RESUMEN
The so-called dibenzyltoluene (H0-DBT) heat transfer oil contains numerous isomers of dibenzyltoluene as well as (benzyl)benzyltoluene (methyl group on the central vs. the side aromatic ring). As it is used as a liquid organic hydrogen carrier (LOHC), a detailed analysis of its composition is crucial in assessing the kinetic rate of hydrogenation for each constituent and studying the mechanism of H0-DBT hydrogenation. To identify all of the compounds in the oil, an in-depth analysis of the GC-MS spectra was performed. To confirm peak attribution, we synthesized some DBTs and characterized the pure compounds using NMR and Raman spectroscopies. Moreover, a fast-GC analysis was developed to rapidly determine the degree of hydrogenation of the mixture.
RESUMEN
Today, the reactions of gas-phase organic peroxy radicals (RO2) with unsaturated Volatile Organic Compounds (VOC) are expected to be negligible at room temperature and ignored in atmospheric chemistry. This assumption is based on combustion studies (T ≥ 360 K), which were the only experimental data available for these reactions until recently. These studies also reported epoxide formation as the only reaction channel. In this work, the products of the reactions of 1-pentylperoxy (C5H11O2) and methylperoxy (CH3O2) with 2,3-dimethyl-2-butene ("2,3DM2B") and isoprene were investigated at T = 300 ± 5 K with Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) and Gas Chromatography/Electron Impact Mass Spectrometry. Unlike what was expected, the experiments showed no measurable formation of epoxide. However, RO2 + alkene was found to produce compounds retaining the alkene structure, such as 3-hydroxy-3-methyl-2-butanone (C5H10O2) with 2,3DM2B and 2-hydroxy-2-methyl-3-butenal (C5H8O2) and methyl vinyl ketone with isoprene, suggesting that these reactions proceed through another reaction pathway under atmospheric conditions. We propose that, instead of forming an epoxide, the alkyl radical produced by the addtion of RO2 onto the alkene reacts with oxygen, producing a peroxy radical. The corresponding mechanisms are consistent with the products observed in the experiments. This alternative pathway implies that, under atmospheric conditions, RO2 + alkene reactions are kinetically limited by the initial addition step and not by the epoxide formation proposed until now for combustion systems. Extrapolating the combustion data to room temperature thus underestimates the rate coefficients, which is consistent with those recently reported for these reactions at room temperature. While slow for many classes of RO2, these reactions could be non-negligible at room temperature for some functionalized RO2. They might thus need to be considered in laboratory studies using large alkene concentrations and in biogenically-dominated regions of the atmosphere.
RESUMEN
Until now the reactions of organic peroxy radicals (RO2) with alkenes in the gas phase have been essentially studied at high temperature (T ≥ 360 K) and in the context of combustion processes, while considered negligible in the Earth's atmosphere. In this work, the reactions of methyl-, 1-pentyl- and acetylperoxy radicals (CH3O2, C5H11O2, and CH3C(O)O2, respectively) with 2-methyl-2-butene, 2,3-dimethyl-2-butene and for the first time the atmospherically relevant isoprene, α-pinene, and limonene were studied at room temperature (298 ± 5 K). Monitoring directly the radicals with chemical ionization mass spectrometry led to rate coefficients larger than expected from previous combustion studies but following similar trends in terms of alkenes, with (in molecule-1 cm3 s-1) = 10-18 to 10-17 × 2/2 and = 10-14 to 10-13 × 5/5. While these reactions would be negligible for CH3O2 and aliphatic RO2 at room temperature, this might not be the case for acyl-, and perhaps hydroxy-, allyl- and other substituted RO2. Combining our results with the Structure-Activity Relationship (SAR) predicts k II(298 K) â¼10-14 molecule-1 cm3 s-1 for hydroxy- and allyl-RO2 from isoprene oxidation, potentially accounting for up to 14% of their sinks in biogenic-rich regions of the atmosphere and much more in laboratory studies.
