- Method for preparing amine through catalytic reduction of nitro compound by cyclic (alkyl) (amino) carbene chromium complex
-
The cyclic (alkyl) (amino) carbene chromium complex is prepared from corresponding ligand salt, alkali and CrCl3 and used for catalyzing pinacol borane to reduce nitro compounds in an ether solvent under mild conditions to generate corresponding amine. The method for preparing amine has the advantages of cheap and accessible raw materials, mild reaction conditions, wide substrate application range, high selectivity and the like, and is simple to operate.
- -
-
Paragraph 0015
(2021/04/17)
-
- Continuous and Selective Hydrogenation of Heterocyclic Nitroaromatics in a Micropacked Bed Reactor
-
The hydrogenation of heterocyclic nitroaromatics is of great importance in the pharmaceutical industry for the synthesis of key intermediates. However, high selectivity is difficult to achieve in conventional batch reactors owing to severe back mixing and poor mass transfer performance, resulting in the high requirement for subsequent separation processes. In this work, a continuous flow system based on a micropacked bed reactor is developed for the selective hydrogenation of heterocyclic nitroaromatics and the reductions of 5-nitroisoquinoline to 5-aminoisoquinoline and 5-amino-1,2,3,4-tetrahydroisoquinoline are selected as the model reactions. With the optimal reaction conditions, maximal yields of 99.9% (5-aminoisoquinoline) and 99.3% (5-amino-1,2,3,4-tetrahydroisoquinoline) are obtained successfully. Moreover, this system exhibits remarkable performance for the selective hydrogenation of relevant heterocyclic nitroaromatics with all yields beyond the level of 97.5%. The continuous flow system enables efficient hydrogenation of heterocyclic nitroaromatics and remarkable selectivity of target products with shorter reaction time and safer operation compared with batch reactors.
- Chen, Xingkun,Duan, Xiaonan,Wang, Xuepeng,Zhang, Jisong
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p. 2100 - 2109
(2021/09/08)
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- Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
-
Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
- Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
-
supporting information
p. 1618 - 1629
(2021/01/25)
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- Palladium supported on metal–organic framework as a catalyst for the hydrogenation of nitroarenes under mild conditions
-
Sustainable development demands an environmentally friendly and efficient method for the hydrogenation of organic molecules, including the hydrogenation of functionalized nitroarenes. In this study, a highly active and selective metal–organic framework-supported palladium catalyst was prepared for the catalytic hydrogenation of nitroarenes. High selectivity (>99%) and excellent yield (98%) of aniline were realized after 2 hours in ethanol under hydrogen (1 atm) at room temperature. The reductions were successfully carried out in the presence of a wide range of other reducible functional groups. More importantly, the catalyst was very stable without the loss of its catalytic activity after five cycles.
- Bao, Lingxiang,Fei, Teng,Li, Jiazhe,Pang, Siping,Sun, Chenghui,Yan, Zhiyuan,Yu, Zongbao
-
-
- Method for reducing aromatic nitro into arylamine
-
The invention relates to a method for reducing aromatic nitro to arylamine. The method comprises the following steps: (1) taking an aromatic nitro compound as a raw material, water as a hydrogen source, a palladium compound, cheap and easy to obtain, as a catalyst and tetrahydroxydiboron as an additive to reduce nitro to obtain a product; (2) taking the aromatic nitro compound as the raw material, a copper salt, cheap and easy to obtain, as the catalyst, the tetrahydroxydiboron as the additive to reduce the nitro to obtain a product; and (3) taking the aromatic nitro compound as the raw material, water as the hydrogen source, and the tetrahydroxydiboron as the additive, without needing a metal catalyst, to reduce the nitro to obtain a product. A preparation method for the arylamine, which is provided by the invention, is mild in reaction condition, low in costs, environment-friendly, high in yield, and suitable for industrial production.
- -
-
Paragraph 0189-0192; 0241-0244; 0281-0284
(2020/07/15)
-
- Visible-Light-Photocatalyzed Reductions of N-Heterocyclic Nitroaryls to Anilines Utilizing Ascorbic Acid Reductant
-
A photoreductive protocol utilizing [Ru(bpy)3]2+ photocatalyst, blue light LEDs, and ascorbic acid (AscH2) has been developed to reduce nitro N-heteroaryls to the corresponding anilines. Based on experimental and computational results and previous studies, we propose that the reaction proceeds via proton-coupled electron transfer between AscH2, photocatalyst, and the nitro N-heteroaryl. The method offers a green catalytic procedure to reduce, e.g., 4-/8-nitroquinolines to the corresponding aminoquinolines, substructures present in important antimalarial drugs.
- Todorov, Aleksandar R.,Aikonen, Santeri,Muuronen, Mikko,Helaja, Juho
-
supporting information
p. 3764 - 3768
(2019/05/24)
-
- Copper(ii)-catalyzed c-n coupling of aryl halides and n-nucleophiles promoted by quebrachitol or diethylene glycol
-
Herein, we report the natural ligand quebrachitol (QCT) as a promoter for a Cu(II) catalyst, which is highly effective for N-Arylation of various amines and related aryl halides. A series of diarylamine derivatives were obtained in high yields by using diethylene glycol (DEG) as both ligand and solvent. The C-N coupling reactions proceed under mild conditions and exhibit good functional group tolerance.
