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Cas Database

107-92-6

107-92-6

Identification

  • Product Name:Butyric acid

  • CAS Number: 107-92-6

  • EINECS:203-532-3

  • Molecular Weight:88.1063

  • Molecular Formula: C4H8O2

  • HS Code:2915600000

  • Mol File:107-92-6.mol

Synonyms:n-Butanoic acid;n-Butyric acid;(3R,4S)-1-Benzoyl-3-(1-methoxy-1-methylethoxy)-4-phenyl-2-azetidinone;Butyricacid (6CI,7CI,8CI);1-Propanecarboxylic acid;Ethylacetic acid;Honey robber;NSC 8415;Propylformic acid;

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Safety information and MSDS view more

  • Pictogram(s):IrritantXi,CorrosiveC

  • Hazard Codes: C:Corrosive;

  • Signal Word:Danger

  • Hazard Statement:H314 Causes severe skin burns and eye damage

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Artificial respiration may be needed. Refer for medical attention. In case of skin contact Remove contaminated clothes. Rinse skin with plenty of water or shower. 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. Do NOT induce vomiting. Refer for medical attention . Inhalation causes irritation of mucous membrane and respiratory tract; may cause nausea and vomiting. Ingestion causes irritation of mouth and stomach. Contact with eyes may cause serious injury. Contact with skin may cause burns; chemical is readily absorbed through the skin and may cause damage by this route. (USCG, 1999) /SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist respirations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Activated charcoal is not effective ... . Do not attempt to neutralize because of exothermic reaction. Cover skin burns with dry, sterile dressings after decontamination ... . /Organic acids and related compounds/

  • Fire-fighting measures: Suitable extinguishing media Use water spray, dry chemical, "alcohol resistant" foam, or CO2. Use water to keep fire-exposed containers cool. On large fires, solid streams of water may not be effective. Excerpt from ERG Guide 153 [Substances - Toxic and/or Corrosive (Combustible)]: Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Those substances designated with a (P) may polymerize explosively when heated or involved in a fire. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form. (ERG, 2016) 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. Personal protection: complete protective clothing including self-contained breathing apparatus. Do NOT let this chemical enter the environment. Collect leaking and spilled liquid in sealable containers as far as possible. Cautiously neutralize remainder with soda lime. Then wash away with plenty of water. Land spill: Dig a pit, pond, lagoon, or holding area to contain liquid or solid material /SRP: If time permits, pits, ponds, lagoons, soak holes, or holding areas should be sealed with an impermeable flexible membrane liner./ Dike surface flow using soil, sand bags, foamed polyurethane, or foamed concrete. Absorb bulk liquid with fly ash or cement powder. Neutralize with agricultural lime (slaked lime), crushed limestone, or sodium bicarbonate.

  • 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. Separated from strong oxidants, strong bases and food and feedstuffs.Store in cool, dry, well-ventilated location, away from any area where fire hazard may be acute.

  • Exposure controls/personal protection:Occupational Exposure limit valuesBiological 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 520 Articles be found

Aqueous-phase hydrogenation of biomass-derived itaconic acid to methyl-γ-butyrolactone over Pd/C catalysts: Effect of pretreatments of active carbon

Li, Sha,Wang, Xicheng,Liu, Xiaoran,Xu, Guoqiang,Han, Sheng,Mu, Xindong

, p. 92 - 96 (2015)

The effect of active carbon pretreatment on the catalytic performance of Pd/C catalysts in the hydrogenation of itaconic acid was studied. The catalysts were prepared by deposition-precipitation and characterized by XRD, BET, NH3-TPD, TEM and F

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Schwenk et al.

, p. 175 (1944)

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CATALYTIC CARBONYLATION OF PROPYLENE WITH CARBON MONOXIDE UNDER PRESSURE IN THE PRESENCE OF A PALLADIUM-ZEOLITE CATALYST

Lapidus, A. L.,Pirozhkov, S. D.,Vellekov, A.,Garanin, V. I.,Slyunyaev, P. I.,Minachev, Kh. M.

, p. 2027 - 2030 (1982)

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Bachman,Strawn

, p. 313 (1968)

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A series of crystal structures of a meta-cleavage product hydrolase from Pseudomonas fluorescens IP01 (CumD) complexed with various cleavage products

Fushinobu, Shinya,Jun, So-Young,Hidaka, Masafumi,Nojiri, Hideaki,Yamane, Hisakazu,Shoun, Hirofumi,Omori, Toshio,Wakagi, Takayoshi

, p. 491 - 498 (2005)

Meta-cleavage product hydrolase (MCP-hydrolase) is one of the key enzymes in the microbial degradation of aromatic compounds. MCP-hydrolase produces 2-hydroxypenta-2,4-dienoate and various organic acids, according to the C6 substituent of the substrate. Comprehensive analysis of the substrate specificity of the MCP-hydrolase from Pseudomonas fluorescens IP01 (CumD) was carried out by determining the kinetic parameters for nine substrates and crystal structures complexed with eight cleavage products. CumD preferred substrates with long non-branched C6 substituents, but did not effectively hydrolyze a substrate with a phenyl group. Superimposition of the complex structures indicated that benzoate was bound in a significantly different direction than other aliphatic cleavage products. The directions of the bound organic acids appeared to be related with the kcat values of the corresponding substrates. The Ile139 and Trp143 residues on helix α4 appeared to cause steric hindrance with the aromatic ring of the substrate, which hampers base-catalyzed attack by water.

The Rhodium-Catalyzed Carbonylation of Linear Primary Alcohols

Deklewa, Thomas W.,Forster, Denis

, p. 3565 - 3567 (1985)

The results of a comprehensive kinetic, spectroscopic, and analytical study into the rhodium-catalyzed carbonylation of primary linear alcohols (R = Me, Et, and n-Pr) are reported.In all cases, the reaction rate is first order in both and added and independent of CO pressure.The only rhodium species observed under catalytic conditions was RhI2(CO)21-.The rates of carbonylation of the alcohols decreased in the order MeOH > EtOH >n-Pr with relative rates at 170 deg C of 21:1:0.47.Apparent activation parameters have been determined.All the data are consistent with the rate-determining step being nucleophilic attack by the rhodium ion on the corresponding alkyl iodide, in agreement with the previous interpretation of the methanol system.Important information was also obatained regarding the stability of the intermediate rhodium alkyl species.Carbonylation of n-PrOH gave a mixture of the two isomeric product butyric acids, the composition of which depended on the CO pressure.The isobutyric acid appears to arise from the isomerization of the initially formed n-alkyl species, and the pressure dependence of this process suggests that loss of CO from the alkyldicarbonylrhodium(III) species is competitive with the migratory insertion reaction which forms the analogous monocarbonyl acyl species observed previously.

Sharp et al.

, p. 1802 (1952)

Kadiera

, p. 332 (1904)

Aerobic oxidation of alcohols to carbonyl compounds catalyzed by N-hydroxyphthalimide (NHPI) combined with Co(acac)3

Iwahama, Takahiro,Sakaguchi, Satoshi,Nishiyama, Yutaka,Ishii, Yasutaka

, p. 6923 - 6926 (1995)

Aerobic oxidation of various alcohols has been accomplished by using a new catalytic system. N-hydroxyphthalimide (NHPI) combined with Co(acac)3. The oxidation of alcohols by NHPI was found to be markedly enhanced by adding a slight amount of Co(acac)3 (0.05 equiv. to NHPI). Thus, secondary alcohols and vic-diols which are difficult to be oxidized by NHPI alone were smoothly oxidized with molecular oxygen (1 atm) to the corresponding carbonyl compounds under relatively mild conditions (65 ~ 75 °C).

