Formation of 1-ethoxyethanol at reaction of ammonium salts containing 2-oxo-3-carbethoxyethyl group with alkaline agents

Manukyan, M. O.; Babakhanyan, A. V.; Gyul'nazaryan, A. Kh.; Saakyan, T. A.

doi:10.1134/s1070363211020307

Cited by 2 publications

(2 citation statements)

References 2 publications

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“…The 13 C NMR signals of [Ru]–OCH(CH 3 )(OEt) are located at 107.1 (−OCH<) and 24 ppm (−CH 3 ) for the O(CH)CH 3 moiety and at 62.04 (−OCH 2 ) and 16.2 ppm (−CH 3 ) for the ethoxide group. As a comparison, the free hemiacetal 1-ethoxyethanol tertiary carbon resonates at 102.9 ppm . The amino proton and nitrogen resonate at 4.67 and 48.5 ppm, respectively .…”

Section: Results and Discussionmentioning

confidence: 97%

“…Noteworthy, treatment of 1-H with an ethanol/acetaldehyde mixture (6.0 and 10 equiv, respectively) at 193 K gave a complex mixture of organometallic species that gradually evolved into 1-OEt as the main organometallic species when raising the temperature from 193 to 300 K. This observation is in line with the higher selectivity toward ethyl acetate in the presence of ethanol (90%) with respect to that without ethanol (60%). In addition, the formation of hemiacetal derivatives was evidenced at low temperature (243 K), according to the observation of characteristic 13 C chemical shift values at 90–95 ppm …”

Section: Results and Discussionmentioning

confidence: 99%

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Deeper Mechanistic Insight into Ru Pincer-Mediated Acceptorless Dehydrogenative Coupling of Alcohols: Exchanges, Intermediates, and Deactivation Species

et al. 2018

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The mechanism of acceptorless dehydrogenative coupling reaction (ADC) of alcohols to esters catalyzed by aliphatic pincer PHNP ruthenium complexes was experimentally studied. Relevant intermediate species involved in the catalytic cycle were isolated and structurally characterized by single-crystal X-ray diffraction studies, and their reactivity (including toward substrates related to the catalytic process) was probed. VT NMR studies unveiled several chemical exchanges connecting the Ru amido hydride, the Ru alkoxide, and the alcohol substrate. Under catalytic conditions, in situ IR spectroscopy monitoring demonstrated the production of ester via aldehyde as intermediate. A Tishchenko-like pathway is proposed as the main path for the production of ester from aldehyde, involving alkoxide and hemiacetaloxide Ru species (the latter being identified in the reaction mixture by NMR). Catalytic system deactivation under base-free conditions was found to be related to water traces in the reaction medium (either as impurity or derived from aldol reactions) that lead to the formation of catalytically inactive acetato Ru complexes. These react with alkali metal alkoxides to afford catalytically active Ru species. In line with this observation, running the ADC reaction in the presence of water scavengers or alkoxides allows maintaining sustained catalytic activity.

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Section: Results and Discussionmentioning

confidence: 97%

Section: Results and Discussionmentioning

confidence: 99%

Deeper Mechanistic Insight into Ru Pincer-Mediated Acceptorless Dehydrogenative Coupling of Alcohols: Exchanges, Intermediates, and Deactivation Species

et al. 2018

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Mechanical Interatomic Bond Formation in Ethanol and Methanol–Ethanol Mixture by Laser‐Driven Shock Waves

Ishikawa,

Sato

2024

ChemPhysChem

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Molecules, which were predicted to be produced by C–C or C–O bond formation between ethanol molecules induced by a laser‐driven shock wave, were identified by gas chromatography–mass spectrometry. Moreover, the laser irradiation of a methanol–ethanol mixture revealed the formation of C–C and C–O bonds between both components. Particularly, four hemiacetals (methoxymethanol, 1‐methoxyethanol, ethoxymethanol, and 1‐ethoxyethanol) were identified in the Ar‐saturated alcohol samples, whereas acetalization dominated sufficiently in the CO2‐saturated samples, significantly reducing the hemiacetals. It was verified that some molecules were produced by the dropout of an ethanol part during the C–C or C–O bond formation, supporting the contribution of laser‐driven shock waves.

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Formation of 1-ethoxyethanol at reaction of ammonium salts containing 2-oxo-3-carbethoxyethyl group with alkaline agents

Cited by 2 publications

References 2 publications

Deeper Mechanistic Insight into Ru Pincer-Mediated Acceptorless Dehydrogenative Coupling of Alcohols: Exchanges, Intermediates, and Deactivation Species

Deeper Mechanistic Insight into Ru Pincer-Mediated Acceptorless Dehydrogenative Coupling of Alcohols: Exchanges, Intermediates, and Deactivation Species

Mechanical Interatomic Bond Formation in Ethanol and Methanol–Ethanol Mixture by Laser‐Driven Shock Waves

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