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The arylhydrazones were treated with ethyl iodide, ethyl chloroacetate to afford the alkyl derivatives, which cyclized to the pyrazole derivatives, also, arylhydrazones were reacted with ethyl chlo...

Attosecond chronoscopy has revealed small but measurable delays in photoionization, characterized by the ejection of an electron on absorption of a single photon. Ionization-delay measurements in atomic targets provide a wealth of information about the timing of the photoelectric effect, resonances, electron correlations and transport. However, extending this approach to molecules presents challenges, such as identifying the correct ionization channels and the effect of the anisotropic molecular landscape on the measured delays. Here, we measure ionization delays from ethyl iodide around a giant dipole resonance. By using the theoretical value for the iodine atom as a reference, we disentangle the contribution from the functional ethyl group, which is responsible for the characteristic chemical reactivity of a molecule. We find a substantial additional delay caused by the presence of a functional group, which encodes the effect of the molecular potential on the departing electron. Such information is inaccessible to the conventional approach of measuring photoionization cross-sections. The results establish ionization-delay measurements as a valuable tool in investigating the electronic properties of molecules. Ionization delays from ethyl iodide around a giant dipole resonance are measured by attosecond streaking spectroscopy. Using theoretical knowledge of the iodine atom as a reference, the contribution of the functional ethyl group can be obtained.

Novel 1,3-cyclopentathiazine and pyrimidothiazine derivatives were synthesized starting from 7-benzyl-4-phenylcyclopenta[d][1,3]thiazin-2-amine (CTA) prepared by a one-pot multicomponent reaction of cyclopentanone, benzaldehyde, and thiourea. Cyclocondensation of CTA with benzylidenemalononitrile gave a pyrimidothiazine. Oxidation of cyclopentathiazine with hydrogen peroxide afforded the corresponding epoxide, while its alkylation with ethyl iodide yielded an N-ethyl derivative. Cyclopentylidenemalononitrile was reacted with formaline and carbon disulfide to obtain pyridine-4-carbonitrile and thiapyrane, respectively, and the reactions of cyclopentylidenemalononitrile with aryl isocyanate and aryl isothiocyanate gave condensed diimino-substituted cyclopentanaphthyridine-1,6-dione and dithiaacenaphthylene-3,8-diylidedibenzamide, respectively. Heating cyclopentanone with benzoyl isothiocyanate and benzoyl chloride produced a sulfide derivative and an enolic dione, respectively. The structures of the newly synthesized compounds were confirmed by spectral analysis, and some products were screened for anticancer activity.

The catalytic system for ethanol carbonylation consists of rhodium with hydroiodic acid, ethyl iodide and lithium iodide as promoters exhibited an attractive catalytic activity at low water content (

Isobaric vapour-liquid equilibrium (VLE) data for the binary systems of ethyl iodide with ethanol, propionic acid and ethyl propionate at 101.3 kPa were measured in an Ellis equilibrium still, and the thermodynamic consistency of the experimental data was checked by the Herington area method and Van Ness method. The non-random two-liquid (NRTL), universal quasichemical (UNIQUAC), and Wilson models were applied to correlate the measured VLE data. All three models represent the experimental values quite well. The system (ethyl iodide + ethanol) presents a minimum azeotropic boiling point at 101.3 kPa, in which the azeotropic temperature and composition are 336.08 K and 63.445 mol% (ethyl iodide). The azeotropic behavior was not found in the other two systems.

In the current research work we have reported a series of N -aryl - 2,3-dihydrobenzo[1,4]dioxine-6-sulfonamides 3 and their N -substituted derivatives 6 and 7 , obtained from 3 with benzyl chloride and ethyl iodide, respectively. The synthesis was accomplished as a multistep sequence. The structural confirmations were established by 1 H NMR, IR and EIMS spectral techniques. Butyrylcholinesterase (BChE), acetylcholinesterase (AChE) and lipoxygenase (LOX) enzymes were used in this study. It was observed that most of the compounds prepared exhibit a moderate activity against BChE and AChE but promisingly good activity against lipoxygenase. Among the parent sulfonamides 3a , 3b , 3c and 3e showed the proficient antimicrobial activities, while from the derivatives 6a , 6c , 7a , 7b and 7c were found active against the selected panel of bacterial and fungal species. Hemolytic activity was also conducted to check their therapeutic utility. All the compounds were computationally docked against LOX, BChE and AChE enzymes.