An unexplored O2-involved pathway for the decarboxylation of saturated carboxylic acids by TiO2 photocatalysis: An isotopic probe study

Wen, Bo,Li, Yue,Chen, Chuncheng,Ma, Wanhong,Zhao, Jincai

, p. 11859 - 11866 (2010)

The aerobic decarboxylation of saturated carboxylic acids (from C 2 to C5) in water by TiO2 photocatalysis was systematically investigated in this work. It was found that the split of C 1-C2 bond of the acids to release CO2 proceeds sequentially (that is, a C5 acid sequentially forms C4 products, then C3 and so forth). As a model reaction, the decarboxylation of propionic acid to produce acetic acid was tracked by using isotopic-labeled H218O. As much as ≈42% of oxygen atoms of the produced acetic acids were from dioxygen (16O2). Through diffuse reflectance FTIR measurements (DRIFTS), we confirmed that an intermediate pyruvic acid was generated prior to the cut-off of the initial carboxyl group; this intermediate was evidenced by the appearance of an absorption peak at 1772 cm-1 (attributed to C=O stretch of α-keto group of pyruvic acid) and the shift of this peak to 1726 cm -1 when H216O was replaced by H 218O. Consequently, pyruvic acid was chosen as another model molecule to observe how its decarboxylation occurs in H2 16O under an atmosphere of 18O2. With the α-keto oxygen of pyruvic acid preserved in the carboxyl group of acetic acid, ≈24% new oxygen atoms of the produced acetic acid were from molecular oxygen at near 100% conversion of pyruvic acid. The other ≈76% oxygen atoms were provided by H2O through hole/OH radical oxidation. In the presence of conduction band electrons, O2 can independently accomplish such C1-C2 bond cleavage of pyruvic acid to generate acetic acid with ≈100% selectivity, as confirmed by an electrochemical experiment carried out in the dark. More importantly, the ratio of O2 participation in decarboxylation increased along with the increase of pyruvic acid conversion, indicating the differences between non-substituted acids and α-keto acids. This also suggests that the O 2-dependent decarboxylation competes with hole/OH-radical-promoted decarboxylation and depends on TiO2 surface defects at which Ti 4c sites are available for the simultaneous coordination of substrates and O2. Acid aerobics! An O2-involved pathway for the decarboxylation of saturated carboxylic acids by TiO2 photocatalysis is clarified, and has been found to be composed of two major tandem steps. An oxygen atom of O2 is incorporated into the product acid in the second step (see scheme).

-

Eccott,Linstead

, p. 911 (1930)

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An Efficient Synthesis of Optically Active 4-Methyloxetan-2-one: Asymmetric Hydrogenation of Diketene catalysed by binap-Ruthenium(II) Complexes

Ohta, Tetsuo,Miyake, Tsutomu,Takaya, Hidemasa

, p. 1725 - 1726 (1992)

Highly enantioselective hydrogenation of diketene with the catalytic system derived from (benzene)>Cl and triethylamine or with Ru2Cl42(NEt3) in tetrahydrofuran gives optically active 4-methyloxetan-2-one in up to 97percent selectivity and 92percent enantiomeric excess (e.e.).

Lid hinge region of Penicillium expansum lipase affects enzyme activity and interfacial activation

Tang, Lianghua,Su, Min,Yan, Junzhe,Xie, Sheng,Zhang, Wenhuang

, p. 1218 - 1223 (2015)

Saturation mutagenesis at sites displaying the highest B factors in the lid and the hinge regions of Penicillium expansum lipase (PEL) has been employed to improve the efficiency of the lipase in biocatalysis. Replacements of amino acid on beneficial mutants were identified as T66L/D70N, T66V/D70N, E83K, E83H and E83N. In substrate specificity assays, T66L/D70N was significantly more active than wild-type PEL on substrates with medium and long chain lengths. In addition this mutant also displayed a 136.4-fold increase in activity on p-nitrophenyl palmitate. Remarkably, E83K lacked interfacial activation while it was observed in wild-type PEL and the other mutants. Insight into the relation between the mutations and enzymatic properties was gained by modeling and docking studies. All these mutants showed an enhanced catalytic activity, indicating their potential in further application. Therefore, these results indicate the amino acid composition of the lid hinge region plays an extremely important role in the interfacial activation, activity and substrate specificity of PEL. Moreover, the results in this work provide a new clue for selecting critical amino acid residues for the enzyme design.

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Durham et al.

, p. 332,334 (1958)

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Effects of diluents on the reaction hazards of tributyl phosphate with nitric acid

Sreekantan, Smitha Velayuthan,Mahadevan, Surianarayanan,Jala, Samuel Vara Kumar,Seshadri, Hariharan,Mandal, Asit Baran

, p. 1821 - 1827 (2014)

A proportion of 30 wt % of tributyl phosphate (TBP) in suitable diluents is the workhorse in the extraction of U and Pu in the plutonium uranium extraction (PUREX) process. Accelerating rate calorimetric (ARC) studies of effects of diluents on TBP behavior reveal a similar thermal behavior irrespective of the nature of diluents. The reactive thermal hazards of 30 wt % of TBP with 4N HNO3 in different diluents show onset temperatures in the range of 105-130 °C with a significant pressure rise. Although the onset points are closer to the operating temperature range of the PUREX process, the heat rates are small. However, the process poses pressurization hazards due to the breakdown of the structure of TBP. Oxidation of butanol to butanoic acid is the main cause for exothermic behavior in all cases.

HYDROCARBONYLATION DE LACTONES EN PRESENCE DE CATALYSEURS A BASE DE COBALT ET DE RHODIUM

Bitsi, Gustave,Kheradmand, Houchang,Jenner, Gerard

, p. 115 - 120 (1986)

The hydrocarbonylation of lactones catalysed by rhodium and cobalt complexes is discussed.Rhodium catalysts promote the formation of mono- and di-acids, but with cobalt catalysts homologation takes place yielding lactones and acids.The addition of iodine promotors is essential.

Adsorption and degradation of Congo red on a jarosite-type compound

Dong, Yu,Wang, Ziting,Yang, Xin,Zhu, Meiying,Chen, Rufen,Lu, Bin,Liu, Hui

, p. 102972 - 102978 (2016)

Natrojarosite particles were prepared by forced hydrolysis. X-ray diffraction and field-emission scanning electron microscopy were used to characterize the resulting products. Degradation of the azo dye Congo red (CR) by natrojarosite was investigated under various conditions, such as in the presence or absence of visible-light irradiation, catalyst loading, H2O2 concentration, and initial pH. Total organic carbon determination, UV-visible spectroscopy, and direct infusion-electrospray ionization mass spectrometry in the negative ion mode provided insight into the nature of the degradation products. Moreover, a complete degradation mechanism of CR on natrojarosite was presented. The degradation of CR in the current system occurred even at neutral pH, and the total degradation rate was close to 99.1% for a 30 mg L-1 CR solution. Approximately 80% of the samples were completely mineralized and the other 20% were degraded to small-molecule products. The novel natrojarosite catalysts are potentially valuable for industrial applications because of their high activity, low iron leaching, and low cost.

Tuning the catalytic selectivity in biomass-derived succinic acid hydrogenation on FeOx-modified Pd catalysts

Liu, Xiaoran,Wang, Xicheng,Xu, Guoqiang,Liu, Qiang,Mu, Xindong,Liu, Haichao

, p. 23560 - 23569 (2015)

Succinic acid is an important biomass-derived C4 building block and is ready to be converted into various value-added chemicals. Here we report that tunable selectivity for the formation of 1,4-butanediol, γ-butyrolactone and tetrahydrofuran from aqueous succinic acid hydrogenation could be achieved on FeOx-promoted Pd/C catalysts. Fe was found to be an efficient promoter for the succinic acid hydrogenation, which not only improved the activity of the catalysts but also tuned the product distribution. Succinic acid could be transformed into 1,4-butanediol with a yield of over 70% in the presence of the Pd-5FeOx/C catalyst under the relatively mild conditions of 200°C and 5 MPa H2. The reaction pathway was also proposed according to the reaction and characterization results.

Study of monometallic Pd/TiO2 catalysts for the hydrogenation of succinic acid in aqueous phase

Tapin, Benoit,Epron, Florence,Especel, Catherine,Ly, Bao Khanh,Pinel, Catherine,Besson, Michele

, p. 2327 - 2335 (2013)

A series of 2 wt % Pd/TiO2 monometallic catalysts were prepared by varying some parameters, such as the nature of the precursor salt, the titania support, and the preparation method. The structural and textural properties of the catalytic systems were fully characterized by several physical and chemical techniques (inductively coupled plasma optical emission spectrometry, N2 physisorption, H2 chemisorption, transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy, powder X-ray diffraction, temperature-programmed reduction, X-ray photoelectron spectroscopy, and gas phase reaction of cyclohexane dehydrogenation). The catalytic performances were further estimated for the hydrogenation of an aqueous solution of succinic acid (SUC) performed in a batch reactor at 160 C and under 150 bar total pressure. The results showed that all the Pd catalysts are very selective to produce γ-butyrolactone, the first hydrogenated product. However, the rate of succinic acid conversion is a function of both the Pd dispersion and the preparation method. The deposition-precipitation method allows one to obtain the highest performing 2 wt % Pd/TiO2 samples during SUC hydrogenation in terms of activity and stability.

