Butyl Ketone Research Articles

Computational Study of SmI2-Catalyzed Intermolecular Couplings of Cyclopropyl Ketones: Links between the Structure and Reactivity.

SmI2-catalyzed intermolecular coupling reactions of cyclopropyl ketones with alkenes or alkynes offer an efficient strategy for furnishing diverse five-membered ring-containing molecular architectures. This study presents a systematic computational investigation to reveal the structure-reactivity relationships in these reactions. The reactivity of aryl cyclopropyl ketones is enhanced by the stabilized ketyl radical and cyclopropyl fragmentation, arising from the conjugation effect of the aryl ring, despite an obstacle emerging from the gauche styrene intermediate that elevates the energy barrier for radical trapping. By contrast, alkyl cyclopropyl ketones lack conjugation and exhibit high barriers for reduction and fragmentation but undergo facile radical trapping due to the minimal steric hindrance. Interestingly, ortho-substituted phenyl cyclopropyl ketones exhibit superior reactivity due to a balance between the moderate conjugation, promoting cyclopropyl fragmentation, and the pretwisted nature of the ortho-substituted phenyl that circumvents the hindrance posed by the gauche intermediate and facilitates the radical trapping. The markedly enhanced reactivity of bicyclo[1.1.0]butyl (BCB) ketones arises from facile fragmentation of the strained BCB motif. Bicyclo[2.1.0]pentyl (BCP) ketones, less strained than BCB ketones, are computationally verified to undergo efficient couplings with various partners, and this can be attributed to their stable fragmentation intermediates that facilitate radical trapping. Our findings provide insights that can aid in designing related reactions.

A catalytic alkene insertion approach to bicyclo[2.1.1]hexane bioisosteres.

C(sp3)-rich bicyclic hydrocarbon scaffolds, as exemplified by bicyclo[1.1.1]pentanes, play an increasingly high-profile role as saturated bioisosteres of benzenoids in medicinal chemistry and crop science. Substituted bicyclo[2.1.1]hexanes (BCHs) are emerging bicyclic hydrocarbon bioisosteres for ortho- and meta-substituted benzenes, but are difficult to access. Therefore, a general synthetic route to BCHs is needed if their potential as bioisosteres is to be realized. Here we describe a broadly applicable catalytic approach that delivers substituted BCHs by intermolecular coupling between olefins and bicyclo[1.1.0]butyl (BCB) ketones. The SmI2-catalysed process works for a wide range of electron-deficient alkenes and substituted BCB ketones, operates with SmI2 loadings as low as 5 mol% and is underpinned by a radical relay mechanism that is supported by density functional theory calculations. The product BCH ketones have been shown to be versatile synthetic intermediates through selective downstream manipulation and the expedient synthesis of a saturated hydrocarbon analogue of the broad-spectrum antimicrobial, phthalylsulfathiazole.

Kinetic and Mechanistic Investigations of OH-Initiated Atmospheric Degradation of Methyl Butyl Ketone.

