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Cas Database

75-07-0

75-07-0

Identification

  • Product Name:Acetaldehyde

  • CAS Number: 75-07-0

  • EINECS:200-836-8

  • Molecular Weight:44.0532

  • Molecular Formula: C2H4O

  • HS Code:2912120000

  • Mol File:75-07-0.mol

Synonyms:Aceticaldehyde;Ethanal;Ethyl aldehyde;NSC 7594;

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Safety information and MSDS view more

  • Pictogram(s):HighlyF+, HarmfulXn, FlammableF, ToxicT

  • Hazard Codes: F+:Highly flammable;

  • Signal Word:Danger

  • Hazard Statement:H224 Extremely flammable liquid and vapourH319 Causes serious eye irritation H335 May cause respiratory irritation H351 Suspected of causing cancer

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Refer for medical attention. In case of skin contact Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer for medical attention . In case of eye contact First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention. If swallowed Rinse mouth. Give one or two glasses of water to drink. Refer for medical attention . Breathing vapors will be irritating and may cause nausea, vomiting, headache, and unconsciousness. Contact with eyes may cause burns and eye damage. Skin contact from clothing wet with the chemical causes burns or severe irritation. (USCG, 1999) Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Aldehydes and Related Compounds/

  • Fire-fighting measures: Suitable extinguishing media Suitable extinguishing media: Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide. Special Hazards of Combustion Products: Produces irritating vapor when heated Behavior in Fire: Vapors are heavier than air and may travel a considerable distance to a source of ignition and flash back. (USCG, 1999) Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Remove all ignition sources. Evacuate danger area! Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment. Collect leaking liquid in sealable containers. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. Do NOT absorb in saw-dust or other combustible absorbents. Remove vapour with fine water spray. Accidental release measures. Personal precautions, protective equipment and emergency procedures: Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Evacuate personnel to safe areas. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas.; Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided.; Methods and materials for containment and cleaning up: Contain spillage, and then collect with an electrically protected vacuum cleaner or by wet-brushing and place in container for disposal according to local regulations.

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Fireproof. Separated from incompatible materials. See Chemical Dangers. Cooled. Keep in the dark. Store only if stabilized.Conditions for safe storage, including any incompatibilities: Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage. Recommended storage temperature: 2 - 8°C.

  • Exposure controls/personal protection:Occupational Exposure limit valuesNIOSH considers acetaldehyde to be a potential occupational carcinogen.NIOSH usually recommends that occupational exposures to carcinogens be limited to the lowest feasible concentration.Biological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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Relevant articles and documentsAll total 1818 Articles be found

Palladium-Copper-exchanged Y Type Zeolites: A True Heterogeneous Wacker Catalyst

Espeel, P. H.,Tielen, M. C.,Jacobs, P. A.

, p. 669 - 671 (1991)

Evidence is presented that faujasite-type zeolites with specific Si:Al framework ratios exchanged with Pd(NH3)42+ and Cu2+, catalyse the oxidation of ethylene into acetaldehyde, in exactly the same way as the homogeneous Wacker system II and CuII in concentrated chloride solution>; the active centre is found to be a partially ammoniated PdII ion, most probably PdII(NH3)2, which itself belongs to an electron transfer chain consisting of the alkene reagent, the faujasite encaged PdII/Pd0 and CuII/CuI redox couples and dioxygen.

Catalytic dehydration of lactic acid to acrylic acid over dibarium pyrophosphate

Tang, Congming,Peng, Jiansheng,Fan, Guoce,Li, Xinli,Pu, Xiaoli,Bai, Wei

, p. 231 - 234 (2014)

Barium phosphate catalysts were prepared by a precipitation method. The catalysts were calcined at 500 C for 6 h in air atmosphere and characterized by SEM for morphological features, by XRD for crystal phases, by N2 sorption for specific surface area, by TPD-NH3 for acidity and by TG for thermal stability. The dibarium pyrophosphate catalyst was found to have the best catalytic performance, ascribing to weak acidity on the surface. Under the optimal reaction conditions, 99.7% of the lactic acid conversion and 76.0% of the selectivity to acrylic acid were achieved over the dibarium pyrophosphate catalyst.

Mechanism of uncatalyzed and osmium(VIII) catalyzed oxidation of L-alanine by Copper(III) periodate complex in aqueous alkaline medium

Lamani, Shekappa D.,Veeresh, Tegginamat M.,Nandibewoor, Sharanappa T.

, p. 394 - 404 (2011)

The kinetics of oxidation of the L-alanine (L-ala) by diperiodatocuprate(III) (DPC) was carried both in the absence and presence of osmium(VIII) catalyst in alkalinemedium at constant ionic strength of 0.01 mol dm-3 spectrophotometrically.The involvement of free radicals was observed in both the reactions. The oxidation products in both the cases were acetaldehyde and Cu(II), identified by spot test and spectroscopic studies. The stoichiometry is the same in both cases; that is, [L-ala]:[DPC] = 1:2. The reaction was first order in [DPC] and has negative fractional order in [OH-] in both the catalyzed and uncatalyzed cases. The order in [osmium(VIII)] was unity. A mechanism involving the formation of a complex between L-ala and DPC in case of uncatalyzed reaction and a mechanism involving the formation of a complex between L-alanine and osmium(VIII) in case of catalyzed reaction were proposed. The reaction constants involved in the different steps of the mechanisms were calculated for both reactions. The catalytic constant (Kc) was also calculated for catalyzed reaction at different temperatures. The activation parameters with respect to slow step of themechanisms were computed and discussed for both the cases. The thermodynamic quantities were also determined for uncatalyzed and catalyzed reactions. Copyright Taylor & Francis Group, LLC.

Photochemical redox reactions of copper(II)-alanine complexes in aqueous solutions

Lin, Chen-Jui,Hsu, Chao-Sheng,Wang, Po-Yen,Lin, Yi-Liang,Lo, Yu-Shiu,Wu, Chien-Hou

, p. 4934 - 4943 (2014)

The photochemical redox reactions of Cu(II)/alanine complexes have been studied in deaerated solutions over an extensive range of pH, Cu(II) concentration, and alanine concentration. Under irradiation, the ligand-to-metal charge transfer results in the reduction of Cu(II) to Cu(I) and the concomitant oxidation of alanine, which produces ammonia and acetaldehyde. Molar absorptivities and quantum yields of photoproducts for Cu(II)/alanine complexes at 313 nm are characterized mainly with the equilibrium Cu(II) speciation where the presence of simultaneously existing Cu(II) species is taken into account. By applying regression analysis, individual Cu(I) quantum yields are determined to be 0.094 ± 0.014 for the 1:1 complex (CuL) and 0.064 ± 0.012 for the 1:2 complex (CuL2). Individual quantum yields of ammonia are 0.055 ± 0.007 for CuL and 0.036 ± 0.005 for CuL2. Individual quantum yields of acetaldehyde are 0.030 ± 0.007 for CuL and 0.024 ± 0.007 for CuL2. CuL always has larger quantum yields than CuL2, which can be attributed to the Cu(II) stabilizing effect of the second ligand. For both CuL and CuL2, the individual quantum yields of Cu(I), ammonia, and acetaldehyde are in the ratio of 1.8:1:0.7. A reaction mechanism for the formation of the observed photoproducts is proposed.