Hetero-aromatic Nitrogen Base Promoted Cr(VI) Oxidation of Butanal in Aqueous Micellar Medium at Room Temperature and Atmospheric Pressure

Malik, Susanta,Ghosh, Aniruddha,Saha, Bidyut

, p. 109 - 125 (2016)

The kinetics of the oxidation of butanal by chromic acid in aqueous and aqueous surfactant (sodium dodecyl sulfate, SDS, Triton X-100 (TX-100) and N-cetylpyridinium chloride, CPC) media have been investigated in the presence of a promoter at 303 K. The pseudo-first-order rate constants (k obs) were determined from a logarithmic plot of absorbance as a function time. The rate constants were found to increase with introduction of heteroaromatic nitrogen base promoters such as picolinic acid (PA), 2, 2′-bipyridine (bipy) and 1,10-phenanthroline (phen). The product, butanoic acid, was characterized by 1H-NMR. Three promoters PA, bpy and phen are used in combination with SDS, TX-100 and CPC surfactants showing an increase in the rate of oxidation compared to the unpromoted pathway. The mechanism of the reaction path has been proposed with the help of kinetic results and spectroscopic studies. The observed net enhancement of rate effects has been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. The TX-100 and PA combination is suitable for butanal oxidation.

Applications of Homogeneous Water-gas-shift Reaction. I. Further Studies of the Hydroformylation of Propene with CO and H2O

Murata, Kazuhisa,Matsuda, Akio

, p. 245 - 248 (1981)

Polar ether solutions prepared in situ from Co2(CO)8 and 1,2-bis(diphenylphosphino)ethane (diphos) are active catalysts for the hydroformylation of propene with CO and H2O.Under the hydroformylation conditions employed, butyl(C4) or isobutyl alcohols, butyric(C4) acids, and dipropyl ketones were found to be formed as by-products.A pronounced formation of C4 alcohols was observed as the reaction temperature was increased; in fact, the catalyst solutions described above actively reduce butyraldehyde to butyl alcohol.The effects of the CO pressure and of the propene concentration on the formation of C4 aldehydes are also examined.It turns out that the water molecule as well as Co2(CO)8 and diphos are essential for the formation of catalytic intermediates, which are themselves responsible for the hydroformylation activity.

-

Bachman,Michalowicz

, p. 1800 (1958)

-

-

Brady,Sharawy

, p. 4082,4083 (1953)

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Aerobic oxidation of primary aliphatic alcohols over bismuth oxide supported platinum catalysts in water

Lu, Tianliang,Du, Zhongtian,Liu, Junxia,Ma, Hong,Xu, Jie

, p. 2215 - 2221 (2013)

Catalytic oxidation of non-activated aliphatic alcohols with molecular oxygen is rather challenging, especially in an aqueous medium in the absence of an additional base. Bismuth is usually used as a promoter of platinum-based catalysts. In this work, bismuth oxide was explored as a support, and Pt 0 nanoparticles supported on bismuth oxide (Pt/Bi2O 3) exhibited high activity for aerobic oxidation of n-butanol using water as a solvent in the absence of an additional base under optimized conditions. Besides n-butanol, liquid primary aliphatic alcohols with low solubility in water could also be smoothly oxidized into the corresponding carbonyl compounds with molecular oxygen. Pt/Bi2O3 reduced by H2 at about 200 °C showed the highest activity for aerobic oxidation of n-butanol. At this temperature, platinum oxide was reduced to Pt0 and bismuth oxide could be reduced partially which might change the surface property of bismuth oxide.

Aqueous-phase aerobic oxidation of alcohols by soluble Pt nanoclusters in the absence of base

Wang, Tao,Xiao, Chao-Xian,Yan, Liang,Xu, Lin,Luo, Jie,Shou, Heng,Kou, Yuan,Liu, Haichao

, p. 4375 - 4377 (2007)

A soluble Pt nanocluster catalyst (Pt-GLY) is efficient in the absence of base for aqueous-phase aerobic oxidation of, in particular, non-activated alcohols with high recyclability. The Royal Society of Chemistry.

A study of the relationship between the structure and physicochemical parameters of a homologous series of oxprenolol esters at various pH values and temperatures

Jordan, C. Geraldine M.

, p. 1085 - 1091 (1997)

A number of β-adrenergic blockers, including timolol and propranolol, are administered in eyedrops for the treatment of glaucoma, but their therapeutic value is limited by a relatively high incidence of cardiovascular and respiratory, side effects. Because of poor ocular bioavailability, many ocular drugs are applied in high concentrations, which give rise to both ocular and systemic side effects. Methods to increase ocular bioavailability include (a) the development of drug delivery devices designed to release drugs at controlled rates, (b) the use of various vehicles that retard precorneal drug loss, and (c) the conversion of drugs to biologically reversible derivatives (prodrugs) with increased cornea penetration properties, from which the active drugs are released by enzymatic hydrolysis. A homologous series of aliphatic esters of oxprenolol were synthesized and investigated as potential prodrugs for ocular use. The stability of each O- acyl derivative was investigated in aqueous solutions over the pH range 2.2- 9.0 at 37°C. The observed rate constants (k(obs)), shelf-lives (t90), lipophilicities, and Arrhenius parameters were determined for each ester. A study of the relationship between the structure and physicochemical parameters of the homologous series of oxprenolol esters at various pH values and temperatures was made.

Electrocatalytic Alcohol Oxidation with TEMPO and Bicyclic Nitroxyl Derivatives: Driving Force Trumps Steric Effects

Rafiee, Mohammad,Miles, Kelsey C.,Stahl, Shannon S.

, p. 14751 - 14757 (2015)

Bicyclic nitroxyl derivatives, such as 2-azaadamantane N-oxyl (AZADO) and 9-azabicyclo[3.3.1]nonane N-oxyl (ABNO), have emerged as highly effective alternatives to TEMPO-based catalysts for selective oxidation reactions (TEMPO = 2,2,6,6-tetramethyl-1-piperidine N-oxyl). Their efficacy is widely attributed to their smaller steric profile; however, electrocatalysis studies described herein show that the catalytic activity of nitroxyls is more strongly affected by the nitroxyl/oxoammonium redox potential than by steric effects. The inexpensive, high-potential TEMPO derivative, 4-acetamido-TEMPO (ACT), exhibits higher electrocatalytic activity than AZADO and ABNO for the oxidation of primary and secondary alcohols. Mechanistic studies provide insights into the origin of these unexpected reactivity trends. The superior activity of ACT is especially noteworthy at high pH, where bicyclic nitroxyls are inhibited by formation of an oxoammonium hydroxide adduct.

Facile preparation of recyclable biocatalyst-decorated magnetic nanobeads in aqueous media

Sim, Yong Kyun,Jung, Suhyun,Lim, Jung Yun,Kim, Juhyun,Kim, Seong-Ho,Song, Bong Keun,Kim, Bum Tae,Lee, Hyuk,Park, Seongsoon

, p. 1041 - 1043 (2011)

A facile process was developed to manufacture biocatalyst-conjugated magnetic nanobeads, which afford no loss of the intrinsic activity and enantioselectivity of biocatalysts. Up to 90% of their activities remained after six-time recycling in aqueous media.

Synthesis of nanostructured carbon on Ni catalysts supported on mesoporous silica, preparation of carbon-containing adsorbents, and preparation and study of lipase-active biocatalysts

Kovalenko,Chuenko,Perminova,Rudina

, p. 394 - 403 (2016)

This work continues a series of our studies on the synthesis of nanostructured carbon (NSC) by the pyrolysis of H2 + C3–C4 alkane mixtures on nickel and cobalt metal catalysts supported on chemically diverse inorganic materials (aluminosilicates, alumina, carbon) having different textural characteristics (mesoporous and macroporous supports) and shapes (granules, foamed materials, and honeycomb monoliths). Here, we consider Ni catalysts supported on granular mesoporous silica (SiO2). It has been elucidated how the yield of synthesized carbon depends on the Ni/SiO2 catalyst preparation method (homogeneous precipitation or impregnation) and on the composition of the impregnating solution, including the molar ratio of its components—nickel nitrate and urea. The morphology of catalytic NSC and Ni distribution in the silica granule have been investigated using a scanning electron microscope with an EDX analyzer. Carbon-containing composite supports (NSC/SiO2) have been employed as adsorbents for immobilizing microbial lipase. The enzymatic activity and stability of the resulting biocatalysts have been estimated in transesterification reactions of vegetable (sunflower and linseed) oils involving methyl or ethyl acetate, esterification, and synthesis of capric acid–isoamyl alcohol esters in nonaqueous media.

