Ethyl Formate Research Articles

Ethyl Formate as a New Sanitary Treatment for Disinfesting the Hitchhiking Insect Pest Halyomorpha halys on Imported Nonfood Agricultural Machinery

With an increase in the international trade of agricultural and non-agricultural products, there is an increase in the possibility of introducing hitchhiking insect pests such as Halyomorpha halys, which has been detected on imported vehicles and agricultural machinery. Although methyl bromide (MB) is provisionally used to control invasive pests, it is classified as a restricted chemical owing to its potential to deplete the ozone layer and pose health risks to humans in cases of inadequate ventilation, as well as concerns regarding consumer safety. Therefore, this study investigated ethyl formate’s (EF’s) efficacy against H. halys and its efficacy and sorption, as an alternative to MB, on main electronic components, including alternators, ignition coils, and motors. Fumigation with 35 and 70 g/m3 EF for 4 h at 15 °C had no damage on the main electronic components as evaluated using various operation tests. In a commercial trial, H. halys infestation was effectively controlled with 35 g/m3 EF fumigated for 4 h at 23 °C using a 30 m3 polyvinyl chloride tarpaulin fumigation chamber. After ventilation, the EF concentration decreased below the safety level within 10 min and reached the zero level within 40 min for worker safety. This novel sanitary treatment using EF fumigation on imported agricultural machinery could be an effective method without causing mechanical damage.

Studying the effect of dusting with ethyl formate on the physical traits of some Iraqi date cultivars

The current study aimed to use three cultivars of Iraqi dates in the date stage, AlZuhdi hard, Sayer semi-hard and soft Paraben) and fumigating these dates with ethyl formate to preserve them and studying the physical traits of the dates under study in three periods (the pre-storage period, the three-month post-storage period and the six-month storage period).The physical traits included (total soluble solids, pH, viscosity, relative viscosity, surface tension, density, refractive index, and electrical conductivity. Keywords: Dates Dusting; Ethyl Formate; Al-Zuhdi; Paraben; Sayer.

Optimizing ethyl formate fumigation in greenhouse cucurbit crops for efficient control of major agricultural pests, Myzus persicae and Thrips palmi

BackgroundEthyl formate (EF) is naturally occurring volatile compound used as quarantine fumigant for pest control. Recently, conversion of uses of EF was tried from quarantine to agricultural field due to its promising efficacy. However, there is a lack of studies on the residue pattern on crops and soil and the phytotoxic mechanism of EF in greenhouse environment. This study aimed to evaluate the efficacy, residue analysis, and phytotoxicity of EF fumigation in controlling Myzus persicae and Thrips palmi, on cucurbit crops and establish an optimized fumigation strategy for use in greenhouses.ResultsThe results showed that EF was more effective against M. persicae than against T. palmi. Residue analysis indicated that EF rapidly decomposed and was not retained after 30 min in leaves and 2 h in soil after fumigation, suggesting the potential for residue-free pest control. Phytotoxicity test revealed that watermelon was the most sensitive crop to EF, and H2O2 accumulation was observed above a concentration of 7.5 g/m3. A strategy to reduce phytotoxicity with sodium bicarbonate during fumigation showed promising results in reducing phytotoxic effects on the crops. The optimized EF fumigation with 6 g/m3 was applied in a greenhouse, resulting in 100% and 40% mortality of M. persicae and T. palmi, respectively, with no notable phytotoxicity and EF residue in the treated crops and soil.ConclusionThis study demonstrates that optimized EF fumigation can be an environmentally sustainable method for controlling pests in greenhouses, paving the way for improved pest management practices and sustainable agriculture. Further research is needed to validate these findings and explore the potential of EF fumigation for other crops and pests.Graphical

Structure-Activity relationship and reaction mechanisms of the Cu/PSAC-Nx catalysts in the oxidation carbonylation of ethanol to diethyl carbonate