Kinetics and Thermochemistry of the CH3CO Radical: Study of the CH3CO + HBr --> CH3CHO + Br Reaction

Niiranen, Jukka T.,Gutman, David,Krasnoperov, Lev N.

, p. 5881 - 5886 (1992)

The kinetics of the reaction between CH3CO and HBr has been studied using a heatable tubular reactor coupled to a photoionization mass spectrometer.CH3CO was produced homogeneously by laser photolysis in the presence and absence of HBr.Radical decays were monitored in time-resolved experiments.Rate constants were determined at five temperatures in the range 300-400 K and fitted to the Arrhenius expression, 6.4 (+/-3.6) * 10-13 exp-1/RT> cm3 molecule-1 s-1.This kinetic information was combined with known rate constants andArrhenius parameters for the reverse reaction to obtain the heat of formation of CH3CO.Both second law and third law procedures were used to obtain this thermochemical information from these rate constants.The two determinations of this heat of formation were in close agreement (differing by only 0.4 kJ mol-1).These results, taken together, provide a CH3CO heat of formation of -10.0 +/- 1.2 kJ mol-1 at 298 K which is 14 kJ mol-1 higher than the value in common use.The current results imply a CH3-CO bond enthalpy of 45.1 (+/-1.5) kJ mol-1 which is 14 kJ mol-1 lower than currently believed and a CH3CO-H bond enthalpy of 373.8 (+/-1.5) kJ mol-1 which is higher by this same figure.Former disparities between reported CH3CO heats of formation associated with the equilibrium systems studied to obtain this thermochemical information are resolved.

Kinetic evidence for an anion binding pocket in the active site of nitronate monooxygenase

Francis, Kevin,Gadda, Giovanni

, p. 167 - 172 (2009)

A series of monovalent, inorganic anions and aliphatic aldehydes were tested as inhibitors for Hansenula mrakii and Neurospora crassa nitronate monooxygenase, formerly known as 2-nitropropane dioxygenase, to investigate the structural features that contri

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Patterson,Day

, p. 1276 (1934)

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Catalytic power of pyruvate decarboxylase. Rate-limiting events and microscopic rate constants from primary carbon and secondary hydrogen isotope effects

Alvarez, Francisco J.,Ermer, Joachim,Hübner, Gerhard,Schellenberger, Alfred,Schowen, Richard L.

, p. 8402 - 8409 (1991)

Isotope effects ([rate constant for light isotopic substrate]/[rate constant for heavy isotopic substrate]) for the action of the thiamin diphosphate dependent pyruvate decarboxylase of Saccharomyces carlsbergensis (EC 4.1.1.1) on pyruvate, pyruvate-1-13C, pyruvate-2-13C, and pyruvate-3-d3 have been determined for each of the steady-state kinetic parameters k/A (second-order in pyruvate), k/B (first-order in pyruvate), and k (zero-order in pyruvate). The 1-13C effects are 1.008 ± 0.010 (k/A), 1.013 ± 0.024 (k/B), and 1.024 ± 0.006 (k). The 2-13C effects are 1.013 ± 0.009 (k/A), 0.951 ± 0.020 (k/B), and 1.039 ± 0.004 (k). The 3-d3 effects are 0.883 ± 0.013 (k/A), 0.881 ± 0.026 (k/B), and 1.057 ± 0.005 (k). Effects with 2-oxobutanoate and 2-oxobutanoate-3-d2 are 0.951 ± 0.012 (k/A), 0.821 ± 0.096 (k/B), and 1.057 ± 0.005 (k). Pyruvate decarboxylase was already known to be hysteretically activated by the substrate, with pyruvate binding to the regulatory site with dissociation constant 8 mM and producing unimolecular activation (0.46 s-1) and deactivation (0.033 s-1). The isotope effects lead to rate constants for substrate binding to the catalytic site of 8.2 × 104 M-1 s-1, for substrate departure from the catalytic site of 120 s-1, for decarboxylation of 640 s-1, and for product release of 640 s-1. Pyruvate decarboxylase increases the rate of decarboxylation of pyruvate by thiamin alone by a factor of 3 × 1012 at pH 6.2, 30°C. Under these conditions, conversion of activated enzyme and pyruvate to the enzymic species preceding decarboxylation is 4 × 1012 times faster than the specific-base-catalyzed addition of thiamin to pyruvate. The enzymic species preceding decarboxylation reverts to activated enzyme and free pyruvate 6 × 109 times faster than the specific-base-catalyzed reversion of the adduct of thiamin and pyruvate to thiamin and free pyruvate. Enzymic decarboxylation is 107 times faster than decarboxylation of the adduct of thiamin and pyruvate.

Kinetics of acid-catalyzed hydration of acetylene. Evidence for the presence in the solution phase of unsubstituted vinyl cation

Lucchini, Vittorio,Modena, Giorgio

, p. 6291 - 6296 (1990)

The rates of acetylene hydration in the convenient range of aqueous sulfuric acid (and those of propyne, tert-butylacetylene, ethylene, propene, and tert-butylethylene, for comparative purposes) have been measured at 25 °C with an NMR technique. The correlation of the kinetic data with the excess acidity function X gives a value of 1.12 for the slope parameter m*, which suggests that the intermediate is protonated acetylene, C2H3+ (probably as vinyl cation 3 rather than as hydrogen-bridged ion 4). The comparison with the m* value for the hydration of ethylene (1.50) indicates that protonated acetylene possesses stronger susceptibility to solvation than ethylium ion C2H5+. The deuteration patterns in the products (acetaldehyde and crotonaldehyde) obtained in deuteriosulfuric acid rule out the reversibility of the protonation process and also the conversion between 3 and 4.

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Fernholz,Ruigh,Stavely

, p. 1554 (1940)

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Reaction of Catalase with Ethylhydrogen Peroxide

Kremer, Mordechai L.

, p. 91 - 104 (1985)

C2H5OOH reacts with catalase in a basically irreversible reaction in the course of which the species called compound (I) is formed and decomposed.The formation of compound (I) is preceded by the formation of a precursor complex which is able to react with a further molecule of C2H5OOH to yield an inactive biperoxy complex.The biperoxy complex causes a diminution of the extent of formation of compound (I) at high .As a consequence, compound (I) can never be formed quantitatively.Some of its physical constants can, nevertheless, be evaluated.Compound (I) with C2H5OOH appears to retrain C2H5OH in its structure.