Origin of autocatalysis in the biphasic alkaline hydrolysis of C-4 to C-8 ethyl alkanoates

Buhse,Lavabre,Nagarajan,Micheau

, p. 10552 - 10559 (1998)

The alkaline hydrolysis of C-4 to C-8 (butanoate to octanoate) ethyl esters shows autocatalytic kinetics when performed under two-phase conditions without any mixing solvent. Alkanoate anions and ethanol are the products of the reaction. A dynamic model is proposed that describes quantitatively this kinetic behavior. The model includes the main processes occurring in the biphasic medium and the corresponding thermodynamic calculations of the average size and stoichiometry of the molecular aggregates. Modeling indicates that salting-in and solvent effects caused by the alkanoate anions and ethanol determine the autocatalytic kinetics in the hydrolysis of C-4 ethyl ester where no aggregation occurs. In the C-5 to C-8 experiments, ester-containing micelles (ECM) are mainly formed by cooperative aggregation of alkanoate anions with ester molecules. ECM is formed only after a threshold concentration of the alkanoate anion has been reached. In a phase-transfer-like process, ECM carries ester molecules into the aqueous phase, where hydrolysis takes place yielding alkanoate anions. Additionally, in C-6 and C-7 ethyl ester hydrolysis, autocatalysis appears to be delayed, since acceleration only starts after the extent of hydrolysis has reached a certain level. A transient storage of alkanoate anions in a reservoir has been assumed to explain this delay. Collective adsorption of alkanoate anions at the oil-water interface, which occurs without any threshold concentration, could play the role of such a transient storage. The model also shows that empty micelles are without any kinetic importance, since they are formed at the end of reaction after the ester is completely depleted.

Reactions of calix[4]resorcinolarene anions with esters of carboxylic acids in H2O-DMF solvent

Mirgorodskaya,Kudryavtseva,Kazakova,Konovalov

, p. 261 - 264 (2000)

Reactions of calix[4]resorcinolarene anions with para-nitrophenyl carboxylates in the H2O-DMF medium were studied. The kinetics of this process was measured by optical spectroscopy and potentiometric titration; the step of formation of acylated calixarene and the subsequent step of its hydrolysis were detected. Self-association of long-chain calixarenes into micelles decreases their reactivity with respect to that of the monomers.

Base-free aqueous-phase oxidation of non-activated alcohols with molecular oxygen on soluble Pt nanoparticles

Wang, Tao,Shou, Heng,Kou, Yuan,Liu, Haichao

, p. 562 - 568 (2009)

Seven soluble metal nanoparticle catalysts including Pt, Ru, Rh, Pd, Ir, Ag and Au were synthesized and studied for the aqueous-phase selective oxidation of non-activated alcohols under atmospheric pressure of O2. The effects of particle size were examined on the Pt catalysts with mean diameters of 1.5-4.9 nm. Pt nanoparticles efficiently catalyze the aerobic oxidation of alicyclic and aliphatic alcohols, in particular, primary aliphatic alcohols in the absence of any base. The particle sizes of the Pt catalysts strongly influence their activities, and the one of 1.5 nm exhibits much higher turnover frequencies. In comparison with the other metals examined in this work, it is concluded that Pt is the best metal of choice for the aerobic alcohol oxidation. Aliphatic primary alcohols reacts on the Pt catalysts more preferentially over their isomeric secondary alcohols with increasing their chain length or as they coexist. These steric effects, and the observed kinetic isotope effects with 1-C4H9OD and 1-C4D9OD are consistent with the general alcohol oxidation mechanism, which includes a sequence of elementary steps involving the formation of the alcoholate intermediates in quasi-equilibrated 1-C4H9OH dissociation on the Pt surfaces and the rate-determining hydrogen abstraction from the alcoholates. The inhibiting effects of hydroquinone, a typical radical scavenger, are indicative of the formation of radical intermediates in the H-abstraction step.

Catalytic oxidation of ethers with H2O2 over zeolites

Sasidharan,Suresh,Sudalai

, p. 9071 - 9072 (1995)

Titanium Silicates (TS-1 and TS-2) catalyzed efficiently the selective oxidation of both linear and cyclic ethers into the corresponding acids and lactones respectively, using dil, H2O2 as the oxidant.

Functional characterisation of a metagenome derived family VIII esterase with a deacetylation activity on β-lactam antibiotics

Mokoena, Nobalanda,Mathiba, Kgama,Tsekoa, Tsepo,Steenkamp, Paul,Rashamuse, Konanani

, p. 342 - 348 (2013)

Family VIII esterases represent a poorly characterised esterase family, with high sequence identity to class C β-lactamases, peptidases and penicillin binding proteins. This study reports on the metagenomic library screening and biochemical characterisation of a novel esterase (Est22) derived from an acidic Leachate environment. The enzyme is 423 amino acids in length and contained 22 aa signal peptide. The Est22 primary structure revealed the presence of N-terminus S-x-x-K sequence, which is also highly conserved in class C β-lactamases, peptidases as well as carboxylesterases belonging to family VIII. Phylogenetic analysis using the representative sequences from class C β-lactamases and family VIII esterases indicated that Est22 is a member of family VIII esterases. Substrate specificity profiling using p-nitrophenyl esters (C2-C16) indicated that Est22 preferred shorter chain p-nitrophenyl esters (C2-C5), a characteristic that is typical for true carboxylesterases. In addition of hydrolysing Nitrocefin, Est22 also hydrolysed first generation cephalosporin based derivatives. Detailed selectivity study using different cephalosporin based substrates indicated that Est22 selectively hydrolyse the ester bond of a cephalosporin derivatives leaving the amide bond of the β-lactam ring intact. The selective nature of Est22 makes this enzyme a potential candidate for the use in the synthesis and modification cephalosporin based molecules.

-

Merrow,Whitnack

, p. 1224 (1958)

-

Cp* iridium precatalysts for selective C-h oxidation with sodium periodate as the terminal oxidant

Zhou, Meng,Hintermair, Ulrich,Hashiguchi, Brian G.,Parent, Alexander R.,Hashmi, Sara M.,Elimelech, Menachem,Periana, Roy A.,Brudvig, Gary W.,Crabtree, Robert H.

, p. 957 - 965 (2013)

Sodium periodate (NaIO4) is shown to be a milder and more efficient terminal oxidant for C-H oxidation with CpIr (Cp* = C 5Me5) precatalysts than ceric(IV) ammonium nitrate. Synthetically useful yields, regioselectivities, and functional group tolerance were found for methylene oxidation of substrates bearing a phenyl, ketone, ester, or sulfonate group. Oxidation of the natural products (-)-ambroxide and sclareolide proceeded selectively, and retention of configuration was seen in cis-decalin hydroxylation. At 60 C, even primary C-H bonds can be activated: whereas methane was overoxidized to CO2 in 39% yield without giving partially oxidized products, ethane was transformed into acetic acid in 25% yield based on total NaIO4. 18O labeling was demonstrated in cis-decalin hydroxylation with 18OH2 and NaIO 4. A kinetic isotope effect of 3.0 ± 0.1 was found in cyclohexane oxidation at 23 C, suggesting C-H bond cleavage as the rate-limiting step. Competition experiments between C-H and water oxidation show that C-H oxidation of sodium 4-ethylbenzene sulfonate is favored by 4 orders of magnitude. In operando time-resolved dynamic light scattering and kinetic analysis exclude the involvement of metal oxide nanoparticles and support our previously suggested homogeneous pathway.

Synthesis Gas Homologation of Aliphatic Carboxylic Acids

Knifton, John F.