Dimethoxymethane (CH3OCH2OCH3, DMM) is the smallest oxymethylene ether and currently discussed as a promising alternative diesel fuel. For an adequate modeling of the DMM combustion chemistry, reliable kinetic parameters are needed. In the present work, shock-tube studies are presented on the kinetics of the DMM + H reaction (R1) and the kinetics of the unimolecular decomposition of DMM (R2). In the case of reaction (R1), ethyl iodide pyrolysis was used as H-atom source. For both reactions, rate coefficients were determined from H-atom concentration-time profiles monitored with atom resonance absorption spectroscopy (ARAS). The following overall rate coefficients were obtained: k1(T) = (1.5 ± 0.7) × 1013 exp(− 1040 K/T) cm3 mol−1 s−1 (T = 850 − 1100 K, p ∼ 1.1 bar, bath gas: Ar) and k2(T) = (6.2 ± 1.9) × 1013 exp(− 31830 K/T) s−1 (T = 1100 − 1550 K, p ∼ 1.1 bar, bath gas: Ar). Additionally, the pyrolysis of DMM was investigated in shock-tube experiments with high-repetition time-of-flight mass-spectrometric (TOF-MS) detection (T = 1100 − 1700 K, p = 0.9 − 1.3 bar, bath gas: Ne). Concentration-time profiles of DMM, CO, CH2O, C2H6, C2H4, and CH4 were recorded simultaneously. Both the ARAS and the TOF-MS profiles can be reproduced with reasonable accuracy by simulation with a recent DMM oxidation mechanism from the literature. Mechanistic aspects are elucidated and possible modifications are proposed and discussed.

We report here the synthesis of a series of N -aryl-2,3-dihydrobenzo[1,4]dioxine-6-sulfonamide and its N -substituted derivatives with benzyl chloride and ethyl iodide. Initially, 2,3-dihydrobenzo[1,4]dioxine-6-sulfonyl chloride (1) was subjected to react with various aryl amines (2a-e) to afford parent compounds N -aryl-2,3-dihydrobenzo[1,4]dioxine-6-sulfonamide (3a-e). At second step, these parent compounds were reacted with benzyl chloride (4) and ethyl iodide (5) as to synthesize N -benzyl- N -aryl-2,3-dihydrobenzo[1,4]dioxine-6-sulfonamide (6a-e) and N -ethyl- N -aryl-2,3-dihydrobenzo[1,4]dioxine-6-sulfonamide (7a-e) in the presence of lithium hydride and N , Nꞌ -dimethylformamide respectively. FT-IR, Nuclear Magnetic Resonance ( 1 H-NMR) and Mass Spectrometry (MS) techniques were used to investigate the structures of these synthesized compounds. A fingerprinted study was conducted against some enzymes like butyrylcholin-esterase (BChE), acetylcholinesterase (AChE) and lipoxygenase (LOX). This study revealed that most of them demonstrated a moderate activity against butyrylcholinesterase (BChE) and acetylcholinesterase (AChE) however promisingly a good activity against lipoxygenase enzyme was observed. Finally, an antimicrobial and hemolytic activities of these sulfonamides were probed which confirmed that the parent sulfonamides 3b have the proficient antimicrobial activities, while the derivatives 6a, 7a, 7b and 7c explored a good activity against the selected panel of bacterial and fungal species. All the compounds were further computationally docked against (LOX), (BChE) and (AChE) enzymes and these interaction highlighted the importance of sulfonamides in the inhibition of the target enzymes.

A method has been proposed for the capture and recovery of organic iodides produced in the iodative dehydrogenation of ethane to ethylene. Bench-scale experiments have identified ethyl iodide as we...

We report the comparison of a series of 2D molecular crystals formed from the intermediates of the dehalogenation reaction of iodoethane versus various fluorinated iodoalkanes on Cu(111). High-resolution scanning tunneling microscopy enables us to distinguish the alkyl groups from the iodine atoms, and we find that the ethyl groups and iodine atoms formed from the dissociation of ethyl iodide are well mixed. However, fluorination of the alkyl tail changes this behavior and leads to local segregation of the two species on the surface. We postulate that the low-polarizability and relatively large dipole moment of the fluorinated species drive the ordered assemblies of the fluorinated alkyl species on the surface and discuss this in the context of how solvophobicity can drive the clustering of fluorinated groups and, hence, phase separation.