- Chen, Guoliang,Chen, Yuanguang,Du, Fangyu,Fu, Yang,Wu, Ying,Zhou, Qifan
-
supporting information
p. 2161 - 2168
(2019/11/25)
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- Divergent Late-Stage (Hetero)aryl C?H Amination by the Pyridinium Radical Cation
-
(Hetero)arylamines constitute some of the most prevalent functional molecules, especially as pharmaceuticals. However, structurally complex aromatics currently cannot be converted into arylamines, so instead, each product isomer must be assembled through a multistep synthesis from simpler building blocks. Herein, we describe a late-stage aryl C?H amination reaction for the synthesis of complex primary arylamines that other reactions cannot access directly. We show and rationalize through a mechanistic analysis the reasons for the wide substrate scope and the constitutional diversity of the reaction, which gives access to molecules that would not have been readily available otherwise.
- Ham, Won Seok,Hillenbrand, Julius,Jacq, Jér?me,Genicot, Christophe,Ritter, Tobias
-
supporting information
p. 532 - 536
(2019/01/04)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
-
In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
- -
-
Paragraph 0257
(2018/03/25)
-
- Mechanochemical catalytic transfer hydrogenation of aromatic nitro derivatives
-
Mechanochemical ball milling catalytic transfer hydrogenation (CTH) of aromatic nitro compounds using readily available and cheap ammonium formate as the hydrogen source is demonstrated as a simple, facile and clean approach for the synthesis of substituted anilines and selected pharmaceutically relevant compounds. The scope of mechanochemical CTH is broad, as the reduction conditions tolerate various functionalities, for example nitro, amino, hydroxy, carbonyl, amide, urea, amino acid and heterocyclic. The presented methodology was also successfully integrated with other types of chemical reactions previously carried out mechanochemically, such as amide bond formation by coupling amines with acyl chlorides or anhydrides and click-type coupling reactions between amines and iso(thio)cyanates. In this way, we showed that active pharmaceutical ingredients Procainamide and Paracetamol could be synthesized from the respective nitro-precursors on milligram and gram scale in excellent isolated yields.
- Portada, Tomislav,Margeti?, Davor,?trukil, Vjekoslav
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supporting information
(2018/12/11)
-
- Cu-catalyzed reduction of azaarenes and nitroaromatics with diboronic acid as reductant
-
A ligand-free copper-catalyzed reduction of azaarenes with diboronic acid as reductant in an aprotic solvent under mild conditions has been developed. Most interestingly, the nitroazaarenes could be reduced exclusively to give the corresponding amines without touching the azaarene moieties. Furthermore, the reductive amination of aromatic nitro compounds and aromatic aldehydes has also been realized. A series of hydrogenated azaarenes and secondary amines were obtained with good functional group tolerance.
- Pi, Danwei,Zhou, Haifeng,Zhou, Yanmei,Liu, Qixing,He, Renke,Shen, Guanshuo,Uozumi, Yasuhiro
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p. 2121 - 2129
(2018/03/23)
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- Preparation of Well-Ordered Mesoporous-Silica-Supported Ruthenium Nanoparticles for Highly Selective Reduction of Functionalized Nitroarenes through Transfer Hydrogenation
-
MCM-41-type mesoporous silica (OMS-IL) was prepared by using an ionic liquid (1-hexadecyl-3-methylimidazolium bromide) as a template. The XRD and TEM results demonstrated that OMS-IL was more stable than the MCM-41 material. Ru nanoparticles were supported on OMS-IL (Ru/OMS-IL) by impregnating OMS-IL with a RuCl3 aqueous solution, and the resulting material was used for the selective reduction of nitroarenes. The effects of the components of the catalysts and the reaction conditions on the catalytic behavior of the prepared catalysts were investigated in detail. Ru/OMS-IL exhibited high catalytic activity and chemoselectivity for the reduction of various substituted nitroarenes to the corresponding aromatic amines in ethanol with hydrazine hydrate as a hydrogen donor under mild conditions. The Ru/OMS-IL catalysts were highly stable and could easily be recovered by simple filtration over at least six recycling reactions without any observable loss in catalytic performance.
- Wei, Ning,Zou, Xiujing,Huang, Haigen,Wang, Xueguang,Ding, Weizhong,Lu, Xionggang
-
supporting information
p. 209 - 214
(2018/01/26)
-
- Nitrogen-doped graphene-activated metallic nanoparticle-incorporated ordered mesoporous carbon nanocomposites for the hydrogenation of nitroarenes
-
Herein, nanoscale metallic nanoparticle-incorporated ordered mesoporous carbon catalysts activated by nitrogen-doped graphene (NGr) were fabricated via an efficient multi-component co-assembly of a phenolic resin, nitrate, acetylacetone, the nitrogen-containing compound 1,10-phenanthroline, and Pluronic F127, followed by carbonization. The obtained well-dispersed nitrogen-doped graphene-activated transition metal nanocatalysts possess a 2-D hexagonally arranged pore structure with a high surface area (~500 m2 g-1) and uniform pore size (~4.0 nm) and show excellent activity for the selective hydrogenation-reduction of substituted nitroarenes to anilines in an environmentally friendly aqueous solution. The high catalytic performance and durability is attributed to the synergistic effects among the components, the unique structure of the nitrogen-doped graphene layer-coated metallic nanoparticles, and electronic activation of the doped nitrogen.