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Murad

, p. 1327 (1961)

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Highly efficient catalyst for the decarbonylation of lactic acid to acetaldehyde

Katryniok, Benjamin,Paul, Sebastien,Dumeignil, Franck

, p. 1910 - 1913 (2010)

The gas phase decarbonylation of lactic acid was performed over various silica-supported heteropolyacids. The obtained performances were, by far, higher than those previously described in the literature. In particular, the best results were obtained for silicotungstic acid-based catalysts, which showed very high yields of acetaldehyde (81-83%) at high lactic acid conversion (up to 91%). The Royal Society of Chemistry 2010.

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Burstyn

, p. 732 (1902)

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Single-turnover studies on brewer's yeast pyruvate decarboxylase: C(2)-proton transfer from thiamin diphosphate

Crane III, Edward J.,Vaccaro, Joseph A.,Washabaugh, Michael W.

, p. 8912 - 8917 (1993)

Rate constants for formation of acetaldehyde from pyruvate catalyzed by the thiamin diphosphate (TDP)-dependent enzyme pyruvate decarboxylase (PDC; EC 4.1.1.1) from Saccharomyces carlsbergensis were determined under single-turnover conditions at 30°C in 100 mM sodium 2-(N-morpholino)ethanesulfonate buffer (pH 6.00) containing 100 mM pyruvamide, 10 mM MgSO4, and 12.5 μM sodium pyruvate. Observed rate constants in the range kobsd = 2.5-6.7 s-1 for 33-104 μM (8-15 mg mL-1) pyruvamide-activated PDC agree with values of kobsd calculated by numerical integration with microscopic rate constants derived previously from steady-state kinetic isotope effects. The observed rate constant kobsd = 6.7 ± 0.4 s-1 is independent of the concentration of pyruvamide-activated PDC in the range 104-150 μM. The decrease in the concentration dependence of the observed rate constants at > 104 μM PDC is consistent with either a change in rate-limiting step or complex formation involving the reactants. There is little or no primary kinetic isotope effect, (kH/kD)obsd ≤ 1.2, for C(2)-hydron exchange from PDC-bound TDP for 33-104 μM pyruvamide-activated PDC. This provides evidence against rate-limiting C(2)-proton transfer between C(2)-H in PDC-bound TDP and a catalytic base with -7 ≤ ΔpKa (= pKaBH - pKaC(2)H) ≤ 7 to form a discrete ylide intermediate during catalysis by PDC.

Unimolecular Decomposition of Pyruvic Acid: An Experimental and Theoretical Study

Saito, Ko,Sasaki, Goki,Okada, Kazumasa,Tanaka, Seiji

, p. 3756 - 3761 (1994)

The thermal decompostion of pyruvic acid diluted in Ar has been studied behind reflected shock waves over the temperature range 850-1000 K, with a total density range of (0.3-1.3) x 10-5 mol/cm3.The decomposition process was monitored by time-resolved IR emission from carbon dioxide product.The vacuum-UV absorption at 193 nm suggested the production of hydroxyethylidene from the initial decomposition.This carbene isomerizes to acetaldehyde at temperatures higher than those used under the present conditions.From the experimental results, we propose that the initial reaction occurs through a five-center transition state (TS) as CH3COCOOH -> CH3COH + CO2 with a rate constant k = 1012.46exp(-40.0 kcal mol-1/RT) s-1.An ab initio molecular orbital calculation at the HF/6-31G**//HF/3-21G level shows that the energy of the five-center TS producing hydroxyethylidene is lower by 60 kcal/mol than that of the four-center TS leading directly to acetaldehyde.A theoretically evaluated rate constant agrees with the experimental value, in support of the proposition that the reaction path occurs through the five-center TS to produce the carbene radical.Also, it appears that the carbene subsequently isomerizes through two routes leading to acetaldehyde and/or vinyl alcohol.

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Evnin et al.

, p. 109,111,115,117 (1973)

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Ammonia promoted barium sulfate catalyst for dehydration of lactic acid to acrylic acid

Li, Xinli,Chen, Zhi,Cao, Ping,Pu, Wenjie,Zou, Weixin,Tang, Congming,Dong, Lin

, p. 54696 - 54705 (2017)

The dehydration of lactic acid (LA) to acrylic acid over ammonia promoted barium sulfate was studied under various conditions. Interplanar spacing (d) calculated from the enlarged (121) diffraction peak of XRD patterns with the Bragg equation is influenced by preparation conditions, which determines the acid-base properties of the prepared barium sulfate. The present work focused on the preparation conditions such as alkaline agents, pH values and calcination temperatures, which affected the d value. It was found that aqueous ammonia was used as an alkaline agent at pH = 5 to synthesize barium sulfate with an appropriate d value, which displayed an excellent catalytic performance for LA dehydration to acrylic acid. In the presence of the prepared barium sulfate with an appropriate d value, the dehydration reaction of lactic acid proceeded efficiently, with 100% lactic acid conversion and ~82% acrylic acid selectivity. The unprecedented catalytic performance is due to a balance between acidic sites and basic sites existing on the surface of the prepared catalyst. The catalyst is very stable for at least 24 h. The deactivation catalyst can be easily regenerated as it is calcined at 500 °C for 10 h under the air atmosphere.

The Dehydrogenation of Ethanol in Dilute Aqueous Solution Photosensitised by Benzophenones

Green, Peter,Green, William A.,Harriman, Anthony,Richoux, Marie-Claude,Neta, Pedatsur

, p. 2109 - 2128 (1988)

The photochemical properties of a series of water-soluble benzophenones have been evaluated in dilute aqueous solution.The compounds possess lowest-energy singlet and triplet excited states demonstrating considerable n,?* character.As such, irradiation of the compounds in aqueous solution containing ethanol (2percent v/v) results in pinacol formation via a triplet-state hydrogen-abstraction process.In the presence of a colloidal Pt catalyst, the intermediate ketyl and 1-hydroxyethyl radicals can be used to reduce water to H2.The rate of H2 formation and its total yield depend upon the nature of the substituent used to solubilise the benzophenone.The rate at which the ketyl radical transfers an electron to the Pt particles can be rationalised in terms of thermodynamic and electrostatic factors.

