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Related Concept Videos

Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview01:32

Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview

4.0K
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
4.0K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism01:10

Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism

4.5K
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
4.5K
Preparation of Nitriles01:12

Preparation of Nitriles

2.7K
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...
2.7K
Basicity of Heterocyclic Aromatic Amines01:25

Basicity of Heterocyclic Aromatic Amines

7.1K
Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
7.1K
Diazonium Group Substitution: –OH and –H01:19

Diazonium Group Substitution: –OH and –H

3.4K
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
3.4K
Acidity and Basicity of Carboxylic Acid Derivatives01:25

Acidity and Basicity of Carboxylic Acid Derivatives

4.4K
Carboxylic acids are the strongest among organic acids, as they readily lose the hydroxyl proton to form a resonance-stabilized carboxylate ion. In comparison, the acid derivatives lack acidic hydrogens directly attached to a functional group. In these compounds, the acidic nature arises from their ability to lose α hydrogens, making them weakly acidic.
The relative acidic strength of the derivatives can be explained based on the extent of resonance stabilization of the conjugate base. The...
4.4K

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Updated: Feb 28, 2026

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
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Gas phase basicities of polyfunctional molecules. Part 6: Cyanides and isocyanides.

Guy Bouchoux1,2

  • 1Département de Chimie, Laboratoire de Chimie Moléculaire, UMR CNRS 9168, Ecole Polytechnique, Palaiseau, France.

Mass Spectrometry Reviews
|June 17, 2017
PubMed
Summary

This review compiles gas-phase basicity data for cyanides and isocyanides, correcting erroneous values and providing new computational insights into their thermochemistry.

Keywords:
isonitrilesmass spectrometrynitrilesproton affinitiesprotonation entropyquantum chemical G4MP2 calculationsthermochemistry

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Area of Science:

  • Physical Chemistry
  • Computational Chemistry
  • Organic Chemistry

Background:

  • Gas-phase basicity (GB), proton affinity (PA), and protonation entropy (ΔpS°) are key thermochemical properties.
  • Cyanides (nitriles) and isocyanides (isonitriles) are important functional groups with unique chemical behaviors.
  • Previous data on their basicity may contain inaccuracies, necessitating a comprehensive reevaluation.

Purpose of the Study:

  • To compile and critically evaluate existing structural and thermochemical data for cyanides and isocyanides.
  • To present a unified and corrected dataset for gas-phase basicity, proton affinity, and protonation entropy.
  • To provide new computational data on heats of formation for selected systems.

Main Methods:

  • Reevaluation of experimental data using the NIST database scale for proton affinity and gas-phase basicity.
  • Application of G4MP2 quantum chemistry computations for structural and energetic analysis.
  • Systematic review of literature data across seven chapters covering various cyanide and isocyanide subclasses.

Main Results:

  • Compilation of GB, PA, and ΔpS° values for approximately 110 cyanides and isocyanides.
  • Identification and correction of erroneous values in existing literature data.
  • Provision of computed heats of formation (ΔfH°) at 0 and 298 K for selected compounds.

Conclusions:

  • The study provides a reliable and updated resource for the thermochemical properties of cyanides and isocyanides.
  • The corrected data and new computational insights enhance understanding of their gas-phase chemistry.
  • This review serves as a valuable reference for researchers in physical organic chemistry and computational chemistry.