- Highly Active Ni Nanoparticles on N-doped Mesoporous Carbon with Tunable Selectivity for the One-Pot Transfer Hydroalkylation of Nitroarenes with EtOH in the Absence of H2
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Cost-effective and environmentally friendly conversion of nitroarenes into value-added products is desirable but still challenging. In this work, highly dispersed Ni nanoparticles (NPs) supported on N-doped mesoporous carbon (Ni/NC-x) were synthesized via novel ion exchange-pyrolysis strategy. Their catalytic performance was investigated for one-pot transfer hydroalkylation of nitrobenzene (NB) with EtOH in absence of H2. Interestingly, the catalytic performance could be easily manipulated by tuning the morphology and electronic state of Ni NPs via varying the pyrolysis temperature. It was found that the Ni/NC-650 achieved 100 % nitrobenzene conversion and approx. 90 % selectivity of N,N-diethyl aniline at 240 °C for 5 h, more active than those of homogeneous catalysts or supported Ni catalysts prepared by impregnation (Ni/NC-650-IM, Ni/SiO2). This can be ascribed to the higher dispersion and better reducibility as well as richer surface basicity of the catalyst. More interestingly, the Ni/NC-650 catalyst achieved complete conversion of various nitroarenes, yielding imines, secondary amines, or tertiary amines selectively by simply controlling the reaction temperature at 180, 200 and 240 °C, respectively. The one-pot hydrogen-free process with non-noble metal catalysts, as demonstrated in this work, shows great promise for selective conversion of nitroarenes with ethanol to various anilines at industrial scale, from an economic, environmental, and safety viewpoint.
- Tao, Yuewen,Nie, Yunqing,Hu, Haitao,Wang, Ke,Chen, Yi,Nie, Renfeng,Wang, Jianshe,Lu, Tianliang,Zhang, Yongsheng,Xu, Chunbao Charles
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p. 4243 - 4250
(2021/08/20)
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- Visible light-induced mono-bromination of arenes with BrCCl3
-
A highly efficient and regioselective bromination of electron-rich arenes and heteroarenes using commercially available BrCCl3as a “Br” source has been developed. The reaction was performed in air under mild conditions with photocatalyst Ru(bpy)3Cl2·6H2O, avoiding the usage of strong acids and strong oxidants. Mono-brominated products were obtained with medium to excellent yields (up to 94%). This strategy has shown good compatibility and highpara-selectivity, which will facilitate the complicated synthesis.
- Fan, Jiali,Wei, Qiancheng,Zhu, Ershu,Gao, Jing,Cheng, Xiamin,Lu, Yongna,Loh, Teck-Peng
-
supporting information
p. 5977 - 5980
(2021/06/18)
-
- A quinone-based ionic compound, a method for producing the same, transparent near infrared ray shielding film containing the quinone-based ionic compound and a method for producing the same
-
The present invention relates to a quinoid-based ionic compound, a method for preparing the same, and a near-infrared ray-blocking film comprising the quinoid-based ionic compound. According to the present invention, the quinoid-based ionic compound can efficiently block a near-infrared ray due to high transmittance in a visible ray region and high absorbance in a near-infrared ray region, can be easily prepared into a thin film due to high solubility in an organic solvent, and can maintain high heat-resistant and high moisture-resistant properties in a thin film state for a long time due to excellent affinity with a polymer. The near-infrared ray-blocking film containing the quinoid-based ionic compound is suitable for being applied to a protective film for protecting electronic devices, and can be used as an insulating film or a light energy absorbing layer.(AA) Example 1-1(BB) Example 1-2(CC) Comparative Example 1-1COPYRIGHT KIPO 2020
- -
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Paragraph 0144-0147
(2020/10/14)
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- Cu-mediated selective bromination of aniline derivatives and preliminary mechanism study
-
A simple and efficient bromination of aniline, aniline derivatives, and analogs have been developed. Forty three examples were given and the highest yield reached was 98%. Different substrates including substituted aniline, pyridin-amine, N-substituted aniline, N,N-disubstituted aniline, N-phenyl-amide, N-phenyl-sulfonamide, and nitrogen-containing heterocycles were all reactive and selectively generated desired bromo-products. The method can be applied to synthesize drug intermediate and quinoxaline derivatives.