Cu catalysts supported on nitrogen-doped carbon with ultra-high specific surface area (2726 m2⋅g−1) derived from peanut shells (PSAC-Nx) were fabricated and investigated in the oxidative carbonylation of ethanol to diethyl carbonate (DEC). The Cu/PSAC-Nx catalysts exhibited superior catalytic performance with a maximum STYDEC of 3371 mg·g−1·h−1, attributed to the higher surface Cu0 and Cu+ concentration. Both Cu0 and Cu+ acted as the active species that accelerated the activation of ethanol molecules and promoted the insertion of CO, respectively, in the DEC synthesis. Among the four by-products, diethoxyethane preferred to be generated at higher temperatures or extended reaction time, while acetaldehyde and ethyl acetate tended to be produced at the Cu2+ species and ethyl formate was inclined to be created at a higher oxygen fraction. This work provided theoretical and experimental guidance for the rational design of efficient catalysts and the optimization of reaction conditions for the ethanol oxidative carbonylation to DEC.

Acute toxicity of ethyl formate to nontarget organisms and reduction effect of sodium silicate on ethyl formate-induced phytotoxicity

Acute toxicity of ethyl formate to nontarget organisms and reduction effect of sodium silicate on ethyl formate-induced phytotoxicity

Photo-thermal Cooperative Carbonylation of Ethanol with CO2 on Cu2 O-SrTiCuO3-x.

Carbonylation of ethanol with CO2 as carbonyl source into value-added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO2 in that the harsh conditions result in undesired activation of α-C-H and even cleavage of C-C bond in ethanol to deteriorate the specific activation of O-H bond. Herein, we propose a photo-thermal cooperative strategy for carbonylation of ethanol with CO2 , in which CO2 is activated to reactive CO via photo-catalysis with the assistance of *H from thermally-catalyzed dissociation of alcoholic O-H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO3-x supported Cu2 O (Cu2 O-SrTiCuO3-x ) has been designed. A production of up to 320 μmol g-1 h-1 for ethyl formate with a selectivity of 85.6 % to targeted alcoholic O-H activation has been afforded in photo-thermal assisted gas-solid process under 3.29 W cm-1 of UV/Vis light irradiation (144 °C) and 0.2 MPa CO2 . In the photo-driven activation of CO2 and following carbonylation, CO2 activation energy decreases to 12.6 kJ mol-1 , and the cleavage of alcoholic α-C-H bond has been suppressed.

Photo‐thermal Cooperative Carbonylation of Ethanol with CO2 on Cu2O‐SrTiCuO3‐x

AbstractCarbonylation of ethanol with CO2 as carbonyl source into value‐added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO2 in that the harsh conditions result in undesired activation of α‐C−H and even cleavage of C−C bond in ethanol to deteriorate the specific activation of O−H bond. Herein, we propose a photo‐thermal cooperative strategy for carbonylation of ethanol with CO2, in which CO2 is activated to reactive CO via photo‐catalysis with the assistance of *H from thermally‐catalyzed dissociation of alcoholic O−H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO3‐x supported Cu2O (Cu2O‐SrTiCuO3‐x) has been designed. A production of up to 320 μmol g−1 h−1 for ethyl formate with a selectivity of 85.6 % to targeted alcoholic O−H activation has been afforded in photo‐thermal assisted gas‐solid process under 3.29 W cm−1 of UV/Vis light irradiation (144 °C) and 0.2 MPa CO2. In the photo‐driven activation of CO2 and following carbonylation, CO2 activation energy decreases to 12.6 kJ mol−1, and the cleavage of alcoholic α‐C−H bond has been suppressed.

Synthesis and phosphonylation of 6-methyl-4-aryl-2-thio-1,2,3,4-tetrahydropyrimidine5-carboxylic acids ethyl esters

A new series of 6-methyl-4-aryl-2-thio-1,2,3,4-tetrahydropyrimidine-5-carboxylic acids ethyl esters was synthesized. The reaction of the obtained esters with dimethyl 2-chloroethynylphosphonate leads to the selective formation of new ethyl 3-(dimethoxyphosphoryl)-5-aryl-7-methyl-5 H -thiazolo[3,2- a ]pyrimidine-6-carboxylates.

