52120-10-2

Upstream product

• 936-61-8 Thiobenzoic acid O-ethyl ester 
• 109-73-9 N-butylamine 
• 15421-91-7 N'-(n-butyl)phenylamidine 
• 100-47-0 benzonitrile 
• 1246287-59-1 C₁₄H₁₄N₄O₂ 
• 618-39-3 benzamidin 
• 109-72-8 n-butyllithium 
• 4222-25-7 3-bromo-3-phenyl-3H-diazirine 
• 825-60-5 benzimidic acid ethyl ester 

Relevant academic research and scientific papers

Radical and Nitrenoid Reactivity of 3-Halo-3-phenyldiazirines

3-Halo-3-phenyl-3H-diazirines (halogen = Br or Cl) undergo a dissociative single-electron transfer from alkyllithiums (RLi) in THF-based solvent mixtures. The resulting 3-phenyldiazirinyl radical, observed by EPR spectroscopy, is eventually transformed to benzonitrile. In Et2O, 2 equiv of RLi add to both nitrogens of halodiazirine N=N bond, affording N,N′-dialkylbenzamidines. The nitrenoid reactivity of some N-alkyl-1H-diazirine intermediates is manifested by their insertion into the α-C-H bond of THF or Et2O.

Aminolysis of an N-diazeniumdiolated amidine as an approach to diazeniumdiolated ammonia

Recent theoretical studies have suggested that the parent diazeniumdiolate ion, H2N-N(O)=NO- ( diazeniumdiolated ammonia ), might be stable enough to be isolated and that it could potentially serve as a uniquely advantageous prodrug form of bioactive nitroxyl (HNO). Here, we report on an attempt to isolate its O2-benzylated derivative by aminolysis of the C=N bond in PhC(NH2)=N-N(O)=NOBn. The reaction proved remarkably sluggish in comparison to aminolysis of unsubstituted benzamidine, and the desired product could not be isolated, apparently because of base sensitivity of the NH2 group. Consistent with this interpretation, O-benzylhydroxylamine and N2O were recovered from the reaction mixture in high yields, along with N,N′-dibutylbenzamidine. Theoretical calculations rationalize the observed slow aminolysis by demonstrating that the diazeniumdiolate group greatly suppresses the electrophilicity of the adjacent C=N carbon center, rendering attack at that position endothermic. The data provide significant insights into the challenges inherent to the pursuit of diazeniumdiolated ammonia.

Samarium diiodide promoted synthesis of N,N′-disubstituted amidines

An efficient one-step preparation of an N,N′-disubstituted amidine by the direct nucleophilic addition of an amine to the parent nitrile using catalytic amounts of SmI2 under relatively mild conditions is developed. Alkyl, benzyl and aryl amidi

Use of Lanthanide(III) Ions as Catalysts for the Reactions of Amines with Nitriles

Catalytic amounts of lanthanide(III) triflates promote reactions between amines and nitriles leading to a variety of products.The Ln3+ ions activate weakly coordinating nitriles at large amine: Ln3+ mole ratios, even in the presence of amines that form thermodynamically stable complexes with Ln3+ ions.The reactions involving primary monoamines and diamines appear to be general and provide a viable synthetic route to N,N'-disubstituted amidines (2) and cyclic amidines (4), respectively.Symmetrically substituted triazines (8 or 9) are observed as byproducts in some of these systems when the reactions are carried out by using excess nitrile.Secondary alicyclic amines or dimethylamine reacts with acetonitrile to yield pyrimidines (6) and 2,4,6-trimethyl-s-triazine (8).Two routes to triazine have been proposed, one involving the reaction of ammonia with the nitrile and the second involving the reaction of an amidine (1 or 5) with the nitrile.The ability of Ln3+ ions to activate nitriles under conditions that oppose nitrile coordination is attributed to the lability of Ln3+ complexes derived from N-donors.