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Upstream product

• 100-42-5 styrene 
• 100-61-8 N-methylaniline 
• 28059-49-6 N-methyl-N-(2-phenylethyl)aniline 

Relevant academic research and scientific papers

Chemo- and Regioselective Hydroarylation of Alkenes with Aromatic Amines Catalyzed by [Ph3C][B(C6F5)4]

A nonmetal catalyst [Ph3C][B(C6F5)4] has been developed to catalyze hydroarylation reaction of alkenes with aromatic primary, secondary, and tertiary amines, which generated aniline derivatives in 32-98% yields. This method is applicable to a wide range of substrates, is highly chemo- and regioselective, and provides a simple and efficient approach for aniline derivative preparation.

Zeolite catalyzed hydroarylation of alkenes with aromatic amines under organic ligand-free conditions

The hydroarylation of alkenes with aromatic amines is recognized as the most atom-economical and straightforward approach to obtain functional aromatic amines, which are versatile building blocks in organic synthesis and material chemistry. However, controllable synthesis of single hydroarylation product is still a significant challenge because hydroarylation reaction often delivers four hydroarylation products and hydroamination products are also produced during the reaction. Herein, we report the first example of heterogeneous zeolite catalyzed hydroarylation of styrene and norbornene with aniline derivatives under organic ligand-free conditions. With the USY zeolite as catalyst, a wide scope of alkenes and aromatic amines with various functional groups are smoothly converted into the corresponding products in 48–95% yields with high regioselectivity. Detailed characterizations revealed that Lewis acid can promote Hofmann-Martius rearrangement of hydroamination products toward hydroarylation products, resulting in high selectivity for hydroarylation products. In addition, it could be found that the weak acid sites of zeolite play a key role in forming hydroarylation products. Furthermore, the catalyst can be reused at least 10 times without obvious deactivation. This work may promote the development of heterogeneous catalyst system for alkene hydroarylation.

On the Superior Activity of In(I) versus In(III) Cations Toward ortho-C-Alkylation of Anilines and Intramolecular Hydroamination of Alkenes

An efficient ortho-C-alkylation of unprotected anilines with a variety of styrenes and alkenes using a univalent cationic indium(I) catalyst is reported. Mechanistic studies revealed that the reaction likely proceeds via a tandem hydroamination/Hofmann-Martius rearrangement. The high compatibility between the cationic indium(I) complex and primary anilines led us to develop an In(I)+-catalyzed hydroamination of alkenes using unprotected primary and secondary alkenylamines. Computations support the catalytic activity of naked In(I)+ ions, with an outer sphere mechanism for the C-N bond formation and a potentially inner sphere protodemetallation.

Method for catalyzing hydrocarbon bond alkylation reaction of aromatic amine

The invention relates to a method for catalyzing hydrocarbon bond alkylation reaction of aromatic amine. The method comprises the step of reacting by virtue of olefin represented by a formula (1) and secondary aromatic amine represented by a formula (2) at 25-130 DEG C in an aprotic solvent under the catalysis of triphenyl carbon tetra(pentafluorophenyl)borate, wherein the formula (1) and the formula (2) are as follows: formulae (shown in the description), wherein R1 is selected from C1-C6 alkyl or aryl, R2 is selected from hydrogen, methyl or halogen, and R3 is selected from C1-C4 alkyl or -(CH2)n- (n is equal to 1 and 2). The method has the beneficial effects that the hydrocarbon bond alkylation reaction efficiency of aromatic amine is effectively improved, the raw materials are easily available, the operation is simple and convenient, reaction conditions are relatively mild, the yield is relatively high, and the application range of a substrate is relatively wide.

Intermolecular hydroamination of vinyl arenes using tungstophosphoric acid as a simple and efficient catalyst

The intermolecular hydroamination of vinyl arene derivatives has been efficiently carried out using a tungstophosphoric acid (TPA) catalyst under solvent free and mild reaction conditions. The present protocol provides an environmentally benign, easy to handle and highly active solid acid catalyst for hydroamination of vinyl arenes. The catalyst yields both hydroamination and hydroarylation products and the selectivity mostly depends on the reaction conditions.

Catalytic alkylation of aromatic amines with styrene in the presence of cationic rhodium complexes and acid

The first transition metal-catalyzed Friedel-Crafts alkylation of aromatic amines with styrene is reported. ortho-Alkylation of anilines occurs using catalytic amounts of [Rh(cod)2]BF4/4 PPh3 and HBF4.

N-H activation vs. C-H activation: Ruthenium-catalysed regioselective hydroamination of alkynes and hydroarylation of an alkene with N-methylaniline

Phenylacetylene and its derivatives undergo regioselective insertion into the N-H bond of N-methylaniline in the presence of Ru3(CO)12 catalyst to afford N-methyl-N-(α-styryl)anilines in high yields, whereas styrene reacts with the ortho C-H bond of N-methylaniline giving 2-(1-phenylethyl)-N-methylaniline.

REACTIONS OF STYRENE WITH AROMATIC AMINES

In alkylation with styrene N,N-dimethylaniline in the presence of aluminum phenoxide, and aniline and N-methylaniline, also in the presence of aluminum phenoxide, as also of the corresponding hydrochlorides, usually form mixtures of mono(α-methylbenzyl)anilines, in which ortho-substitution products predominate.When aluminum phenoxide is used as catalyst, the yields of o-aralkylanilines attain 92-94percent.In the alkylation of N-methyl- and N,N-dimethyl-anilines demethylation and disproportionation occur.

MOLECULAR REARRANGEMENTS, XVIII. PHOTOLYSIS OF N-ALKYL-ARYLAMINES

The direct photolysis of N-benzyl-N-methyl-aniline in isopropanol at 25 deg C for 15 hours in air gives benzaldehyde, toluene, bibenzyl, N-methylaniline and a mixture of o- and p-benzyl-N-methylaniline.Analogous products are also obtained from the photolysis of N-α- or -β-phenethyl-N-methyl-aniline in addition to trans-2,3-diphenylbutene-2 and 9,10-dimethyl-phenanthrene.The results are interpreted in terms of an intramolecular free radical mechanism starting by homolysis of the N-aralkyl bond into N-methyl-anilino and aralkyl free radicals that subsequently contribute to the formation of the identified products.