Development of a Concurrent Treatment Technique of Ethyl Formate and Mixtures (Nitrogen, Phosphine) to Control Citrus Mealybug (Planococcus citri).

Currently, the fumigant ethyl formate (EF) is stored as a liquified gas in metal cylinders mixed with carbon dioxide (CO2), but this product type is expensive to manufacture, transport, and maintain in cylinders. To address these problems, we developed a new EF fumigation technique with a nitrogen (N2) carrier. In this report, the susceptibility of citrus mealybugs, one of the most resistant mealybugs to fumigants, to EF was assessed; the phytotoxicity of an EF + N2 concurrent treatment applied to banana fruit was examined to evaluate the efficacy compared to the current EF + CO2 product; and the increased efficacy with a phosphine (PH3) addition to EF + N2 was also assessed. Concurrent treatment of EF and N2 was performed at an LC50 concentration of EF. N2 was applied in seven doses from concentrations of 79% to 95%. The phytotoxicity of EF to bananas was assessed by applying EF at 35 mg/L with N2 at 79%, and the color, sugar content, and weight loss of bananas were measured for 14 days after treatment. The EF with N2 treatment resulted in more than 50% mortality at all growth stages of the mealybug, and there was no significant difference between the untreated and treated banana fruits. EF mixed with PH3 showed a higher efficacy than treatment with EF alone, but only a slight increase in efficacy was observed when the PH3 concentration increased. These results indicate that concurrent treatment with EF and N2 can be used to control mealybugs on banana fruits, and combined treatment with EF and PH3 can also enhance the efficacy against mealybugs.

Solid-liquid phase equilibrium and thermodynamic properties analysis of Bazedoxifene acetate in fifteen kinds of mono-solvents

Crystallization is widely used for the isolation and purification of active pharmaceutical ingredients (APIs) in the final manufacturing stage. Bazedoxifene (BZD) acetate, classified as a third-generation selective estrogen receptor modulator, is employed in the treatment of postmenopausal osteoporosis. This work reports the equilibrium solubility data of BZD acetate in fifteen different mono-solvents, including methanol, ethanol, n-propanol, i-propanol, n-butanol, ethyl formate, methyl acetate, ethyl acetate, acetone, 2-butanone, cyclohexanone, tetrahydrofuran (THF), 2-methyltetrahydrofurane (2-MeTHF), 1,4-dioxane and acetonitrile (ACN), within the temperature range “T = 283.15–323.15 K” under p = 0.1 MPa. The solubilities of BZD acetate in various solvents increase with increasing temperature. Among the alcoholic solvents, the solubility order is as follows: methanol > ethanol > n-propanol > n-butanol > i-propanol. In esters solvent, the solubility of BZD acetate decreases in the following order: methyl acetate > ethyl acetate > ethyl formate. For ketones solvent, the solubility decreases in the following order: cyclohexanone > acetone > 2-butanone. The maximum value of BZD acetate solubility was 0.011 mol·mol−1 in tetrahydrofuran at T = 323.15 K, but the least data was found in ethyl formate at 283.15 K. Four thermodynamic models, i.e., the Yaws model, modified Apelblat model, λh model, and Wilson model were applied to fit the solubility data of BZD acetate in different solvents. Among them, the Wilson model represents the most accurate fitting outcomes. Finally, the thermodynamic functions of mixing (including enthalpy, entropy, and Gibbs energy) were calculated, and the results indicate a mixing process that is both spontaneous and driven by entropy. The solubility data, correlated models, and derived thermodynamic functions present essential thermodynamic fundamentals for the industrial production of BZD acetate crystallization, facilitating efficient separation and purification.

