A process for preparing 4-aminodiphenylamine (4-ADPA) comprising steps of coupling of aniline with nitrobenzene in presence of a suitable base, e.g. tetramethylammonium hydroxide (TMAH), hydrogenation of the coupling mass, phase separation, hydrogenation of azobenzene in the separated organic mass and fractional distillation for 4-ADPA recovery. An improvement in 4-ADPA recovery and a lowering of tar formation are obtained due to azobenzene reduction prior to 4-ADPA isolation. Also a gain in volume productivity of 4-ADPA is obtained by suitably altering the batch cycle time of the coupling reaction.

A process for preparing 4-aminodiphenylamine (4-ADPA) comprising steps of coupling of aniline with nitrobenzene in presence of a suitable base, e.g. tetramethylammonium hydroxide (TMAH), hydrogenation of the coupling mass, phase separation, hydrogenation of azobenzene in the separated organic mass and fractional distillation for 4-ADPA recovery. An improvement in 4-ADPA recovery and a lowering of tar formation are obtained due to azobenzene reduction prior to 4-ADPA isolation. Also a gain in volume productivity of 4-ADPA is obtained by suitably altering the batch cycle time of the coupling reaction.

Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

The method relates to the field of asymmetric allylic amination and comprises preparing a chiral N-substituted allylic amine compound from the corresponding allylic substrates and substituted hydroxylamines, in the presence of a catalyst, said catalyst comprising copper compounds and a chiral ligand. Examples of chiral amine compounds which can be made using the method include Vigabatrin, Ezetimibe Terbinafine, Naftifine 3-methylmorphine, Sertraline, Cinacalcet, Mefloquine hydrochloride, and Rivastigmine. There are over 20,000 known bioactive molecules with chiral N-substituted allylic amine substructure. The method may also be used to produce non-natural chiral -aminoacid esters, a sub-class of chiral N-substituted allylic amine compounds. Examples of -aminoacid ester which can be produced by the disclosed method, include, but are not limited to, N-(2-methylpent-1-en-3-yl)benzenamine and Ethyl 2-methylene-3-(phenylamino)butanoate. Further, the products of the method described herein can be used to produce chiral heterocycles and bioactive molecules or materials. A novel chiral copper-BINAM nitrosoarene complex is also set forth.

The method relates to the field of asymmetric allylic amination and comprises preparing a chiral N-substituted allylic amine compound from the corresponding allylic substrates and substituted hydroxylamines, in the presence of a catalyst, said catalyst comprising copper compounds and a chiral ligand. Examples of chiral amine compounds which can be made using the method include Vigabatrin, Ezetimibe Terbinafine, Naftifine 3-methylmorphine, Sertraline, Cinacalcet, Mefloquine hydrochloride, and Rivastigmine. There are over 20,000 known bioactive molecules with chiral N-substituted allylic amine substructure. The method may also be used to produce non-natural chiral -aminoacid esters, a sub-class of chiral N-substituted allylic amine compounds. Examples of -aminoacid ester which can be produced by the disclosed method, include, but are not limited to, N-(2-methylpent-1-en-3-yl)benzenamine and Ethyl 2-methylene-3-(phenylamino)butanoate. Further, the products of the method described herein can be used to produce chiral heterocycles and bioactive molecules or materials. A novel chiral copper-BINAM nitrosoarene complex is also set forth.

The present invention provides novel synthetic methods for making acyclic secondary amines by reacting an azide with a compound bearing one or more CH groups, catalyzed by a Fe.sup.II-dipyrromethene complex. The acyclic secondary amines are thought to be formed through an intermolecular nitrene transfer. Also provided herein are methods of synthesizing protected (e.g., Boc- or Fmoc-protected) cyclic secondary amines (e.g., 5-, 6-, and 7-membered cyclic secondary amines) by reacting an azide that bears one or more CH groups, catalyzed by a Fe.sup.II-dipyrromethene complex. The protected cyclic secondary amines are thought to be formed through an intramolecular nitrene transfer and may be subsequently deprotected to yield cyclic secondary amines.

The present invention provides novel synthetic methods for making acyclic secondary amines by reacting an azide with a compound bearing one or more CH groups, catalyzed by a Fe.sup.II-dipyrromethene complex. The acyclic secondary amines are thought to be formed through an intermolecular nitrene transfer. Also provided herein are methods of synthesizing protected (e.g., Boc- or Fmoc-protected) cyclic secondary amines (e.g., 5-, 6-, and 7-membered cyclic secondary amines) by reacting an azide that bears one or more CH groups, catalyzed by a Fe.sup.II-dipyrromethene complex. The protected cyclic secondary amines are thought to be formed through an intramolecular nitrene transfer and may be subsequently deprotected to yield cyclic secondary amines.

The present invention provides novel synthetic methods for making acyclic secondary amines by reacting an azide with a compound bearing one or more CH groups, catalyzed by a Fe.sup.II-dipyrromethene complex. The acyclic secondary amines are thought to be formed through an intermolecular nitrene transfer. Also provided herein are methods of synthesizing protected (e.g., Boc- or Fmoc-protected) cyclic secondary amines (e.g., 5-, 6-, and 7-membered cyclic secondary amines) by reacting an azide that bears one or more CH groups, catalyzed by a Fe.sup.II-dipyrromethene complex. The protected cyclic secondary amines are thought to be formed through an intramolecular nitrene transfer and may be subsequently deprotected to yield cyclic secondary amines.

An organometallic complex of a tridentate bis(phosphine)-carbodicarbene ligand and a transition metal, is described. In some embodiments the ligand has the structure of Formula (I): The complexes are useful in methods of making an allylic amine carried out by reacting a 1,3-diene with a substituted amine in the presence of such an organometallic complex to produce by intermolecular hydroamination the allylic amine.

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