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Adams,Williams

, p. 2420 (1921)

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Oxidation of threonylmethionine by peroxynitrite. Quantification of the one-electron transfer pathway by comparison to one-electron photooxidation

Jensen, Jana L.,Miller, Brian L.,Zhang, Xiaoping,Hug, Gordon L.,Sch?neich, Christian

, p. 4749 - 4757 (1997)

Peroxynitrite can modify methionine by one- and two-electron oxidation pathways. Here, we have quantified the extent of one-electron oxidation of threonylmethionine (Thr-Met) by peroxynitrite using a characteristic reaction according to which Thr-Met sulfur radical cations decompose via fragmentation of the Thr side chain, yielding acetaldehyde. The efficiencies, f(acet, photo) for the formation of acetaldehyde from Thr-Met sulfur radical cations were obtained by means of one-electron photooxidation using triplet 4- carboxybenzophenone. Exact quantum yields for the formation of Thr-Met sulfur radical cations by triplet 4-carboxybenzophenone were obtained by laser flash photolysis and time-resolved UV spectroscopy. Acetaldehyde yields were measured for the reaction of peroxynitrite with Thr-Met, and division of these acetaldehyde yields by f(acet, photo) yielded the extents to which peroxynitrite reacted with Thr-Met via the one-electron transfer pathway. There was little one-electron oxidation of Thr-Met by peroxynitrite at pH 7.4, i.e., 1.5%, 1.8%, and 5.3% based on the total chemical conversion of Thr-Met for Thr-Met concentrations of 1 x 10-3, 5 x 10-4, and 1.75 x 10- 4 M, respectively. In all cases the major reaction product was the two- electron oxidation product threonylmethionine sulfoxide. However, at pH 6.0, one-electron oxidation of Thr-Met showed a significantly higher efficiency of 14% for [Thr-Met] = 1.75 x 10-4 M. Under all experimental conditions the extent of one-electron oxidation increased with decreasing peptide concentration in agreement with a recently established mechanism according to which the one-electron oxidation of Met by peroxynitrite requires a unimolecular transformation of peroxynitrous acid to an excited species which is the ultimate one-electron oxidant.

4,5-Dihydro-1,2,3-oxadiazole: A Very Elusive Key Intermediate in Various Important Chemical Transformations

Banert, Klaus,Singh, Neeraj,Fiedler, Benjamin,Friedrich, Joachim,Korb, Marcus,Lang, Heinrich

, p. 15092 - 15099 (2015)

4,5-Dihydro-1,2,3-oxadiazoles are postulated to be key intermediates in the industrial synthesis of ketones from alkenes, in the alkylation of DNA in vivo, and in the decomposition of N-nitrosoureas; they are also a subject of great interest for theoretical chemists. In the presented report, the formation of 4,5-dihydro-1,2,3-oxadiazole and the subsequent decay into secondary products have been studied by NMR monitoring analysis. The elusive properties evading characterization have now been confirmed by 1H, 13C, and 15N NMR spectroscopy, and relevant 2D experiments at very low temperatures. Our experiments with suitably substituted N-nitrosoureas using thallium(I) alkoxides as bases under apolar conditions answer important questions on the existence and the secondary products of 4,5-dihydro-1,2,3-oxadiazole. Short-lived! 4,5-Dihydro-1,2,3-oxadiazole is generated by treatment of N-(2-chloroethyl)-N-nitrosourea with thallium alkoxides at low temperatures, but it is not formed by nucleophilic dealkylation of the corresponding N-methyloxadiazolinium salt. Even at -90 °C, 4,5-dihydro-1,2,3-oxadiazole cannot be detected directly. However, it was identified by analysis of its decay products, acetaldehyde, ethylene oxide, and diazomethane (see scheme).

Zur Acetalbildung aus Alkoholen und Acetylen mit Platin- und Palladiumverbindungen als Katalysator

Steinborn, Dirk,Nuenthel, Ralph,Krause, Katrin

, p. C54 - C58 (1991)

The platinum and palladium catalyzed addition of alcohols to acetylene to give acetals was investigated.The catalytic activity and productivity in dependence on the platinum compound and alcohol used, on the oxidation state of platinum and the cocatalytic effect of HCl are discussed.Systems of the type X2/HX (X = ClO4-, BF4-) are introduced as the first catalytically active palladium-containing systems.

Bulgakov, R. G.,Minsker, S. K.,Maistrenko, G. Ya.,Tolstikov, G. A.,Kazakov, V. P.

, (1988)

Kinetic Studies of Secondary Alcohol Photo-oxidation on ZnO and TiO2 at 348 K Studied by Gas-chromatographic Analysis

Cunningham, Joseph,Hodnett, Benjamin K.

, p. 2777 - 2802 (1981)

Kinetics of conversion of propan-2-ol and butan-2-ol to the corresponding ketones by photoassisted dehydrogenation, (-H2)*, to lower aldehydes by a photoassisted Cα-Cβ bond cleavage process, (α-β)*, and to trace quantities of alkene by photoassisted dehydration (-H2O)* have been investigated at oxygen partial pressures in the range 0-700 Torr and at alcohol partial pressures of 0-60 Torr, utilising dynamic flow photoreactors and gas-chromatographic analysis.Qualitatively similar results were obtained either with a 'continuous reactant flow plus continuous u.v. illumination' procedure allied to intermittent sampling, or with a 'pulsed reactant and analysis' procedure.Both procedures yielded dependence upon alcohol pressure indicative of two parallel photoassisted pathways to (-H2)* product, one being Langmuir-Hinshelwood (LH*) and the other Eley-Rideal (ER*) in character.A decline in activity of the metal oxide surfaces as photoassisted conversion of alcohol increased was observed with both procedures and affected the LH* process for (-H2)* more strongly.It is proposed that this LH* process involved alcohol chemisorption and hole localisation at coordinatively unsaturated O2-cus ions.The ER* process is envisaged to have involved encounter of alcohol (from the gas phase or from a reversibly adsorbed weakly bound state) with a much more numerous type of surface location capable of being photoactivated by hole capture.The proposed mechanisms account for observed dependences of the (-H2)* process upon square root of the incident light intensity, upon alcohol pressure and upon oxygen pressure.

Highly selective production of hydrogen peroxide on graphitic carbon nitride (g-C3N4) photocatalyst activated by visible light

Shiraishi, Yasuhiro,Kanazawa, Shunsuke,Sugano, Yoshitsune,Tsukamoto, Daijiro,Sakamoto, Hirokatsu,Ichikawa, Satoshi,Hirai, Takayuki

, p. 774 - 780 (2014)

Photocatalytic production of hydrogen peroxide (H2O2) on semiconductor catalysts with alcohol as a hydrogen source and molecular oxygen (O2) as an oxygen source is a potential method for safe H 2O2 synthesis because the reaction can be carried out without the use of explosive H2/O2 mixed gases. Early reported photocatalytic systems, however, produce H2O2 with significantly low selectivity (~1%). We found that visible light irradiation (λ > 420 nm) of graphitic carbon nitride (g-C 3N4), a polymeric semiconductor, in an alcohol/water mixture with O2 efficiently produces H2O2 with very high selectivity (~90%). Raman spectroscopy and electron spin resonance analysis revealed that the high H2O2 selectivity is due to the efficient formation of 1,4-endoperoxide species on the g-C 3N4 surface. This suppresses one-electron reduction of O2 (superoxide radical formation), resulting in selective promotion of two-electron reduction of O2 (H2O2 formation).