- Zhao, Hong-Yi,Yang, Xue-Yan,Lei, Hao,Xin, Minhang,Zhang, San-Qi
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supporting information
p. 1406 - 1415
(2019/05/01)
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- A Catalyst-Free Amination of Functional Organolithium Reagents by Flow Chemistry
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Reported is the electrophilic amination of functional organolithium intermediates with well-designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C?N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method. Based on stopped-flow NMR analysis, the reaction time for the preparation of the aminating reagent was quickly optimized without the necessity of work-up. Integrated one-flow synthesis consisting of the generation of an aryllithium, the preparation of an aminating reagent, and their combined reaction was successfully achieved to give the desired amine within 5 minutes of total reaction time.
- Kim, Heejin,Yonekura, Yuya,Yoshida, Jun-Ichi
-
supporting information
p. 4063 - 4066
(2018/03/21)
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- Environmentally benign indole-catalyzed position-selective halogenation of thioarenes and other aromatics
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Halogenated aromatic compounds are the cores of many pharmaceutical, agricultural and chemical products but they are commonly prepared using electrophilic halogenation reactions in non-green chlorinated solvents under harsh conditions. A separate problem happens in the aromatic halogenation of thioarenes because they readily undergo oxidative side-reactions. Herein we report an environmentally benign electrophilic bromination of aromatics using an indole-catalytic protocol, which is suitable for a wide range of substrates including thioarenes.
- Shi, Yao,Ke, Zhihai,Yeung, Ying-Yeung
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supporting information
p. 4448 - 4452
(2018/10/17)
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- PHOSPHOINOSITIDE 3-KINASE INHIBITORS WITH ZINC BINDING MOIETY
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PROBLEM TO BE SOLVED: To provide phosphoinositide 3-kinase inhibitors with a zinc binding moiety. SOLUTION: There is provided a compound represented by formula (I) in the figure. (X is S, O or the like; Y is CH, N or the like; G1 is optionally substituted N or the like; R1 and R2 are each independently H or the like; C is a substituted heterocycle or the like; B is a linear alkyl or the like; Ra and Rb together with the nitrogen atom coupled to them are morpholino or the like; G2 is an indazole ring or the like; q, r and s are independently from 0 to 1, provided that at least one of them is 1; t is from 0 to 1; n is from 0 to 4; and p is from 0 to 2.) COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0460; 0464
(2016/10/07)
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- Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu-Mo/TiO2
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It is highly desirable to develop efficient heterogeneous photocatalysts for organic reactions. Here, we show the preparation and catalytic performance of a novel TiO2 (P25) supported Cu and Mo photocatalyst (Cu-Mo/TiO2) for N-alkylation of amines with alcohols under UV irradiation at room temperature. A variety of aromatic and aliphatic amines were selectively converted into the corresponding secondary amines or tertiary amines in moderate to excellent yields without the addition of any co-catalysts such as bases and organic ligands. Noteworthy, this catalytic system is feasible in the alkylation of anilines containing halogen substituents with alcohols and the yields of the desired products are up to 95%.
- Zhang, Lina,Zhang, Yan,Deng, Youquan,Shi, Feng
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p. 3226 - 3234
(2015/06/08)
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- Aerobic photooxidative bromination of aromatic compounds using carbon tetrabromide mediated by anthraquinone-2-carboxylic acid
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We developed the aerobic photooxidative bromination of aromatic compounds using carbon tetrabromide in the presence of anthraquinone-2-carboxylic acid under visible light irradiation.
- Tanaka, Masanori,Kamito, Yuji,Lei, Cui,Tada, Norihiro,Itoh, Akichika
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p. 5886 - 5888
(2015/11/02)
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- Aerobic oxidative bromination of arenes using an ionic liquid as both the catalyst and the solvent
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A method for the bromination of alkoxy-substituted benzenes and naphthalenes was developed by using the residual oxygen in the reaction tube as the oxidant, and [Bmim]NO3 (1-butyl-3-methylimidazolium nitrate) ionic liquid as both the catalyst and the solvent. No other reagent apart from the ionic liquid and molecular bromine was used in the reactions, and basically all the bromine atoms in the bromine source were transferred to the bromination products, showing that the presented protocol is highly atom economic and practical.
- Ren, Yun-Lai,Wang, Binyu,Tian, Xin-Zhe,Zhao, Shuang,Wang, Jianji
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supporting information
p. 6452 - 6455
(2015/11/16)
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- Selective bromination of pyrrole derivatives, carbazole and aromatic amines with DMSO/HBr under mild conditions
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Bromination of pyrrole derivatives, carbazole and aromatic amines using the DMSO/HBr system affords high yields of the corresponding bromo compounds. Temperature control used in the bromination of anilines helped to promote selective formation of mono- or di-brominated products. Simple operation, low toxicity and high selectivity make this a promising new procedure for the bromination of aromatic compounds.
