Unsaturated compounds containing nitrogen. Part I. The synthesis and disproportionation of 1-chloro-azines, and their reactions with nucleophiles

Inter- and Innermolecular Reactions of Chloro(phenyl)carbene

“…3-Chloro-3-phenyl-3 H -diazirine ( 8 ) was prepared from benzamidine hydrochloride ( 14 ·HCl) and sodium hypochlorite (NaOCl) in ca. 70% yield. 18a, In addition to diazirine 8 , other more polar compounds were formed in the following relative yields: benzaldehyde (PhCHO, 9%), benzonitrile (PhCN, 16%), x -(1-chloro-1-phenylmethyl)pentanes ( 20i , 4%), , benzyl benzoate (BzOBn, 54%), 1,2-dichloro-1,2-diphenylethene ( 17 , 3%), 2,5-diphenyl-1,3,4-oxadiazole (PPD, trace), and bis(1-chloro-1-phenylmethylidene)hydrazine ( 18 , 14%) . However, most of these byproducts can be attributed to the decomposition of diazirine 8 .…”

“…It was observed during this study that the photolysis of neat diazirine 8 at room temperature afforded azine 18 in high yield and purity. Therefore, the diazirine route to 18 could become the leading alternative to Stollé's classical reaction involving chlorination of benzaldehyde azine ( 29 ). , …”

Nucleophile-Induced Intramolecular Dipole 1,5-Transfer and 1,6-Cyclization: Experimental and ab Initio Studies of Formation, Thermolysis, and Molecular and Electronic Structures of 3,6-Diphenyl-1-propanesulfenimido-1,2,4,5-tetrazine

“…It was obtained in 63% yield by chlorination of benzaldazine in CCl4 at 50 °C, according to a literature procedure: 39 mp 117-119 °C (lit. 39 ] was identified as the major byproduct. The identification of 5 and the disulfide in the mixture was confirmed by NMR of the pure compounds in the same solvent.…”

A facile route to amino-azines

“…IR spectra were recorded with a Shimadzu IR-408 spectrometer (KBr). 1 H NMR spectra were determined in chloroform-d and/or DMSO-d 6 solution on a F7 NMR Bruker AC-80 (80 MHz); chemical shifts are reported in δ ppm.…”

“…1,4-Diamino-1,4diphenyl-2,3-diazabutadiene, 3,5-diphenyltriazole, and diphenyltetrazine were also obtained as by-products. 1 Another route to amino-azine (3) was reported by van der Burg, 5 who claimed that the reaction of amidrazones with benzaldehyde would give their N 1 -benzylidene derivatives, which are amino-azines. However, conflicting reports have appeared in the literature concerning the products formed in such reactions.Taylor 6 and Case 7 came to the same conclusion as van der Berg, and stated that the reaction of amidrazones with monocarbonyl compounds would give their aryl or alkylidene derivatives.…”