Dirhodium(II)-Catalyzed Synthesis of N-(Arylsulfonyl)hydrazines by N–H Amination of Aliphatic Amines

This study reports the development of Rh(II)-catalyzed N–N bond-forming reaction of amino acid derivatives or aliphatic amines to provide hydrazine derivatives through the combined use of Rh2(esp)2 and [(3,4-dimethoxyphenyl)sulfonylimino]-2,4,6-trimethylphenyliodinane (3,4-(MeO)2C6H3SO2N=IMes). This is the first report of N–H amination of aliphatic amines with metal–nitrene species.

Room temperature synthesis of perylene diimides facilitated by high amic acid solubility

A novel protocol for the synthesis of perylene diimides (PDIs), by reacting perylene dianhydride (PDA) with aliphatic amines is reported. Full conversions were obtained at temperatures between 20 and 60˚C,...

Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst

Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over...

Iron-Catalyzed One-pot Synthesis of Indole-tethered Tetrasubstituted Pyrroles and Their Transformations to Indolizino[8,7-b]indole Derivatives

We have developed an efficient iron-catalyzed one-pot reaction of tryptamines, ynones and nitroolefins affording indole-tethered tetrasubstituted pyrroles in acceptable to good yields. Other aromatic and aliphatic amines can also be utilized in this process delivering corresponding highly functionalized tetrasubstituted pyrroles. Indolizino[8,7-b]indole derivatives could be obtained through TFA, TfOH or Fe(OTf)3-mediated cyclizations via dearomatization of indole. Unexpected dibrominated products, 7,9-dibromo-6,11-dihydro-5H-indolizino[8,7-b]indoles, were formed when PTAP was employed as electrophilic cyclization promoter.

Mild biamidine transfer conditions for the synthesis of aliphatic biguanides

This study focuses on the development of new synthetic pathways to monosubstituted biguanides from amines. An exhaustive comparison of the conditions and reagents used for biamidine transfer was performed. New reagents were synthesized and optimized conditions for the synthesis of substituted biguanides under mild conditions were developed. Eventually, two high-yielding and straightforward protocols for the transfer of a biamidine group to various amines are proposed and their scope and limitations have been explored. These conditions include: i) a direct chromatography-free procedure and ii) an eco-friendly procedure in water compatible with bio-inspired molecules. They are particularly efficient for the demanding conversion of aliphatic amines.

Quantum Chemical Analysis of the Corrosion Inhibition Potential by Aliphatic Amines

Destructive corrosion processes lead to the loss of primary mechanical properties of metal construction materials, which generates additional costs during their maintenance connected with repairs and protection. The effectiveness of corrosion inhibitors can be determined by using many methods, in particular quantum chemical modeling. The subject of the theoretical analyses presented in this work involves the anticorrosion properties of amines with various chemical structures. Evaluation of the corrosion inhibition properties of selected amines was performed on the basis of the HOMO–LUMO energy gap, dipole moment (µ), electronegativity (χ) determined as a result of the energy of the highest occupied molecular orbital (HOMO) and the energy of the lowest unoccupied molecular orbital (LUMO). Moreover, the HSAB (Hard and Soft Acids and Bases) theory was used to explain the reactivity of the analyzed amines, while the Mulliken population analysis was used to determine their electrostatic interactions with the surface of protected metal. The obtained results indicate that the protonation reaction of aliphatic amines leads to a change in the nature of the formation of a coordination bond with the surface of the protected metal. In turn, the quantum chemical calculations showed that the protonation reaction of aliphatic amines leads to a decrease in their corrosion inhibition efficiency. Most of the analyzed parameters indicated that tertiary amines are characterized by the highest corrosion inhibition efficiency.

Additive-free selective methylation of amines with formic acid over a Pd/In2O3 catalyst

Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.