Measurements of the laminar burning velocities of small alkyl esters using the heat flux method: A comparative study

Consistent datasets of the laminar burning velocity, LBV, for homologous fuels are indispensable for the elucidation of the structure-reactivity trends and the development and validation of pertinent detailed kinetic models. In the present study, all available LBV measurements for small alkyl esters obtained using the heat flux method have been reviewed. New results of the LBV for methyl propionate + air flames employing this method have been acquired at atmospheric pressure and initial gas temperatures from 298 to 348 K over equivalence ratios, ɸ = 0.7–1.5. Earlier experimental data for alkyl esters scattered across non-archival reports were re-examined and corrected when necessary. To prove the validity of the correction, additional LBV measurements for methyl formate and methyl butanoate were performed as well, and successfully demonstrated the consistency of the data obtained using different installations over an extended period of time. Then, the LBV of different families, such as methyl esters of various acids, formates, and acetates, along with isomers, were compared and structure-reactivity trends were assessed. Furthermore, the detailed kinetic mechanism of the authors was expanded by the reactions of methyl propionate and successfully compared with the LBV measurements for methyl formate, methyl acetate, methyl propionate, and ethyl formate. Distinct reactions controlling their flame propagation were revealed using sensitivity analysis and the origin of their rate constants is briefly discussed.

Direct Observation of the Ethyl Radical in the Pyrolysis of Ethane.

We report the first direct detection of ethyl radical in the pyrolysis of ethane. Observation of this vital intermediate was made possible in this extremely reactive environment by the use of a microreactor coupled with synchrotron radiation and photoelectron photoion coincidence (PEPICO) spectroscopy, despite its short lifetime and low concentration. Together with ab-initio master equation-calculated rates and fully coupled computational fluid dynamics simulations, our measurements show that even under the low pressures and short residence times in our experiment, ethyl formation can only be explained by bimolecular reactions; the most important is the catalytic attack of ethane by H atoms, which are then regenerated by decomposition of the nascent ethyl radicals. Our results complete the observation of all hypothesized intermediates in this industrially important process and highlight the need for further studies under additional conditions using similar methods to improve existing models and optimize process chemistries.

Direct Observation of the Ethyl Radical in the Pyrolysis of Ethane

AbstractWe report the first direct detection of ethyl radical in the pyrolysis of ethane. Observation of this vital intermediate was made possible in this extremely reactive environment by the use of a microreactor coupled with synchrotron radiation and photoelectron photoion coincidence (PEPICO) spectroscopy, despite its short lifetime and low concentration. Together with ab‐initio master equation‐calculated rates and fully coupled computational fluid dynamics simulations, our measurements show that even under the low pressures and short residence times in our experiment, ethyl formation can only be explained by bimolecular reactions; the most important is the catalytic attack of ethane by H atoms, which are then regenerated by decomposition of the nascent ethyl radicals. Our results complete the observation of all hypothesized intermediates in this industrially important process and highlight the need for further studies under additional conditions using similar methods to improve existing models and optimize process chemistries.

A Novel Ethyl Formate Fumigation Strategy for Managing Yellow Tea Thrips (Scirtothrips dorsalis) in Greenhouse Cultivated Mangoes and Post-Harvest Fruits.

The effects of climate change and shifting consumer preferences for tropical/subtropical mango fruits have accelerated their greenhouse cultivation in South Korea, which has consequently exacerbated the risk of unexpected or exotic insect pest outbreaks. This study used the pest risk analysis (PRA) of greenhouse-cultivated mangoes provided by the Animal & Plant Quarantine Agency in Korea to evaluate the potential of ethyl formate (EF) fumigation as a new pest management strategy against the yellow tea thrips (Scirtothrips dorsalis), which is considered a surrogate pest in the thrips group according to the PRA. The efficacy and phytotoxicity of EF were evaluated in greenhouse-cultivated mango tree (Irwin variety) and post-harvest mango fruit scenarios. EF efficacy ranged from 6.25 to 6.89 g∙h/m³ for lethal concentration time (LCt)50 and from 17.10 to 18.18 g∙h/m³ for LCt99, indicating similar efficacy across both scenarios. Application of 10 g/m³ EF for 4 h at 23 °C could effectively control S. dorsalis (100% mortality) without causing phytotoxic damage to the greenhouse-cultivated mango trees, while post-harvest mango fruit fumigation with 15 g/m³ EF for 4 h at 10 °C showed potential for complete disinfestation of S. dorsalis without compromising fruit quality.