- Huang, Haigen,Wang, Xueguang,Sheng, Yao,Chen, Chenju,Zou, Xiujing,Shang, Xingfu,Lu, Xionggang
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p. 8898 - 8909
(2018/03/08)
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- N-doped graphitic carbon-improved Co-MoO3 catalysts on ordered mesoporous SBA-15 for chemoselective reduction of nitroarenes
-
Metallic Co-MoO3 catalysts supported on ordered mesoporous SBA-15 were first prepared through in situ reaction of SBA-15-supported Co-Mo oxides with 1,10-phenanthroline. The resulting Co-MoO3/NC@SBA-15 catalysts with N-doped carbon (NC) exhibited high catalytic activity and chemoselectivity for selective reduction of various functionalized nitroarenes to the corresponding arylamines in ethanol with hydrazine hydrate at near room temperature (30 °C). For reduction of all tested substrates (28 examples), the catalyst could afford a conversion of >99% and arylamine selectivity of >99%. The excellent catalytic performance of the Co-MoO3/NC@SBA-15 was attributed to the Co-Nχ(C)-Mo active sites generated through the interaction between the surface Co-Nχ(C) and MoO3 species, promoting the dissociation of hydrazine molecule into the active H* species for the reduction of nitro groups. After the seventh cycle for reduction of 4-methoxylnitrobenzene, the 2%Co-MoO3/NC@SBA-15 showed little change in catalytic performance, textural properties, size and dispersion of metal species and valence states of elements, indicating high stability and recyclability.
- Huang, Haigen,Liang, Xiangcheng,Wang, Xueguang,Sheng, Yao,Chen, Chenju,Zou, Xiujing,Lu, Xionggang
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p. 127 - 137
(2018/05/04)
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- Highly chemoselective reduction of nitroarenes over non-noble metal nickel-molybdenum oxide catalysts
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The chemoselective reduction of nitroarenes is an important transformation for the production of arylamines, which are the primary intermediates in the synthesis of pharmaceuticals, agrochemicals and dyes. Heterogeneous non-noble metal nickel-molybdenum oxide catalysts supported on ordered mesoporous silica SBA-15 (Ni-MoO3/CN@SBA-15) were prepared for the first time by treating SBA-15-supported nickel-molybdenum oxide materials with 1,10-phenanthroline, and exhibited unprecedented catalytic activity and chemoselectivity for the reduction of various substituted nitroarenes to the corresponding aromatic amines in ethanol with hydrazine hydrate as a hydrogen donor under mild conditions owing to the synergistic effect of metal Ni and MoO3 species, affording excellent yields of >99% within very short reaction periods (≤60 min). The Ni-MoO3/CN@SBA-15 catalysts were highly stable and could easily be recovered by simple filtration or by an external magnetic field for at least ten recycling reactions without any observable loss of catalytic performance or leaching of metal components.
- Huang, Haigen,Wang, Xueguang,Li, Xu,Chen, Chenju,Zou, Xiujing,Ding, Weizhong,Lu, Xionggang
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p. 809 - 815
(2017/08/15)
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- NOVEL QUINOLINE DERIVATIVES AND PHARMACEUTICAL COMPOSITIONS FOR PREVENTING OR TREATING CANCER CONTAINING THE SAME
-
The present invention refers to an excellent cancer antiproliferative potency relative to the quinoline compounds, a pharmaceutically acceptable salt, or hydrate and, number of active ingredient containing bath method and pharmaceutical composition for the prevention or treatment of cancer disease relates to search, said present invention according to compound, a pharmaceutically acceptable salt thereof, or hydrate number and number and mutant kinase protein kinase activity number of excellent cancer billion billion number activity and thus, new anticancer number is useful as the effective component can be. (by machine translation)
- -
-
Paragraph 0147-0148; 0155-0158
(2017/11/10)
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- Water as a hydrogen source in palladium-catalyzed reduction and reductive amination of nitroarenes mediated by diboronic acid
-
An unprecedented palladium-catalyzed chemoselective reduction and reductive amination of nitroarenes with water as a hydrogen source mediated by diboronic acid have been discovered. A series of aryl amines containing various reducible functional groups were obtained in good to excellent yields.
- Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Pi, Danwei,Shen, Guanshuo
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p. 3898 - 3904
(2017/06/13)
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- Synthesis of fluorine-containing 1,10-phenanthrolines using mild versions of Skraup and Doebner-von Miller reactions
-
A versatile route for the synthesis of new 1,10-phenanthroline derivatives with fluorine-containing groups is described. Skraup reactions were performed with yields of 19 up to 48% and overall yields of 5 up to 13% based on different fluorinated anilines as starting materials. Ten formerly unknown derivatives were synthesized and characterized by NMR spectroscopy (1H,13C,19F), ESI mass spectrometry and elemental analysis.