The behavior of the benzoxazinone derivative 1 toward nitrogen and carbon nucleophiles was investigated and yielded compounds 2–4, 6, and 7. The oxadiazol derivatives 9–12 were obtained from the interaction of hydrazide 8 with benzoic acid in the presence of phosphoryl chloride and/or carbon disulfide in the presence of KOH followed by alkylation with ethyl iodide and hydrazinolysis with hydrazine hydrate, respectively. The quinazolinone derivatives 13 and 22 were utilized to construct new heterocyclic systems 15–21, 23, and 24 via interaction with different carbon electrophiles. Some of the newly synthesized compounds were characterized on the bases of spectroscopic data. Some of the synthesized compounds were screened for antimicrobial activity.

International audience; Femtosecond time-resolved velocity map ion imaging experiments are reported on the second absorption band (B-band) of ethyl iodide at 201.19 and 200.08 nm, corresponding to the 000 and 1810 transitions, i.e., the origin of the band and the first most intense vibronic state assigned to one quantum of excitation in the methyl torsion mode. Electronic predissociation lifetimes and the temporal evolution of the anisotropy have been determined by time-resolved resonance-enhanced multiphoton ionization of iodine and ethyl fragment images. A shorter lifetime measured at the origin of the band in comparison with methyl iodide indicates that predissociation in ethyl iodide is more favorable due to a stronger coupling between the initial Rydberg state and the valence repulsive state correlating with the dissociation fragments. Moreover, vibrational activity in the methyl torsion in the Rydberg state seems to enhance the probability of transfer of population to the valence repulsive state leading to a faster dissociation. The perpendicular character of the transition at early times and the loss of anisotropy as a function of time have been determined from the time-resolved angular distributions of the iodine and ethyl ion images. The initial anisotropy value is consistent with a purely perpendicular transition compatible with the excitation of the [6A′′, 7A′] states with a minor parallel component to the C–I bond. The loss of initial anisotropy over time highlights the parent molecular rotation during predissociation and is compatible with a rotational temperature of the parent molecule of 100 K.

The advancement of attosecond chronoscopy has made it possible to reveal ultrashort time dynamics of photoionization [1]. Ionization delay measurements in atomic targets provide a wealth of information about the timing of the photoelectric effect [2], resonances, electron correlations and transport. The extension of this approach to molecules, however, presents great challenges. In addition to the difficulty of identifying correct ionization channels, it is hard to disentangle the role of the anisotropic molecular landscape from the delays inherent to the excitation process itself. Here, we present the measurements of ionization delays from ethyl iodide around the 4d giant dipole resonance of iodine. We employ attosecond streaking spectroscopy, which enables to disentangle the contribution to the delay from the functional ethyl group, being responsible for the characteristic chemical reactivity of the molecule. An attosecond extreme ultraviolet (XUV) pulse ionizes the molecule around the energy of the giant resonance and the released electron is exposed to the ponderomotive force of a synchronized near-infrared (NIR) field, which yields a streaking spectrogram (see figure). Comparative phase analysis of the spectrograms corresponding to iodine 4d and neon 2p emission permits extracting overall photoemission delays for ethyl iodide. The data is recorded for multiple photon energies around the iodine 4d resonance and compared to classical Wigner propagation [3] and quantum scattering [4] calculations. Here the outgoing electron, produced via inner shell ionization of the iodine atom in ethyl iodide, and thereby hardly influenced by the molecular potential during the birth process, acquires the necessary information about the influence of the functional ethyl group during its propagation. We find significant delay contributions that can distinguish between different functional groups, providing a sensitive probe of the local molecular environment [5]. This would stimulate to perform further angle resolved measurements in molecules to probe the potential landscape in three dimension.