Efficacy of the Fumigants Propylene Oxide and Ethyl Formate to Control Two Pest Species of Dry-Cured Hams

The ham mite Tyrophagus putrescentiae and the red-legged ham beetle Necrobia rufipes are harmful pests to several high-valued stored products. The regulatory phase-out of the fumigant methyl bromide necessitates the search for alternative fumigants. Propylene oxide (PPO) and ethyl formate (EF) were therefore evaluated in the laboratory for controlling these pests of dry-cured hams. Concentration–mortality studies at 25 °C of PPO and EF found that the mobile stages of the mites were very susceptible to low concentrations of 10 mg/L and less of each gas, while mite eggs were very tolerant and required 20 mg/L for PPO and 80 mg/L of EF for 100% mortality. Mixed life stage cultures of mites and beetles were treated for 24 h with either PPO or EF at 1× and 2× the estimated 99% lethal doses and confirmed effectiveness for controlling simulated pest populations. The sorptive properties of each gas in chambers with ham pieces, dog food kibbles, or fish meal were minimal for a reduction in mite toxicity when compared to treatments in empty chambers. There was no evidence that any desorbed gas occurred at a level toxic to mite eggs in any of the fumigated commodities. These fumigation studies with ham pests support further work with PPO and EF on any changes in the sensory quality of dry-cured hams for human taste and for commercial-scale fumigations toward regulatory approval.

Synthesis and crystal structure of a mixed-ligand zinc(II) complex derived from ethyl (2,6-dimethylphenylcarbamoyl) formate and 1,10-phenanthroline

ABSTRACT. A mixed-ligand zinc(II) complex, [Zn(Hpma)(phen)Cl] (where Hpma– = N-(2,6-dimethylphenyl)oxamate and phen = 1,10-phenanthroline), has been prepared by the reaction of zinc chloride, ethyl (2,6-dimethylphenylcarbamoyl)formate (Hdmp) and 1,10-phenanthroline under basic conditions in dimethylformamide. The structure of the complex was characterised by elemental analysis, IR, 1H-NMR, UV-Vis absorption and X-ray crystallography. The metal complex crystallises in the monoclinic system (space group P21/c) and is composed of the five-coordinate zinc ion in a distorted spherical square pyramidal geometry. Stabilisation of single crystals occurs through hydrogen bonds and π-π stacking interactions.
 
 KEY WORDS: Zinc(II), N-(2,6-Dimethylphenyl)oxamate, 1,10-Phenanthroline, Crystal structure, Hydrogen bonding, π-π Stacking, Mixed-ligand
 Bull. Chem. Soc. Ethiop. 2023, 37(4), 891-900. 
 DOI: https://dx.doi.org/10.4314/bcse.v37i4.7

Confirmatory evaluation of eFUME for control of brown marmorated stink bug, Halyomorpha halys (Hemiptera: Pentatomidae).

The governments of Australia and New Zealand require a phytosanitary treatment to control adult brown marmorated stink bug, Halyomorpha halys (Stål) (Hemiptera: Pentatomidae), as overwintering aggregations have been intercepted in the importation pathway of various nonhorticultural consignments, including vehicles. The commercialized fumigant, eFUME, a 16.7% by mass dilution of ethyl formate in carbon dioxide, resulted in complete control of ca. 1,000 field-collected, naturally diapausing adult H. halys in each of 3 independent trials at 10 ± 0.5 °C (x¯±2s) when ethyl formate levels in enclosure headspace were maintained steady-state at ca. 14.5 mg/liter for 4 h to yield Ct exposures ranging from 57.9 to 63.1 mg/liter h. Consistent with previous findings where greenhouse reared H. halys were controlled using laboratory formulations of this ethyl formate-carbon dioxide mixture, these confirmatory methods and results further inform technical and operational features of commercial practice.

Effective Phytosanitary Treatment for Export of Oriental Melons (Cucumis melo var L.) Using Ethyl Formate and Modified Atmosphere Packaging to Control Trialeurodes vaporariorum (Hemiptera: Aleyrodidae).