- Lüdtke, Carsten,Haupt, Axel,Wozniak, Martin,Kulak, Nora
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- PVP-Pd nanoparticles as efficient catalyst for nitroarene reduction under mild conditions in aqueous media
-
The catalytic activity of PVP-Pd nanoparticles synthesized by electrochemical methods was explored in nitroaromatic hydrogenation reaction. In this transformation, the colloidal nanocatalyst proved to have outstanding catalytic activity under sustainable reaction conditions. This mild process efficiently reduced the nitroaromatic group at room temperature, without high pressure of molecular hydrogen and in aqueous medium. Furthermore, several functional groups were tolerated, given the corresponding substituted arylamines in excellent yields and with high TOF. In addition, one-pot reactions and tandem process were explored, in which nitroaromatic hydrogenation reaction was included in the synthesis of modified amines. This methodology was effectively incorporated in tandem reactions and one-pot procedures, achieving N-arylamines functionalized in good isolated yields. Finally, comparison of sustainable chemistry metrics analysis demonstrated that this methodology is a reliable approach to perform the nitro compound hydrogenation process.
- Uberman, Paula M.,García, Carolina S.,Rodríguez, Julieta R.,Martín, Sandra E.
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supporting information
p. 739 - 748
(2017/05/19)
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- Fine-Bubble-Based Strategy for the Palladium-Catalyzed Hydrogenation of Nitro Groups: Measurement of Ultrafine Bubbles in Organic Solvents
-
Fine bubbles of hydrogen were employed as a new reaction medium for the autoclave-free gas-liquid-solid multiphase hydrogenation of nitro groups on a multigram scale. Furthermore, ultrafine bubbles were examined by nanoparticle-tracking analysis in organic solvents.
- Mase, Nobuyuki,Nishina, Yuki,Isomura, Shogo,Sato, Kohei,Narumi, Tetsuo,Watanabe, Naoharu
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supporting information
p. 2184 - 2188
(2017/09/26)
-
- High Performance and Active Sites of a Ceria-Supported Palladium Catalyst for Solvent-Free Chemoselective Hydrogenation of Nitroarenes
-
Cerium oxide-supported palladium catalysts (Pd/CeO2) prepared by a simple impregnation method exhibit exciting catalytic activity and high chemoselectivity for the solvent-free hydrogenation of a variety of substituted nitroarenes including the reducible functional groups to the corresponding aromatic amines under mild reaction conditions. Taking nitrobenzene as an example, the Pd/CeO2 catalyst can afford aniline yields of >99 % with turnover frequencies as high as 11 411 h?1 and 69 824 h?1 at 40 °C and 100 °C, respectively. Pd2+ ion species exist as isolated single atoms with ?Pd2+?O2??Ce4+? linkages on the surface of PdxCe1?xO2?σ solid solution and are found to be active sites for the selective hydrogenation of nitroarenes in the absence of solvent. The superior catalytic performance can be attributed to the cooperative effect between Pd2+ ions and unique surface sites of CeO2. A possible mechanism is proposed for the hydrogenation of nitroarenes with H2 over the Pd/CeO2. The Pd/CeO2 catalyst can be recovered easily and reused for at least seven recycling reactions without loss of catalytic properties.
- Shi, Xiuxiu,Wang, Xueguang,Shang, Xingfu,Zou, Xiujing,Ding, Weizhong,Lu, Xionggang
-
p. 3743 - 3751
(2017/10/16)
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- Heteroatom-doped Carbon Spheres from Hierarchical Hollow Covalent Organic Framework Precursors for Metal-Free Catalysis
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Covalent organic frameworks (COFs) with hollow structures hold great promise for developing new types of functional materials. Herein, we report a hollow spherical COF with a hierarchical shell, which serves as an effective precursor of B,N-codoped hierarchical hollow carbon spheres. Benefiting from the synergistic effects of hierarchical porosity, high surface area, and B,N-codoping, the as-synthesized carbon spheres show prospective utility as metal-free catalysts in nitroarene reduction. A mechanistic hypothesis is proposed based on theoretical and experimental studies. Boron atoms situated meta to pyridinic N atoms are identified to be the main catalytic active sites. The anti-aromaticity originating from the codoping of B and pyridinic N atoms, not charge distribution and deformation energy, is confirmed to play a pivotal role in the catalytic reaction.
- Li, Liuyi,Li, Lu,Cui, Caiyan,Fan, Hongjun,Wang, Ruihu
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p. 4921 - 4926
(2017/12/26)
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- Non-deprotonative primary and secondary amination of (hetero)arylmetals
-
Herein we disclose a novel method for the facile transfer of primary (-NH2) and secondary amino groups (-NHR) to heteroaryl-as well as arylcuprates at low temperature without the need for precious metal catalysts, ligands, excess reagents, protecting and/or Erecting groups. This one-pot transformation allows unprecedented functional group tolerance and it is wellsuited for the amination of electron-rich, electron-deficient as well as structurally complex (hetero)arylmetals. In some of the cases, only catalytic amounts of a copper (l) salt is required.