- Liu, Cong,Dai, Rongji,Yao, Guowei,Deng, Yulin
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p. 593 - 596
(2015/01/09)
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- Reductive amination of tertiary anilines and aldehydes
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An unprecedented oxidant-mediated reductive amination of tertiary anilines and aldehydes without external reducing agents was developed via the nucleophilic attack of the oxygen atom of the carbonyl group to in situ generated iminium ions, in which tertiary anilines were used as both nitrogen source and reducing agent for the first time. The Royal Society of Chemistry 2013.
- Lv, Yunhe,Zheng, Yiying,Li, Yan,Xiong, Tao,Zhang, Jingping,Liu, Qun,Zhang, Qian
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supporting information
p. 8866 - 8868
(2013/09/24)
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- TREATMENT OF CANCERS HAVING K-RAS MUTATIONS
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The present invention provides a method of treating a cancer associated with a K-ras mutation in a subject in need thereof. The method comprises the steps of: (1) identifying a subject with a cancer associated with a K-ras mutation; and (2) administering to the subject (i) an inhibitor of PI3 kinase and (ii) an HDAC inhibitor, wherein the PI3 kinase inhibitor and the HDAC inhibitor are administered in amounts which together are therapeutically effective.
- -
-
Paragraph 0546
(2013/05/08)
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- One-pot photo-reductive N-alkylation of aniline and nitroarene derivatives with primary alcohols over Au-TiO2
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We report the photo-catalytic N-alkylation of aniline by Au-TiO 2. We successfully alkylate aniline with several primary alcohols. The combined selectivities of mono- and di-alkylated products were always in excess of 70% and dependent on the alkylating alcohol used. A one-pot reaction from nitrobenzene was found to be possible with several substrates. Preliminary experiments showed that this approach could be adopted for the production of lactams using terminal amino-alcohols. The Royal Society of Chemistry 2013.
- Stibal, David,Sa, Jacinto,Bokhoven, Jeroen A. Van
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- Copper-catalyzed electrophilic amination of arylsilanes with hydroxylamines
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A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl] dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.
- Miki, Yuya,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information
p. 172 - 175
(2013/03/28)
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- A facile, regioselective and controllable bromination of aromatic amines using a CuBr2/Oxone system
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A combination of cupric bromide and Oxone serves as a facile, mild and effective reagent for the bromination of aromatic amines. Primary, secondary and tertiary aromatic amines are all suitable substrates. The reaction possesses high regioselectivity and functional group tolerance, and mono- and multi-brominated products can be obtained controllably in moderate to excellent yields. The Royal Society of Chemistry 2013.
- Li, Xin-Le,Wu, Wei,Fan, Xin-Heng,Yang, Lian-Ming
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p. 12091 - 12095
(2013/09/02)
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- Copper-catalyzed amination of arylboronates with N,N-dialkylhydroxylamines
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A tolerant coupling: The title reaction has been developed to deliver arylamines (see scheme; Bz=benzoyl, dppbz=1,2-bis(diphenylphosphino)benzene). The catalysis is based on electrophilic, umpolung amination and enables the use of secondary acyclic amines. Various functional groups are tolerated, thus opening up a new substrate class for the Chan-Lam-type coupling.
- Matsuda, Naoki,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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p. 3642 - 3645
(2012/05/20)
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- Nitromethane with IBX/TBAF as a nitrosating agent: Synthesis of nitrosamines from secondary or tertiary amines under mild conditions
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Aliphatic or aromatic N,N-disubstituted nitrosamine was generated in fair to excellent yield from the reaction of a secondary or tertiary amine with o-iodoxybenzoic acid (IBX) or o-iodosylbenzoic acid (IBA)/R4NX (X = halide) and nitromethane. The product yield was strongly influenced by both the halide of R4NX and iodanes. IBX gave a higher yield than IBA, while the halides follow F- > Cl- > Br- ～ I-. Nitrous acid formed in situ from nitromethane and IBX (or IBA)/halides is likely responsible for the observed reaction.
- Potturi, Hima K.,Gurung, Ras K.,Hou, Yuqing
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experimental part
p. 626 - 631
(2012/02/16)
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- A Green protocol for the bromination and iodination of the aromatic compounds using H5IO6/NaBr and H5IO 6/NaI in the water
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Bromination and iodination of the aromatic compounds have efficiently been carried out at room temperature and 70 °C, respectively, in short reaction times using orthoperiodic acid/sodium bromide (1:2) and orthoperiodic acid/sodium iodide (1:2) in water to prepare the corresponding halo compounds with excellent yields.
