103-69-5Relevant articles and documents
Hydroamination of ethylene by aniline: Catalysis in water
Dub, Pavel A.,Rodriguez-Zubiri, Mireia,Baudequin, Christine,Poli, Rinaldo
, p. 1392 - 1396 (2010)
The platinum-catalyzed and halide-promoted hydroamination of ethylene with aniline is reported for the first time in the presence of simple sodium halides in water. Compounds K2PtX4 (X = Cl or Br), PtX2 or PtX4 (0.3% mol) in the presence of an aqueous solution of excess NaX and aniline under ethylene pressure (25 bar) affords N-ethylaniline with 60-85 turnovers after 10 h at 150°C. The best result (TON = 85) was obtained in the presence of excess NaBr, whereas a slightly lower activity was observed with NaCl (60 cycles) and practically no activity with NaF or NaI (2-4 cycles). The reaction also produces N,N-diethylaniline (up to 1 cycle) and 2-methylquinoline (up to 8 cycles) as by-products. The influence of added H + and different oxidizing agents was also examined.
A novel and efficient approach to mono-N-alkyl anilines via addition of Grignard reagents to aryl azides
Sampath Kumar,Subba Reddy,Anjaneyulu,Yadav
, p. 8305 - 8306 (1999)
Mono-N-alkyl anilines were obtained in high yields within a short reaction time when various aromatic azides were reacted with alkyl magnesium halides at room temperature.
Reduction of Amides to Amines under Mild Conditions via Catalytic Hydrogenation of Amide Acetals and Imidates
Kadyrov, Renat
, p. 185 - 191 (2019)
A simple and general protocol was developed for selective conversion of amides into amines. Amides were converted into amide acetals and imido esters by O-alkylation and then hydrogenated without isolation into amines under very mild reaction conditions over standard hydrogenation catalysts. Triethyloxonium tertafluoroborate, methyl trifluoromethanesulfonate, dimethyl sulfate and ethyl chloroformate were validated as alkylating agent. The synthetic utility of this approach was demonstrated by the selective carbonyl reduction of peptide groups. Carbonyl reduction of peptide group proceeds chemoselective without racemization of the neighboring chiral center. (Figure presented.).
Enhanced Aniline Alkylation Activity of Silica-supported Vanadia Catalysts over Simple Oxides
Narayanan, Sankarasubbier,Prasad, Boppana P.
, p. 1204 - 1205 (1992)
A very high aniline alkylation activity under vapour-phase conditions by silica-supported vanadia catalyst is reported.
Alanine triazole iridium-catalyzed C–N bond formation through borrowing hydrogen strategy
Yu, Xiaoli,Zhao, Ranran,Wan, Huida,Yang, Yongchun,Wang, Dawei
, p. 4588 - 4591 (2016)
An efficient synthesis of secondary amines has been described through alanine triazole iridium-catalyzed C–N bond formation of an aromatic amine and an alkyl amine using the borrowing hydrogen strategy. In addition, it was observed that alanine triazole iridium is also an efficient catalyst to promote C–N bond formation of an aromatic amine and alcohols with good to excellent yields.
High-pressure alkylation of azomethines 1. Synthesis of N-monoalkylanilines
Agafonov,Dudin,Preobrazhenskii,Zhulin
, p. 1005 - 1007 (1999)
Reaction of anils with alkyl halides under high pressure (10 kbar) was studied. Alkylation in polar media (dioxane or acetonitrile) followed by hydrolysis yields pure N-monoalkylanilines in high yields. Optimum conditions for high-pressure alkylation were found.