Methyl butyl ketone (MBK, 2-hexanone) is a common atmospheric oxygenated volatile organic compound (OVOC) owing to broad industrial applications, but its atmospheric oxidation mechanism remains poorly understood. Herein, the detailed mechanisms and kinetic properties of MBK oxidation initiated by OH radicals and subsequent transformation of the resulting intermediates are performed by employing quantum chemical and kinetic modeling methods. The calculations show that H-abstraction at the C4 position of MBK is more favorable than those at the other positions, with the total rate coefficient of k(T) = 4.13 × 10-14 exp(1576/T) cm3 molecule-1 s-1 at 273-400 K. The dominant pathway of unimolecular degradation of the C-centered alkyl radical is 1,2-acyl group migration. For the isomerization of the peroxy radical RO2, 1,5- and 1,6-H shifts are more favorable than 1,3- and 1,4-H shifts. The multiconformer rate coefficient kMC-TST of the first H-shift of the RO2 radical is estimated to be 1.40 × 10-3 s-1 at room temperature. Compared to the H-shifts of analogous aliphatic RO2 radicals, it can be concluded that the carbonyl group enhances the H-shift rates by as much as 2-4 orders of magnitude. The rate coefficients of the RO2 radical reaction with the HO2 radical exhibit a weakly negative temperature dependence, and the pseudo-first-order rate constant k'HO2 = kHO2[HO2] is calculated to be 3.32-22.10 × 10-3 s-1 at ambient temperature. The bimolecular reaction of the RO2 radical with NO leads to the formation of 3-oxo-butanal as the main product with the formation concentration of 2.2-7.4 μg/m3 in urban areas. The predicted pseudo-first-order rate constant k'NO = kNO[NO] is 2.20-9.98 s-1 at room temperature. By comparing the kMC-TST, k'HO2, and k'NO, it can be concluded that reaction with NO is the dominant removal pathway for the RO2 radical formed from the OH-initiated oxidation of MBK. These findings are expected to deepen our understanding of the photochemical oxidation of ketones under realistic atmospheric conditions.

Mesityl Oxide Reduction by Using Acid-Modified Phonolite Supported NiW, NiMo, and CoMo Catalysts

Mesityl oxide is standardly used to produce methyl iso butyl ketone but it can be also used to produce other useful compounds. Three catalysts were used for the reaction of the mesityl oxide reduction. They were NiW, NiMo, and CoMo supported on phonolite modified by HCl (metals/Ph-HCl). The fresh catalysts were characterized by XRD, XRF, BET surface, Hg porosimetry, SEM, H2-TPR, NH3-TPD, CO2-TPD. The materials were directly used, previously reduced in H2 or sulfided for the mesityl oxide reduction under H2 atmosphere. The reaction was performed in an autoclave at T = 375 °C, p = 50 bar (H2), and TOS = 1.5 h. The products were analyzed by GC/MS, GC/FID-TCD, ATR. The main products were methyl isobutyl ketone, 2-methyl pentane, and 2-methyl-2-pentene. Sulfided metal catalysts were the most active in the methyl isobutyl ketone, where the NiWSx/Ph-HCl catalyst showed the highest activity. For the non-previously-activated and hydrogen activated catalysts the most active catalyst was the NiMo/Ph-HCl for the production of methyl isobutyl ketone. The catalyst CoMo/Ph-HCl activated in hydrogen was the most active for the production of 2-methyl pentane compared to the other two hydrogen-activated materials.

Ternary Liquid–Liquid Equilibrium for Phosphoric Acid Extraction from Aqueous Solutions with 1-Pentanol or Methyl Butyl Ketone at T = (298.2, 308.2, and 318.2) K

The tie-line values of the aqueous mixture (H2O + phosphoric acid + organic solvents) were checked at several temperatures and air pressures. Methyl butyl ketone or 1-pentanol was selected as the organic solvent. Solubility data were specified for an aqueous ternary mixture employing the cloud point measurements. All the ternary mixtures exhibit the type-1 liquid–liquid phase behavior system. Experimental data were determined employing the refractive index method, the Karl–Fischer technique, and acidimetric titration. Binary interaction parameters were predicted employing liquid–liquid equilibrium modeling. The NRTL and UNIQUAC models were employed to define which model is more reliable. The trustworthiness of the experiment outcome was approved by considering the Hand and Othmer-Tobias equations. Selectivity factors and distribution coefficients were derived to determine the solvents’ extraction capacity. The effect of temperature change was checked on the solubility curve and extraction process at different temperatures.

