Related Experiment Video
Updated: Nov 18, 2025
16:11
Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
2.5K
Dynamic Effects in Intramolecular Schmidt Reactions: Entropy, Electrostatic Drag, and Selectivity Prediction
Qing Sun1, Xin Lu2, Dean J Tantillo3
1Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang, 330063, China.
Summary
Electrostatic drag, a phenomenon in chemical reactions, was studied in azidopropylcyclohexanones. This drag, despite favorable interactions, hinders nitrogen gas loss, impacting product formation control.
Area of Science:
- Organic Chemistry
- Computational Chemistry
Background:
- The Schmidt reaction is a key organic transformation for synthesizing nitrogen-containing compounds.
- Intramolecular variants present unique mechanistic pathways and potential for complex product formation.
Purpose of the Study:
- To characterize the electrostatic drag phenomenon in intramolecular Schmidt reactions.
- To elucidate the role of electrostatic drag in nitrogen (N₂) loss during product formation.
Main Methods:
- Density Functional Theory (DFT) calculations were employed to model the reaction.
- Direct dynamics simulations were utilized to analyze the reaction pathway and kinetics.
Main Results:
- Electrostatic drag was identified as a significant factor influencing the reaction rate.
- This drag effect, arising from favorable interactions, was found to impede N₂ loss.
- The study observed that electrostatic drag slows the formation of bridged lactam products.
Conclusions:
- Electrostatic drag plays a crucial role in modulating the kinetics of intramolecular Schmidt reactions.
- Understanding and potentially controlling electrostatic drag offers a pathway to influence product selectivity in these reactions.
Related Concept Videos
01:31Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors
5.5K
The Diels–Alder reaction is thermally reversible, meaning that the reaction reverts to the starting diene and dienophile under suitable temperatures. The forward reaction gives a cyclohexene derivative and is favored at low to medium temperatures. The reverse process, also called retro-Diels–Alder reaction, is a ring-opening process favored at high temperatures.
5.5K
02:26SN2 Reaction: Transition State
11.2K
An SN2 reaction of an alkyl halide is a single-step process in which bond formation between the nucleophile and the substrate and bond breaking between the substrate and the halide occurs simultaneously through a transition state without forming an intermediate.
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
11.2K
02:49Second Law of Thermodynamics
25.8K
In the quest to identify a property that may reliably predict the spontaneity of a process, a promising candidate has been identified: entropy. Processes that involve an increase in entropy of the system (ΔS > 0) are very often spontaneous; however, examples to the contrary are plentiful. By expanding consideration of entropy changes to include the surroundings, a significant conclusion regarding the relation between this property and spontaneity may be reached. In thermodynamic models, the...
25.8K
02:24Predicting Reaction Outcomes
9.2K
Kinetics describes the rate and path by which a reaction occurs. In contrast, thermodynamics deals with state functions and describes the properties, behavior, and components of a system. It is not concerned with the path taken by the process and cannot address the rate at which a reaction occurs. Although it does provide information about what can happen during a reaction process, it does not describe the detailed steps of what appears on an atomic or a molecular level. On the other hand,...
9.2K
02:05Entropy and Solvation
7.9K
The process of surrounding a solute with solvent is called solvation. It involves evenly distributing the solute within the solvent. The rule of thumb for determining a solvent for a given compound is that like dissolves like. A good solvent has molecular characteristics similar to those of the compound to be dissolved. For example, polar solutions dissolve polar solutes, and apolar solvents dissolve apolar solutes. A polar solvent is a solvent that has a high dielectric constant (ϵ...
7.9K
03:00Standard Entropy Change for a Reaction
22.6K
Entropy is a state function, so the standard entropy change for a chemical reaction (ΔS°rxn) can be calculated from the difference in standard entropy between the products and the reactants.
22.6K