70660-38-7

Upstream product

• 100-42-5 styrene 
• 540-23-8 p-toluidine hydrochloride 
• 106-49-0 p-toluidine 
• 33863-82-0 4-methyl-N-(1-phenylethyl)aniline 

Downstream Products

• 70660-42-3 N-(4-methyl-2-(1-phenylethyl)phenyl)acetamide 
• 1152309-77-7 (4-methyl-2-(sec-phenethyl)phenyl)NCMe(C₅H₃N)CMeN(4-methyl-2-(sec-phenethyl)phenyl) 

Relevant academic research and scientific papers

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.

Cobalt-Catalyzed Hydroarylations and Hydroaminations of Alkenes in Tunable Aryl Alkyl Ionic Liquids

Tunable aryl alkyl ionic liquids (TAAILs) are a promising class of imidazolium- or triazolium-based ionic liquids. Contrary to "standard" all-alkyl ionic liquids, these carry an aryl ring together with a linear or branched alkyl chain. Their application i

Room-temperature Suzuki-Miyaura cross-coupling reaction with α-diimine Pd(II) catalysts

An α-diimine Pd(II) complex containing chiral sec-phenethyl groups, {bis[N,N′-(4-methyl-2-sec-phenethylphenyl)imino]-2,3-butadiene}dichloropalladium (rac-C1), was synthesized and characterized. rac-C1 was applied as an efficient catalyst for the Suzuki-Miyaura cross-coupling reaction between various aniline halides and arylboronic acid in PEG-400-H2O at room temperature. Among a series of aniline halides, rac-C1 did not catalyze the cross-coupling of aniline chlorides and fluorides but efficiently catalyzed the cross-coupling of aniline bromides and iodides with phenylboronic acid. The catalytic activity reduced slightly with increasing steric hindrance of the aniline bromides. The complexes {bis[N,N′-(4-fluoro-2,6-diphenylphenyl)imino]-2,3-butadiene}dichloropalladium and {bis[N,N′-(4-fluoro-2,6-diphenylphenyl)imino]acenaphthene}dichloropalladium were also found to be efficient catalysts for the reaction.

New nickel(II) diimine complexes bearing phenyl and sec-phenethyl groups: Synthesis, characterization and ethylene polymerization behaviour

A series of nickel(II) catalysts containing phenyl and chiral sec-phenethyl groups, {[(4-R1-2-R2C6H2-Rfnet C)2Nap]NiBr2} (Nap: 1,8-naphthdiyl, R1=Me, R2=Ph (3a); R1=Me, R2=sec-phenethyl (3b); R1=Cl, R2=sec-phenethyl (3c); R1=Me, R 2=Me (3d) were synthesized and characterized. All organic compounds were fully characterized by FT-IR and NMR spectroscopy and elemental analysis. The single crystal for X-ray crystallography was isolated from 3a in CH 2Cl2/n-hexane under air; the crystal structure showed a binuclear complex 3a, in which each nickel atom was six-coordinate. The two nickel atoms together with two bromine atoms form a planar four-membered ring, with a bromine and H2O axial ligands. These complexes, activated by diethylaluminum chloride and chiral nickel pre-catalysts rac-3c, exhibited good activities (up to 2.85×106g PE (mol Ni h bar)-1) for ethylene polymerization, and produced polyethylene products with a high degree of branching (up to 117 branched per 1000 carbons) at high temperature. The type and amount of branches of the polyethylenes obtained were determined by 1H and 13C NMR spectroscopy. Copyright

New chiral α-diimine nickel(II) complexes bearing ortho-sec-phenethyl groups for ethylene polymerization

A series of new α-diimine nickel(II) catalysts bearing bulky chiral sec-phenethyl groups have been synthesized and characterized. The molecular structure of representative chiral ligand, bis[N,N′-(4-methyl-2,6-di-sec- phenethylphenyl)imino]-1,2-dimethylethane rac-1c and chiral complexes, {bis[N,N′-(4-methyl-2-sec-phenethylphenyl)imino]-2,3-butadiene} dibromidonickel rac-2a and bis{bis[N,N′-(4-methyl-2-sec-phenethylphenyl) imino]-2,3-butadiene}dibromidonickel rac-2b, were confirmed by X-ray crystallographic analysis. Complex rac-2c bearing two chiral sec-phenethyl groups in the ortho-aryl position and a methyl group in the para-aryl position, activated by diethylaluminum chloride (DEAC), showed highly catalytic activity for the polymerization of ethylene [4.12 × 106 g PE (mol Ni.h.bar)-1], and produced highly branched polyethylenes under low ethylene pressure (branching degree: 104, 118 and 126 branches/1000 C at 20, 40 and 60°C, respectively). Chiral 20-electron bis-α-diimine Ni(II) complex rac-2b also exhibited high activity toward ethylene polymerization [1.71 × 106 g PE (mol Ni · h · bar)-1]. The type and amount of branches of the polyethylenes obtained were determined by 1H and 13C NMR. Copyright

An unsymmetrical iron(II) bis(imino)pyridyl catalyst for ethylene polymerization: Effect of a bulky ortho substituent on the thermostability and molecular weight of polyethylene

Three new iron(II) 2,6-bis(imino)pyridyl complexes bearing bulky and unsymmetrical substituted aniline groups, [2-(CH(CH3)(C 6H5))-4-R1-6-R2-C6H 2N - C(CH3)]2C5H 3NFeCl2 (1, R1 = H, R2 = methyl; 2, R1 = methyl, R2 = methyl; 3, R1 = H, R 2 = methoxy), were synthesized. The unsymmetrical bis(imino)pyridyl ligand L2 contains three isomers that can be detected by 1H NMR and 13C NMR spectroscopy. However, the corresponding complex 2 exhibits only one isomer in solution. X-ray diffraction of 2 confirms that the iron complex adopts a Cs configuration. These complexes activated by methylaluminoxane (MAO) have high catalytic activities for ethylene polymerization and produce linear polyethylenes with bimodal or broad molecular weight distribution. The steric and electronic effects of the ortho substituents on the aniline moiety distinctly affect the molecular weight of the obtained polyethylene. In comparison with 1 and 3, having a single ortho substituent on the aryl rings, and the typical complex 4, containing o-diisopropyl substitution, complex 2 has better thermal stability and produces much higher molecular weight polyethylene. Even at 70 °C, the 2/MAO system still keeps high activity and relatively stable kinetics.

A simple catalyst for the efficient benzylation of arenes by using alcohols, ethers, styrenes, aldehydes, or ketones

The compound [IrCp* (OTf)2(InBu)] (I nBu = 1,3-di-n-butyl-imidazolylidene) is an effective catalyst in the benzylation of arenes with different benzylating agents, such as alcohols, ethers and styrenes, representing an unprecedented highly versatile catalyst for this type of process. The same compound also catalyses a remarkable tandem process that allows the use of aldehydes and ketones as benzylating agents, through the base-free hydrogenation of C=O bonds with iPrOH and further use of the resulting primary or secondary alcohols as benzylating agents.

Acid-catalyzed ortho-alkylation of anilines with styrenes: An improved route to chiral anilines with bulky substituents

(Chemical Equation Presented) Reaction of para-substituted anilines with styrene derivatives at elevated temperatures, when catalyzed by CF 3SO3H, results in highly chemoselective ortho-alkylation of the aniline. When R = H, dialkylation can be achieved by varying the ratio of styrene to aniline. Several different substituted anilines and styrenes were examined, and good yields (42-87%) were obtained, except in the case where electron-withdrawing substituents are present on the styrene.