319016-36-9

Upstream product

• 873-74-5 4-Aminobenzonitrile 
• 27757-85-3 2-Aminomethylthiophene 
• 180143-65-1 4-cyanophenyl pivalate 
• 554-14-3 2-Methylthiophene 

Downstream Products

• 319015-49-1 4-[N-(4-hydroxybenzyl)-N-(2-thenyl)amino]benzonitrile 

Relevant academic research and scientific papers

METHOD FOR PREPARING BENZYL AMINE COMPOUND

Disclosed is a method for preparing a benzyl amine compound, i.e., synthesizing a benzyl amine compound by means of an oxidation reaction between a methylbenzene/ethylbenzene compound and arylamine by using an ionic iron (III) complex containing 1,3-di-tert-butylimidazolium cation and having a molecular formula of [(RNCHCHNR)CH][FeBr4] (R being tert-butyl) and di-t-butyl peroxide as an oxidant. The present invention is not only applicable to a methylbenzene compound containing a benzylic primary carbon-hydrogen bond but also applicable to an ethylbenzene compound containing a benzylic secondary carbon-hydrogen bond, and therefore is widely applicable. This is the first case where the preparation of a benzyl amine compound by means of an oxidation reaction between a methylbenzene/ethylbenzene compound and arylamine is implemented by an iron catalyst.

Iron-Catalyzed Oxidative Amination of Benzylic C(sp3)–H Bonds with Anilines

Iron-catalyzed oxidative amination of benzylic C(sp3)–H bonds with anilines bearing electron-withdrawing groups (EWGs) or electron-donating groups (EDGs) is realized based on simple variations of N-substituents on imidazolium cations in novel ionic Fe(III) complexes. The structural modification of the imidazolium cation resulted in regulation of the redox potential and the catalytic performance of the iron metal center. Using DTBP as oxidant, [HItBu][FeBr4] showed the highest catalytic activity for anilines bearing EWGs, while [HIPym][FeBr4] was more efficient for EDG-substituted anilines. This work provides alternative access to benzylamines with the advantages of both a wide substrate scope and iron catalysis.

Mechanistic Studies of Hydride Transfer to Imines from a Highly Active and Chemoselective Manganate Catalyst

We introduce a highly active and chemoselective manganese catalyst for the hydrogenation of imines. The catalyst has a large scope, can reduce aldimines and ketimines, and tolerates a variety of functional groups, among them hydrogenation sensitive examples such as an olefin, a ketone, nitriles, nitro groups, and an aryl iodo substituent or a benzyl ether. We could investigate the transfer step between imines and the hydride complex in detail. We found that double deprotonation of the ligand is essential and excess base does not lead to a higher rate in the transfer step. We identified the actual hydrogenation catalyst as a K-Mn-bimetallic species and could obtain a structure of the K-Mn complex formed after hydride transfer by X-ray analysis. NMR experiments indicate that the hydride transfer is a well-defined reaction, which is first order in imine, first order in the bimetallic (K-Mn) hydride, and independent in rate from the concentration of the potassium base. We propose an outer-sphere mechanism in which protons do not seem to be involved in the rate-determining step, leading to a transiently negatively charged nitrogen atom in the substrate which reacts rapidly with HOtBu (2-methylpropan-2-ol) to produce the amine. This is based on several observations, such as no dependency of the reaction rate on the HOtBu concentration, no observable manganese amide complex, and a high reaction constant in a conducted Hammett study. Furthermore, hydrogen transfer of the catalytic cycle was experimentally probed and monitored by NMR with subsequent quantitative regeneration of the catalyst by H2.

Method of preparing benzylamine compound

The invention discloses a method of preparing a benzylamine compound. The method comprises the following steps of by taking 1,3-di-tert-butylimidazolin cation contained ionic iron (III) complex with amolecular formula being [(RNCHCHNR)CH][FeBr4] (wherein R is a tertiary butyl group) as a catalyst and di-tert-butyl peroxide as an oxidizing agent, and performing oxidizing reaction on a methylbenzene/ethylbenzene compound and arylamine to synthesize the benzylamine compound. The method is wide in application range, is suitable for a methylbenzene compound containing benzyl-position primary carbon-hydrogen bonds and also suitable for an ethylbenzene compound containing benzyl-position secondary carbon-hydrogen bonds. The method is a first case that preparation of the benzylamine compound through oxidizing reaction of the methylbenzene/ethylbenzene compound and the arylamine is realized with an iron catalyst.

Application of ionic iron (III) complex as catalyst in preparation of benzylamine compound

The invention discloses the application of an ionic iron (III) complex as a catalyst in preparation of a benzylamine compound, that is, an ionic iron (III) complex having a formula of [(RNCHCHNR)CH][FeBr4] (R is tert-butyl) and containing 1,3-di-tert-butyl imidazolium cation is used as a catalyst, di-tert-butyl peroxide is used as an oxidizing agent, and a benzylamine compound is synthesized by oxidation reaction of a toluene/ethylbenzene compound with an aromatic amine. The application of an ionic iron (III) complex as a catalyst in preparation of a benzylamine compound has wide application range, and is applicable not only to a toluene compound containing a benzylic primary carbon-hydrogen bond but also to an ethylbenzene compound containing a benzyl secondary carbon-hydrogen bond. Thisis the first example of the preparation of a benzylamine compound by oxidation reaction of a toluene/ethylbenzene compound and an aromatic amine by an iron-based catalyst.

Nickel-Catalyzed Cross-Coupling of Ammonia or Primary Alkylamines with (Hetero)aryl Sulfamates, Carbamates, or Pivalates

A catalyst system capable of effecting the cross-coupling of ammonia or primary alkylamines with (hetero)aryl sulfamates, carbamates, or pivalates is reported for the first time. The air-stable nickel(II) pre-catalyst C1 tolerates a broad spectrum of heterocyclic functionality within both reaction partners, as well as ether, nitrile, pyrrole, trifluoromethyl, and boronate ester substituents. In the case of reactions involving primary alkylamines and (hetero)aryl sulfamates and carbamates, room-temperature cross-couplings were achieved.

PHENYL SULFAMATE DERIVATIVES

Phenyl sulfamate derivatives represented by the following formula or salts thereof have a powerful inhibitory effect on steroid sulfatase and are hence useful for the prophylaxis or treatment of diseases associated with steroids such as estrogens, such as breast cancer, corpus uteri cancer, endometrial hyperplasia, infertility, endometriosis, adenomyosis uteri, autoimmune disease, dementia or Alzheimer's disease. wherein R1 and R2 each independently represent a hydrogen atom or a lower alkyl group; R3 represents a hydrogen atom, a halogen atom, a lower alkyl group, -OSO2NR1R2, a lower alkanoylamino group, a nitro group or a cyano group; and A represents a substituted or unsubstituted phenyl group, a group of the formula -X-NR4R5, or the like.