DFT and experimental studies on the PtX2/X--catalyzed olefin hydroamination: Effect of halogen, amine basicity, and olefin on activity, regioselectivity, and catalyst deactivation
Dub, Pavel A.,Bethegnies, Aurelien,Poli, Rinaldo
, p. 294 - 305 (2012)
A DFT/B3LYP study with inclusion of solvent and temperature effects has probed the olefin activation mechanism for the intermolecular hydroamination of ethylene and 1-hexene by aniline derivatives catalyzed by the PtX 2/X- system on the basis of a variety of experimental results, including new experiments on catalyst deactivation. For ethylene and aniline, the calculated ΔG?cycle between the resting state [PtX3(C2H4)]-, 1X, and the TOF-determining transition state of the C-H reductive elimination from [PtX3(H)-(CH2CH2NHPh)]-, TS2 X, is slightly smaller for X = Br than for Cl or I. The ΔG?cycle decreases as the aniline basicity decreases. For the slightly less efficient hydroamination of 1-hexene, ΔG? cycle is greater than that for the hydroamination of ethylene, with a preference for the Markovnikov addition, in agreement with experiment and with essentially equivalent ΔG?cycle values for the Br and I systems. In general, the results of the calculations are in agreement with the experimental observation. A clear-cut comparison of trends is hampered by the small energy differences and by the possibility, proven in certain cases, that the reaction parameters under investigation affect the catalyst degradation rate in addition to its intrinsic activity. Extrapolation of the computational study to the fluoride system suggests that this should be even more active. However, experimental studies show that this is not the case. The reason for this anomaly has been traced to the basicity of the fluoride ion, which triggers more rapid catalyst decomposition. A bonding analysis of 1X indicates a significant push-pull π interaction between the C2H4 and the trans-F ligand.
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Lyle,Troscianiec
, p. 1757,1758,1759 (1955)
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Connor,Fischer
, p. 1024 (1967)
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PLATINUM COMPLEX CATALYZED TRANSFORMATION OF AMINE. N-ALKYLATION AND N-ALLYLATION USING PRIMARY ALCOHOLS
Tsuji, Yasushi,Takeuchi, Ryo,Ogawa, Hiroshi,Watanabe, Yoshihisa
, p. 293 - 294 (1986)
Amines reacted with primary alcohols in the presence of a platinum complex catalyst at 120-180 deg C to give N-alkylated or N-alyllated compounds.
DEPENDENCE OF THE COMPOSITION OF THE PRODUCTS OF THERMAL FRAGMENTATION OF THIACYANINE DYES ON THE LENGTH OF THEIR POLYMETHINE CHAIN
Khesin, V. G.,Al'perovich, M. A.,Abramenko, P. I.,Raikhina, R. D.,Medvedeva, T. D.
, (1982)
The pathways of thermal fragmentation of thiacyanine dyes with different lengths of the external polymethine chain were investigated.The results of thermolysis of the thiacyanines are compared with the results of quantum-chemical calculations of their mol
RUTHENIUM CATALYZED SYNTHESIS OF QUINOLINE DERIVATIVES FROM NITROARENES AND ALIPHATIC ALCOHOLS.
Watanabe,Tsuji,Shida
, p. 435 - 438 (1984)
Nitroarenes are reductively converted into quinoline derivatives with aliphatic alcohols in the presence of a catalytic amount of ruthenium compound at 180 degree C. Ruthenium(III) chloride is the most effective catalyst. The reaction of nitrobenzene with 1-propanol and 1-butanol gave 2-ethyl-3-methylquinoline and 3-ethyl-2-propylquinoline in 65 and 70% yields respectively. p-Methoxynitrobenzene gave 3-ethyl-6-methoxy-2-propyquinoline in 70% yield with 1-butanol. The reaction appears to include the redox reaction between the nitroarenes and the alcohols, that is, a catalytic hydrogen transfer reaction which generates the aminoarenes and aldehydes. Thus, the alcohol plays roles as both a reductant and an aldehyde precursor.
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Diamond et al.
, p. 490 (1979)
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Suzuki et al.
