryltetrahydroisoquinolines

In this communication we describe the oxidative C C bond formation of tertiary amines with various nucleophiles under very mild and environmental friendly conditions by using mesoporous graphitic carbon nitride (mpg‐C₃N₄) semiconductor as a heterogeneous, metal‐free photosensitizer in combination with visible light and oxygen as the terminal oxidation agent. This system can be further combined with proline‐organocatalysis to achieve oxidative tandem photocatalysis, demonstrating a rich cascade of chemical possibilities of the current photosynthesis system.     

Photocatalytic Selective Oxidation of 4‐Methoxybenzyl Alcohol to Aldehyde in Aqueous Suspension of Home‐Prepared Titanium Dioxide Catalyst

The photocatalytic oxidation of 4‐methoxybenzyl alcohol to p‐anisaldehyde (PAA) was performed in water with organic‐free suspensions of home‐prepared and commercial titanium dioxide (TiO₂) catalysts. The nanostructured TiO₂ samples were synthesised by boiling aqueous solutions of titanium tetrachloride (TiCl₄), under mild conditions, for different times. The crystallinity increased with the boiling time. The 4‐methoxybenzyl alcohol oxidation rate followed the same pattern but the highest yield (41.5 % mol) to PAA was found for the least crystalline sample, that showed a quantum efficiency of 0.116 %. A comparison with two commercial TiO₂ samples showed that all the home‐prepared catalysts exhibited a PAA yield higher than that of commercial ones. The only by‐products present were traces of 4‐methoxybenzoic acid and aliphatic products, carbon dioxide being the other main oxidation product.     

Iron‐Catalyzed Oxidative Mono‐ and Bis‐Phosphonation of N,N‐Dialkylanilines

The dehydrogenative α‐phosphonation of substituted N,N‐dialkylanilines by dialkyl H‐phosphonates was achieved under mild conditions by using environmentally benign iron(II) chloride as catalyst and tert‐butyl hydroperoxide as oxidant. The reaction proceeded in the presence of electron‐donating (methoxy, methyl, benzyl) and electron‐withdrawing ring‐substitutents (bromo, carbonyl, carboxyl, m‐nitro) in moderate to good yields. The X‐ray crystal structure of N‐(5,5‐dimethyl‐2‐oxo‐2λ⁵‐[1,3,2]dioxaphosphinan‐2‐yl‐methyl)‐N‐methyl‐p‐toluidine was determined. Bis‐(4‐(dimethylamino)phenyl)methane and bis‐4,4′‐(dimethylamino)benzophenone underwent bisphosphonation selectively by respective monophosphonation at the remote dimethylamino groups. Furthermore, the use of excess dialkyl H‐phosphonate and oxidant allowed us to functionalize both methyl groups of N(CH₃)₂ in N,N‐dimethyl‐p‐toluidine and N,N‐dimethylaminomesidine, respectively, to obtain α,α′‐bisphosphonatoamines in high yield.     

Organocatalytic Radical Involved Oxidative Cross‐Coupling of N‐Hydroxyphthalimide with Benzylic and Allylic Hydrocarbons

The cross‐coupling reaction between N‐hydroxyphthalimide and various benzylic and allylic hydrocarbons was realized through an organocatalytic radical‐mediated process involving C(sp³) O bond formation using tert‐butyl hydroperoxide (t‐BuOOH) as an oxidant and tetra‐n‐butylammonium iodide [(n‐Bu]₄NI] as a catalyst, during which the phthalimide N‐oxyl (PINO) radical and benzylic and allylic radicals were generated in situ and underwent the selective radical/radical cross‐coupling reaction. This novel method provides a convenient metal‐free approach to the synthesis of O‐alkylated hydroxy imides under mild reaction conditions.

     

Effect of Polyoxyethylene Chain Length on the Physicochemical Properties of N,N‐Dimethyl‐N‐dodecyl Polyoxyethylene Amine Oxide Hybrid Surfactants (C12EOnAO,with n = 1–4)