- Zhou, Zhe,Ma, Zhiwei,Behnke, Nicole Erin,Gao, Hongyin,Kürti, László
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supporting information
p. 115 - 118
(2017/05/16)
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- Carbon nitride supported palladium nanoparticles: An active system for the reduction of aromatic nitro-compounds
-
Synthesis of carbon nitride supported highly dispersed ultrafine palladium nanoparticles has been reported for the reduction of aromatic nitro-compounds using hydrazine hydrate as a reducing agent. As a demonstration, the as-synthesized carbon nitride-palladium composite was shown to be a highly active and chemo-selective for the title reaction. Utilizing the optimized reaction conditions a set of aromatic nitro compounds have been converted to their corresponding amine derivatives with good to excellent yield ranging from 80% to 99%. The catalyst can be used for multiple times without affecting the catalytic performance and can also be stored for a long time at ambient condition maintaining the high catalytic efficiency.
- Nandi, Debkumar,Siwal, Samarjeet,Choudhary, Meenakshi,Mallick, Kaushik
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- Novel 5-substituted-2-anilinoquinolines with 3-(morpholino or 4-methylpiperazin-1-yl)propoxy moiety as broad spectrum antiproliferative agents: Synthesis, cell based assays and kinase screening
-
A series of new 2-anilinoquinolines possessing 3-(morpholino or 4-methylpiperazin-1-yl)propoxy moiety at C5 of quinoline has been designed and synthesized as potential anticancer agents. Their antiproliferative activities were evaluated against a panel of 60 cancer cell lines at NCI and compared with gefitinib as a reference compound. Most of the tested compounds displayed potent and broad spectrum antiproliferative activities. Compounds 7d, 7f and 7g showed strong inhibitory and lethal effects at 10?μM concentration. Moreover, they manifested superior potencies and efficacies than gefitinib across the most tested cell lines. Compound 7d, with 4-chloro-3-trifluoromethylphenyl group, proved to be the most potent and efficacious derivative in this series, with mean GI50and TGI values of 1.62?μM and 3.47?μM, respectively. Kinase screening of 7d against a panel of 47 oncogenic kinases revealed its selective inhibitory effect (96% inhibition) towards TrkA kinase. Furthermore, the most potent compounds showed low cytotoxic effects against HFF-1 normal cell line.
- El-Damasy, Ashraf Kareem,Cho, Nam-Chul,Pae, Ae Nim,Kim, Eunice Eunkyeong,Keum, Gyochang
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p. 3307 - 3312
(2016/07/12)
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- Safe and Selective Nitro Group Reductions Catalyzed by Sustainable and Recyclable Fe/ppm Pd Nanoparticles in Water at Room Temperature
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As a result of a unique synergy between ligand-free Fe/ppm Pd nanoparticles and PEG-containing designer surfactants, a facile and selective reduction of nitro-containing aromatics and heteroaromatics can be effected in water at room temperature in the presence of NaBH4. This new nanotechnology involves low catalyst loadings, is highly chemoselective, and tolerates a wide variety of functional groups. The process, which includes recycling of the entire aqueous medium, offers a general, environmentally responsible, and notably safe approach to highly valued reductions of nitro-containing compounds.
- Feng, Jie,Handa, Sachin,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 8979 - 8983
(2016/07/26)
-
- Factors influencing voltammetric reduction of 5-nitroquinoline at boron-doped diamond electrodes
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The voltammetric signal of 5-nitroquinoline with reducible nitro and quinoline moieties largely depends on the pH of the indifferent electrolyte, electrode pretreatment, activation between individual scans, and boron concentration of the BDD film electrod
- Voshlov, Jana,Zavzalov, Jaroslava,Petrk, Vclav,Schwarzov-Peckov, Karolina
-
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- Solvent-Free Selective Hydrogenation of Nitroarenes Using Nanoclusters of Palladium Supported on Nitrogen-Doped Ordered Mesoporous Carbon
-
The selective hydrogenation of nitroarenes is a key transformation for the production of aromatic amines, which are primary intermediates in the synthesis of pharmaceuticals, agrochemicals, and dyes. However, most reaction processes require toxic organic solvents and suffer from poor selectivity in the presence of other reducible groups. Herein, we report a successful example of nanoclusters of ultrafine Pd supported on N-modified ordered mesoporous CMK-3 carbon (Pd/N-CMK-3) prepared by a facile two-step impregnation route with aqueous solutions of 1,10-phenanthroline and H2PdCl4 that hydrogenated various nitroarenes highly efficiently and selectively to the corresponding aromatic amines with hydrogen in the absence of solvent. The Pd/N-CMK-3 catalyst could be recovered easily for multiple recycling reactions without a loss of catalytic performance.
- Huang, Haigen,Wang, Xueguang,Tan, Mingwu,Chen, Chenju,Zou, Xiujing,Ding, Weizhong,Lu, Xionggang
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p. 1485 - 1489
(2016/05/02)
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- A Reusable Mesoporous Nickel Nanocomposite Catalyst for the Selective Hydrogenation of Nitroarenes in the Presence of Sensitive Functional Groups
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The synthesis of aromatic amines from nitroarenes through hydrogenation is an industrially and academically important reaction. In addition, the employment of base metal catalysts in reactions that are preferentially mediated by rare noble metals is a desirable aim in catalysis and an attractive element-conservation strategy. Especially appealing is the observation of novel selectivity patterns with such inexpensive metal catalysts. Herein, we report a novel mesostructured Ni nanocomposite catalyst. It is the first example of a reusable Ni catalyst that is able to hydrogenate nitroarenes selectively to anilines in the presence of highly sensitive functional groups such as C=C bonds and nitrile, aldehyde, and iodo substituents.
