Understanding the solubilization of Ca acetylide with a new computational model for ionic pairs

Polynski, Mikhail V.; Sapova, Mariia D.; Ananikov, Valentine P.

doi:10.1039/d0sc04752j

Cited by 20 publications

(13 citation statements)

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“…The presence of a semihydrolyzed Ca-containing intermediate is possible, and a carbide molecule is bound to one molecule of water (half-hydrolyzed). This intermediate was solvated by DMSO, which prevents hydrolysis at the second stage [ 33 ]. CaC 2 + nDMSO = [(DMSO) n (CaC 2 )] [(DMSO) n (CaC 2 )] + H 2 O = [(DMSO) n (Ca(C≡CH)(OH))] [(DMSO) n (Ca(C≡CH)(OH))] + H 2 O = HC≡CH + Ca(OH) 2 + nDMSO …”

Section: Resultsmentioning

confidence: 99%

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Thermal Mapping of Self-Promoted Calcium Carbide Reactions for Performing Energy-Economic Processes

Rodygin

Лоцман

Erokhin

et al. 2022

IJMS

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The syntheses of various chemical compounds require heating. The intrinsic release of heat in exothermic processes is a valuable heat source that is not effectively used in many reactions. In this work, we assessed the released heat during the hydrolysis of an energy-rich compound, calcium carbide, and explored the possibility of its usage. Temperature profiles of carbide hydrolysis were recorded, and it was found that the heat release depended on the cosolvent and water/solvent ratio. Thus, the release of heat can be controlled and adjusted. To monitor the released heat, a special tube-in-tube reactor was assembled using joining part 3D-printed with nylon. The thermal effect of the reaction was estimated using a thermoimaging IR monitor. It was found that the kinetics of heat release are different when using mixtures of water with different solvents, and the maximum achievable temperature depends on the type of solvent and the amount of water and carbide. The possibility of using the heat released during carbide hydrolysis to initiate a chemical reaction was tested using a hydrothiolation reaction—the nucleophilic addition of thiols to acetylene. In a model experiment, the yield of the desired product with the use of heat from carbide hydrolysis was 89%, compared to 30% in this intrinsic heating, which was neglected.

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Section: Resultsmentioning

confidence: 99%

Section: Optimization Of the Heat Release Profilementioning

confidence: 99%

Thermal Mapping of Self-Promoted Calcium Carbide Reactions for Performing Energy-Economic Processes

Rodygin

Лоцман

Erokhin

et al. 2022

IJMS

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“…Oxidative addition of iodoarene 1 to a Pd(0) species, which is generated most commonly from the reaction of palladium(II) diacetate with dppb, [22] forms an arylpalladium iodide ( A ). Meanwhile, calcium carbide is hydrolyzed to yield acetylene calcium hydroxide ( B ) [23] . A reacts with B to obtain palladium complex C. C undergoes reductive elimination to give arylacetylene calcium hydroxide D and lose Pd(0) to enter a new cycle.…”

Section: Resultsmentioning

confidence: 99%

“…The reaction was also affected by the amount of water. It was observed that 2 equivalents of water based on calcium carbide was an appropriate amount for the formation of 2 a (Table 1, entries 8,23,24,and SI,Table S3).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 1,3‐Diynes Using Calcium Carbide as an Alkyne Source

Liu

2020

Eur J Org Chem

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A simple method for the synthesis of 1,3‐diynes from iodoarenes using calcium carbide as an alkyne source and air as an oxidant is described. A series of 1,4‐diarylbuta‐1,3‐diynes were efficiently synthesized by this strategy. The salient features of this protocol are the use of inexpensive and easy‐to‐handle alkyne source, broad substrate scope, open‐air condition, and simple operation procedure.

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“…DFTB3 was previously shown to produce good geometries and adequate energy for a wide range of scenarios. It performed well for biomolecular systems [ 61 , 62 , 63 ], systems with metal cations in general [ 29 , 64 , 65 , 66 ], and Ca 2+ specifically [ 67 , 68 ], achieving better energies then DFT calculations with a double-ζ basis set. In both tasks, QM simulation was run in parallel by 10 walkers each sampling for 100 ps thus accumulating 1 ns of QM/MM trajectory.…”

Section: Methodsmentioning

confidence: 99%

Probing the Suitability of Different Ca2+ Parameters for Long Simulations of Diisopropyl Fluorophosphatase

et al. 2021

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Organophosphate hydrolases are promising as potential biotherapeutic agents to treat poisoning with pesticides or nerve gases. However, these enzymes often need to be further engineered in order to become useful in practice. One example of such enhancement is the alteration of enantioselectivity of diisopropyl fluorophosphatase (DFPase). Molecular modeling techniques offer a unique opportunity to address this task rationally by providing a physical description of the substrate-binding process. However, DFPase is a metalloenzyme, and correct modeling of metal cations is a challenging task generally coming with a tradeoff between simulation speed and accuracy. Here, we probe several molecular mechanical parameter combinations for their ability to empower long simulations needed to achieve a quantitative description of substrate binding. We demonstrate that a combination of the Amber19sb force field with the recently developed 12-6 Ca2+ models allows us to both correctly model DFPase and obtain new insights into the DFP binding process.

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Understanding the solubilization of Ca acetylide with a new computational model for ionic pairs

Abstract: The unique reactivity of the acetylenic unit in DMSO gives rise to ubiquitously developed synthetic methods. We theoretically consider CaC2 solubility and protolysis in DMSO and formulate a strategy for...

Cited by 20 publications

References 126 publications

Thermal Mapping of Self-Promoted Calcium Carbide Reactions for Performing Energy-Economic Processes

Thermal Mapping of Self-Promoted Calcium Carbide Reactions for Performing Energy-Economic Processes

Synthesis of 1,3‐Diynes Using Calcium Carbide as an Alkyne Source

Probing the Suitability of Different Ca2+ Parameters for Long Simulations of Diisopropyl Fluorophosphatase

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