In order to determine the structure‐performance relationship of nonionic‐zwitterionic hybrid surfactants, N,N‐dimethyl‐N‐dodecyl polyoxyethylene (n) amine oxides (C₁₂EO_nAO) with different polyoxyethylene lengths (EO_n, n = 1–4) were synthesized. For homologous C₁₂EO_nAO, it was observed that the critical micelle concentration (CMC), the maximum surface excess (Γ_m), CMC/C₂₀, and the critical micelle aggregation number (N_m,c) decreased on going from 1 to 4 in EO_n. However, there were concomitant increases in surface tension at the CMC (γ_CMC), minimum molecular cross‐sectional area (A_min), adsorption efficiency (pC₂₀), and the polarity ([I₁/I₃]_m) based on the locus of solubilization for pyrene. The values of log CMC and N_m,c decreased linearly with EO_n lengthening from 1 to 4, although the impact of each EO unit on the CMC of C₁₂EO_nAO (n = 1–4) was much smaller than that typically seen for methylene units in the hydrophobic main chains of traditional surfactants. Compared to the structurally related conventional surfactant N,N‐dimethyl‐N‐dodecyl amine oxide (C₁₂AO), C₁₂EO_nAO (n = 1–4) have smaller CMC, A_min, and CMC/C₂₀, but larger pC₂₀, Γ_m, and N_m,c with a higher [I₁/I₃]_m. This may be attributed to the moderately amphiphilic EO_n (n = 1–4) between the hydrophobic C₁₂ tail and the hydrophilic AO head group.     

Hydroperoxidation of Tertiary Alkylaromatics Catalyzed By N‐Hydroxyphthalimide and Aldehydes under Mild Conditions

A metal‐free catalytic system consisting of an aldehyde and N‐hydroxyphthalimide (NHPI) for the selective oxidation of tertiary alkylaromatics with molecular oxygen has been developed. Cumene was oxidized efficiently to the corresponding hydroperoxide under mild conditions. The molecule‐induced homolysis between peracids generated in situ and NHPI ensured the formation of the phthalimide N‐oxyl (PINO) radical even at room temperature. Investigations on aldehyde, solvent and temperature effects allowed us to achieve good conversions with high selectivity in hydroperoxide. The optimized procedure was successfully extended to phenylcyclohexane, a valuable alternative for the production of phenol. The mechanism is discussed in detail.     

Sunlight Induced Oxidative Photoactivation of N‐Hydroxyphthalimide Mediated by Naphthalene Imides

We report the aerobic photoactivation of N‐hydroxyphthlimide (NHPI) to the phthalimido‐N‐oxyl (PINO) radical mediated by naphthalene monoimides (NI) for promoting the selective oxidation of alkylaromatics and allylic compounds to the corresponding hydroperoxides. In the absence of either NI or NHPI no oxidation was observed, meaning that the two molecules operate in a synergistic way. Sunlight as well as artificial UV‐light irradiation was necessary in order to perform the process at low temperature (30–35 °C). EPR spectroscopy confirmed the role of NI and oxygen in promoting the formation of the superoxide radicals O₂^.− which, in turn, increased the concentration of PINO radicals during the UV light irradiation of NI/NHPI mixtures in MeCN. The investigation was extended to NI bearing different substituents on the naphthalene moiety. Finally, the synthesis and application of a unique photocatalyst including the NI and NHPI moieties linked by a suitable spacer was also considered. In this case the photocatalyst showed a substrate‐dependent behaviour with some peculiarities in comparison to the system where NI and NHPI are independent units in the same reacting system. This photocatalytic system paves the way to a non‐thermal, metal‐free approach for C H bond activation towards aerobic oxidation under very mild conditions.

     

Novel and Mild Route to Phthalocyanines and 3‐Iminoisoindolin‐1‐ones via N,N‐Diethylhydroxylamine‐Promoted Conversion of Phthalonitriles and a Dramatic Solvent‐Dependence of the Reaction

Refluxing a mixture of phthalonitrile C₆R¹R²R³R⁴(CN)₂ 1 (R¹–R⁴=H), or its substituted derivatives 2 (R¹, R³, R⁴=H, R²=Me), or 3 (R¹, R⁴=H, R², R³=Cl) (1 equiv.) and N,N‐diethylhydroxylamine, Et₂NOH, (4 equivs.) in methanol for 4 h results ( Route A ) in precipitation of the symmetrical ( 6 and 8 ) and an isomeric mixture of unsymmetrical ( 7 ) phthalocyanines, isolated in good (55–65 %) yields. The reaction of phthalonitriles 1 , 2 , or 4 (R¹, R³, R⁴=H, R²=NO₂) (4 equivs.) with Et₂NOH (8 equivs.) in the presence of a metal salt MCl₂ (M=Zn, Cd, Co, Ni) (1 equiv.) in n‐BuOH or without solvent results in the formation of metallated phthalocyanine species ( 9 – 17 ). Upon refluxing in freshly distilled dry chloroform, phthalonitrile 1 or its substituted analogues 2 , 3 or 5 (R¹–R⁴=F) (1 equiv.) react with N,N‐diethylhydroxylamine (2 equivs.) affording 3‐iminoisoindolin‐1‐ones 18 – 21 ( Route B ) isolated in good yields (55–80 %). All the prepared compounds were characterized with C, H, and N elemental analyses, ESI‐MS, IR, and compounds 18 – 21 also by 1D (¹H, ¹³C{¹H}), and 2D (¹H,¹⁵N‐HMBC and ¹H,¹³C‐HMQC, ¹H,¹³C‐HMBC) NMR spectroscopy.     