, p. 4329 (1971)
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A covalent organic framework-based route to the: In situ encapsulation of metal nanoparticles in N-rich hollow carbon spheres
Chen, Liyu,Zhang, Lei,Chen, Zhijie,Liu, Hongli,Luque, Rafael,Li, Yingwei
, p. 6015 - 6020 (2016)
Metal nanoparticles (NPs) encapsulated in hollow nanostructures hold great promise for a variety of applications. Herein, we demonstrate a new concept where covalent organic frameworks (COFs) doped with metal cations can be readily used as novel precursors for the in situ encapsulation of metal NPs into N doped hollow carbon spheres (NHCS) through a controlled carbonization process. The obtained Pd@NHCS composites show a significantly enhanced catalytic activity and selectivity in the hydrogenation of nitrobenzene in ethanol and oxidation of cinnamyl alcohol compared with that of the conventional Pd/N-C and commercial Pd/C catalysts. The excellent catalytic performance should be related to the synergism of the porous hollow spheric structure, highly dispersed Pd NPs, and uniform distribution of N dopants on the materials. We believe that this newly developed methodology could be extended to the synthesis of other metal NPs@NHCS composites for a variety of advanced applications.
Regiospecific rearrangement of hydroxylamines to secondary amines using diisobutylaluminum hydride
Cho, Hidetsura,Sugimoto, Kenji,Iwama, Yusuke,Mitsuhashi, Nakako,Okano, Kentaro,Tokuyama, Hidetoshi
, p. 1633 - 1644 (2011)
A systematic investigation of a reductive ring-expansion reaction of N-monosubstituted hydroxylamines with diisobutylaluminum hydride (DIBALH) was carried out. The reaction regiospecifically provided a variety of bicyclic or tricyclic heterocycles or linear secondary amines containing nitrogen attached to an aromatic ring. The Japan Institute of Heterocyclic Chemistry.
Photochemical hydrogen abstraction by singlet and triplet nπ* states of aromatic nitrogen: Fragmentation of 4-alkylpyrimidines and 2-alkylquinolines
Prathapan, Sreedharan,Loft, Sarah,Agosta, William C.
, p. 3940 - 3944 (1990)
On either direct irradiation in water or triplet-sensitized irradiation in acetone, pyrimidines 1a-c undergo hydrogen abstraction from an nπ* triplet state, fragmentation, and rearomatization to form 5 (eq 1). Similarly, direct irradiation of quinolines 2a-c in benzene or tert-butyl alcohol furnishes 6 from an nπ* singlet state. Quantum yields for products (Φ5 and Φ6) and Stern-Volmer quenching studies on these reactions (Tables I and II) provide mechanistic information concerning abstraction by aromatic nitrogen. Unlike Φ for abstraction by carbonyl triplets, Φ5 and Φ6 do not increase in hydrogen-bonding solvent, and there is little rate difference in transferring primary, secondary, and tertiary hydrogen in the initial step. Singlet and triplet abstractions show little difference in selectivity, but the singlet reaction is ? 104 faster. Concentration studies show that fragmentation of 1a-c is self-quenched, while reaction of 2a-c is enhanced with increasing concentration.
THE RUTHENIUM COMPLEX CATALYZED REDUCTIVE TRANSFORMATION OF NITROBENZENE. A NOVEL ROUTE TO 2,3-DIALKYLQUINOLINES AND N-ALKYLANILINES USING SATURATED ALCOHOLS
Watanabe, Yoshihisa,Tsuji, Yasushi,Suzuki, Naoki
, p. 1067 - 1068 (1981)
Nitrobenzene reacts with saturated alcohols in the presence of a catalytic amount of ruthenium complex at 180 deg C to give 2,3-dialkylquinolines and N-alkylanilines in good yields.The reaction appears to include reduction of nitrobenzene with the alcohols by hydrogen transfer reaction.
Tandem reduction studies of bromo compounds using tetrabutylammonium borohydride
Narasimhan,Swarnalakshmi,Balakumar,Velmathi
, p. 685 - 689 (1999)
Tetrabutylammonium borohydride can be used for multifunctional transformations through tandem reductions of halo compounds in THF.