Carbonylation of ethanol is a potentially attractive route for propionic acid production, while its industrial practice is greatly hampered by the low space-time yield. To improve the reaction rate of ethanol carbonylation, a series of diphosphine ligands were investigated in the homogeneous rhodium complex catalyst system. The catalyst activity and stability were enhanced by using bis(diphenylphosphino)methane monosulfide (dppmS) as hemilabile diphosphine ligand and the space-time yield of propionic acid was increased significantly. In the presence of dppmS, not only the effect of ligand addition, the content of ethyl iodide, lithium iodide, and rhodium catalyst on catalytic performance were carried out, but also the reaction conditions were systematically investigated in a titanium alloy autoclave reactor. Consequently, the carbonyl space-time yield reached 6.21 mol·L−1·h−1 under the optimal reaction conditions. Additionally, the corresponding mechanism of ethanol carbonylation with addition of dppmS was proposed. A kinetic model of the reaction was established in the temperature range of 433–473 K. The reaction orders of catalyst, ethyl iodide, and iodide ion concentrations were determined to be 0.86, 0.36, and 0.20, respectively. The activation energy was found to be 25.23 kJ·mol−1. Residual error distribution n and a statistical test showed that the kinetic model is reasonable and acceptable.

While methanol carbonylation has been extensively studied, higher alcohol carbonylation has received relatively little attention, even though, for example, ethanol carbonylation could be a useful route for the production of propionates. Here we use Rh/Na13X to investigate the vapor phase carbonylation of ethanol with an ethyl iodide co-feed. In the base case, the catalyst is ∼40% selective to propionates, with the remainder forming ethylene and diethyl ether. Deposition of additional alkali can increase selectivities to ∼60%. Isotopic labeling of ethyl iodide demonstrates reversible formation of ethyl iodide from ethanol, and that preferential incorporation of ethyl iodide initiates the Rh-catalyzed carbonylation cycle. XPS and in situ X-ray absorption spectroscopy are consistent an active anionic Rh I iodide species at a zeolite exchange site. This proposed structure and the attendant catalytic reaction network are directly analogous to those of classic solution-phase Rh catalysts and other supported Rh catalysts. However, important differences are noted in the reaction orders and apparent activation barrier, which suggest that the rate of ethyl iodide formation is overall rate limiting under these conditions and for this catalyst.

Herein, we report the novel axially chiral bis-Ag(I)-MIC and, bis-Au(I)-MIC complexes bearing axially chiral bis-1,2,3-triazolium-derived mesoionic carbene (tz-MIC) ligands were synthesized. The enantiopure R-BINOL was employed as a basic unit to synthesize a axially chiral bis-1,2,3-triazolium-derived mesoionic carbene (tz-MIC) ligands (1–2)a. In particular, the axially chiral bis-1,2,3-triazolium-derived mesoionic carbene (tz-MIC) ligands (1–2)a, were obtained from the reaction of corresponding bis-1,2,3-triazole ligand precursor with methyl and ethyl iodide in 82−90% yields. Novel axially chiral bis-Ag(I)-MIC complexes (1 − 2)b, were prepared by the treatment of corresponding axially chiral bis-1,2,3-triazolium-derived mesoionic carbene (tz-MIC) iodide salts, (1 − 2)a, with Ag2O via in-situ deprotonation method in 69−86% yields. Novel axially chiral bis-Au(I)-MIC complex-2c was synthesized from their respective novel axially chiral bis-Ag(I)-MIC complex-2b, using transmetallation reaction with (SMe2)AuCl in 70% yield. All these novel axially chiral bis-Ag(I)-MIC and bis-Au(I)-MIC complexes were isolated for the first time and structurally characterized by 1H NMR and 13C{1H}-NMR spectroscopy, FT-IR spectroscopy, mass spectrometry, elemental analysis, specific optical rotation and, single crystal X-ray crystallography.

A novel green synthesis process about ethyl-β-Cyclodextrin have been investigated through the reaction between β-cyclodextrin and diethyl carbonate by used anhydrous potassium carbonate as catalyst in DMF. The influence of experimental factors including reaction time, the molar ratio of β-cyclodextrin to diethyl carbonate, reaction temperature and contents of anhydrous potassium carbonate on the average degree of substitution of ethyl-β-cyclodextrin were carried out by a design method of orthogonal experiments. The results shown that the average degree of substitution of ethyl-β-cyclodextrin can be depend on the reaction temperature and the molar ratio of raw material primarily. The optimal maximum average degree of substitution of ethyl-β-cyclodextrin is 6.0 when the molar ratio of β-cyclodextrin to diethyl carbonate, reaction temperature, reaction time and dosage of catalyst are 1:28, 120°C, 24h and 2.0 g, respectively. The structures of ethyl-β-cyclodextrin were characterized by TLC, IR, MS, 1H-NMR and 13C-NMR, and these results are concordant with former ones which synthesized ethyl-β-cyclodextrin by diethyl sulfate or ethyl iodide.