Water‐sorption and metal‐uptake behavior of pH‐responsive poly (N‐acryloyl‐N′‐methylpiperazine) gels

Hydrogels based on N‐acryloyl‐N′‐methylpiperazine (AcrNMP) swelled extensively in solutions of low pH due to the protonation of the tertiary amine. The water transport in the gels under an acidic condition was non‐Fickian and nearly Fickian in neutral pH with the collective diffusion coefficients determined as 2.08 × 10⁻⁷ and 5.00 × 10⁻⁷ cm⁻² s⁻¹, respectively. These gels demonstrated good metal‐uptake behavior with various divalent metal ions, in particular, copper and nickel, with the uptake capacity increased with increasing pH. The swelling ratio of the gel in the presence of metal ions decreased with increasing metal ion uptake. The results suggest that high metal ion uptake can lead to physical crosslinking arising from the interchain metal complex formation. The metal‐loaded gels could be stripped easily with 1M H₂SO₄ without any loss in their uptake capacity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 268–273, 2001     

A Highly Regioselective Preparation of 4‐Chloromethyl‐5‐methyl‐2‐aryl‐1,3‐oxazoles

A facile highly regioselective process is described for the formation of 4‐chloromethyl‐1,3‐oxazoles from 1,3‐oxazole N‐oxide/HCl salts. An explanation is presented for the high regioselectivity in deoxygenation‐chlorination using POCl₃ with HCl salts compared to the corresponding free N‐oxides. The method is quite general and the products are isolated by direct precipitation in all cases studied.     

Metal‐chloride‐anion‐containing polymers with expanded π‐conjugation systems derived from through‐space interactions in the piperazinium ring

Reactions of N‐(2,4‐dinitrophenyl)pyridinium chloride (salt(Cl)) with H⁺MCl₄^?1 (M ≡ Fe and Bi) resulted in an anion exchange between Cl^? and MCl₄^? to yield Zincke salts with metal chloride anions, namely salt(Fe) and salt(Bi), respectively. Reactions of the Zincke salts with piperazine resulted in ring‐opening of the pyridinium ring, yielding ionic polymers with 5‐piperazinium‐2,4‐dienylideneammonium metal chloride units, namely polymer(Fe) and polymer(Bi). The corresponding model compounds were synthesized via reactions using salt(Bi) or salt(Cl) as starting materials. The UV–visible spectra of the polymers had absorption maxima at longer wavelengths than those of the model compounds. This indicated that the π‐conjugation system is expanded along the polymer main chain. Superconducting quantum interference device measurements indicated that polymer(Fe) was paramagnetic. Cyclic voltammetry analysis suggested that the polymers underwent electrochemical oxidation. © 2019 Society of Chemical Industry     

Adamantane Selective Hydroxylation by 2,6‐Dichloropyridine N‐Oxide and Organoruthenium(II) Polyoxometalates as Catalyst Precursors

Organoruthenium polyoxometalates with general formula [{Ru(C₆Me₆)}₃M₅O₁₈], M  Mo, W, serve as catalyst precursors, together with 2,6‐dichloropyridine N‐oxide, to effect the hydroxylation of adamantane with conversion up to 94%, and C³‐H/C²‐H selectivity >100. Under analogous conditions, hydroxylation of cis‐decalin occurred with complete stereoretention. Control experiments and kinetic evidence suggest the in‐situ formation of a high valent Ru‐oxo species as the competent oxidant.     