Synthesis and development of Chitosan anchored copper(II) Schiff base complexes as heterogeneous catalysts for N-arylation of amines
Anuradha,Kumari, Shweta,Pathak, Devendra D.
, p. 4135 - 4142 (2015)
Abstract The Chitosan anchored Cu(II) Schiff base complexes (C1-C3) have been synthesized and characterized by FTIR, UV, FE-SEM, EDAX, TGA, AAS and elemental analysis. These complexes have been found to be efficient and recyclable heterogeneous catalysts for the Chan-Lam C-N coupling reaction of various aromatic/aliphatic amines with arylboronic acid under mild reaction conditions. These complexes can be easily filtered out from the reaction medium and reused up to five times without significant loss of catalytic activity.
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Yakhontov,Marshalkin
, p. 2807 (1973)
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Rice,Kohn
, p. 4052 (1955)
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Nanosized CdS as a Reusable Photocatalyst: The Study of Different Reaction Pathways between Tertiary Amines and Aryl Sulfonyl Chlorides through Visible-Light-Induced N-Dealkylation and C-H Activation Processes
Firoozi, Somayeh,Hosseini-Sarvari, Mona
, p. 2117 - 2134 (2021/02/05)
It has been found that the final products of the reaction of sulfonyl chlorides and tertiary amines in the presence of cadmium sulfide nanoparticles under visible light irradiation are highly dependent on the applied reaction conditions. Interestingly, with the change of a reaction condition, different pathways were conducted (visible-light-induced N-dealkylation or sp3 and sp2 C-H activation) that lead to different products such as secondary amines and various sulfonyl compounds. Remarkably, all of these reactions were performed under visible light irradiation and an air atmosphere without any additive or oxidant in benign solvents or under solvent-free conditions. During this study, the CdS nanoparticles as affordable, heterogeneous, and recyclable photocatalysts were designed, successfully synthesized, and fully characterized and applied for these protocols. During these studies, intermediates resulting from the oxidation of tertiary amines are trapped during the photoinduced electron transfer (PET) process. The reaction was carried out efficiently with a variety of substrates to give the corresponding products at relatively short times in good to excellent yields in parallel with the use of the visible light irradiation as a renewable energy source. Most of these processes are novel or are superior in terms of cost-effectiveness, safety, and simplicity to published reports.
Novel hybrid conjugates with dual estrogen receptor α degradation and histone deacetylase inhibitory activities for breast cancer therapy
Zhao, Chenxi,Tang, Chu,Li, Changhao,Ning, Wentao,Hu, Zhiye,Xin, Lilan,Zhou, Hai-Bing,Huang, Jian
, (2021/05/10)
Hormone therapy targeting estrogen receptors is widely used clinically for the treatment of breast cancer, such as tamoxifen, but most of them are partial agonists, which can cause serious side effects after long-term use. The use of selective estrogen receptor down-regulators (SERDs) may be an effective alternative to breast cancer therapy by directly degrading ERα protein to shut down ERα signaling. However, the solely clinically used SERD fulvestrant, is low orally bioavailable and requires intravenous injection, which severely limits its clinical application. On the other hand, double- or multi-target conjugates, which are able to synergize antitumor activity by different pathways, thus may enhance therapeutic effect in comparison with single targeted therapy. In this study, we designed and synthesized a series of novel dual-functional conjugates targeting both ERα degradation and histone deacetylase inhibiton by combining a privileged SERD skeleton 7-oxabicyclo[2.2.1]heptane sulfonamide (OBHSA) with a histone deacetylase inhibitor side chain. We found that substituents on both the sulfonamide nitrogen and phenyl group of OBHSA unit had significant effect on biological activities. Among them, conjugate 16i with N-methyl and naphthyl groups exhibited potent antiproliferative activity against MCF-7 cells, and excellent ERα degradation activity and HDACs inhibitory ability. A further molecular docking study indicated the interaction patterns of these conjugates with ERα, which may provide guidance to design novel SERDs or PROTAC-like SERDs for breast cancer therapy.