The photodissociation dynamics and stereodynamics of ethyl iodide from the origin of the second absorption B-band have been investigated combining pulsed slicFe imaging with resonance enhanced multiphoton ionization (REMPI) detection of all fragments, I(2P3/2), I*(2P1/2) and C2H5. The I*(2P1/2) atom action spectrum recorded as a function of the excitation wavelength permits one to identify and select the 000 origin of this band at 201.19 nm (49 704 cm−1). Translational energy distributions and angular distributions for all fragments and semiclassical Dixon's bipolar moments for the C2H5 fragment are presented and discussed along with high-level ab initio calculations of potential energy curves as a function of the C–I distance. A predissociative mechanism governs the dynamics where in a first step a bound Rydberg state corresponding to the 5pπI → 6sI transition is populated by the 201.19 nm-photon absorption. A curve crossing with a repulsive state located within the Franck–Condon geometry leads to direct dissociation into the major channel C2H5 + I*(2P1/2). A small amount of I(2P3/2) atoms is nevertheless observed and presumably attributed to a second curve crossing with a repulsive state from the A-band.

tert-Butyl dicarbonate (Boc2O) and ethyl iodide (EtI) reactions with uracil (U), thymine (T) and 6-methyluracil (6-MU) were performed following routine procedures in pyridine/DMF solvents and with DMAP as the catalyst. Among 20 synthesized compounds, a derivative of 6-methyluracil substituted by the Boc-pyridine moiety at the C5 position appeared unexpectedly. The NMR spectra confirmed the molecular structure of all uracil derivatives. Parallel quantum mechanical DFT calculations supported the experimental findings.

1-Benzyl-3-ethylbenzimidazolium iodide (1) and 1-benzyl-3-(2′-nitrilebenzyl)benzimidazolium bromide (2) were prepared by the reaction of 1-benzylbenzimidazole with ethyl iodide or 2-bromomethylbenzonitrile to act as N-heterocyclic carbene (NHC) precursors. Bis-NHC silver(I) complexes having halide (3a and 4a) as well as hexafluorophosphate (3b and 4b) counterions were yielded by the reaction of NHC precursors with silver(I) oxide. Subsequent reactions of the silver(I) halide/hexafluorophosphate complexes with [PdCl2(CNCH3)2] in methanol afforded the NHC palladium(II) complexes (5 and 6) via carbene transfer method. All synthesized compounds were fully characterized by analytical and spectrometric methods. Preliminary catalytic studies evinced that the nitrile-functionalized palladium(II)-NHC complex 6 is highly active in the oxidation of 1-octene as well as styrene in the presence of aqueous hydrogen peroxide as an oxidizing agent. Both the olefins were oxidized to their corresponding oxidized products with 45-52% conversion with moderate selectivity in the presence of NHC palladium complexes, which acted as oxidation catalysts. In order to investigate the suggested structure of the title complexes, density functional theory was used to find the stable structures of the palladium complexes and their isomers. Geometry parameters, molecular orbital energies, electronic energy, band gap, and vibrational frequencies were calculated.

Refluxing 3-perfluoroalkyl-6,7-dihydro-1H-indazol-4(5H)-ones with 4-fold excess of hydroxylamine hydrochloride in pyridine afforded their (E)-oximes. The obtained oximes were alkylated with ethyl iodide and acylated with carboxylic acids chlorides to obtain (E)-O-alkyl- and (E)-O-acyloximes respectively. Heating oximes in PPA at 120°C results in their aromatization by Semmler-Wolff reaction, hydrolysis of perfluoroalkyl groups, and generation of 4-amino-1-aryl-5,6-dimethyl-1H-indazole-3-carboxylic acids from of 3-tri-fluoromethylindazolone oximes and 1-(4-amino-1-aryl-5,6-dimethyl-1H-indazol-3-yl)-fluoroalkan-1-ones from of 3-perfluoroethyl- and 3-perfluoropropylindazolone oximes.