Comprehensive characterization and health assessment of occupational exposures to volatile organic compounds (VOCs) in Xi'an, a major city of northwestern China

The personal exposure to volatile organic compounds (VOCs) was determined in five occupational groups (including printing shop employees, office workers, furniture store employees, bus and taxi drivers) in the capital city of Xi'an in northwest China. The highest personal exposure concentration (258.7 ± 10.0 μg m−3) to the 64 Air Toxics VOCs classified by the United States Environmental Protection Agency (U.S.EPA), as well as associated health risk potential, were seen in the furniture store employees. These could be attributed to off-gassing from brand new furniture and volatiles from cleaning reagents. Aromatic species were the dominant class in the personal exposure samples collected from the groups of printing shop employees, office workers, and bus and taxi drivers, with the concentrations of 49.8–74.4 μg m−3 and mass compositions of 34.8–43.2% of the sum of the 64 Air Toxics for the cases studied. The highest personal exposure to carbonyls (C≥3) of 100.4 ± 25.6 μg m−3 and composition of 38.8% were again seen in the furniture store employees. The unique VOC composition profiles represented potential indoor or in-vehicle sources in each workplace. Moreover, environmental tobacco smoke (ETS) contributed to the personal exposure to many of the Air Toxics species, especially methyl butyl ketone and 1,2-dibromoethane. The cancer risks of Class 1 carcinogens of vinyl chloride, 1,3-butadiene, and benzene, were 1.4, 12, and 5.2 times, respectively, of the threshold of carcinogenicity (1 × 10−6). Acrolein showed the highest non-cancer risk which was ~150 times the acceptable level (1.0). The results could offer a scientific basis for the government to establish the occupational air quality standards to the toxic VOCs in China.

Optimal Design of a Sustainable Extraction Process for the Treatment of Acidic Wastewater

The wastewater from the fluid catalytic cracking refinery is difficult to treat because of its high organic and oil content. A sustainable extraction process is designed to treat the wastewater. In this process, oil is first separated from wastewater to facilitate further removal of phenol from wastewater. The purification process of oil phase makes use of parazole to extract phenol from oil and wastewater to back-extract parazole, while the purification process of water phase makes use of Methyl Butyl Ketone (MBK) to extract phenol from wastewater followed by distillation recycling of MBK. The extraction mechanism is explained by molecular simulation from micro-level. Compared to traditional extraction operations, this treatment process reduces the make-up of extractant greatly and is sustainable. Subsequently, the extraction process is optimised by sensitivity analysis and Heat Integration with Aspen Plus software. The simulation result exhibits high purity of disposed oil and wastewater (up to 99.50 % and 99.99 %) and a great reduction of energy consumption, utility cost, and CO2 emission. Finally, one control scheme is designed for this process after its anti-disturbance ability is verified with Aspen Dynamics software.

Accelerated doping of trans-4-stilbenemethanol into polymer optical fibers by binary non-solvent/solvent mixtures

Abstract Solution-mediated doping of photosensitive molecules into polymer optical fibers (POFs) has been proved to be a feasible way to prepare photoactive POFs. To accelerate the doping process, this study uses binary non-solvent/solvent mixtures rather than pure non-solvents to swell PMMA fibers and to facilitate diffusion of trans-4-stilbenemethanol into fibers. Binary solvent mixtures are composed of methanol and one good solvent of PMMA. Three mixtures containing three different solvents, namely, acetone, methyl butyl ketone and dimethylformamide, are investigated. It is found that addition of these solvents can effectively increase the doping speed. The doping process is faster as more solvents are added, up to 30% in volume ratio of the solution. The time for reaching diffusion equilibrium is reduced from more than 60 h in methanol to about 20 h in the mixture of methanol/acetone in 70/30 v/v. However, the attenuation of solution-processed POFs by binary mixtures significantly increases compared to pristine POFs, and it should be considered when applying the technique to prepare photoactive POFs. Among the three studied solvents, methyl butyl ketone is recommended for real applications since its addition results significant acceleration to the doping process while the attenuation increase is moderate.