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Kanoh et al.

, p. 372,377 (1979)

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The 4-Oxalocrotonate Tautomerase- and YwhB-Catalyzed Hydration of 3E-Haloacrylates: Implications for the Evolution of New Enzymatic Activities

Wang, Susan C.,Johnson Jr., William H.,Whitman, Christian P.

, p. 14282 - 14283 (2003)

4-Oxalocrotonate tautomerase (4-OT) catalyzes the conversion of 2-oxo-4E-hexenedioate to 2-oxo-3E-hexenedioate through the intermediate, 2-hydroxy-2,4E-hexadienedioate. 4-OT and a homologue found in Bacillus subtilis (designated YwhB) share sequence identity and two key catalytic groups, Pro-1 and Arg-11, with the two subunits comprising trans-3-chloroacrylic acid dehalogenase (CaaD). 4-OT and YwhB have now been found to display a low-level hydratase activity, resulting in the dehalogenation of 3E-haloacrylates. The enzymes are highly selective for the (E)-isomer, and Pro-1 is critical for the activity while an arginine is likely required. Two mechanisms are proposed in which Pro-1 functions as a general base or a general acid catalyst and, along with the arginine, facilitates the Michael addition of water. Both mechanisms suggest an intriguing route for the evolution of the CaaD activity. One or more mutations could decrease the hydrophobic environment of the active site, which would make it more favorable for a hydrolytic reaction, thereby raising the pKa of Pro-1 and increasing the concentration of enzyme in the reactive form. Copyright

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Cohen

, p. 141 (1920)

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Direct Polynitroaliphatic Alcohol Addition to Alkenes. 2. One-Step Synthesis of β-Substituted Polynitroalkyl Vinyl Ethers via an Alternative Transetherfication Pathway

Shackelford, Scott A.,McGuire, Raymond R.,Cochoy, Robert E.

, p. 2950 - 2953 (1992)

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Translational energy of products in the K + CH3COCl KCl + CH3CO reaction

Pauluth, M.,Rotzoll, G.

, p. 1515 - 1516 (1984)

-

Catalytic oxidation of ethyl acetate over LaBO3 (B = Co, Mn, Ni, Fe) perovskites supported silver catalysts

Qin, Yu,Shen, Fangxia,Zhu, Tianle,Hong, Wei,Liu, Xiaolong

, p. 33425 - 33431 (2018)

A series of silver catalysts supported on lanthanum based perovskites LaBO3 (B = Co, Mn, Ni, Fe) were synthesized and evaluated in the catalytic oxidation of ethyl acetate. XRD, BET, TEM/HRTEM, HAADF-STEM, XPS and H2-TPR were conducted, and the results indicate that redox activity of the catalysts is of great importance to the oxidation reaction. Activity tests demonstrated that Ag/LaCoO3 was more active than the other samples in ethyl acetate oxidation. Moreover, the CO2 selectivity, COx yields and byproduct distributions for all catalysts were studied, and Ag/LaCoO3 showed the best catalytic performance. Besides, Ag/LaCoO3 also showed excellent catalytic activity for other OVOCs.

-

Bernardini,Cherniak

, p. 1371 (1973)

-

Linkage of catalysis and regulation in enzyme action. Carbon isotope effects, solvent isotope effects, and proton inventories for the unregulated pyruvate decarboxylase of Zymomonas mobilis

Sun, Shaoxian,Duggleby, Ronald G.,Schowen, Richard L.

, p. 7317 - 7322 (1995)

The pyruvate decarboxylase of the bacterium Zymomonas mobilis (ZMPDC), in contrast to that of yeast (SCPDC), is not regulated by substrate and shows simple Michaelis-Menten kinetics with rate constants k/B (equivalent to kcat/Km) and k (equivalent to kcat). C1-carbon-13 isotope effects obtained by direct measurement with 99% 13C-labeled substrate, which permits determination of the isotope effect on both k/B and k, give 13(klB) = 1.010 ± 0.008 and 13k = 1.019 ± 0.008. These are similar to the effects with SCPDC and show that decarboxylation is about 20% rate-limiting at low pyruvate levels and about 40% rate-limiting at high pyruvate levels. From these values, the rate constants for individual events in the catalytic cycle can be estimated (to within about a factor of 2) for ZMPDC: addition of pyruvate to the enzyme, 8 × 105 M-1 s-1; off-reaction of pyruvate, 300 s-1; decarboxylation, 1200 s-1; product release, 750 s-1. Solvent isotope effects are small and normal (k/B[HOH]/k/B[DOD] = 1.25 ± 0.05, k[HOH]/ k[DOD] = 1.30 ± 0.01), in strong contrast to those for SCPDC (e.g., an inverse isotope effect of 2 on k/B), which were considered to arise from sulfhydryl-addition reactions coupled to regulation. The proton inventories for ZMPDC are also quite different from those for SCPDC. The overall picture suggests that ZMPDC possesses a similar chemical mechanism but somewhat greater catalytic power than SCPDC because of both stronger uniform binding of all states and greater specific stabilization of transition states relative to reactant states. Thus introduction of the regulatory features of SCPDC is coincident with a reduction in catalytic power.

Piria, R.

, p. 126 - 132 (1856)

Rhodium-Iodide Catalyzed Carbonylation of Methyl Formate into Acetaldehyde or Methyl Acetate: Mechanistic Aspects

Fontaine, Marc,Castanet, Yves,Mortreux, Andre,Petit, Francis

, p. 324 - 336 (1997)

Under CO pressure, the rhodium/ionic-iodide system catalyzes either the reductive carbonylation of methyl formate into acetaldehyde or its homologation into methyl acetate. The influence of the reaction conditions on the selectivity of these two reactions was investigated and it was found that the former occurs selectively only in N-methylpyrrolidone (NMP) (or related solvents), for low I-/Rh ratio, low substrate concentration, and high CO pressure, whereas methyl acetate is preferentially formed, in the same solvent, at higher I- and substrate concentrations and under lower CO pressure. By using labeled methyl formate (H13CO2CH3) it was also shown that the carbonyl group of acetaldehyde or methyl acetate does not result from that of methyl formate. In situ IR studies conducted under catalytic conditions (high-pressure, high-temperature) have not enabled the identification of any other catalytic species than RhI2(CO)-2 (which is also the active species in methanol or methyl acetate carbonylations), whatever the reaction conditions ([I-], PCO . . .). Plausible mechanisms are proposed for these reactions in which the essential role played by NMP in controlling the CH3I content in the reaction medium is clarified and taking into account these experimental data.