, p. 41 - 43 (1981)

A new preparative route to aliphatic carboxylic acids is described involving a novel homologation using synthesis gas catalysed by soluble ruthenium species coupled with iodide promotors.

Ag+-CATALYZED OXIDATION OF ALKANAL CYANOHYDRINS BY PEROXYDISULFATE

Ogibin, Yu. N.,Velibekova, D. S.,Katsin, M. I.,Troyanskii, E. I.,Nikishin, G. I.

, p. 1511 - 1515 (1981)

-

Bioreduction of aldehydes and ketones using Manihot species

Machado, Luciana L.,Souza, Joao Sammy N.,de Mattos, Marcos Carlos,Sakata, Solange K.,Cordell, Geoffrey A.,Lemos, Telma L.G.

, p. 1637 - 1643 (2006)

Biocatalysis constitutes an important tool in organic synthesis, especially for the preparation of chiral molecules of biological interest. A series of aliphatic and aromatic aldehydes and two ketones were reduced using plant cell preparations from Manihot esculenta and Manihot dulcis roots. The reduced products were typically obtained in excellent yields (80-96%), and with excellent enantiomeric excess (94-98%), except for vanillin. Esters, a nitrile, and an amide were also examined, but were not reduced. Preliminary conversion rate studies are reported. This is the first attempt to perform the biotransformation of carbonyl compounds using Manihot species.

-

Leete,E.

, p. 2509 - 2513 (1964)

-

Selective oxidation of n-butanol using gold-palladium supported nanoparticles under base-free conditions

Gandarias, Inaki,Miedziak, Peter J.,Nowicka, Ewa,Douthwaite, Mark,Morgan, David J.,Hutchings, Graham J.,Taylor, Stuart H.

, p. 473 - 480 (2015)

The base-free selective catalytic oxidation of n-butanol by O2 in an aqueous phase has been studied using Au-Pd bimetallic nanoparticles supported on titania. Au-Pd/TiO2 catalysts were prepared by different methods: wet impregnation, physical mixing, deposition-precipitation and sol immobilisation. The sol immobilisation technique, which used polyvinyl alcohol (PVA) as the stabilizing agent, gave the catalyst with the smallest average particle size and the highest stable activity and selectivity towards butyric acid. Increasing the amount of PVA resulted in a decrease in the size of the nanoparticles. However, it also reduced activity by limiting the accessibility of reactants to the active sites. Heating the catalyst to reflux with water at 90°C for 1 h was the best method to enhance the surface exposure of the nanoparticles without affecting their size, as determined by TEM, X-ray photoelectron spectroscopy and CO chemisorption analysis. This catalyst was not only active and selective towards butyric acid but was also stable under the operating conditions.

Production of isobutyric acid from methanol by: Clostridium luticellarii

Petrognani, Camille,Boon, Nico,Ganigué, Ramon

, p. 8389 - 8402 (2020)

Renewable methanol can be used as a feedstock to generate value-added multicarbon components through fermentation technologies. Recently, researchers reported the production of isobutyric acid using methanol as an electron donor with open culture systems dominated by Eubacterium sp. and Clostridium sp. Here we report the ability of Clostridium luticellarii wild-type strain to produce isobutyric acid from methanol and CO2 & H2. When growing on methanol, the supplementation of acetic and butyric acid enhanced isobutyric acid final concentration, selectivity and production rate. A maximum of 5.04 ± 0.08 g L-1 isobutyric acid was produced at a rate of 0.420 ± 0.012 g L-1 d-1and selectivity of 0.70 electron per electron of total products in batch with acetic and butyric acid as electron acceptors. The pH was also found to be a major factor influencing isobutyric acid formation with maximal production at pH 6.50. Finally, in addition to its ability to produce isomers, C. luticellarii was able to perform C2-unit elongation from methanol. Overall, this study positions C. luticellarii as a promising platform for the production of isocarboxylic acids.

-

Simmons,Kreuz

, p. 836 (1968)

-

Wurster et al.

, p. 327,328,330,331 (1958)

Hybrid composites octyl-silica-methacrylate agglomerates as enzyme supports

Fernández, Oscar,Díaz, Isabel,Torres, Carlos F.,Tobajas, Montserrat,Tejedor, Víctor,Blanco, Rosa M.

, p. 204 - 210 (2013)

The use of immobilized enzymes as catalysts may be limited by particle size which must be larger than the mesh that retains them in the reactor. Octyl-silica (OS) beads of 70 μm average size were agglomerated to obtain hybrid organic-inorganic composites with particle sizes between 100 and 200 μm. The agglomeration process has been achieved by polymerization of methacrylate from glycidyl methacrylate and ethylene dimethacrylate in the presence of silica beads and further functionalization of the composite with octyl groups. Methacrylate content of the composite (20%) is high enough to stick OS beads, and low enough to preserve the advantages of these particles as supports. The properties of the octyl silica particles for lipase immobilization have been very closely reproduced with the octyl-silica-methacrylate (OSM) composite. Enzyme loading of 210 mg lipase per gram of support has been achieved on OSM vs 230 mg/g on OS. Also catalytic activity values are close for both catalysts, OSM-lipase remaining fully active and stable after 15 cycles in acetonitrile.

Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism

De Nooy,De Nooy, Arjan E. J.,Besemer,Besemer, Arie C.,Van Bekkum,Van Bekkum, Herman

, p. 8023 - 8032 (1995)

The kinetics of the TEMPO-mediated oxidation of methyl α-D- glucopyranoside to sodium methyl α-D-glucopyranosiduronate were studied. An intermediate was found which was identified as the hydrated aldehyde. This was oxidised in the same manner as the alcohol, with pseudo first order rate constants ratio k(obs,ald)/k(obs,alc) = 7. The reaction mechanism is discussed with emphasis on steric factors and compared to literature data. Two different reaction pathways are postulated; under basic reaction conditions via a cyclic transition state 3 and under acid reaction conditions through an acyclic transition state 4.

Biotransformation of aromatic and heterocyclic amides by amidase of whole cells of Rhodococcus sp. MTB5: Biocatalytic characterization and substrate specificity

Ismailsab, Mukram,Monisha,Reddy, Pooja V.,Santoshkumar,Nayak, Anand S.,Karegoudar, Timmanagouda B.

, p. 74 - 85 (2017)

In this study, an amidohydrolase activity of amidase in whole cells of Rhodococcus sp. MTB5 has been used for the biotransformation of aromatic, monoheterocyclic and diheterocyclic amides to corresponding carboxylic acids. Benzoic acid, nicotinic acid and pyrazinoic acid are carboxylic acids which have wide industrial applications. The amidase of this strain is found to be inducible in nature. The biocatalytic conditions for amidase present in the whole cells of MTB5 were optimized against benzamide. The enzyme exhibited optimum activity in 50 mM potassium phosphate buffer pH 7.0. The optimum temperature and substrate concentrations for this enzyme were 50 °C and 50 mM, respectively. The enzyme was quite stable for more than 6 h at 30 °C. It showed substrate specificity against different amides, including aliphatic, aromatic and heterocyclic amides. Under optimized reaction conditions, the amidase is capable of converting 50 mM each of benzamide, nicotinamide and pyrazinamide to corresponding acids within 100, 160 and 120 min, respectively, using 5 mg dry cell mass (DCM) per mL of reaction mixture. The respective percent conversion of these amides was 95.02%, 98.00% and 98.44% achieved by whole cells. The amidase in whole cells can withstand as high as 383 mM concentration of product in a reaction mixture and above which it undergoes product feedback inhibition. The results of this study suggest that Rhodococcus sp. MTB5 amidase has the potential for large-scale production of carboxylic acids of industrial value.