Influence of acid-metal functions on product distribution in valorization of biomass-derived acetone and catalysts’ deactivation behaviour

Availability of acetone from processes such as phenol manufacturing and that from biomass fermentation offers an impetus to look for ways out to value added chemicals as acetone as such on its own little profit. The techniques towards this include its hydrogenation/aldolization, alkylation, etc. In this work, the former is dealt with. To exploit previously established enhanced hydrogen spillover on multi-walled carbon nanotubes (MWCNT), 0.5 wt% Pd was impregnated on MWCNT. This afforded chiefly hydrogenation product iso-propyl alcohol, and very little of methyl isobutyl ketone (MIBK) was observed. A product of successive aldolization, diiso butyl ketone (DIBK), was totally absent. This catalyst afforded higher acetone conversions at higher operating pressures. Also, there was no sign of catalyst deactivation with time-on-stream. However, when this catalyst was physically mixed with an acid catalyst HZSM-5 in equal mass proportion (thus, reducing Pd content to 0.25 wt%), acetone aldolization reaction took over its hydrogenation, and MIBK and DIBK were the main products. This catalyst showed a slow rate of deactivation. Further, when this latter catalyst was modified by impregnating it with 5 wt% Cu to provide a synergistic effect for hydrogenation reaction, as reported in the literature, this modification afforded 10 wt% point enhancement of IPA+MIBK+DIBK yields over the previous catalyst thanks to higher acetone conversions. It also showed slightly less rate of deactivation over the previous catalyst. It is proposed that the rate of deactivation can be reduced employing higher hydrogen to acetone molar ratio in the feed and fine-tuning the acidity of zeolites.

Dielectric spectroscopic study of solutions of amino silicone oil in the polar solvent mixtures of methyl ethyl ketone and methyl iso butyl ketone

The complex permittivity, complex modulus, alternating current electrical conductivity and complex impedance of the ternary mixtures of amino silicone oil in methyl ethyl ketone and methyl iso butyl ketone have been investigated at 303.15 K temperature over the frequency regime 200 Hz to 2 MHz. Complex permittivity and complex impedance data have been fitted to the Coelho model and Nyquist plot respectively. The Coelho model of complex permittivity data provides the electrode polarization relaxation time related to electric double layer relaxation processes. Nyquist plot of complex impedance data exhibits Debye type dispersion corresponding to conduction relaxation processes and electric double layer relaxation processes. Electrode polarization relaxation time (τEP), relaxation time (τEP′), ionic conductivity relaxation time (τσ), geometric relaxation time (τg) and double layer relaxation time (τdl) have been calculated using the different formalism. Static permittivity (ε0), DC conductivity (σdc) and refractive index (nD) have also been determined for all the ternary mixtures. Solvent effect interaction in amino silicone oil with methyl ethyl ketone, methyl iso butyl ketone and with their mixtures is also discussed in the paper. Systematic variation is observed in all the parameters with change in concentration of amino silicone oil in methyl ethyl ketone and methyl iso butyl ketone.

Liquid-liquid equilibrium for methyl butyl ketone + o-, m-, p-cresol + water ternary systems and COSMO-SAC predictions

The liquid–liquid equilibrium (LLE) data for the three ternary systems, methyl butyl ketone (MBK) + o-, m-, p-cresol + water, were measured at 333.2 K and 353.2 K under 101 kPa in this work. Distribution coefficient and selectivity for cresols were calculated from the experimental tie-line data to evaluate the performance of MBK extracting cresols from the aqueous solution. The experimental tie-line data were correlated by the NRTL and UNIQUAC activity coefficient models, and both models showed good agreement with the experimental data. The COSMO-SAC model (conductor-like screening model for segment activity coefficient) was employed to predict LLE phase diagrams for the studied systems with root mean square deviations less than 3%.