- Hahn, Gabriela,Ewert, Julia-Katharina,Denner, Christine,Tilgner, Dominic,Kempe, Rhett
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p. 2461 - 2465
(2016/08/24)
-
- Functionally substituted Schiff bases in reduction reactions
-
Functionally substituted Schiff bases obtained by the condensation of nitroaniline, pyrimidinylaminoaniline, 5-aminoquinoline, 5-aminoquinaldine derivatives with 4-methylformylbenzoate were studied in the reactions of sodium borohydride with acidic activators, hydrazine hydrate in the presence of Raney nickel, Raney alloy in the presence of potassium hydroxide. By the reduction of azomethines new benzyl derivatives of aniline, quinolylamine, arylaminopyrimidine, and phenylenediamine were obtained.
- Koroleva,Gusak,Ignatovich,Ermolinskaya
-
p. 212 - 220
(2013/07/25)
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- A new class of heterogeneous platinum catalysts for the chemoselective hydrogenation of nitroarenes
-
A new series of nanostructured platinum catalysts able to catalyze the selective reduction of nitroarenes has been developed. The materials, made of organosilica physically doped with nanostructured platinum(0), are stable and efficient. Reactions in general proceed with high yield and often go to completion, while the catalysts can be reused in further reaction runs. This establishes a new class of relevant solid catalysts for synthetic organic chemistry named SiliaCat Platinum-Hydrogel.
- Pandarus, Valerica,Ciriminna, Rosaria,Beland, Francois,Pagliaro, Mario
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scheme or table
p. 1306 - 1316
(2011/06/25)
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- An expedient synthesis of novel 2-substituted thiazolo[4,5-f]isoquinolines/ quinolines and benzo[1,2-d:4,3-d']bisthiazoles and their potential as inhibitors of COX-1 and COX-2
-
An efficient, general synthesis of 2-substituted thiazolo[4,5-f] isoquinolines, thiazolo[4,5-f]-quinolines and benzo[1,2-d:4,3-d']bisthiazoles has been accomplished from 5-nitroisoquinoline/quinoline and 6-nitrobenzothiazole, respectively, and all the products have been thoroughly identified spectroscopically (IR, 1H and 13C NMR, LR/HR EI/FAB/ESI-MS). The synthesis of thiazolo[4,5-f]isoquinolines constitutes the first synthesis of this class of heteroarenes. Eighteen compounds, covering all three types, were screened for inhibition of COX-1 and COX-2, and some of them showed moderate activities. ARKAT-USA, Inc.
- Chakrabarty, Manas,Mukherji, Ajanta,Karmakar, Sulakshana,Mukherjee, Ratna,Nagai, Kenichiro,Geronikaki, Athina,Elenic, Pitta
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experimental part
p. 265 - 290
(2011/02/24)
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- Development of (S)-N6-(2-(4-(isoquinolin-1-yl)piperazin-1-yl) ethyl)-N6-propyl-4,5,6,7-tetrahydrobenzo[d]-thiazole-2,6-diamine and its analogue as a D3 receptor preferring agonist: Potent in vivo activity in Parkinson's disease anima
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Here we report structure - activity relationship study of a novel hybrid series of compounds where structural alteration of aromatic hydrophobic moieties connected to the piperazine ring and bioisosteric replacement of the aromatic tetralin moieties were
- Ghosh, Balaram,Antonio, Tamara,Zhen, Juan,Kharkar, Prashant,Reith, Maarten E. A.,Dutta, Aloke K.
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experimental part
p. 1023 - 1037
(2010/08/06)
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- The synthesis of 4-(3,3-dimethyl-3H-pyrrolo[2,3-f] quinolin-2-yl)pyrazoles and 4-(3,3-dimethyl-3H-pyrrolo[3,2-h] quinolin-2-yl)pyrazoles
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(Chemical Equation Presented) 5-Hydrazinoquinoline and 8-hydrazinoquinoline were converted via Fischer syntheses with 3-methylbutan-2-one into pyrido-indolenines 2,3,3-trimethyl-3H-pyrrolo[2,3-f]quinoline 7 and 2,3,3-trimethyl-3H-pyrrolo[ 3,2-h]quinoline 11, respectively. Exposure of the indolenines to the Vilsmeier reagent produced aminomethylene-malondialdehydes 8 and 12, which reacted with hydrazine or arylhydrazines to give 4-(3H-pyrrolo[2,3-f]quinolin-2-yl)- and 4-(3H-pyrrolo[3,2-h]quinolin-2-yl)- pyrazoles, 9 and 13.
- Rashidi,Afghan,Baradarani, Mehdi M.,Jouleb, John A.
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experimental part
p. 428 - 431
(2009/09/25)
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- Molybdenum hexacarbonyl and DBU reduction of nitro compounds under microwave irradiation
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An ethanolic mixture of molybdenum hexacarbonyl and DBU mediates the reduction of nitroarenes to the corresponding anilines in excellent yields in 15-30 minutes under microwave irradiation. Georg Thieme Verlag Stuttgart.