Trialeurodes vaporariorum (Hemiptera: Aleyrodidae), commonly known as greenhouse whitefly, is one of the main insect pests of Oriental melon (Cucumis melo var L.) in South Korea. T. vaporariorum is of concern as a quarantine pest for the exportation of C. melo in Southeast Asian countries. Due to future restrictions on the use of methyl bromide (MB) during quarantine, ethyl formate (EF) represents a potential alternative. In this study, we evaluated EF for its efficacy (probit-9 values) in enabling the export of Oriental melons. The probit-9 value of EF for controlling T. vaporariorum was 3.02 g·h/m3 after 2 h of fumigation. We also assessed the phytotoxicity of EF on melons when using modified atmosphere packaging (MAP) under low-temperature conditions, which is required for export and trade, to extend shelf-life. In scaled-up trials, we found 8 g/m3 EF for 2 h at 5 °C to be suitable as a new phytosanitary treatment against greenhouse whitefly for exported Oriental melons when using MAP. No phytotoxic damage was found 28 d after fumigation at 5 °C in terms of five quality parameters (firmness, sugar content, mass loss, color change, and external damage).

Influence of ethanol content on the detection of volatile components in Huangjiu

Huangjiu (Chinese rice wine) is a traditional Chinese fermented wine with a unique flavor. The components of this wine are complex, and the ethanol content of different Huangjiu preparations varies greatly. In this study, changes in the chromatographic peak areas of the volatile components of Huangjiu samples with different ethanol contents were measured using headspace-gas chromatography (HS-GC). The influence of ethanol on the quantitative detection of different volatile components of Huangjiu at gas-liquid equilibrium was also analyzed. When the ethanol content of Huangjiu was in the range of 10%-19% vol, the peak areas of 16 volatile components (i. e., sec-butanol, n-propanol, isobutanol, n-butanol, isoamyl alcohol, β-phenyl-ethanol, acetaldehyde, isovaleraldehyde, benzaldehyde, ethyl formate, ethyl acetate, isobutyl acetate, isoamyl acetate, ethyl hexanoate, ethyl lactate, and diethyl succinate) were negatively correlated with the ethanol content. Increases in the ethanol content of the liquor changed the gas-liquid equilibrium of most other trace volatile components. In addition, only the peak area of acetal was positively correlated with ethanol content. The content of acetal in Huangjiu was affected by the alcohol content, and its decomposition reaction occurred along with the dilution process. The influence coefficient of ethanol content on the peak area of the above compounds ranged from -12.4% to 4.9%. The vapor pressure of most volatile components decreased with increasing ethanol content, and different components were affected in different ways. Compared with those of other components, the peak areas of methanol, furfural, and acetic acid were less affected by the ethanol content. These components were also affected by other factors, such as ionization and chemical reactions occurring during the dilution process. When different wine samples were adjusted to the same ethanol content, the concentration of volatile components in these samples became proportional to the total chromatographic peak area and the influence of the matrix effect of ethanol on the quantitative analysis was effectively eliminated. Thus, when researchers use pretreatment methods based on the principle of gas-liquid balance to carry out the quantitative detection of flavor components, they should adjust different rice wine samples to the same alcohol content to effectively control the matrix effect caused by differences in ethanol content and achieve accurate quantitative analysis.

Radiative efficiencies and global warming potentials of agricultural fumigants

A rounded assessment of the environmental impacts of fumigants used within the agricultural sector must consider the potential climate impacts of their release into the atmosphere. Within policy settings, the 100-year Global Warming Potential (GWP100) is the most commonly used metric. While GWP100 values are available for the widely used fumigant sulfuryl fluoride, no estimates are available for 4 alternative fumigants: ethyl formate, cyanogen, hydrogen cyanide and phosphine. Existing laboratory measurements of the infrared spectra and reaction rate coefficients of these gases are used to produce new estimates of their radiative efficiencies and atmospheric lifetimes, and the first estimates of their GWP100 and other climate emission metrics. Although uncertainties are considerable, their GWP100 values are estimated to be no more than 2% of the GWP100 value of sulfuryl fluoride. These new estimates will enable informed estimates of the climate impact of the use of these fumigants, which must account for the differing usage and release rates to achieve the same fumigant efficacy.