RESUMEN
Aza-Prins and the pauper: Aza-Prins cyclization between γ,δ-unsaturated tosylamines and aldehydes was successfully performed under solvent-free and metal-free conditions. When applied to ß,γ-unsaturated sulfonamides, the corresponding δ-sultams were isolated in good yields (see scheme). This approach constitutes a new route to cyclic sulfonamides.
Asunto(s)
Aldehídos/química , Compuestos Aza/química , Sulfonamidas/química , Sulfonamidas/síntesis química , Ciclización , Estructura MolecularRESUMEN
Pd/C in HFIP was used to hydrogenate indole derivatives under relatively mild conditions, leading to potential synthetic intermediates of bioactive compounds. Depending on their substitution, tetrahydroindoles or octahydroindoles could selectively be obtained.
RESUMEN
Prins cyclization between a homoallylic alcohol and an aldehyde, promoted by trimethylsilyl halide, afforded 4-halo-tetrahydropyrans with good to excellent yields. Thanks to the absence of the solvent and metal, the THP thus obtained have been implicated without purification in several other reactions, in a sequential way, affording in particular new indole derivatives.
Asunto(s)
Tecnología Química Verde/métodos , Piranos/química , Piranos/síntesis química , Alcoholes/química , Aldehídos/química , Ciclización , Dióxido de Silicio/química , EstereoisomerismoRESUMEN
A single addition of the catalyst, Pd(OAc)(2), was realised to mediate two transformations as different as allylic alcohol oxidation under O(2) and C-C bond formation of the Heck type, to give substituted alpha,beta-unsaturated ketones without intermediate purification.
RESUMEN
Building upon the discovery of Suggs and Pires that N-(2-hydroxyethyl)glycine amides undergo rapid amide cleavage under mild conditions [ Suggs, J. W. ; Pires, R. M. Tetrahedron Lett. 1997, 38, 2227-2230 ], we synthesized the derivatives (4aalpha,8beta,8aalpha)-1-ethylamido-8-hydroxydecahydroquinoline ( 4) and (4aalpha,8alpha,8abeta)-1-ethylamido-8-hydroxydecahydroquinoline ( 5). These two species are conformationally constrained, but steric compression is not introduced between the hydroxyl group and the amide functionality it attacks. At 20 degrees C and slightly basic pH, derivatives 4 and 5 undergo amide cleavage with half-lives of 21 min and 14 h, respectively, which correspond to rate increases of 251- and 6.3-fold relative to the acyclic analogue N-(2-hydroxyethyl)glycine amide ( 3).
Asunto(s)
Amidas/química , Glicina/análogos & derivados , Amidas/metabolismo , Glicina/química , Concentración de Iones de Hidrógeno , Cinética , Conformación Molecular , Péptido Hidrolasas/química , Péptido Hidrolasas/metabolismo , Quinolinas/químicaRESUMEN
The synthesis of a series of fully O-derivatised para-acyl-calix[8]arenes is described, where the acyl function is either octanoyl or hexadecanoyl. The groups attached at the phenolic face are, carboxymethoxy (anionic), carboxypropoxy (anionic), 4-sulfonatobutoxy (anionic), ethoxycarboxymethoxy (neutral), ethoxycarboxypropoxy (neutral), 2-methoxyethoxy (neutral) and 2-(2-methoxy)diethoxy (neutral). The use of specific synthetic routes has allowed complete substitution in high yields for all the compounds obtained. The interfacial properties of the compounds have been studied and stable monolayers have been obtained for certain compounds in the series having para-octanoyl substituents; all compounds studied in the series having para-hexadecanoyl substituents formed stable monolayers at the air-water interface. The interactions between O-4-sulfonatobutoxy-para-ocatanoylcalix[8]arene and a series of serum albumins have been studied by dynamic light scattering and specific adsorption of the calix-[8]-arene derivative onto the proteins observed. The anionic derivatives O-4-sulfonatobutoxy-para-ocatanoylcalix[8]arene and O-carboxymethoxy-para-ocatanoylcalix[8]arene have been shown to possess anticoagulant properties but to have no haemolytic toxicity.