Influence of Mg surface layer for induction period of Grignard reagent formation

Tanaka, Kuninori; Kumasaki, Mieko; Miyake, Akira

doi:10.1007/s10973-013-2995-5

Cited by 9 publications

(5 citation statements)

References 16 publications

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“…The definition and the calculation of the induction period have been previously described [6]. The results show that the induction period increased with an increasing amount of impurities, i.e.…”

Section: Resultsmentioning

confidence: 97%

“…The features of a SuperCRC and a detailed experimental procedure have been described previously [6,[19][20][21][22].…”

Section: Measurement Of Exothermic Behaviour During the Grignard Reagmentioning

confidence: 99%

“…These authors previously studied the effect of a magnesium (Mg) surface layer on the induction period of the formation of Grignard reagents [6]. Grignard reagents are commonly used in organic synthesis and are generally formed by the reaction of Mg with an alkyl halide in ether [7].…”

Section: Introductionmentioning

confidence: 99%

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Influence of deteriorated solvent on induction period of Grignard reagent formation

Kumasaki

Tanaka

Otsuka

2015

J Therm Anal Calorim

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The influence of a degraded solvent on Grignard reagent formation was investigated in terms of heat release behaviour. Since degraded solvent is supposed to contain peroxide by oxidation with air as well as water from atmosphere, peroxide in this study was intentionally produced by the storage of tetrahydrofuran in a pressurized oxygen atmosphere and the induction periods were measured. The induction period which appears prior to the main exothermic reaction increased with increasing amounts of peroxide and water content, respectively. However, there was a difference in heat release behaviour; the reaction including peroxide showed a delay in the heat release and two exothermic peaks, while the solvent that included water simply showed a delay in the start of the reaction. c-Butyrolactone was found to be a product derived from peroxide, by component analysis of the oxidized solvent. c-Butyrolactone caused an induction period when it was added to the solvent. This work suggests a deteriorated solvent can lead to inappropriate handling which cause a runaway reaction and gives insight to the chemical industry that manages the risk of potentially hazardous chemical reactions.

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Section: Resultsmentioning

confidence: 97%

“…The features of a SuperCRC and a detailed experimental procedure have been described previously [6,[19][20][21][22].…”

Section: Measurement Of Exothermic Behaviour During the Grignard Reagmentioning

confidence: 99%

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Influence of deteriorated solvent on induction period of Grignard reagent formation

Kumasaki

Tanaka

Otsuka

2015

J Therm Anal Calorim

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“…Nevertheless, Grignard reagent formation remains challenging for the following reasons: ,, varying induction periods due to a passivating oxide layer on the magnesium surface or due to traces of moisture, high exothermicity with the risk of a potential run-away reaction, side-product formation such as the Wurtz coupling product by reaction of a halide molecule and a Grignard reagent molecule (Figure ) or decomposition of the Grignard reagent upon contact with air or moisture. …”

Section: Introductionmentioning

confidence: 99%

Selectivity of Grignard Reagent Formation: From Semibatch to Continuous Lab and Pilot Scale

Deitmann,

Dahms,

Maskos

et al. 2023

Org. Process Res. Dev.

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“…The reaction typically requires some induction periods before an exothermic reaction takes place. The formation of a passive layer of magnesium hydroxide and carbonate and the presence of water and peroxide contaminants in the solvent both contribute to the increased induction period. Numerous attempts have been made to facilitate the Grignard reagent formation, which involves some kind of metal surface activation including the addition of an etching agent such as iodine, 1,2-dibromoethane, or diisobutylaluminum hydride (DIBAL-H) or by using a freshly prepared highly dispersed magnesium powder .…”

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confidence: 99%

Crush It Safely: Safety Aspects of Mechanochemical Grignard Synthesis

Vilaivan

2022

ACS Chem. Health Saf.

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The Grignard reaction has been one of the most versatile workhorses for synthetic organic chemists for more than a century. Typically, the preparation of Grignard reagents and their subsequent reactions require anhydrous solvents and a protective inert atmosphere. A recent report showed that the reactions could be performed under mechanochemical conditions by ball-milling magnesium metal, an organic halide, and a small amount of an ethereal solvent together followed by the addition of an electrophile. Excellent results were reported for a broad range of substrates even when the reaction was performed under the ambient atmosphere, making the process highly appealing to a wide synthetic community. In this commentary, some safety aspects of this mechanochemical Grignard reaction are pointed out so that appropriate risk management plans can be devised to ensure its safe use.

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Influence of Mg surface layer for induction period of Grignard reagent formation

Cited by 9 publications

References 16 publications

Influence of deteriorated solvent on induction period of Grignard reagent formation

Influence of deteriorated solvent on induction period of Grignard reagent formation

Selectivity of Grignard Reagent Formation: From Semibatch to Continuous Lab and Pilot Scale

Crush It Safely: Safety Aspects of Mechanochemical Grignard Synthesis

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