- Spencer, John,Anjum, Nazira,Patel, Hiren,Rathnam, Rajendra P.,Verma, Jason
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p. 2557 - 2558
(2008/02/13)
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- Expedited palladium-catalyzed amination of aryl nonaflates through the use of microwave-irradiation and soluble organic amine bases
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Microwave-assisted, palladium-catalyzed C-N bond-forming reactions with aryl/heteroaryl nonaflates and amines using the soluble amine bases DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or MTBD (7-methyl-1,5,7-triazabicyclo[4.4. 0]dec-5-ene) and ligands (1-3) resulted in good to excellent yields (71-99%) of arylamines in short reaction times (1-45 min).
- Tundel, Rachel E.,Anderson, Kevin W.,Buchwald, Stephen L.
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p. 430 - 433
(2007/10/03)
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- Chemokine receptor binding heterocyclic compounds
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This invention relates to a novel class of heterocyclic compounds that bind chemokine receptors, inhibiting the binding of their natural ligands thereby. These compounds result in protective effects against infection by HIV through binding to chemokine receptors, including CXCR4 and CCR5, thus inhibiting the subsequent binding by these chemokines. The present invention provides a compound of Formula I wherein, W is a nitrogen atom and Y is absent or, W is a carbon atom and Y═H; R1to R7may be the same or different and are independently selected from hydrogen or straight, branched or cyclic C1-6alkyl; R8is a substituted heterocyclic group or a substituted aromatic group Ar is an aromatic or heteroaromatic ring each optionally substituted at single or multiple, non-linking positions with electron-donating or withdrawing groups; n and n′ are independently, 0-2; X is a group of the formula: Wherein, Ring A is an optionally substituted, saturated or unsaturated 5 or 6-membered ring, and P is an optionally substituted carbon atom, an optionally substituted nitrogen atom, sulfur or oxygen atom. Ring B is an optionally substituted 5 to 7-membered ring. Ring A and Ring B in the above formula can be connected to the group W from any position via the group V, wherein V is a chemical bond, a (CH2)n″group (where n″=0-2) or a C═O group. Z is, (1) a hydrogen atom, (2) an optionally substituted C1-6alkyl group, (3) a C0-6alkyl group substituted with an optionally substituted aromatic or heterocyclic group, (4) an optionally substituted C0-6alkylamino or C3-7cycloalkylamino group, (5) an optionally substituted carbonyl group or sulfonyl. These compounds further include any pharmaceutically acceptable acid addition salts and metal complexes thereof and any stereoisomeric forms and mixtures of stereoisomeric forms thereof.
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Page column 41-42
(2008/06/13)
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- Pyrazole compounds
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Pharmaceutical compositions and compounds are provided. The compounds of the invention demonstrate anti-proliferative activity, and may promote apoptosis in cells lacking normal regulation of cell cycle and death. In one embodiment of the invention, pharmaceutical compositions of the compounds in combination with a physiologically acceptable carrier are provided. The pharmaceutical compositions are useful in the treatment of hyperproliferative disorders, which disorders include tumor growth, lymphoproliferative diseases, angiogenesis. The compounds of the invention are substituted pyrazoles and pyrazolines.
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- PROCESS FOR CONVERTING HYDROXY HETEROAROMATICS TO ARYLAMINES
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A process of converting a hydroxy heteroaromatic compound to an arylamine, comprising the steps of : 1) treating a salt of a hydroxy heteroaromatic compound with an alkylating agent; and 2) treating the reaction mixture with a Smiles solvent system and raising the temperature of the reaction mixture; and a compound made according to the above process.
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- Process for converting hydroxy heteroaromatics to arylamines
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A process of converting a hydroxy heteroaromatic compound to an arylamine, comprising the steps of: (1) treating a salt of a hydroxy heteroaromatic compound with an alkylating agent; and (2) treating the reaction mixture with a Smiles solvent system and raising the temperature of the reaction mixture; and A compound made according to the above process.
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- Reactivity of heterocyclic enaminones: Regioselective synthesis of polyfused indolones
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Photocyclization of heterocyclic enaminones to give partial hydrogenated derivatives of indolo[2,3-c]quinoline, pyrido[2,3-c]carbazole, and pyrido[4,3-a]carbazole is described. In addition, 3-[(5'-quinolinyl)- benzylamino]cyclohex-2-en-1-one and 3-[(8'-quinolinyl)benzylamino]cyclohex-2- en-1-one undergo C-N bond cleavages and a benzyl migration on the C-6 and C-7 positions respectively.
- Blache, Yves,Benezech, Veronique,Chezal, Jean-Michel,Boule, Pierre,Viols, Henri,Chavignon, Olivier,Teulade, Jean-Claude,Chapat, Jean-Pierre
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p. 905 - 916
(2007/10/03)
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- Reductions using ZrCl4/NaBH4: A novel and efficient conversion of aromatic, aliphatic nitro compounds to primary amines
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A highly novel and efficient reagent system ZrCl4/NaBH4 is used for the production of primary amines from aromatic, aliphatic nitro compounds is described.
