ХЛОРДИМЕТИЛАМИН

Description

Chlordimethylamine (N-chlorodimethylamine, N,N-dimethylchloramine) is a chloramine derivative of dimethylamine in which the chlorine atom is bonded directly to a nitrogen atom rather than to a carbon. Such N-chloramines are sources of electrophilic chlorine and nitrogen at the same time: the nitrogen-chlorine bond is heterolytically cleaved under the action of nucleophiles or reducing agents, releasing a chloride ion or acting as a donor of an aminyl radical, depending on the reaction conditions, which determines the use of the compound as a chlorinating and aminating reagent in organic synthesis.

Basic Attributes

• CAS No: 1585-74-6
• Chemical formula: C2H6ClN
• English name: Chlorodimethylamine
• Molecular weight: 79.527
• Exact weight: 79.019
• DSSTox ID: DTXSID40166437
• PSA specifications: 3.2
• XLogP3: 0.6

Physico-chemical characteristics

• Density: 0.9313 (approximate estimate)
• Melting point: 200–203 °C
• Boiling point: 90.19°C (approximate estimate)
• Refractive Index: 1.4202 (estimate)

Scope of application

• reagent for electrophilic chlorination and amination in organic synthesis
• source of nitrogen-chlorine bonds for obtaining chloramine derivatives and studying their reactivity
• model compound for studying the mechanisms of homolytic and heterolytic cleavage of the N-Cl bond

Storage and transportation

N-chloramines, including chlorodimethylamine, are thermally and photochemically unstable: the nitrogen-chlorine bond can break when heated or exposed to light, releasing chlorine and forming the initial amine or further oxidation products. The substance is stored in an airtight container, in a cool, dark place, away from heat sources and reducing agents that can initiate premature decomposition of the N-Cl bond.

Reactivity mechanism

A key feature of N-chloramines, including chlorodimethylamine, is the dual nature of the nitrogen-chlorine bond. When interacting with nucleophilic substrates, the reagent is able to act as a source of electrophilic “positive” chlorine (Cl+), transferring it to the nucleophilic center of the substrate - a mechanism similar to the action of hypochlorites and N-chlorosuccinimide in the chlorination reactions of amines, enols and aromatic rings. Under other conditions, in particular during photolysis or thermolysis, the N-Cl bond is cleaved homolytically to form an aminyl radical (CH3)2N•, which initiates radical chain processes, including functionalization by the hydrogen atom transfer (HAT) mechanism, where the aminyl radical abstracts a hydrogen atom from the substrate, and the resulting carbon radical then enters into chlorination by a chain mechanism Hoffmann-Leffler-Freytag.

Additional Applications

• reagent for electrophilic chlorination of nucleophilic substrates - amines, enolates, some aromatic compounds
• source of aminyl radical for radical functionalization via the hydrogen atom transfer mechanism in the Hoffmann-Leffler-Freitag rearrangement and related transformations
• model compound for studying the general patterns of reactivity of the nitrogen-chlorine bond in chloramines