Catalytic dehydration of lactic acid to acrylic acid using calcium hydroxyapatite catalysts

Ghantani, Vidhya C.,Lomate, Samadhan T.,Dongare, Mohan K.,Umbarkar, Shubhangi B.

, p. 1211 - 1217 (2013)

A series of calcium hydroxyapatite (HAP) catalysts were synthesised with a Ca/P ratio ranging from 1.3 to 1.89 by a co-precipitation method that involved changing the pH of the calcium and phosphorous precursors. The physicochemical characterization by XRD, SEM, BET surface area and CO2 and NH 3-TPD techniques confirmed the hydroxyapatite formation. These HAP catalysts were used for the vapour phase dehydration of lactic acid to acrylic acid. The HAP catalyst with a Ca/P ratio of 1.3 was found to be the most efficient catalyst among the synthesised series, which gave 100% conversion of lactic acid and 60% selectivity towards acrylic acid at 375 °C when a 50% (w/w) aqueous solution of lactic acid was used. The higher selectivity towards acrylic acid has been correlated to the increased acidity and reduced basicity of the HAP catalyst with a Ca/P ratio of 1.3 compared to the other HAP catalysts. The catalyst was found to be very stable and no deactivation was observed even after 300 h of reaction time. In situ FTIR studies were performed for understanding the mechanistic aspects and showed the formation of calcium lactate as an intermediate species during the dehydration of lactic acid to acrylic acid.

Faith,Peters,Keyes

, p. 924 (1932)

Ethanol steam reforming over Rh and Pt catalysts: Effect of temperature and catalyst deactivation

Bilal, Muhammad,Jackson, S. David

, p. 754 - 766 (2013)

In this study 0.2% Rh/alumina and 0.2% Pt/alumina catalysts were tested for ethanol steam reforming (ESR) over a range of temperatures (773-873 K) at 20 barg with a 5:1 steam to ethanol ratio. Hydrogen was always the main product over Rh/Al2O3 although liquid products such as acetaldehyde, diethyl ether and acetone were also produced (2O3 also produced hydrogen as the main product but at 773 K significant levels of ethene were formed. Less liquid product was formed over the Pt/Al2O3 (-1) however the platinum catalyst gave a low activation energy more typical of a diffusion controlled system (~20 kJ mol-1). At 873 K the platinum catalyst is more active (90% conversion cf. ~60%) and gives a higher hydrogen selectivity (55% cf. 49%) than the rhodium catalyst. Temperature-programmed oxidation (TPO), Raman spectroscopy, BET and SEM analysis were used to characterise the nature of the coke species for reactions at 773 K, 823 K and 873 K. The TPO results indicated that different types of coke were deposited on both catalysts during ESR. Carbon nanotubes and filamentous coke were observed on the catalysts after ESR at 873 K. Raman analysis revealed that the coke deposited on the catalysts was graphitic in nature and the disorder in the graphitic type coke generally increased with an increase in the reaction temperature.

-

Fujimoto et al.

, p. 237 (1974)

-

Identification of a hypothetical protein from podospora anserina as a nitroalkane oxidase

Tormos, Jose R.,Taylor, Alexander B.,Daubner, S. Colette,Hart, P. John,Fitzpatrick, Paul F.

, p. 5035 - 5041 (2010)

The flavoprotein nitroalkane oxidase (NAO) from Fusarium oxysporum catalyzes the oxidation of primary and secondary nitroalkanes to their respective aldehydes and ketones. Structurally, the enzyme is a member of the acyl-CoA dehydrogenase superfamily. To date no enzymes other than that from F. oxysporum have been annotated as NAOs. To identify additional potential NAOs, the available database was searched for enzymes in which the active site residues Asp402, Arg409, and Ser276 were conserved. Of the several fungal enzymes identified in this fashion, PODANSg2158 from Podospora anserina was selected for expression and characterization. The recombinant enzyme is a flavoprotein with activity on nitroalkanes comparable to the F. oxysporum NAO, although the substrate specificity is somewhat different. Asp399, Arg406, and Ser273 in PODANSg2158 correspond to the active site triad in F. oxysporum NAO. The kcat/KM-pH profile with nitroethane shows a pK a of 5.9 that is assigned to Asp399 as the active site base. Mutation of Asp399 to asparagine decreases the kcat/KM value for nitroethane over 2 orders of magnitude. The R406K and S373A mutations decrease this kinetic parameter by 64- and 3-fold, respectively. The structure of PODANSg2158 has been determined at a resolution of 2.0 A, confirming its identification as an NAO.

Formation of Acetaldehyde from L-Ascorbic Acid and Related Compounds in Various Oxidation Systems

Miyake, Takashi,Shibamoto, Takayuki

, p. 1669 - 1672 (1995)

The quantities of acetaldehyde formed from L-ascorbic acid, L-threonic acid, and D-erythrose upon oxidation with Fenton's reagent and upon UV irradiation were determined by gas chromatography.When 10 μmol of L-ascorbic acid was oxidized with Fenton's reagent, 316 nmol of acetaldehyde was recovered.When 10 μmol of L-ascorbic acid was irradiated (λ=300 nm) for 12 h, 297 nmol of acetaldehyde was produced.Upon oxidation with Fenton's reagent, L-threonic acid (10 μmol) and D-erythrose (10 μmol) produced 112 and 81.5 nmol of acetaldehyde, respectively.Acetaldehyde was formed from D-erythrose but not from L-threonic acid by photolysis, suggesting that acetaldehyde formation involved a Norrish type II reaction.Acetaldehyde was also formed from aqueous solutions of L-asorbic acid (122 nmol/10μmol), D-erythrose (37.0 nmol/10μmol), or L-threonic acid (27.9 nmol)/10μmol) with the presence of Fe2+ at 37 deg C under an air stream.This study is the first to report formation of acetaldehyde from ascorbic acid. Keywords: Antioxidant; acetaldehyde; ascorbic acid; low-density lipoprotein

-

Polishchuk et al.

, (1971)

-

-

Inoue,K.,Tanahashi,T.

, p. 359 (1982)

-

Effect of ascorbic acid and its derivatives on the radiation-induced transformations of oxygenated ethanol and its aqueous solutions

Brinkevich

, (2015)

Upon irradiation ascorbic acid and 5,6-O-isopropylidene-2,3-O-dimethylascorbic acid are capable of lowering the yields of the main products of γ-radiolysis of oxygen-saturated ethanol or its aqueous solutions at pH 7 by virtue of reduction of peroxyl radi

Generation, Microwave Spectrum, andAb InitioMO Calculation oftrans-1-Nitrosopropene, CH3CHCH - NO (synform)

Sakaizumi, Takeshi,Tanaka, Hideki,Hirano, Kouji,Kuze, Nobuhiko,Ohashi, Osamu

, p. 79 - 86 (1999)

trans-1-Nitrosopropene (synform) was generated in the gas phase by pyrolysis of 1-chloro-1-methyl-2-(hydroxyimino)ethane and identified by microwave spectroscopy. The microwave spectrum of the pyrolysate was observed in the frequency range from 8.0 to 40.