Destruction of pentachlorophenol using glow discharge plasma process

Sharma,Josephson,Camaioni,Goheen

, p. 2267 - 2272 (2000)

Pentachlorophenol (PCP), found in wood preservatives and pesticides, is an a cutely toxic recalcitrant organochlorine carcinogenic compound. A point- to-plane glow discharge plasma (GDP) process was used to study the destruction of 30-50 ppm (120-188 μM) sodium salt of pentachlorophenol (PCP) in an aqueous solution. PCP was converted to less than 10% of its initial concentration in 1-3 h, at room temperature and low pressure (50 Torr). Effects of varying the headspace gas chemistry, stirring rate, pH, and current upon rate of PCP conversion were investigated. Organic acids, including formate, acetate, butyrate, and oxalate, were formed as byproducts after 1-3 h of GDP treatment of PCP. The chloride recovery suggests 50-70% dechlorination. The PCP removal rate exhibited mixed order kinetics. A reaction model developed to verify mixed order kinetics compares well with the experimental data. The increase in order may be due to the production and subsequent destruction of several reaction products throughout the process. An increase n current and stirring rate increased the rate of PCP removal in the GDP reactor. However, the rate of PCP removal decreased when the initial pH of the solution is raised to 11.4. Rapid removal of PCP was observed when the headspace gas was argon, air, or oxygen. Bench scale data was used to compare the power efficiency of the GDP process with atmospheric pressure corona discharge. Results suggest that the cost of power for PCP conversion by glow discharge was less than that of atmospheric pressure corona discharge. Additionally, the operating cost for PCP destruction in aqueous solution using UV based advanced oxidation technologies was found to be comparable with power costs for PCP conversion using GDP. Pentachlorophenol (PCP), found in wood preservatives and pesticides, is an acutely toxic recalcitrant organochlorine carcinogenic compound. A point-to-plane glow discharge plasma (GDP) process was used to study the destruction of 30-50 ppm (120-188 μM) sodium salt of pentachlorophenol (PCP) in an aqueous solution. PCP was converted to less than 10% of its initial concentration in 1-3 h, at room temperature and low pressure (50 Torr). Effects of varying the headspace gas chemistry, stirring rate, pH, and current upon rate of PCP conversion were investigated. Organic acids, including formate, acetate, butyrate, and oxalate, were formed as byproducts after 1-3 h of GDP treatment of PCP. The chloride recovery suggests 50-70% dechlorination. The PCP removal rate exhibited mixed order kinetics. A reaction model developed to verify mixed order kinetics compares well with the experimental data. The increase in order may be due to the production and subsequent destruction of several reaction products throughout the process. An increase in current and stirring rate increased the rate of PCP removal in the GDP reactor. However, the rate of PCP removal decreased when the initial pH of the solution is raised to 11.4. Rapid removal of PCP was observed when the headspace gas was argon, air, or oxygen. Bench scale data was used to compare the power efficiency of the GDP process with atmospheric pressure corona discharge. Results suggest that the cost of power for PCP conversion by glow discharge was less than that of atmospheric pressure corona discharge. Additionally, the operating cost for PCP destruction in aqueous solution using UV based advanced oxidation technologies was found to be comparable with power costs for PCP conversion using GDP.

Photoactivable heterocyclic cages in a comparative release study of butyric acid as a model drug

Piloto, Ana M.,Hungerford, Graham,Sutter, Jens U.,Soares, Ana M.S.,Costa, Susana P.G.,Gonc?alves, M. Sameiro T.

, p. 44 - 53 (2015)

Aiming: at the improvement of the photorelease of butyric acid - a model carboxylic acid drug, a set of heteroaromatic compounds based on acridine, naphtho[2,1-b]pyran, 3H-benzopyran fused julolidine and thioxo-naphtho[2,1-b]pyran were evaluated as benzyl-type phototriggers, in comparison with the well-known o-nitrobenzyl group. The corresponding ester cages were irradiated in a photochemical reactor at 254, 300, 350 and 419 nm, in two solvent systems (methanol or acetonitrile in 80:20 mixtures with HEPES buffer). Photolysis studies showed that, for some of the cages, the release of the active molecule occurred with short irradiation times using 419 nm. Time-resolved fluorescence was used to elucidate their photophysical properties and determine the decay kinetics. Studies were also carried out to assess the suitability of using two-photon excitation to address these compounds, which is advantageous if their use in biological systems is to be considered.

Combined high degree of carboxylation and electronic conduction in graphene acid sets new limits for metal free catalysis in alcohol oxidation

Blanco, Matiás,Mosconi, Dario,Otyepka, Michal,Medve?, Miroslav,Bakandritsos, Aristides,Agnoli, Stefano,Granozzi, Gaetano

, p. 9438 - 9445 (2019)

Graphene oxide, the most prominent carbocatalyst for several oxidation reactions, has severe limitations due to the overstoichiometric amounts required to achieve practical conversions. Graphene acid, a well-defined graphene derivative selectively and homogeneously covered by carboxylic groups but maintaining the high electronic conductivity of pristine graphene, sets new activity limits in the selective and general oxidation of a large gamut of alcohols, even working at 5 wt% loading for at least 10 reaction cycles without any influence from metal impurities. According to experimental data and first principles calculations, the selective and dense functionalization with carboxyl groups, combined with excellent electron transfer properties, accounts for the unprecedented catalytic activity of this graphene derivative. Moreover, the controlled structure of graphene acid allows shedding light upon the critical steps of the reaction and regulating precisely its selectivity toward different oxidation products.

One-step solvent-free aerobic oxidation of aliphatic alcohols to esters using a tandem Sc-Ru?MOF catalyst

Feng, Tingkai,Li, Conger,Li, Tao,Zhang, Songwei

supporting information, p. 1474 - 1480 (2022/03/08)

Esters are an important class of chemicals in industry. Traditionally, ester production is a multi-step process involving the use of corrosive acids or acid derivatives (e.g. acid chloride, anhydride, etc.). Therefore, the development of a green synthetic protocol is highly desirable. This work reports the development of a metal-organic framework (MOF) supported tandem catalyst that can achieve direct alcohol to ester conversion (DAEC) using oxygen as the sole oxidizing agent under strictly solvent-free conditions. By incorporating Ru nanoparticles (NPs) along with a homogeneous Lewis acid catalyst, scandium triflate, into the nanocavities of a Zr MOF, MOF-808, the compound catalyst, Sc-Ru?MOF-808, can achieve aliphatic alcohol conversion up to 92% with ester selectivity up to 91%. A mechanistic study reveals a unique “via acetal” pathway in which the alcohol is first oxidized on Ru NPs and rapidly converted to an acetal on Sc(iii) sites. Then, the acetal slowly decomposes to release an aldehyde in a controlled manner for subsequent oxidation and esterification to the ester product. To the best of our knowledge, this is the first example of DAEC of aliphatic alcohols under solvent-free conditions with high conversion and ester selectivity.

Disproportionation of aliphatic and aromatic aldehydes through Cannizzaro, Tishchenko, and Meerwein–Ponndorf–Verley reactions

Sharifi, Sina,Sharifi, Hannah,Koza, Darrell,Aminkhani, Ali

, p. 803 - 808 (2021/07/20)

Disproportionation of aldehydes through Cannizzaro, Tishchenko, and Meerwein–Ponndorf–Verley reactions often requires the application of high temperatures, equimolar or excess quantities of strong bases, and is mostly limited to the aldehydes with no CH2 or CH3 adjacent to the carbonyl group. Herein, we developed an efficient, mild, and multifunctional catalytic system consisting AlCl3/Et3N in CH2Cl2, that can selectively convert a wide range of not only aliphatic, but also aromatic aldehydes to the corresponding alcohols, acids, and dimerized esters at room temperature, and in high yields, without formation of the side products that are generally observed. We have also shown that higher AlCl3 content favors the reaction towards Cannizzaro reaction, yet lower content favors Tishchenko reaction. Moreover, the presence of hydride donor alcohols in the reaction mixture completely directs the reaction towards the Meerwein–Ponndorf–Verley reaction. Graphic abstract: [Figure not available: see fulltext.].

Biochemical and biophysical characterisation of a small purified lipase from Rhizopus oryzae ZAC3

Ayinla, Zainab A.,Ademakinwa, Adedeji N.,Gross, Richard A.,Agboola, Femi K.