Ethanol carbonylation is a potential route to valuable C3 products. Here, Rh supported on porous, Cs-exchanged heteropolyacid Cs3PW12O40, is demonstrated as an effective catalyst for vapor-phase ethanol carbonylation, with higher selectivity and conversion to propionates than existing catalysts. Residual acidity or a Mo polyatom was strongly detrimental to yields. Propionate selectivity was maximized at 96% at 170 °C and with added H2O. The catalyst displayed stable selectivity over 30 h on stream and up to 77% conversion. Ethyl iodide is a required co-catalyst but at levels as low as 2% relative to ethanol. XPS and in situ XANES indicate partial Rh reduction, consistent with the formation of low-valent reactive intermediates and slow deactivation through formation of Rh nanoparticles. With further optimization and understanding, these Rh/heteropolyacid catalysts may lead to stable and selective catalysts for the production of propionates through ethanol carbonylation.

2-Thioxo/oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate derivatives 2a, 2b, 2c, 2d were prepared by the reaction of ethyl acetoacetate and thiourea or urea with aldehydes using NH4Cl as a catalyst. Compounds 2a and 2c reacted with mono and bihalogenated compounds such as ethyl iodide, chloroacetonitrile, epichlorohydrin, acetyl chloride, ethyl bromoacetate, chloroacetic acid, chloroacetylchloride, and/or oxalyl chloride to afford compounds 3, 4a, 4b, 5, 6a, 6b, 7, 8, 9 and 10, respectively. Compounds 2a, 2c, and 7 were allowed to react with p-fluorobenzaldehyde to yield the corresponding products 11a, 11b, and 12, respectively. Oxidation of 2a and 2c gave 2b, 13a, 13b, 14, 15, 16 dependent on the oxidizing agent used. Vilsmeiere-Haack formylation of 2a and 2b with POCl3/DMF afforded 17a and 17b. Chlorination of 2b and 2d gave the chlorinated derivative 18a and 18b, which reacted with thiourea to give thioureidopyrimidine 19a and 19b. Reactions of 2a with hydrazine monohydrate, semicarbazide hydrochloride, and sodium hydroxide gave compounds 20, 21, 22, respectively. The cytotoxicity and in vitro anticancer evaluation of some prepared compounds have been assessed against two different human tumor cell lines including breast adenocarcinoma MCF-7 and human hepatocellular carcinoma HepG2. Antimicrobial and antioxidant activities of some compounds were investigated. The newly synthesized compounds were characterized by IR, 1H-NMR, 13C-NMR, and mass spectral data.

Nanochemistry is an emerging new field of chemistry, in particular of solid-state chemistry, which emphasizes the study and development of preparation methods of useful materials with nanometer-size dimensions (1–100 nm), as defined by Geoffry Ozin, a pioneer in the field. The direct synthesis of metal complexes and organometallic compounds from zerovalent metals is a known methodology that was well developed during the past 165 years, since the first preparation of Zn(CH 2 CH 3 ) 2 by Frankland from the direct reaction of metallic zinc powder and ethyl iodide. Although comparatively, the dimensions of the simplest and smaller nanoparticles are a thousand times larger than the most common coordination or organometallic compounds, there are several interesting characteristics that may serve as bridges to extrapolate several of the synthetic tools developed around the direct synthesis of metal complexes toward the preparation of inorganic nanomaterials. First of all, the surface of inorganic nanomaterials (metallic, metal oxides, or metal chalcogenides, among several others) is very reactive and unstable, unless a coordinating surfactant is used to coat the surface. It is relatively easy to understand that the surfactant behaves as a coordination ligand and that it may play an important role not only on stabilization, but also on the control of the structure and properties of the resulting nanomaterial. Here, we discuss several bridging concepts among coordination compounds and nanochemistry, and present direct synthesis as a novel and useful synthetic tool for the preparation of several useful and interesting inorganic nanomaterials.