Liquid-Liquid Equilibrium for the Ternary Systems of Solvent+ m/o/p-Cresol+Water: Thermodynamic Modeling

In this study, NRTL and UNIQUAC thermodynamic models were used to predict the composition of ternary mixtures of solvents+ m/o/p-cresol+ water in organic and aqueous phases. Various solvents are used for the separation of cresols from water. In this study, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, and methyl isobutyl ketone solvents were investigated. Intermolecular interaction parameters were considered to be a function of temperature. The binary interaction parameters of water and cresols (m, o, or p) in the presence of each type of solvent were considered to be the same. Also, regardless of the type of cresol (m, o, or p), the parameters of binary interaction between water and each solvents were considered to be the same. The results proved the accuracy of the presented models, though the parameters of binary interaction parameters were considered to be the same. The root mean square deviation for NRTL and UNIQUAC models was 0.0086 and 0.0089, respectively.

Preparation of lamellar-stacked TS-1 and its catalytic performance for the ammoximation of butanone with H2O2

A SiO2 particle was prepared with different alkali sources, and then lamellar-stacked TS-1 catalysts were hydrothermally synthesized using the SiO2 particle as a silica source. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectra, nitrogen adsorption–desorption and UV–vis absorption spectra were used to characterize the TS-1 catalysts. The effect of the alkali source during the preparation of the SiO2 particle on the textural properties and catalytic performance of the TS-1 catalyst was thoroughly investigated. The TS-1 catalyst that was prepared with a SiO2 particle using tetrapropylammonium hydroxide (TPAOH) as an alkali source (TS-1-TPAOH) possessed more meso- and macro-pores and a higher framework Ti content than the catalyst that was prepared with a SiO2 particle using NH3·H2O as an alkali source (TS-1-NH3·H2O). As a result, the TS-1-TPAOH catalyst had a better catalytic performance for butanone ammoximation with H2O2 than conventional TS-1 and TS-1-NH3·H2O catalysts. Furthermore, the influences of reaction conditions, including reaction temperature, reaction time, the amount of catalyst and the molar ratio between H2O2 and butyl ketone oxime on the catalytic performance of the TS-1-TPAOH catalyst were evaluated. The unique structure of the lamellar-stacked TS-1 catalyst can effectively avoid the diffusing of large reactant molecules into zeolite channels and has potential applications in other oxidation reactions.

Experimental Determination and Correlation of Liquid–Liquid Equilibria for Methyl Isopropyl Ketone + Phenol + Water Mixtures at 298.15, 313.15, and 323.15 K

Liquid–liquid equilibria (LLE) data for the ternary system, methyl isopropyl ketone (MIPK) + phenol + water, were measured at 298.15 K, 313.15 and 323.15 K under atmospheric pressure by gas chromatography. Distribution coefficients and separation factors were calculated to evaluate the extracting performance of methyl isopropyl ketone, which was proven to be a very efficient solvent to extract phenol from aqueous solution, with distribution coefficients for phenol even higher than those of methyl isobutyl ketone (MIBK) or methyl butyl ketone (MBK). The nonrandom two-liquid (NRTL) and universal quasi-chemical activity coefficient (UNIQUAC) models were used to correlate the experimental data to yield binary interaction parameters for phenol extraction process design or optimization.

Ternary and Quaternary Liquid–Liquid Equilibria for Systems of Methyl Butyl Ketone + Water + Hydroquinone + Phenol at 313.2 K and Atmospheric Pressure

Liquid–liquid equilibria (LLE) data of the quaternary system {methyl butyl ketone + phenol + hydroquinone + water} and two relevant ternary systems, {methyl butyl ketone + phenol + water} and {methyl butyl ketone + hydroquinone + water}, were measured at T = 313.2 K and p = 101.3 kPa. The experimental data were correlated with the nonrandom two-liquid (NRTL) and universal quasichemical (UNIQUAC) models. The root-mean-square deviation of the NRTL and UNIQUAC models were 0.144 and 0.0476%, respectively. Good agreement was found between experimental LLE data and those calculated from the NRTL or UNIQUAC equations for all systems studied in this work.