, (2021/02/16)

The characteristics of a purified lipase from Rhizopus oryzae ZAC3 (RoL-ZAC3) were investigated. RoL-ZAC3, a 15.8 kDa protein, which was optimally active at pH 8 and 55 °C had a half-life of 126 min at 60 °C. The kinetic parameters using p-nitrophenylbuty

Time-Dependent Self-Assembly of Copper(II) Coordination Polymers and Tetranuclear Rings: Catalysts for Oxidative Functionalization of Saturated Hydrocarbons

Costa, Ines F. M.,Kirillova, Marina V.,André, Vania,Fernandes, Tiago A.,Kirillov, Alexander M.

supporting information, p. 14491 - 14503 (2021/07/19)

This study describes a time-dependent self-assembly generation of new copper(II) coordination compounds from an aqueous-medium reaction mixture composed of copper(II) nitrate, H3bes biobuffer (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), ammonium hydroxide, and benzenecarboxylic acid, namely, 4-methoxybenzoic (Hfmba) or 4-chlorobenzoic (Hfcba) acid. Two products were isolated from each reaction, namely, 1D coordination polymers [Cu3(μ3-OH)2(μ-fmba)2(fmba)2(H2O)2]n (1) or [Cu2(μ-OH)2(μ-fcba)2]n (2) and discrete tetracopper(II) rings [Cu4(μ-Hbes)3(μ-H2bes)(μ-fmba)]·2H2O (3) or [Cu4(μ-Hbes)3(μ-H2bes)(μ-fcba)]·4H2O (4), respectively. These four compounds were obtained as microcrystalline air-stable solids and characterized by standard methods, including the single-crystal X-ray diffraction. The structures of 1 and 2 feature distinct types of metal-organic chains driven by the μ3- or μ-OH- ligands along with the μ-benzenecarboxylate linkers. The structures of 3 and 4 disclose the chairlike Cu4 rings assembled from four μ-bridging and chelating aminoalcoholate ligands along with μ-benzenecarboxylate moieties playing a core-stabilizing role. Catalytic activity of 1-4 was investigated in two model reactions, namely, (a) the mild oxidation of saturated hydrocarbons with hydrogen peroxide to form alcohols and ketones and (b) the mild carboxylation of alkanes with carbon monoxide, water, and peroxodisulfate to generate carboxylic acids. Cyclohexane and propane were used as model cyclic and gaseous alkanes, while the substrate scope also included cyclopentane, cycloheptane, and cyclooctane. Different reaction parameters were investigated, including an effect of the acid cocatalyst and various selectivity parameters. The obtained total product yields (up to 34% based on C3H8 or up to 47% based on C6H12) in the carboxylation of propane and cyclohexane are remarkable taking into account an inertness of these saturated hydrocarbons and low reaction temperatures (50-60 °C). Apart from notable catalytic activity, this study showcases a novel time-dependent synthetic strategy for the self-assembly of two different Cu(II) compounds from the same reaction mixture.

A 3D MOF based on Adamantoid Tetracopper(II) and Aminophosphine Oxide Cages: Structural Features and Magnetic and Catalytic Properties

?liwa, Ewelina I.,Nesterov, Dmytro S.,Kirillova, Marina V.,K?ak, Julia,Kirillov, Alexander M.,Smoleński, Piotr

supporting information, p. 9631 - 9644 (2021/06/30)

This work describes an unexpected generation of a new 3D metal-organic framework (MOF), [Cu4(μ-Cl)6(μ4-O)Cu(OH)2(μ-PTAO)4]n·2nCl-EtOH·2.5nH2O, from copper(II) chloride and 1,3,5-triaza-7-phosphaadamantane 7-oxide (PTAO). The obtained product is composed of diamandoid tetracopper(II) [Cu4(μ-Cl)6(μ4-O)] cages and monocopper(II) [Cu(OH)2] units that are assembled, via the diamandoid μ-PTAO linkers, into an intricate 3D net with an nbo topology. Magnetic susceptibility measurements on this MOF in the temperature range of 1.8-300 K reveal a ferromagnetic interaction (J = +20 cm-1) between the neighboring copper(II) ions. Single-point DFT calculations disclose a strong delocalization of the spin density over the tetranuclear unit. The magnitude of exchange coupling, predicted from the broken-symmetry DFT studies, is in good agreement with the experimental data. This copper(II) compound also acts as an active catalyst for the mild oxidation and carboxylation of alkanes. The present study provides a unique example of an MOF that is assembled from two different types of adamantoid Cu4 and PTAO cages, thus contributing to widening a diversity of functional metal-organic frameworks.

Process route upstream and downstream products

Process route

p-nitrophenyl butyrate
2635-84-9

p-nitrophenyl butyrate

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
With alkaline solution; In water; acetonitrile; at 24.9 - 25.1 ℃; Rate constant; carbonate buffer pH 10.70;
With 1-methyl-1H-imidazole; 2-(cyclohexylamino)ethanesulfonic acid; In acetonitrile; at 27 ℃; Rate constant;
With Carbonate buffer; alpha cyclodextrin; In water; dimethyl sulfoxide; at 25 ℃; Rate constant; also with β-cyclodextrin;
With phosphate buffer pH 11.6; dimethyl-β-cyclodextrin; In water; at 25 ℃; Rate constant; reaction with γ-cyclodextrin or without cyclodextrin reagent;
With fipronilβ-cyclodextrin; at 25 ℃; Rate constant; in a phosphate buffer (pH 11.6); effect of simple alcohols on cleavage rate;
With bovine pancreatic cholesterol esterase; phenyl-N-butylcarbamate; water; Rate constant; different substituted phenyl-N-butylcarbamates;
With octa(dimethylaminopropyl)resorcin<4>arene; water; at 25 ℃; Rate constant;
With pH 11.6 phosphate buffer; cetyltrimethylammonim bromide; sodium bromide; In acetonitrile; at 25 ℃; Rate constant;
With pH=5.1 buffer; polypeptide KO-42; In water; acetonitrile; at 16.9 ℃; Rate constant; other polypetides vith var. amino acids sequences;
With MES buffer; water; 1-Dodecyl-4-[1-(hydroxyimino)ethyl]pyridinium bromide; at 25 ℃; pH=7.2; Further Variations:; Reagents; Kinetics;
human serum albumin; In phosphate buffer; at 25 ℃; pH=7.4; Further Variations:; Temperatures; Activation energy;
With sodium phosphate buffer; Aspergillus niger ZD11 pyrethroid hydrolase; In acetonitrile; at 30 ℃; pH=6.8; Enzyme kinetics;
With sodium phosphate buffer; Klebsiella sp. ZD112 pyrethroid-hydrolyzing esterase; In acetonitrile; at 30 ℃; pH=7.0; Enzyme kinetics;
With hexa-arginine tagged esterase; Further Variations:; Reagents; Enzyme kinetics;
With Burkholderia xenovorans LB400 BphD; In phosphate buffer; at 25 ℃; pH=7.0; Enzyme kinetics;
With phosphate buffer; subtilisin; In water; at 37 ℃; pH=5; Further Variations:; Reagents; pH-values; Enzyme kinetics;
With 6-aminohexanoate cyclic dimer hydrolase Arthrobacter sp.; at 30 ℃; pH=7; aq. phosphate buffer; Enzymatic reaction;
With Acinetobacter johnsonii dioxygenase Dke1; at 25 ℃; pH=7.5; Reagent/catalyst; Time; Kinetics; aq. buffer; Enzymatic reaction;
With water; at 20 ℃; pH=8;
With human intestinal carboxylesterase; pH=7.4; Reagent/catalyst; Kinetics; aq. buffer; Enzymatic reaction;
With EstEH112 esterase; water; at 25 ℃; pH=8; pH-value; Temperature; Solvent; Reagent/catalyst; Kinetics; GTA buffer; Enzymatic reaction;
With hydrogenchloride; recombinant Sulfolobus solfataricus P1 esterase; water; sodium taurocholate; 2-amino-2-hydroxymethyl-1,3-propanediol; at 60 ℃; pH=8.0; Kinetics; Enzymatic reaction;
With carboxylesterase EstSt7 from Sulfolobus tokodaii strain 7; water; In ethanol; at 80 ℃; pH=9; Temperature; pH-value; Kinetics; Enzymatic reaction;
With lipase from Candida rugosa; In aq. phosphate buffer; pH=7; Catalytic behavior; Enzymatic reaction;
With lipase immobilized poly(ethylene glycol)-decorated polystyrene; In isopropyl alcohol; at 25 ℃; Reagent/catalyst; Catalytic behavior; Enzymatic reaction;
With recombinant esterase from Rhizomucor miehei; In isopropyl alcohol; at 50 ℃; for 0.166667h; pH=7.5; Catalytic behavior; Kinetics; Enzymatic reaction;
With porcine pancreatic lipase (Sigma); water; In dimethyl sulfoxide; at 37 ℃; for 0.5h; pH=7.7; Reagent/catalyst; Enzymatic reaction;
With truncated Candida antarctica lipase A; water; In acetonitrile; pH=7.6; Reagent/catalyst; Kinetics; Enzymatic reaction;
With lipase; Enzymatic reaction;
With Dactylosporangium aurantiacum subsp. Hamdenensis NRRL 18085 esterase WDEst17; water; In acetonitrile; Kinetics; Enzymatic reaction;
With Lipase from Pseudomonas fluorescens on zeolite imidazolate framework-zni; In isopropyl alcohol; pH=5; Reagent/catalyst; Catalytic behavior; Enzymatic reaction;
With Dactylosporangium aurantiacum esterase WDEst9; sodium chloride; In ethanol; acetonitrile; at 30 ℃; for 0.0833333h; pH=8.0; Concentration; pH-value; Reagent/catalyst; Solvent; Temperature; Catalytic behavior; Kinetics; Enzymatic reaction;
With water; Rhizopus oryzae ZAC3 lipase; In aq. phosphate buffer; isopropyl alcohol; at 55 ℃; pH=8; Concentration; pH-value; Solvent; Temperature; Catalytic behavior; Kinetics; Enzymatic reaction;
(E)-2-Hexen-1-ol
928-95-0

