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Intermolecular vs Intramolecular Forces03:00

Intermolecular vs Intramolecular Forces

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Intermolecular forces (IMF) are electrostatic attractions arising from charge-charge interactions between molecules. The strength of the intermolecular force is influenced by the distance of separation between molecules. The forces significantly affect the interactions in solids and liquids, where the molecules are close together. In gases, IMFs become important only under high-pressure conditions (due to the proximity of gas molecules). Intermolecular forces dictate the physical properties of...
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Intramolecular Aldol Reaction01:18

Intramolecular Aldol Reaction

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Intramolecular aldol reaction occurs in dicarbonyl compounds such as dialdehydes, diketones, and keto-aldehydes. The dicarbonyl compounds possess more than one nucleophilic ⍺ carbon for the base to deprotonate and form the enolates. For example, in symmetrical diketones, there are four ⍺ carbons. Hence, four types of enolates are possible when treated with a base. However, since the molecule is symmetrical, the enolates formed on either side of one carbonyl group are equivalent to those...
3.1K
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

2.2K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
2.2K
Aldehydes and Ketones with Amines: Imine Formation Mechanism01:23

Aldehydes and Ketones with Amines: Imine Formation Mechanism

8.4K
Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
8.4K
Intramolecular Claisen Condensation of Dicarboxylic Esters: Dieckmann Cyclization01:13

Intramolecular Claisen Condensation of Dicarboxylic Esters: Dieckmann Cyclization

3.3K
Dieckmann cyclization is an intramolecular Claisen condensation of diesters. The reaction occurs in the presence of a base and generates a cyclic β-ketoester as the final product. Commonly, 1, 6 and 1, 7-diesters are preferred substrates for the reaction since the generated five, and six-membered cyclic β-keto esters are particularly more stable.
3.3K
Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview01:16

Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview

6.5K
Primary amines react with carbonyl compounds—aldehydes and ketones—to generate imines. Imines consist of a C=N double bond and are named Schiff bases after its discoverer—the German chemist Hugo Schiff. On the other hand, secondary amines react with carbonyl compounds to give enamines. In enamines, the presence of a C=C double bond adjacent to the nitrogen atom leads to the delocalization of the lone pair.
6.5K

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Related Experiment Video

Updated: Jan 30, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
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Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

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An intramolecular C(sp3)-H imination using PhI-mCPBA.

Anima Bose1, Saikat Maiti, Sudip Sau

  • 1School of Chemical Sciences, National Institute of Science Education and Research (NISER), HBNI, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Bhubaneswar, Odisha 752050, India. pmal@niser.ac.in.

Chemical Communications (Cambridge, England)
|January 29, 2019
PubMed
Summary

A novel organocatalysis method enables selective C-H imination of acidic C(sp3)-H groups. This highly exothermic reaction utilizes a primary amine-polyvalent iodine system for efficient functionalization under ambient conditions.

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • Selective functionalization of C(sp3)-H bonds remains a significant challenge in organic synthesis.
  • Dehydrogenative C-H functionalization offers a more atom-economical approach compared to traditional methods.

Purpose of the Study:

  • To develop a novel organocatalytic method for selective C(sp3)-H imination.
  • To achieve functionalization of acidic C(sp3)-H groups via a dehydrogenative pathway.

Main Methods:

  • Utilized a highly exothermic reaction between a primary amine and a polyvalent iodine compound.
  • Employed organocatalysis with phenyliodine (PhI) and meta-chloroperoxybenzoic acid (mCPBA) at 10 mol% loading.
  • Conducted the reaction under ambient conditions.

Main Results:

  • Successfully achieved selective functionalization of acidic C(sp3)-H groups.
  • Demonstrated efficient C(sp3)-H imination at 1,5-distances through a 4H elimination process.
  • The organocatalytic system proved effective under mild, ambient conditions.

Conclusions:

  • The developed primary amine-polyvalent iodine reaction provides a facile route for dehydrogenative C-H imination.
  • This method offers a selective and efficient strategy for functionalizing C(sp3)-H bonds.
  • Organocatalysis presents a promising approach for achieving complex molecular transformations.