- Chary, K. Purushothama,Ram, S. Raja,Iyengar
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p. 683 - 685
(2007/10/03)
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- Direct Conversion of Hydroxy Aromatic Compounds to Heteroarylamines via a One-Pot Smiles Rearrangement Procedure
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8-Hydroxyquino line (9) was converted to 8-aminequinoline (10) in a one-pot procedure involving alkylation with 2-bromo-2-methylpropionamide (2) followed by Smiles rearrangement and hydrolysis, in 41% yield. The scope and limitations of this new procedure were explored with additional hydroxyquinolines.
- Weidner, John J.,Peet, Norton P.
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p. 1857 - 1860
(2007/10/03)
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- Synthesis of novel intranuclear diazasteroids
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By use of the aza Diels-Alder reaction a series of aminoisoquinolines and aminoquinolines have been elaborated to provide an effective synthesis of diverse diazasteroids. In particular, representative 1, 11-diaza-, 3, 11- diaza-, and 4,11-diazasteroids have been synthesized from cyclopentadiene. From dihydropyran a 4, 11-diaza-15-oxa-D-homosteroid has been obtained.
- Mellor, John M.,Merriman, Glynn D.
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p. 693 - 698
(2007/10/02)
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- REDUCTION OF HETERO-AROMATIC NITRO COMPOUNDS WITH BAKER'S YEAST
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Reduction of nitro group on hetero-aromatics with baker's yeast has been examined.
- Takeshita, Mitsuhiro,Yoshida, Sachiko
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p. 2201 - 2204
(2007/10/02)
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- Ligand-Receptor Interactions via Hydrogen-Bond Formation. Synthesis and Pharmacological Evaluation of Pyrrolo and Pyrido Analogues of the Cardiotonic Agent 7-Hydroxycyclindole
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The syntheses of N,N-dimethyl-6,7,8,9-tetrahydro-3H,10H-pyrrolocarbazol-7-amine (8), N,N-dimethyl-7,8,9,10-tetrahydro-11H-pyridocarbazol-8-amine (9a), and the N,N,11-trimethyl analogue (9b) are described.The in vitro inotropic activity of these compounds, as well as the known cardiotonics amrinone and 7-hydroxycyclindole (7), was investigated.Compound 8, a pyrrolo analogue of 7, was devoid of inotropic activity, while the pyrido analogues 9 were equiactive to 7 and amrinone.These results suggest that the hydroxyl group of 7 functions as an H-bondacceptor, rather than a donor, and that on interaction of 7, and the pyrido analogues 9, with a common receptor, an orbital occupied by one of the oxygen lone pair electrons of 7 must assume the same orientation as the orbital occupied by the pyridine nitrogen lone pair.
- Dionne, Gervais,Humber, Leslie G.,Asselin, Andre,McQuillan, Juanita,Treasurywala, Adi M.
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p. 1452 - 1457
(2007/10/02)
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- Pyrolysis of Aryl Azides. VI Identification of Neighbouring Group Effects in Pyrolysis of Azidopyridines and Azidoquinolines
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Although there are literature reports of anomalous behaviour on pyrolysis of ortho-nitroazidopyridines and ortho-nitroazidoquinolines, we find that these compounds cyclize to the expected furazan 1-oxides in near-quantitative yields, and with a high degree of neighbouring group participation by the nitro group.Kinetic studies in decalin solution reveal the following rate enhancements by the ortho-nitro group: 3-azido-2-nitropyridine, 466 at least; 4-azido-3-nitropyridine, 5400; 4-azido-3,5-dinitropyridine, 640; 4-azido-3-nitroquinoline, 82.4; 5-azido-6-nitroquinoline,27.6; 2-nitro-1-azidonaphthalene, 12.7.The unstable furazan oxide, oxadiazolopyridine 1-oxide, has now been characterized. Oxadiazolopyridine 1-oxide decomposed in decalin at 145 deg to give products indicative of a nitrene intermediate.
- Dyall, Leonard K.,Wah, Wong Ming
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p. 1045 - 1059
(2007/10/02)
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- Photolysis of Quinolyl and Isoquinolyl Azides in Primary and Secondary Aliphatic Amines: Synthesis of Bicyclic Azepines, Diazepines, and Quinolyl- and Isoquinolyl-diamines
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Photolysis of the title compounds in primary aliphatic amines gave in some cases bicyclic azepines and diazepines as well as o-diamines, while in secondary amines mainly the appropriate o-diamines are obtained.On the basis of the many examples studied guidelines are put forward to predict the nature of products from photolysis of bicyclic azides in primary and secondary amines and to obtain maximum yields.
- Hollywood, Frank,Nay, Barry,Scriven, Eric F. V.,Suschitzky, Hans,Khan, Zafar U.,Hull, Roy
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p. 421 - 429
(2007/10/02)
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- Photolysis of Quinolyl Azides in Aliphatic Thiols. Synthesis of o-Alkylthioquinolylamine
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Photolysis of 5- or 8-quinolyl azide in various thiols gives o-alkylthioquinolylamines.The beneficial effect of a 6-methoxy-group in 8-quinolyl azide on the yields is noted.
- Khan, Zafar U.,Nay, Barry,Scriven, Eric F.V.,Suschitsky, Hans
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p. 671 - 672
(2007/10/02)
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