(E)-2-Hexen-1-ol

(E)-2-Hexenoic acid
13419-69-7

(E)-2-Hexenoic acid

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
With N-hydroxyphthalimide; cobalt(III) acetylacetonate; oxygen; In acetonitrile; at 65 ℃; for 5h;
50 % Turnov.
16 % Turnov.
C<sub>36</sub>H<sub>60</sub>O<sub>30</sub>*C<sub>4</sub>H<sub>8</sub>O<sub>2</sub>

C36H60O30*C4H8O2

alpha cyclodextrin
10016-20-3

alpha cyclodextrin

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
With phosphate buffer; In water-d2; at 25 ℃; Equilibrium constant; Thermodynamic data; standard molar enthalpy ΔrH0, standard molar Gibbs energy ΔrG0, standard molar entropy ΔrS0;
n-propylfumaric acid
5469-28-3

n-propylfumaric acid

formic acid
64-18-6

formic acid

2-oxopentanoic acid
1821-02-9

2-oxopentanoic acid

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
Produkt5: Malonsaeure;
p-Methoxyvalerophenon
1671-76-7

p-Methoxyvalerophenon

4-methoxybenzoic acid
100-09-4

4-methoxybenzoic acid

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
D-sorbitol
50-70-4

D-sorbitol

TETRAHYDROPYRANE
142-68-7

TETRAHYDROPYRANE

2-methyltetrahydrofuran
96-47-9

2-methyltetrahydrofuran

2,5-dimethyltetrahydrofuran
1003-38-9

2,5-dimethyltetrahydrofuran

methanol
67-56-1

methanol

propan-1-ol
71-23-8

propan-1-ol

2-Methylcyclopentanone
1120-72-5

2-Methylcyclopentanone

3-methyl-cyclopentanone
1757-42-2,6195-92-2

3-methyl-cyclopentanone

propylene glycol
57-55-6,63625-56-9

propylene glycol

ethanol
64-17-5

ethanol

n-hexan-3-ol
623-37-0

n-hexan-3-ol

2-methylpentan-1-ol
105-30-6

2-methylpentan-1-ol

(S)-Ethyl lactate
687-47-8

(S)-Ethyl lactate

pentan-1-ol
71-41-0

pentan-1-ol

vinyl formate
692-45-5

vinyl formate

n-hexan-2-one
591-78-6

n-hexan-2-one

n-hexan-3-one
589-38-8

n-hexan-3-one

Isopropyl acetate
108-21-4

Isopropyl acetate

3-Hydroxy-2-pentanone
3142-66-3,113919-08-7

3-Hydroxy-2-pentanone

acetic acid
64-19-7,77671-22-8

acetic acid

propionaldehyde
123-38-6

propionaldehyde

2-Pentanone
107-87-9

2-Pentanone

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

propionic acid

1-Hydroxy-2-butanone
5077-67-8

1-Hydroxy-2-butanone

2,5-hexanedione
110-13-4

2,5-hexanedione

isopropyl alcohol
67-63-0,8013-70-5

isopropyl alcohol

acetone
67-64-1

acetone

pentan-3-one
96-22-0

pentan-3-one

isobutyric Acid
79-31-2

isobutyric Acid

butanone
78-93-3

butanone

iso-butanol
78-92-2,15892-23-6

iso-butanol

hexanoic acid
142-62-1

hexanoic acid

Isosorbide
652-67-5

Isosorbide

butyric acid
107-92-6

butyric acid

2.3-butanediol
513-85-9

2.3-butanediol

hexan-1-ol
111-27-3

hexan-1-ol

valeric acid
109-52-4

valeric acid

Conditions
Conditions Yield
platinum on carbon; In water; for 3h; Direct aqueous phase reforming;
2-methylenesuccinic acid
97-65-4,25119-64-6

2-methylenesuccinic acid

3-methyltetrahydrofuran
13423-15-9

3-methyltetrahydrofuran

dihydro-4-methyl-2(3H)-furanone
64190-48-3,65284-00-6,70470-05-2,1679-49-8

dihydro-4-methyl-2(3H)-furanone

2-methyl-1,4-butandiol
2938-98-9

2-methyl-1,4-butandiol

isobutyric Acid
79-31-2

isobutyric Acid

3-methyltetrahydro-2-furanone
1679-47-6

3-methyltetrahydro-2-furanone

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
With hydrogen; In water; at 200 ℃; for 20h; under 30003 Torr; Autoclave;
2-butenoic acid
3724-65-0

2-butenoic acid

(E/Z)-2-buten-1-ol
6117-91-5,542-72-3

(E/Z)-2-buten-1-ol

butyric acid
107-92-6

butyric acid

butan-1-ol
71-36-3

butan-1-ol

Conditions
Conditions Yield
With hydrogen; In aq. phosphate buffer; at 40 ℃; for 24h; under 3750.38 Torr; pH=6.5; chemoselective reaction; Autoclave;
14.9%
18.2%
32.5%
benzyl butanoate
103-37-7

benzyl butanoate

benzyl alcohol
100-51-6,185532-71-2

benzyl alcohol

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
With cetyltrimethylammonim bromide; In aq. buffer; at 20 ℃; for 4h; pH=7; Reagent/catalyst; Electrochemical reaction;
pyrrolidine
123-75-1

pyrrolidine

1-pyrroline
5724-81-2

1-pyrroline

2-pyrrolidinon
616-45-5

2-pyrrolidinon

4-butanolide
96-48-0

4-butanolide

4-hydroxybutanoic acid
591-81-1

4-hydroxybutanoic acid

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

propionic acid

butyric acid
107-92-6

butyric acid

Conditions
Conditions Yield
In water; at 225 ℃; for 6h; under 4500.45 Torr; Inert atmosphere;

Global suppliers and manufacturers

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  • Simagchem Corporation
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  • Contact Tel:+86-592-2680277
  • Emails:sale@simagchem.com
  • Main Products:110
  • Country:China (Mainland)
  • Hangzhou Dingyan Chem Co., Ltd
  • Business Type:Manufacturers
  • Contact Tel:86-571-86465881,86-571-87157530,86-571-88025800
  • Emails:sales@dingyanchem.com
  • Main Products:95
  • Country:China (Mainland)
  • EAST CHEMSOURCES LIMITED
  • Business Type:Manufacturers
  • Contact Tel:86-532-81906761
  • Emails:josen@eastchem-cn.com
  • Main Products:97
  • Country:China (Mainland)
  • Shaanxi BLOOM TECH Co.,Ltd
  • Business Type:Lab/Research institutions
  • Contact Tel:+86-29-86470566
  • Emails:sales@bloomtechz.com
  • Main Products:79
  • Country:China (Mainland)
  • Chemwill Asia Co., Ltd.
  • Business Type:Manufacturers
  • Contact Tel:021-51086038
  • Emails:sales@chemwill.com
  • Main Products:56
  • Country:China (Mainland)
  • Afine Chemicals Limited
  • Business Type:Lab/Research institutions
  • Contact Tel:+86-571-85134551
  • Emails:info@afinechem.com
  • Main Products:92
  • Country:China (Mainland)
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