64372-87-8

Basic information

• Product Name: 2,4-Cyclohexadien-1-imine, 6-methylene-
• Synonyms: 6-methylidenecyclohexa-2,4-dien-1-imine;6-Methylene-2,4-cyclohexadien-1-imine;aza-ortho-xylylene;6-methylenecyclohexa-2,4-dienylideneamine;2,4-Cyclohexadien-1-imine,6-methylene
• CAS NO: 64372-87-8
• Molecular Formula: C7H7N
• Molecular Weight: 105.139
• Mol File: 64372-87-8.mol
• Article Data: 7

Chemical Properties

• CAS DataBase Reference: 2,4-Cyclohexadien-1-imine, 6-methylene-(CAS DataBase Reference)
• NIST Chemistry Reference: 2,4-Cyclohexadien-1-imine, 6-methylene-(64372-87-8)
• EPA Substance Registry System: 2,4-Cyclohexadien-1-imine, 6-methylene-(64372-87-8)

Safety Data

• Hazardous Substances Data: 64372-87-8(Hazardous Substances Data)

Upstream product

• 4403-69-4 2-amino-1-benzylamine 
• 171359-95-8 N'-(2-aminobenzylidene)-4-methylbenzenesulfonohydrazide 
• 529-23-7 o-aminobenzaldehyde 
• 111248-89-6 1,3-dihydro-2,1-benzisothiazole 2,2-dioxide 
• 31656-92-5 1-azido-2-methyl-benzene 
• 148291-93-4 (o-aminophenyl)diazomethane 
• 7095-75-2 benzazetidine 
• 635-46-1 1,2,3,4-tetrahydroisoquinoline 
• 5344-90-1 2-Aminobenzyl alcohol 

Downstream Products

• 1666-96-2 3-phenylquinoline 
• 22514-82-5 2,3-diphenyl quinoline 

Relevant articles and documents

The thermal isomerisation benzoazetine - 6-methylene-2,4-cyclohexadien-1-imine: A photoelectron investigation

The flash vacuum thermolyses of 1,2,3,4-tetrahydroquinoline 3, o-aminobenzylalcohol 4 and o-aminobenzylamine 5 were performed at temperatures from 923 to 1273 K and monitored by photoelectron spectrometry. While thermolyses at 923-1073 K led to the until now undescribed benzoazetine 2a, 6-methylene-2,4- cyclohexadien-1-imine 1a was obtained at 1173-1273 K.

Metal- and Protection-Free [4 + 2] Cycloadditions of Alkynes with Azadienes: Assembly of Functionalized Quinolines

A base promoted, protection-free, and regioselective synthesis of highly functionalized quinolines via [4 + 2] cycloaddition of azadienes (generated in situ from o-aminobenzyl alcohol) with internal alkynes has been discovered. The reaction tolerates a wide variety of functional groups which has been successfully extended with diynes, (2-aminopyridin-3-yl)methanol, and 1,4-bis(phenylethynyl)benzene to afford (Z)-phenyl-2-styrylquinolines, phenylnaphthyridine, and alkyne-substituted quinolines, respectively. The proposed mechanism and significant role of the solvent were well supported by isolating the azadiene intermediate and deuterium-labeling studies.

Intramolecular Hydrogen Transfer in (2-Aminophenyl)carbene and 2-Tolylnitrene. Matrix Isolation of 6-Methylene-2,4-cyclohexadien-1-imine

Flash vacuum pyrolysis (FVP) or matrix photolysis of 2-(diazomethyl)phenylamine, 1-azido-2-methylbenzene (2-tolyl azide), o-aminobenzyl alcohol, or 2-indolinone provide entries into the C7H7N hypersurface.The matrix-isolated (argon, 10 K) products have been characterized by IR and UV-vis spectroscopy in combination with high level (MP2/6-31G(d) and HF/6-31G(d,p)) ab-initio calculations.FVP (500-800 deg C) of the first three of these precursors produces high yields of E/Z-mixtures of 6-methylene-2,4-cyclohexadien-1-imine (o-iminoquinone methide), while the bicyclic isomer benzoazetine is not formed under these conditions.FVP of 2-tolyl azide at very high temperatures (>900 deg C) leads to the formation of benzaldimine and benzonitrile.Photolysis of the matrix-isolated precursors allows one to selectively generate the E- and Z-isomer of the iminoquinone methide as well as benzoazetine.In addition, 2-tolylnitrene and 1-aza-3-methyl-1,2,4,6-cycloheptatetraene are produced as intermediates in the photolysis of 2-tolyl azide.The nitrene is thermally stable up to 80 K (in xenon matrix), although the hydrogen migration to give (E)-o-iminoquinone methide is calculated to be exothermic by 42 kcal/mol.Irradiation of 2-(diazomethyl)phenylamine directly yields the quinone methide while (o-aminophenyl)carbene, which is the most reasonable intermediate, is not observed.