Reactions of benzotriazole with formaldehyde and aliphatic primary amines: selective formation of 1 : 1 : 1, of 2 : 2 : 1, and of 2 : 3 : 2 adducts and a study of their reactions with nucleophiles

Abstract

Benzotriazole ( BtH) reacts easily with aliphatic primary amines and formaldehyde in aqueous media to give one or more of three types of product: (i) (BtCH,),NR(5), (ii) (BtCH,NR),CH, (6), and/or (iii) BtCH,NHR (7). The product formed depends on the molar ratio of the substrates, and on the degree of steric hindrance in the amine, and is also influenced by the nature of the solvent. Primary aliphatic 1,2or 1,3-diamines yield cyclic aminals which are imidazolidine (8a) and hexahydropyrimidine (8b) derivatives. Reactions of these aminals with Grignard reagents, and with cyanide anion as nucleophiles, are also described.

RuO4-mediated oxidation of secondary amines 2. imines as main reaction intermediates

“…The NMR and MS data for 3b, 8f, 14d and 26-28 are presented as Supplementary material to this paper. Compound 14d was described either as a solid (m.p., 62-64 °C) 33 or as an oil, 34 but the reported NMR characteristics were quite similar. A new, simpler method of preparation of 14d (obtained as a solid) is proposed in the Supplementary material.…”

Benzotriazole-Mediated Synthesis of Nitrogen-Containing Heterocycles

“…Hydrogenation gave the corresponding cis-and trans-2,5-disubstituted pyrrolidines 40 and 41 (Scheme 13) [52]. N,N-Bis(benzotriazol-1-ylmethyl)amines 42 [18,53] exist in equilibria with their ionic form 43 in solution. Such solutions were treated with samarium diiodide to generate radicals 44 which were rapidly reacted with various alkenes to provide more stable radicals 45.…”

“…of benzotriazole provided 1,3-bis(benzotriazol-1-ylmethyl)imidazolidines 187. The reaction of crude 187 with KCN in acetonitrile gave dinitrile 188 and with Grignard reagents in THF afforded 1,3-dialkylimidazolidines 189 (Scheme 69) [53]. …”

2,2′-(1,3-Diazinane-1,3-diyl)diacetonitrile: a second monoclinic polymorph

“…For the original monoclinic polymorph, see: Shoja & Saba (1993). For the synthesis of the title compound, see: Rivera et al (2004); Katritzky et al (1990). For the use of nitriles in synthesis, see: Prasad & Bhalla (2010).…”

“…Single crystals of title compound were obtained by recrystallization from EtOH solution. An alternative synthetic method for the preparation of title compound involves the substitution of benzotriazolyl groups by cyano anion from the key benzotriazolyl intermediate 1,1′-(dihydropyrimidine-1,3(2H,4H)-diyldimethanediyl)-bis(1H-benzotriazole) (Katritzky et al, 1990) The molecular structure and atom-numbering scheme for (I) are shown in…”