Two different approaches have been employed to enhance the reactivity of 1-alkyl-1,2-diphospholes – the introduction of electron-withdrawing groups either at the phosphorus atoms or in the para-position of the arene ring. The alkylation of sodium 1,2-diphospha-3,4,5-triphenylcyclopentadienide with alkyl halides Hal-CH2-R (R = CN, COOEt, OMe, CH2OEt) results in corresponding 1-alkyl-3,4,5-triphenyl-1,2-diphospholes (alkyl = CH2CN (1a), CH2COOEt (1b), CH2OMe (1c), and (CH2)2OEt (1d)), which spontaneously undergo the intermolecular [4 + 2] cycloaddition reactions at room temperature to form the mixture of the cycloadducts, 2a–c, respectively. However the alkylation of sodium 1,2-diphospha-3,4,5-tri(p-fluorophenyl)cyclopentadienide with ethyl iodide leads to stable 1-ethyl-3,4,5-tris(p-fluorophenyl)-1,2-diphosphole (1e), which forms the [4 + 2] cycloadduct 2,3,4,4a,5,6-hexa(p-fluorophenyl)-1-ethyl-1,7,7a-triphospha-4,7-(ethylphosphinidene)indene (2e) only upon heating up to 60 °C. With further heating to 120 °C with N-phenylmaleimide, the cycloadducts 2a–c and 2e undergo the retro-Diels–Alder reaction and form only one product of the [4 + 2] cycloaddition reaction 3a–с, 3e with good yields up to 65%.

The photoionization electron attachment ion mobility spectrometry (PI-EA-IMS), with photoelectrons formed by photoionization of organic compound like acetone, has been developed to study electron attachment reactions. With this apparatus, the rate constants for electron attachment to alkyl iodides including ethyl iodide (C 2 H 5 I), 1-propyl iodide (1-C 3 H 7 I), 1-butane iodide (1-C 4 H 9 I) and 2-propyl iodide (2-C 3 H 7 I) have been determined over the average electron energy from 0.29 to 0.96 eV. The rate constants are in the order of magnitude of ∼10 −9 cm 3 molecule −1 s −1 . The experimental measurements show that for straight-chain alkyl iodides, the values of the rate constants follow the order of: k (C 2 H 5 I) k (1-C 3 H 7 I) ≈ k (1-C 4 H 9 I) which can be explained by the energy threshold for the formation of iodine anion via dissociative electron attachment. For the isomers, 2-C 3 H 7 I has a lower rate constant than 1-C 3 H 7 I which may be caused by the effect of branched chain.

This study aims to optimize sodium iodide (NaI) derivatization headspace-GC/MS described in European Pharmacopoeia by using vitamin C as an alternative antioxidant for the determination of mutagenic alkyl toluenesulfonate impurities in an active pharmaceutical ingredient (API) of a candidate drug with an artemisinin derivative. Alkyl toluenesulfonates are transformed into their corresponding alkyl iodides (methyl iodide, ethyl iodide, propyl iodide, and isopropyl iodide) by utilizing the derivatization reagent NaI. Results show that the MS response of methyl iodide is a critical indicator of method robustness because of the deteriorating effects of methyl iodide on stability when sodium thiosulfate is used as an antioxidant originally described in the pharmacopoeia. With vitamin C as a newly developed antioxidant, the robustness of this method is improved significantly. The optimized method is further validated and applied successfully for the quality control and safety of the API of an artemisinin derivative.

Background Isatin as a product was first obtained from the oxidation of indigo dye by nitric acid and chromic acids by Otto Linne Erdman and Auguste Laurent in 1841. Objective This study presents the synthesis of some new isatin derivatives and examines their biological activities. Materials and methods 2-Cyano-N’-(5-nitro-2-oxoindolin-3-ylidene)acetohydrazide (2) reacted with some reagents, namely, salicylaldehyde, phenyl isothiocyanate, ethyl chloroacetate, ethyl iodide, ethyl cyanoacetate, thioglycolic acid, phenyl isothiocyanate, malononitrile, and hydrazine hydrate to produce compounds 3, 4, 5, 6, 8, 9, 10, 11, and 12, respectively. Moreover, compound 6 reacted with hydrazine hydrate to produce compound 7. Antimicrobial activities of some newly synthesized compounds were studied. Results Antioxidant, anticoagulant, and fibrinolytic activities of the new synthesized compounds (1–12) were studied. Compound 10 exhibited highest fibrinolytic activity. On the contrary, compound 12 exhibited highest anticoagulant activities. Moreover, it was noticed that compound 9 exhibited highest antioxidant activity. Conclusion In summary, 14 novel isatin derivatives were synthesized and screened for their antioxidant, anticoagulant, and fibrinolytic activities. Some compounds displayed moderate-to-excellent activities such as antioxidant, anticoagulant, and fibrinolytic agents.