ChemInform Abstract: Highly Chemoselective and Versatile Method for Direct Conversion of Carboxylic Acids to Ketones Utilizing Zinc Ate Complexes.

AbstractConditions for the efficient transformation of a broad range of aryl, hetaryl, alkyl, and alkenyl carboxylic acids into the corresponding methyl, ethyl, and butyl ketones are elaborated.

Liquid Phase Equilibria of the Water + Propionic or Butyric Acid + Methyl tert-Butyl Ketone Ternary Systems at (298.15 and 323.15) K

In the present work, liquid–liquid equilibria (LLE) data for ternary systems, water + propionic acid or butyric acid + methyl tert-butyl ketone (MTBK), at (298.15 and 323.15) K under atmospheric pressure were measured. The reliability of the experimental LLE data was verified by the Othmer–Tobias and Hand equations. The distribution coefficient, together with the selectivity, was used to assess the extraction performance of MTBK. The universal quasichemical activity coefficient (UNIQUAC) and nonrandom two-liquid (NRTL) models were used to correlate the experimental tie-line data, and binary interaction parameters for relevant process simulation were thus obtained.

Liquid–liquid equilibria in the ternary systems water + cresols + methyl butyl ketone at 298.2 and 313.2 K: Experimental data and correlation

Liquid–liquid equilibrium data for ternary systems (water+o-, m- or p-cresol+methyl butyl ketone) were measured at 298.2 and 313.2K under atmospheric pressure by gas chromatography. Distribution coefficients and separation factors were calculated to evaluate the extracting performance of methyl butyl ketone. For each system, the Hand and Othmer–Tobias equations were used to assess the quality of LLE data. These data were also correlated using NRTL and UNIQUAC models to yield binary interaction parameters for designing or optimizing cresols extracting process.

Effect of Diluents on the Extraction of Fumaric Acid by Tridodecyl Amine (TDA)

Separation of fumaric acid from aqueous media with tridodecyl amine (TDA), which is a long chain aliphatic amine, was carried out at 298 K. Different categories of diluents, ketones (methyl iso butyl ketone (MIBK), 2-heptanone, and 2-octanone) and alcohols (isoamyl alcohol, 1-octanol, and 1-decanol) were used to dissolve TDA. Distribution coefficients (KD), extraction efficiency (E), and loading factors (Z) were obtained as a function of experimental results. The most operative diluent was determined as heptan-2-one with the highest distribution coefficient (KD) value of 26.00. In additional to experimental studies, the linear solvation energy relationship (LSER) modeling with included Hidebrand–Hansen solubility parameters was applied for alcoholic diluents. Predicted data by LSER gave good agreement with experimental data.

Separation of Penicillin G from Fermentation Broth Using N,N-Dioctyloctan-1-amine Extractant in Different Diluents

The extraction of penicillin G was investigated using N,N-Dioctyloctan-1-amine (TOA) with different diluents having distinct functional groups. Nine diluents were used in the study, namely, octan-1-ol, nonan-1-ol, isoamyl alcohol, ethyl ethanoate, propyl ethanoate, methyl iso butyl ketone(MIBK), octan-2-one, octane, and decane. The measurements were performed at a temperature of 298.2 K. The experimental results of batch extractions were used to calculate distribution coefficients (KD), loading factors (Z), and extraction efficiency (E). The highest distribution coefficient (KD = 5.79) was obtained with isoamyl alcohol, and its extraction efficiency was 85.27%. Further, the highest loading factor was reached to a value of 0.130 at 0.374 mol.kg−1 amine concentration. Overloading was not observed at any amine concentration. Solvatochromic model (Linear solvation Energy Relationship (LSER)) for data which obtained from alcohols experiments gives the good results as near as same to experimental results. Suitability of data between experiments and model predictions have been tested with root main square deviation (RMSD) with 0.99.