-

De Graff,Le Fevre

, p. 315 (1925)

-

Formation of CH3CHO in the Combination of CH3 with CHO

Callear, Anthony B.,Cooper, Ian A.

, p. 1763 - 1776 (1990)

By reacting atomic hydrogen with mixtures of CH3Br and CO to generate CH3 and CHO radicals simultaneously, the formation of CH3CHO by combination of CH3 with CHO has been observed.For experiments at 473K, it is shown that the rate coefficient for this reaction is twice the product of the square roots of those for mutual termination of CH3 and CHO, to within the error limits.With this approximation, a model reaction scheme has been developed to analyse the effects of varying the pressures of CH3Br and CO; thereby the yields of CH3CHO produced by the combination of CHO with CH3 have been derived in the temperature range 373-473K, with a total pressure of 600 Torr.The yield appears to decrease slightly with increasing temperature, falling from ca. 0.55 at 373K to ca. 0.42 at 473K.The competing reaction generates CH4 plus CO, and it is argued that the two reactions proceed through different transition states.By computer simulation, it is shown that deviations from the model at lower temperatures are due to participation of CH3CO.

-

v. Lebedew,Polonski

, (1923)

-

Efficient and selective conversion of lactic acid into acetaldehyde using a mesoporous aluminum phosphate catalyst

Tang, Congming,Peng, Jiansheng,Li, Xinli,Zhai, Zhanjie,Bai, Wei,Jiang, Ning,Gao, Hejun,Liao, Yunwen

, p. 1159 - 1166 (2015)

Although acetaldehyde is a very important compound and has been utilized as a useful synthon for various important chemicals, it has been synthesized in industry through a petroleum route until now. Herein, we have successfully developed a sustainable route using a heterogeneous catalyst. In the presence of mesoporous aluminum phosphate (MAP3), the decarbonylation reaction of lactic acid proceeded efficiently, with 100% lactic acid conversion and ~92% acetaldehyde selectivity. The catalyst shows high stability for at least 248 h. The unprecedented catalytic performance is due to rich medium acidic sites existing on the catalyst surface. This journal is

Binary Au–Cu Reaction Sites Decorated ZnO for Selective Methane Oxidation to C1 Oxygenates with Nearly 100% Selectivity at Room Temperature

Gong, Zhuyu,Liu, Huifen,Luo, Lei,Ma, Jiani,Tang, Junwang,Xing, Jialiang,Xu, Youxun

supporting information, p. 740 - 750 (2022/01/03)

Direct and efficient oxidation of methane to methanol and the related liquid oxygenates provides a promising pathway for sustainable chemical industry, while still remaining an ongoing challenge owing to the dilemma between methane activation and overoxidation. Here, ZnO with highly dispersed dual Au and Cu species as cocatalysts enables efficient and selective photocatalytic conversion of methane to methanol and one-carbon (C1) oxygenates using O2 as the oxidant operated at ambient temperature. The optimized AuCu–ZnO photocatalyst achieves up to 11225 μmol·g–1·h–1 of primary products (CH3OH and CH3OOH) and HCHO with a nearly 100% selectivity, resulting in a 14.1% apparent quantum yield at 365 nm, much higher than the previous best photocatalysts reported for methane conversion to oxygenates. In situ EPR and XPS disclose that Cu species serve as photoinduced electron mediators to promote O2 activation to ?OOH, and simultaneously that Au is an efficient hole acceptor to enhance H2O oxidation to ?OH, thus synergistically promoting charge separation and methane transformation. This work highlights the significances of co-modification with suitable dual cocatalysts on simultaneous regulation of activity and selectivity.

Ethanol Steam Reforming by Ni Catalysts for H2 Production: Evaluation of Gd Effect in CeO2 Support

Assaf, Elisabete M.,Ferreira, Gabriella R.,Lucrédio, Alessandra F.,Nogueira, Francisco G. E.

, (2022/01/19)

Abstract: Ni-based catalysts supported on CeO2 doped with Gd were prepared in this work to investigate the role of gadolinium on ethanol conversion, H2 selectivity, and carbon formation on ethanol steam reforming reaction. For this, catalysts containing 5 wt% of Ni impregnated on supports of ceria modified with different amounts of Gd (1, 5, and 10 wt%) were used. Ex-situ studies of XRPD suggest an increase of the lattice parameters, indicating a solid solution formation between Gd and Ce. Results of TPR showed an increase in metal-support interactions as the content of Gd increased. In situ XRPD studies indicated the formation of a GdNiO ternary phase for the catalysts containing Gd, which is in agreement with the results obtained by XANES. The catalysts were tested at three temperatures: 400?°C, 500?°C, and 600?°C. The conversion and productivity showed dependence with the Gd content and also with the temperature of the reaction. After the catalytic tests, catalysts containing Gd presented filamentous carbon possible due to a change in the reaction pathway. The highest ethanol conversion and H2 productivity were obtained at 600?°C for all catalysts and the best catalyst at this temperature was 5Ni_5GdCeO2. The promising performance of this catalyst may be associate with the lowest formation of GdNiO ternary phase, among the catalysts containing Gd, which means more Ni0 active species available to convert ethanol. Graphical Abstract: [Figure not available: see fulltext.]

Photophysics of Perylene Diimide Dianions and Their Application in Photoredox Catalysis

Li, Han,Wenger, Oliver S.

supporting information, (2021/12/23)

The two-electron reduced forms of perylene diimides (PDIs) are luminescent closed-shell species whose photochemical properties seem underexplored. Our proof-of-concept study demonstrates that straightforward (single) excitation of PDI dianions with green

Catalytic Oxidation of Ethylene in Solutions of Palladium(II) Cationic Complexes in Binary and Ternary Aqueous Organic Solvents

Oshanina, I. V.,Pestunova, U. V.,Podtyagina, A. V.,Rusnak, I. N.,Temkin, O. N.

, p. 734 - 743 (2022/01/13)

Abstract: The effect of organic solvents on the rate of ethylene oxidation with p-benzoquinone to acetaldehyde in aqueous organic solutions of palladium cationic complexes has been studied. It was found that the reaction rate increased when the acceptor number of the solvent increased and the donor number decreased. The oxidation of ethylene and cyclohexene in binary (N-methylpyrrolidone–H2O) and ternary (acetonitrile–N-methylpyrrolidone–H2O) solvents was studied in more detail. In contrast to the acetonitrile–Н2О system, in the N-methylpyrrolidone–Н2О binary solvent hydrogen peroxide oxidizes ethylene to acetaldehyde in the presence of Pd(II) cationic complexes. The use of a solvent N-methylpyrrolidone acceptable for cyclohexene (CH) oxidation technology leads to a decrease in the rate and selectivity of cyclohexanone synthesis.