In limited prior reports, molybdenum hexacarbonyl has been shown to be active in catalyzing ethylene carbonylation promoted by ethyl iodide. Here, we assess the productivity of this reaction with respect to various reaction parameters and provide an understanding of the mechanism by NMR and mass spectrometric studies of isotopically labeled reactants. 13C labeled reactants show that ethyl iodide promotes initiation but is not a participant in the primary catalytic cycle, in contrast to classical mechanisms for alcohol carbonylation with an iodide co-catalyst, such as in the Monsanto process. NMR spectroscopy shows incorporation of only one D from D2O into the carbon backbone of propionic acid products, and in a manner consistent with direct, reversible addition of ethylene to a Mo hydride intermediate. CO migratory insertion and a formal hydroxylation then yield propionic acid. Under the conditions described here, the overall cycle gives propionic acid in high selectivity and requiring low promoter loads.

It has been demonstrated that alkylzinc halides efficiently destroy the passivating film on the zinc-copper pair in the course of its alkylation with ethyl bromide to give ethylzinc bromide. The alkylzinc halides efficiency is comparable to that of ethyl iodide and exceeds that of salts of transition or non-transition metals as well as of ultraviolet irradiation. Addition of alkylzinc halides or metal salts as well as ultraviolet irradiation have practically no effect on the developed reaction. The results have demonstrated that the organometallic component of the binary systems is polyfunctional; this permits a generalization of known features of a number of known methods promoting direct synthesis of organometallic compounds.

A new type of tricyclic triazolooxazine derived N-heterocyclic carbene precursors were developed by the alkylation reaction of a tricyclic triazolooxazine framework. In particular, the reaction of 5a,6,7,8,9,9a-hexahydro-4H-benzo[b][1,2,3]triazolo[1,5-d][1,4]oxazine with methyl iodide and ethyl iodide yielded the tricyclic triazolooxazine derived N-heterocyclic carbene precursors, (1-2)a, in 67 -84% yield. The tricyclic triazolooxazinium iodide salts, (1-2)a, underwent metallation in a straight forward manner upon treatment with PdCl2 in the presence of K2CO3 in pyridine to give the trans-{3-(R)-5a,6,7,8,9,9a-hexahydro-4H-benzo[b][1,2,3]triazolo[1,5-d][1,4]oxazin-4-ylidene} PdI2(pyridine) [R = Me (1b), Et (2b)] complexes in 23 -25% yield. The new tricyclic triazolooxazine derived N-heterocyclic carbene moiety, as stabilized upon binding to palladium in the (1-2)b complexes, was structurally characterized by the X-ray single crystal diffraction studies.

A series of N-(aryl) and their quaternary N-(aryl) chitosan derivatives were synthesized and evaluated for their antifungal activity against crop-threatening fungus Botrytis cinerea. Schiff bases were firstly synthesized by the reaction of chitosan with cinnamaldehyde, cuminaldehyde and 4-dimethylaminobenzaldehyde followed by reduction with sodium borohydride to form N-(aryl) chitosans. Quaternary N-(aryl) chitosans were then obtained by reaction of N-(aryl) chitosan compounds with ethyl iodide. The chemical structures were characterized by 1H-NMR, FT-IR and UV spectroscopic techniques. The antifungal activity was evaluated in vitro against B. cinerea by mycelial growth inhibition method and in vivo by application of compounds to tomato plants prior to inoculation with fungal spores. In an in vitro experiment, all quaternized chitosans were more active than N-(aryl) chitosan derivatives and N,N,N-(diethylcinnamyl) chitosan (QC1) was the most potent (EC50 = 1,147 mg/L) against mecelia however, N,N,N-(diethyl-p-dimethylaminobenzyl) chitosan (QC3) was the most potent (EC50 = 334 mg/L) against spores. In an in vivo study, no disease incidence (0.0 %) was observed with QC1 and QC3 at 1,000 mg/L. Spray liquid chitosan enhanced total phenolics and guaiacol peroxidase in inoculated leaves.