Ring-opened Products Research Articles

Theoretical Study of the Mechanism of Furfural Conversion on the NiCuCu(111) Surface.

The full potential energy surface for the hydrodeoxygenation of furfural to furan and other ring-opening products has been systematically investigated using periodic density functional theory including dispersion corrections (PBE-D3) on the bimetallic NiCuCu(111) surface. For furan formation, the most favorable first step is the dehydrogenation of furfural into furoyl (F-CHO + H = F-CO + 2H), the successive step is decarbonylation of furoyl into furanyl (F-CO + H = F + CO + 2H), and the third step of furan formation from the hydrogenation of furanyl (F + CO + 2H = FA + CO + H) is the rate-determining step. In addition, on the basis of the most stably adsorbed furan and H, the ring opening of furan was found to be more favorable for producing many chemicals such as propane, butanal, butanol, and butene. In summary, furan is the main product of furfural conversion on the NiCuCu(111) surface. Since results have been obtained only for the NiCuCu(111) surface constructed by replacing the topmost Cu atoms by Ni atoms, the entire experimentally observed reactivity and selectivity of bimetallic CuNi catalysts for different construction methods cannot be fully rationalized. Nevertheless, the results provide the basis for investigating the intrinsic activity of CuNi catalysts in the hydrodeoxygenation of oxygenates involved in the refining of biomass-derived oils.

Photodecomposition of Thienylsulfonyl Azides: Generation and Spectroscopic Characterization of Triplet Thienylsulfonyl Nitrenes and 3-Thienylnitrene.

The photochemistry of 2-thienylsulfonyl azide (1) and 3-thienylsulfonyl azide (6) has been disclosed by combining matrix-isolation spectroscopy with quantum chemical calculations. Two novel heteroaryl sulfonyl nitrenes, 2-thienylsulfonyl nitrene (2) and 3-thienylsulfonyl nitrene (7), have been generated during the 266 nm laser photolysis of 1 and 6, respectively. Both nitrenes in the triplet ground state have been characterized with matrix-isolation IR (15N-labeling) in solid Ar (10.0 K), N2 (10.0 K), and Ne (2.8 K) matrixes and EPR spectroscopy (2, |D/hc| = 1.452 cm-1 and |E/hc| = 0.0058 cm-1; 7, |D/hc| = 1.492 cm-1 and |E/hc| = 0.0060 cm-1) in solid toluene at 5.0 K. Upon subsequent UV-light irradiation (365 nm), no Curtius rearrangement but decomposition of 2 occurs by SO2-elimination and the concurrent formation of ring-opening product (s-Z)-4-thioxo-2-butenenitrile (3) via the intermediacy of the putative 2-thienylnitrene (4). In contrast, violet-light irradiation (400 ± 20 nm) of 7 causes SO2-elimination to yield triplet 3-thienylnitrene (8), for which the IR spectroscopic identification is supported by quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) level. 3-Thienylnitrene is highly reactive, since it not only combines with SO2 to furnish 3-thienyl-N-sulfonylamine (9) but also undergoes ring-opening to (s-E)-4-thioxo-2-butenenitrile (10) under the UV-light irradiation (365 nm).

Divergent Pathways for Reactions of 3-Formylchromone with Cyclic Secondary Amines in Alcoholic Media

Reaction of 3-formylchromone with cyclic secondary amines in methanol results in (E)-2-methoxy-3-(R2N-methylene)chroman-4-ones, while use of ethanol leads to (E)-2-morpholino-3-(morpholino­methylene)chroman-4-one or enaminoketones as dihydropyran ring-opening products. The solubility of the formed products in alcoholic media is postulated to be a key factor that determines the reaction pathway.

Influence of the Brønsted Acidity on the Ring Opening of Decalin for Pt-USY Catalysts

A challenging hot topic faced by the oil refinery industry is the upgrading of low-quality distillate fractions, such as light cycle oil (LCO), in order to meet current quality standards for diesel fuels. An auspicious technological alternative entails the complete saturation of the aromatic structures followed by the selective cleavage of endocyclic carbon-carbon bonds in the formed naphthenic rings (selective ring opening—SRO). This work reports the influence of Brønsted acid sites of platinum-ultra stable Y zeolite (Pt-USY) catalysts in the SRO of decalin as a model naphthenic feed. A maximum combined yield to selective ring opening products (ROP: C10-alkylcycloalkanes + OCD: C10-alkanes) as high as 28.6 wt% was achieved for 1.6Pt-NaUSY-im catalyst. The molar carbon distribution curve of the hydrocracked (C9-) products varied from M-shaped for 1.4Pt-USY-im catalyst, indicating mainly C–C bond cleavage of the ring opening products with one remaining naphthenic ring via carbocations and the paring reaction, to not M-shaped for the 1.6Pt-NaUSY-im catalyst, where carbon-carbon bond cleavage occurs preferentially through a hydrogenolysis mechanism on metal sites. High (hydro)thermal stability and secondary mesoporosity of the 1.6Pt-NaUSY-im catalysts make this system highly prospective for upgrading low-quality real distillate feeds.