Dual utility of a single diphosphine-ruthenium complex: A precursor for new complexes and, a pre-catalyst for transfer-hydrogenation and Oppenauer oxidation

Mukherjee, Aparajita,Bhattacharya, Samaresh

, p. 15617 - 15631 (2021/05/19)

The diphosphine-ruthenium complex, [Ru(dppbz)(CO)2Cl2] (dppbz = 1,2-bis(diphenylphosphino)benzene), where the two carbonyls are mutually cis and the two chlorides are trans, has been found to serve as an efficient precursor for the synthesis of new complexes. In [Ru(dppbz)(CO)2Cl2] one of the two carbonyls undergoes facile displacement by neutral monodentate ligands (L) to afford complexes of the type [Ru(dppbz)(CO)(L)Cl2] (L = acetonitrile, 4-picoline and dimethyl sulfoxide). Both the carbonyls in [Ru(dppbz)(CO)2Cl2] are displaced on reaction with another equivalent of dppbz to afford [Ru(dppbz)2Cl2]. The two carbonyls and the two chlorides in [Ru(dppbz)(CO)2Cl2] could be displaced together by chelating mono-anionic bidentate ligands, viz. anions derived from 8-hydroxyquinoline (Hq) and 2-picolinic acid (Hpic) via loss of a proton, to afford the mixed-tris complexes [Ru(dppbz)(q)2] and [Ru(dppbz)(pic)2], respectively. The molecular structures of four selected complexes, viz. [Ru(dppbz)(CO)(dmso)Cl2], [Ru(dppbz)2Cl2], [Ru(dppbz)(q)2] and [Ru(dppbz)(pic)2], have been determined by X-ray crystallography. In dichloromethane solution, all the complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the complexes shows redox responses within 0.71 to -1.24 V vs. SCE. [Ru(dppbz)(CO)2Cl2] has been found to serve as an excellent pre-catalyst for catalytic transfer-hydrogenation and Oppenauer oxidation.

Process route upstream and downstream products

Process route

1,1-dipentyloxyethane
13002-08-9

1,1-dipentyloxyethane

pentanal
110-62-3

pentanal

decane
124-18-5

decane

1-ethoxypentane
17952-11-3

1-ethoxypentane

1-pentyl acetate
628-63-7

1-pentyl acetate

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Conditions
Conditions Yield
With di-tert-butyl peroxide; at 150 ℃; Product distribution; Kinetics; Mechanism; termperature 120 - 150 deg C, E(activ.), preexponential factors and velocity const.;
N,N,N',N'-Tetraethylethylenediamine
150-77-6

N,N,N',N'-Tetraethylethylenediamine

N,N,N'-triethylethanediamine
105-04-4

N,N,N'-triethylethanediamine

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

diethylamine
109-89-7

diethylamine

N,N-diethylethylenediamine
100-36-7

N,N-diethylethylenediamine

Conditions
Conditions Yield
Product distribution; controlled potentiostatic electrolysis, carbonate buffer pH 10, glassy-carbon plate electrode, E=0.50 V vs. SCE, 4.0 F/mol;
C<sub>11</sub>H<sub>13</sub>NO<sub>3</sub>S
130436-12-3

C11H13NO3S

pent-4-en-2-one
13891-87-7

pent-4-en-2-one

1,5-Hexadien
592-42-7

1,5-Hexadien

Pent-4-en-2-ol
111957-98-3,625-31-0

Pent-4-en-2-ol

di(p-nitrophenyl) disulfide
100-32-3

di(p-nitrophenyl) disulfide

allyl 4-nitrophenyl sulfide
32894-70-5

allyl 4-nitrophenyl sulfide

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Conditions
Conditions Yield
In benzene; Product distribution; Irradiation;
3-Cyclohexyl-1-(1,1-dideuterio-2-hydroxyethyl)-1-nitrosourea
77081-30-2

3-Cyclohexyl-1-(1,1-dideuterio-2-hydroxyethyl)-1-nitrosourea

<2,2-D2>oxirane
57178-82-2

<2,2-D2>oxirane

1,1-Dideuterio-2-hydroxyethyl Cyclohexylcarbamate
77081-44-8

1,1-Dideuterio-2-hydroxyethyl Cyclohexylcarbamate

3-Cyclohexyl-1-(1,1-dideuterio-2-hydroxyethyl)urea
77081-27-7

3-Cyclohexyl-1-(1,1-dideuterio-2-hydroxyethyl)urea

2,2-Dideuterio-2-hydroxyethyl Cyclohexylcarbamate
77081-41-5

2,2-Dideuterio-2-hydroxyethyl Cyclohexylcarbamate

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Cyclohexyl isocyanate
3173-53-3

Cyclohexyl isocyanate

Conditions
Conditions Yield
With water; at 37 ℃; for 168h; Mechanism; Product distribution; pH 7.0; also in the presence of chloride ion;
chloromethylmercurioacetaldehyde
71840-36-3

chloromethylmercurioacetaldehyde

N-methylaniline
100-61-8

N-methylaniline

4,4'-methylenebis(N-methylaniline)
1807-55-2

4,4'-methylenebis(N-methylaniline)

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Conditions
Conditions Yield
at 20 ℃; for 0.5h;
39%
53%
vinyl n-butyrate
123-20-6,24991-31-9

vinyl n-butyrate

hexan-1-ol
111-27-3

hexan-1-ol

hexyl butyrate
2639-63-6

hexyl butyrate

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Conditions
Conditions Yield
With molecular sieve; Lipase PS; In various solvent(s); at 45 ℃; other hydrolases and oxidoreductase; other solvent; influence of solvent geometry and enzyme catalysis on rate of transesterification;
Propionic acid 1-(3-nitro-phenoxy)-ethyl ester

Propionic acid 1-(3-nitro-phenoxy)-ethyl ester

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

propionic acid
802294-64-0,79-09-4

propionic acid

Conditions
Conditions Yield
With water; In acetonitrile; Rate constant; var. pH;
C<sub>12</sub>H<sub>16</sub>N<sub>2</sub>O<sub>3</sub>

C12H16N2O3

1-Phenylethanol
98-85-1,13323-81-4

1-Phenylethanol

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Conditions
Conditions Yield
With sodium perchlorate; In acetonitrile; at 25 ℃; Rate constant;
water
7732-18-5

water

cis-2,3-epoxysuccinic acid
16533-72-5,51274-37-4

cis-2,3-epoxysuccinic acid

DL-tartaric acid
133-37-9,138508-61-9

DL-tartaric acid

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Conditions
Conditions Yield
Conditions
Conditions Yield

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