Enhanced water flux through graphitic carbon nitride nanosheets membrane by incorporating polyacrylic acid

Membranes assembled from two‐dimensional (2‐D) layered materials have shown potential use in water purification. Recently, a 2‐D graphitic carbon nitride (g‐C₃N₄) nanosheets membrane exhibits considerable separation performance in water purification. In this study, to further improve this water separation performance, polyacrylic acid (PAA) was introduced to tune the nanochannels formed between the g‐C₃N₄ nanosheets. The fabricated g‐C₃N₄‐PAA hybrid membranes possessed higher water flux without sacrificing much rejection rate compared with that of the g‐C₃N₄ membrane; however, noticeable fouling was observed upon addition of the PAA into the membrane composite structure. In addition, the effect of PAA on the morphology, surface hydrophilicity, separation performance, and antifouling properties of the g‐C₃N₄ membrane were examined in detail. Overall, incorporating PAA into the g‐C₃N₄ nanosheets membrane was an effective and convenient method to improve the water separation performance, which could promote the application of the 2‐D g‐C₃N₄ nanosheets membrane in practical ultrafiltration processes. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2181–2188, 2018     

Hydroxylamine as a Source for Nitric Oxide in Metal‐Free 2,2,6,6‐ Tetramethylpiperidine N‐Oxyl Radical (TEMPO) Catalyzed Aerobic Oxidation of Alcohols

The communication reports on the metal‐free 2,2,6,6‐tetramethylpiperidine N‐oxyl radical (TEMPO) catalyzed aerobic oxidation of various alcohols to aldehydes and ketones. A novel catalyst system that uses 1–4 mol% of TEMPO in combination with 4–6 mol% of aqueous hydroxylamine is introduced. No other additives are necessary and corrosive by‐products are not formed during oxidation. Nitric oxide which is important for the catalytic cycle is generated in situ by reaction of the hydroxylamine with TEMPO. A catalytic cycle for the overall oxidation process is suggested.     

Synthese potentieller Pflanzenschutzwirkstoffe auf 2, 3‐Dihydrothiazol‐2‐thion‐Basis. I. Strukturvariationen am N3 und C4

A considerable number of potential plant protecting compounds with the core structure of 2,3‐dihydrothiazol‐2‐thione has been prepared by the reaction of dithiocarbamates with halomethylcarbonyl compounds forming N‐substituted 4‐substituted 4‐hydroxythiazolidin‐2‐thiones 2—4 , which can split off water to yield 5 . The structural variability at N₃ is given either by the amine used for dithiocarbamate synthesis or by acylation of N‐unsubstituted 2,3‐dihydrothiazol‐2‐thiones like 4i . The variability at C₄ is either achieved by the kind of the halomethylcarbonyl compound or by reactions of 4‐chloromethyl derivatives 5 , which can be transformed by a number of nucleophilic reagents to derivatives like thioethers 8 , ethers 9 , amines 10 , nitriles 11 , azides 12a , thiocyanates 12b , the primary amine 14 and derived from that the amides 15 or the ureas 16 .     

Single‐Pot Ethane Carboxylation Catalyzed by New Oxorhenium(V) Complexes with N,O Ligands

The oxorhenium(V) chelates [ReOCl(N,O‐L)(PPh₃)] [N,O‐L=(OCH₂CH₂)N(CH₂CH₂OH)(CH₂COO) ( 2 ), (OCH₂CH₂)N(CH₂COO)(CH₂COOCH₃) ( 3 )] and [ReOCl₂(N,O‐L)(PPh₃)] [N,O‐L=C₅H₄N(COO‐2) ( 4 ) C₅H₃N(COOCH₃‐2)(COO‐6) ( 5 )] have been prepared by reaction of [ReOCl₃(PPh₃)₂] ( 1 ), in refluxing methanol, with N,N‐bis(2‐hydroxyethyl)glycine [bicine; N(CH₂CH₂OH)₂(CH₂COOH)], N‐(2‐hydroxyethyl)iminodiacetic acid [N(CH₂CH₂OH)(CH₂COOH)₂], picolinic acid [NC₅H₄(COOH‐2)] or 2,6‐pyridinedicarboxylic acid [NC₅H₃(COOH‐2,6)₂], respectively, with ligand esterification in the cases of 3 and 5 . All these complexes have been characterized by IR and multinuclear NMR spectroscopy, FAB⁺‐MS, elemental and X‐ray diffraction structural analyses. They act as catalysts, in a single‐pot process, for the carboxylation of ethane by CO, in the presence of potassium peroxodisulfate K₂S₂O₈, in trifluoroacetic acid (TFA), to give propionic and acetic acids, in a remarkable yield (up to ca. 30%) and under relatively mild conditions, with some advantages over the industrial processes. The picolinate complex 4 provides the most active catalyst and the carboxylation also occurs, although much less efficiently, by the TFA solvent in the absence of CO. The selectivity can be controlled by the ethane and CO pressures, propionic acid being the dominant product for pressures about ca. 7 and 4 atm, respectively (catalyst 4 ), whereas lower pressures lead mainly to acetic acid in lower yields. These reactions constitute an unprecedented use of Re complexes as catalysts in alkane functionalization.