Rh(I)-catalyzed ring-opening of cyclobutanols via C–C bond activation: Synthesis of cis-olefin with a remote aldehyde

A Rh(I)-catalyzed ring-opening of cyclobutanols has been developed with ring opening products bearing cis-olefin and a remote aldehyde. Various substrates bearing different substituted aryl groups, heterocyclic groups and alkyl groups were compatible with the mild reaction conditions. A β-C elimination pathway was proposed based on the results of preliminary mechanistic studies.

Preparation of dihydroxy polycyclic aromatic hydrocarbons and activities of two dioxygenases in the phenanthrene degradative pathway

Dihydroxy phenanthrene, fluoranthene, and pyrene derivatives are intermediates in the bacterial catabolism of the corresponding parent polycyclic aromatic hydrocarbon (PAH). Ring-opening of the dihydroxy species followed by a series of enzyme-catalyzed reactions generates metabolites that funnel into the Krebs Cycle with the eventual production of carbon dioxide and water. One complication in delineating these pathways and harnessing them for useful purposes is that the initial enzymatic processing produces multiple dihydroxy PAHs with multiple ring opening possibilities and products. As part of a systematic effort to address this issue, eight dihydroxy species were synthesized and characterized as the dimethoxy or diacetate derivatives. Several dihydroxy compounds were examined with two dioxygenases in the phenanthrene degradative pathway in Mycobacterium vanbaalenii PYR-1. One, 3,4-dihydroxyphenanthrene, was processed by PhdF with a kcat/Km of 6.0 × 106 M−1s−1, a value that is consistent with the annotated function of PhdF in the pathway. PhdI processed 1-hydroxy-2-naphthoate with a kcat/Km of 3.1 × 105 M−1s−1, which is also consistent with the proposed role in the pathway. The observations provide the first biochemical evidence for these two reactions in M. vanbaalenii PYR-1 and, to the best of our knowledge, the first biochemical evidence for the reaction of PhdF with 3,4-dihydroxyphenanthrene. Although PhdF is upregulated in the presence of pyrene, it did not process two dihydroxypyrenes. Methodology was developed for product analysis of the extradiol dioxygenases.

Ring-Opening Reactions of Donor-Acceptor Cyclobutanes with Electron-Rich Arenes, Thiols, and Selenols.

Donor-acceptor (D-A) cyclobutanes with two geminal ester groups as acceptors are reacted with electron-rich arenes as nucleophiles to afford ring-opened products. AlCl3 mediates this Friedel-Crafts-type reaction. A variety of donors and electron-rich arenes are used. Nucleophilic thiols and selenols also trigger this ring-opening reaction. Furthermore, a comparison of various physical parameters has been carried out for several D-A cyclobutanes.

TiO2 and N-TiO2-photocatalytic degradation of salicylic acid in water: characterization of transformation products by mass spectrometry.

The aim of this work is to study the byproducts formed as a result of the photocatalytic process under different conditions of light wavelength and photocatalyst doping, rendering valuable information about the fate of pollutants for water treatment applications. Salicylic acid was selected as a model emerging pollutant and powders of nitrogen-doped titanium dioxide (N-TiO2) and TiO2 were prepared by the sol-gel process, using TiO2 P-25 Degussa as benchmark. Two light sources, UVA fluorescent tubes (372 nm) and blue LEDs (462 nm), were employed for photolysis and photocatalysis experiments. Transformation products formed during the process were studied by high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS). Major differences were found in the amount and identity of the transformation products due to the different light sources, detecting similar transformation products among the studied catalysts. Under UVA light, hydroxylated and carbonylated byproducts were the first intermediates to reach maximum abundances whereas presumed ring opening products were the last ones. On the other hand, under blue LED illumination byproducts accumulated with decreased mineralization. Photocatalytic degradation pathways were proposed based on the findings.

Iridium-catalyzed ring-opening reactions of unsymmetrical oxabenzonorbornadienes with water and alcohol nucleophiles

The iridium-catalyzed ring-opening reaction of unsymmetrical oxabenzonorbornadienes (OBD) with water and alcohol nucleophiles is reported, with the effects of various C1-substituents explored. Electron-donating alkyl groups lead entirely to the substituted naphthol derivatives in excellent yields while substitution of the C1 position for electron-withdrawing groups afforded ring-opened products in fair to excellent yields with excellent regioselectivity. The reaction was demonstrated to be highly regioselective for the C2 position with no C3 regioisomer observed in all cases. A proposed mechanism for the formation of C2 regioisomeric ring-opened products has been included.

Initial pyrolysis mechanism of cellulose revealed by in-situ DRIFT analysis and theoretical calculation

Cellulose is one of the major components of biomass. The study on its pyrolysis process will be beneficial to the in-depth understanding of biomass pyrolysis mechanism. In this work, in-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFT) combined with two-dimensional perturbation correlation infrared spectroscopy (2D-PCIS) was first used to characterize the evolution process of the functional groups in cellulose during pyrolysis. The results showed that the degradation of carbon skeleton was prior to the dehydration of free hydroxyls after the destruction of hydrogen bond networks during pyrolysis. The thermal stability of CO in cellulose followed by the order of glycosidic bond <CO in glucopyranose ring <CO between glucopyranose ring and hydroxyl. Followingly, micro pyrolysis experiment was performed to analyze the pyrolysis products of cellulose at various temperatures. It was found that the rupture of glucopyranose rings to form 2C and 4C products was more difficult than the dissociation of C6 hydroxymethyls, and required higher pyrolysis temperature. Quantum chemistry calculation was further carried out to study the key reaction pathways including dehydration, cleavage of glycosidic bond, ring opening and fragmentation in the initial stage of cellulose pyrolysis. The result showed that the concerted cleavage of glycosidic bond to form LG-end short chain was the most favored with the lowest activation energy. The ring opening of the glucose unit in the chain occurred via the cleavage of C1-O. The formed ring opening product was more likely to degrade via the dissociation of C6 hydroxymethyl compared with the breakage of C2–C3 to form 2C and 4C products. Besides, the dehydration of hydroxyls in glucose units required high energy barriers and was difficult to occur.

Reversible Polymer-Chain Modification: Ring-Opening and Closing of Polylactone.

A reversible polymer modification involving structural changes of the polymer chains was accomplished for the copolymer of CO2 and butadiene. The bicyclic structures were opened by hydrolysis and aminolysis reactions of the lactone moiety. For the hydrolysis product, the ring-closing of the ring-opened product was achieved by simply heating without any reagents or solvents. Nuclear magnetic resonance and matrix assisted laser desorption/ionization time-of-flight analyses and size-exclusion chromatography measurement of the polymer before ring-opening and after ring-closure suggested the retention of the polymer structure as well as the molecular weight and polydispersity during the reversible processes, proving that the modification can be performed without significant macroscopic changes of the polymer structure.

Metalated azolo[1,2,4]triazines. II. Generation, C(4)-substituent dependent stability and electrophile trapping of 7-lithiopyrazolo[5,1-c][1,2,4]triazines

7-Lithio-3-tert-butylpyrazolo[5,1-c][1,2,4]triazines have been generated for the first time using one-pot nucleophilic addition and metal-halogen exchange reactions in 7-bromopyrazolo[5,1-c][1,2,4]triazines. It was found that the stability of 7-lithio species depends highly on the substitution pattern at the C(4) ring position. The rate of the pyrazole ring opening reaction roughly followed the order of the electronegativity of substituents: rapid cycle cleavage took place already at −97 °C for C(4) = O, CH–Ar, CH–C≡CPh, while CH–Alk and CH2 substituted derivatives were stable in these conditions (Ar = Ph, 4-tolyl; Alk = t-Bu, n-Bu, n-Pr). Quantum chemical modeling showed that the ring opening is accompanied with simultaneous shift of the Li atom towards N(6). Calculated free activation energies are in range from 12.7 to 15.0 kcal*mol−1. Electrophile trapping of fairly stable 4-alkyl-1,7-metalated derivatives at −97 °C using H2O, DMF or PhCHO allowed the selective side-chain functionalization. Tautomeric exo- and endocyclic double bond equilibrium in the isolated 4-oxo and 4-aryl substituted ring opening products is also discussed on the basis of IR, 1H, 13C NMR, high resolution mass spectra and X-ray powder diffraction analysis.

Efficient atrazine degradation catalyzed by manganese porphyrins: Determination of atrazine degradation products and their toxicity evaluation by human blood cells test models.

Atrazine (ATZ) is an herbicide that has been considered an environmental pollutant worldwide. ATZ contaminates groundwaters and can persist in soils for up to a year causing several environmental and health problems. This study aimed to investigate ATZ degradation catalyzed by manganese porphyrins as biomimetic cytochrome P450 models. We used PhIO, PhI(OAc)2, H2O2, t-BuOOH, m-CPBA, or Oxone® as oxidant under mild conditions and evaluated a range of manganese porphyrins as catalyst. Concerning oxidant, iodosylbenzene provided the best result-ATZ degradation catalyzed by one of the studied manganese porphyrins in acetonitrile was as high as 47%. We studied the same catalyst/oxidant systems in natural water from a Brazilian river as solvent and obtained up to 100% ATZ degradation when iodobenzene diacetate was the oxidant, regardless of the manganese porphyrin. Besides the already known ATZ degradation products, we also identified unexpected degradation compounds (ring-opening products). Toxicity tests showed that the latter products were capable of proliferate blood cells because they did not show toxicity under the evaluated conditions.

Palladium/Lewis Acid Cocatalyzed Ring-Opening Reactions of Unsymmetrical Oxabenzonobornadienes with Oximes.

The palladium/Lewis acid cocatalyzed ring-opening reaction of various C1-substituted unsymmetrical oxabenzonorbornadienes (OBD) with oxime nucleophiles was investigated. The effects of various C1 substituents were explored. Moderate to excellent yields and excellent regioselectivities were obtained for electron-withdrawing groups. The presence of electron-donating alkyl groups leads to isomerization of the corresponding OBD to afford the substituted naphthol derivatives. Additionally, a mechanism for the formation of C2 regioisomeric ring-opened products has been proposed.

Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene.

Background:Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate capable of undergoing multiple types of transformations due to three key structural features: a free alkene, a bridged oxygen atom, and a highly strained ring system. Most notably, ring-opening reactions of OBD using transition metal catalysts and nucleophiles produce multiple stereocenters in a single step. The resulting dihydronaphthalene framework is found in many natural products, which have been shown to be biologically active.Objective:This review will provide an overview of transition metal-catalyzed reactions from the past couple of years including cobalt, copper, iridium, nickel, palladium and rhodium-catalyzed reactions. In addition, the recent derivatization of OBD to cyclopropanated oxabenzonorbornadiene and its reactivity will be discussed.Conclusion:It can be seen from the review, that the work done on this topic has employed the use of many different transition metal catalysts, with many different nucleophiles, to perform various transformations on the OBD molecule. Additionally, depending on the catalyst and ligand used, the stereo and regioselectivity of the product can be controlled, with proposed mechanisms to support the understanding of such reactions. The use of palladium has also generated a cyclopropanated OBD, with reactivity similar to that of OBD. An additional reactive site exists at the distal cyclopropane carbon, giving rise to three types of ring-opened products.

Catalytic Asymmetric Reactions of α-Isocyanoacetates and meso-Aziridines Mediated by an in-Situ-Generated Magnesium Catalytic Method.

A catalytic asymmetric ring-opening reaction between α-isocyanoacetates and meso-aziridines has been realized by developing an in-situ-generated magnesium catalytic method. Chiral oxazoline-OH ligands were employed in the magnesium catalyst and diphenylphosphinamide was improved as a powerful achiral additive in this reaction. The ring-opening products of the desired reaction were obtained in good chemical yields and enantioselectivities. Moreover, these enantio-enriched adducts can be smoothly transformed into tetrahydropyrimidines mediated by a silver salt under mild conditions.

Formation of Aryl [1-Cyano-4-(dialkylamino)butadienyl] Ketones from Pyridines

Treatment of 2-chloropyridine with LDA and the Weinreb amide of benzoic acid afforded three unusual products, namely N-methylbenzamide, 2-chloropyridine-3-methanol, and the ring-opened addition product. This same final product could also be obtained from 2-chloro-3-benzoylpyridine on treatment with LDA. Mechanistic insight for the formation of these products is provided.

Simulation of SOA formation from the photooxidation of monoalkylbenzenes in the presence of aqueous aerosols containing electrolytes under various NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; levels

Abstract. The formation of secondary organic aerosols (SOAs) from the photooxidation of three monoalkylbenzenes (toluene, ethylbenzene, and n-propylbenzene) in the presence of inorganic seeds (SO42-–NH4+–H2O system) under varying NOx levels has been simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. The evolution of the volatility–reactivity distribution (mass-based stoichiometric coefficient, αi) of oxygenated products, which were created by the near-explicit gas kinetic mechanism, was integrated with the model using the parameters linked to the concentrations of HO2 and RO2 radicals. This dynamic distribution was used to estimate the model parameters related to the thermodynamic constants of the products in multiple phases (e.g., the gas phase, organic phase, and inorganic phase) and the reaction rate constants in the aerosol phase. The SOA mass was predicted through the partitioning and aerosol chemistry processes of the oxygenated products in both the organic phase and aqueous solution containing electrolytes, with the assumption of organic–inorganic phase separation. The prediction of the time series SOA mass (12 h), against the aerosol data obtained from an outdoor photochemical smog chamber, was improved by the dynamic αi set compared to the prediction using the fixed αi set. Overall, the effect of an aqueous phase containing electrolytes on SOA yields was more important than that of the NOx level under our simulated conditions or the utilization of the age-driven αi set. Regardless of the NOx conditions, the SOA yields for the three aromatics were significantly higher in the presence of wet electrolytic seeds than those obtained with dry seeds or no seed. When increasing the NOx level, the fraction of organic matter (OM) produced by aqueous reactions to the total OM increased due to the increased formation of relatively volatile organic nitrates and peroxyacyl-nitrate-like products. The predicted partitioning mass fraction increased as the alkyl chain length increased but the organic mass produced via aerosol-phase reactions decreased due to the increased activity coefficient of the organic compounds containing longer alkyl chains. Overall, the lower mass-based SOA yield was seen in the longer alkyl-substituted benzene in both the presence and absence of inorganic-seeded aerosols. However, the difference of mole-based SOA yields of three monoalkylbenzenes becomes small because the highly reactive organic species (i.e., glyoxal) mainly originates from ring opening products without an alkyl side chain. UNIPAR predicted the conversion of hydrophilic, acidic sulfur species to non-electrolytic dialkyl organosulfate (diOS) in the aerosol. Thus, the model predicted the impact of diOS on both hygroscopicity and acidity, which subsequently influenced aerosol growth via aqueous reactions.

Ruthenium-catalyzed ring-opening reaction of a 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with amines — an unexpected mode of ring-opening

The ruthenium-catalyzed ring-opening reaction of a 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with amines was investigated. In the presence of an amine and a ruthenium catalyst, the N–O bond is cleaved, forming a ring-opened allylic alcohol product. Through a possible ruthenium-catalyzed redox isomerization, the allylic alcohol is transformed into a saturated carbonyl product. This unexpected mode of ruthenium-catalyzed ring-opening reaction of a 3-aza-2-oxabicyclo[2.2.1]hept-5-ene leads to the formation of a cyclopentanone derivative in moderate yields.

Oxidation of isoprothiolane by ozone and chlorine: Reaction kinetics and mechanism

Isoprothiolane (IPT) was one of the most commonly used pesticides around the world. It was reported to be the highest concentration and frequency of detection of 13 most commonly used pesticides in Mekong Delta recently. The oxidation degradation kinetic of ozone and chlorine with IPT and the identification of the degradation products was investigated in this research. The results showed that both ozone and chlorine oxidized IPT rapidly under typical water treatment condition, and that both reactions followed second order reaction kinetics. The ozone reaction rates exhibited no pH dependence with the rate constant of 247.1 (±11.0) M−1s−1 at 25 °C, whereas chlorine reaction rates increased dramatically with decreasing pH. The rate constant for hypochloric acid was 73.3 (±3.1) M−1s−1 at 25 °C, while the reaction of hypochlorite was negligible. The degradation products by chlorine and ozone were identified by LC-MS/MS and the reaction pathways were proposed. The thioether and the carbon-carbon double bond in IPT were the reactive sites during chlorine and ozone oxidation. The thioether group was oxidized into sulfoxide and further sulfone group, and the carbon-carbon double bone were cleaved to form diisopropyl ester of malonic acid, diisopropyl ester of tartronic acid and diisopropyl ester of ketomalonic acid monohydrate. Compared to ozone reaction, it was more complicated for chlorine reaction, which yielded chlorine substituted, hydroxylated and dithiolane ring-opening products.