- Yousefi-Seyf, Jaber,Tajeian, Kazem,Kolvari, Eskandar,Koukabi, Nadiya,Khazaei, Ardeshir,Zolfigol, Mohammad Ali
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p. 2619 - 2622
(2012/10/29)
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- TREATMENT OF CANCERS HAVING K-RAS MUTATIONS
-
The present invention provides a method of treating a cancer associated with a K- ras mutation in a subject in need thereof. The method comprises the steps of (1) identifying a subject with a cancer associated with a K-ras mutation; and (2) adminsiterign to the subject (i) an inhibitor of PI3 kinase and (ii) an HDAC inhibitor, wherein the PI3 kinase inhibitor and the HDAC inhibitor are administered in amounts which together are therapeutically effective.
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Page/Page column 220
(2011/11/01)
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- Chemo-and regioselective bromination of aromatic compounds in the presence of γ-picolinium bromochromate (γ-PBC)/CH3CN
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Regioselective oxidative bromination of activated aromatic compounds has been studied using γ-Picolinium bromochromate in either CH3COOH or CH3CN is reported. The results obtained revealed excellent yields of monobromo compounds at para-position under thermal condition especially in methyl cyanide.
- Mahmoodi,Yazdanbakhsh,Hassanzadeh
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experimental part
p. 429 - 434
(2012/04/04)
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- Efficient and regioselective bromination of aromatic compounds with ethylenebis(N-methylimidazolium) ditribromide (EBMIDTB)
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A regioselective and highly efficient method for bromination of phenol and aniline derivatives using ethylenebis(N-methylimidazolium) ditribromide (EBMIDTB) as an efficient reagent in dichloromethane at ambient temperature is reported. The reagent can be recovered and reused several times.
- Hosseinzadeh, Rahman,Tajbakhsh, Mahmood,Mohadjerani, Maryam,Lasemi, Zahra
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experimental part
p. 868 - 876
(2010/05/18)
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- Electrophilic bromination of alkenes, alkynes, and aromatic amines with iodic acid/potassium bromide under mild conditions
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Bromination of alkenes, alkynes, and aromatic amines has efficiently been carried out at room temperature in short reaction times using HIO 3/KBr in CH2Cl2/H2O (1:1) to prepare corresponding brominated compounds in excellent yields.
- Khazaei, Ardeshir,Zolfigol, Mohammad Ali,Kolvari, Eskandar,Koukabi, Nadiya,Soltani, Hamid,Bayani, Leyla Sharaf
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experimental part
p. 2954 - 2962
(2010/10/20)
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- Elctrophilic bromination of alkenes, alkynes, and aromatic amines with potassium bromide/orthoperiodic acid under mild conditions
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Bromination of alkenes, alkynes, and aromatic amines has efficiently been carried out at room temperature in short reaction times using potassium bromide/orthoperiodic acid in dichloromethane-water (1:1) to prepare the corresponding bromo compounds with excellent yields.
- Khazaei, Ardeshir,Zolfigol, Mohammad Ali,Kolvari, Eskandar,Koukabi, Nadiya,Soltani, Hamid,Komaki, Fatemeh
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experimental part
p. 3672 - 3676
(2010/04/05)
-
- Catalytic Sandmeyer bromination
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An efficient catalyst system for Sandmeyer bromination is proposed. Aryl bromides and dibromides can be obtained with excellent yield by this synthetic protocol. Georg Thieme Verlag Stuttgart.
- Beletskaya, Irina P.,Sigeev, Alexander S.,Peregudov, Alexander S.,Petrovskii, Pavel V.
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p. 2534 - 2538
(2008/03/13)
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- Copper(II) bromide: A simple and selective monobromination reagent for electron-rich aromatic compounds
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Copper(II) bromide was found to be a simple and efficient reagent for monobromination of electron-rich aromatic compounds at room temperature. The reaction proceeded smoothly with phenols, aryl alkyl ethers, and aromatic amines to afford the corresponding monobrominated product selectively in moderate to good yields. Copyright Taylor & Francis Group, LLC.
- Bhatt, Suchitra,Nayak, Sandip K.
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p. 1381 - 1388
(2008/02/01)
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- {[K.18-Crown-6]Br3}n: a unique tribromide-type and columnar nanotube-like structure for the oxidative coupling of thiols and bromination of some aromatic compounds
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Reaction of 18-crown-6 with KBr and then with bromine (Br2) afforded a unique tribromide salt with a nanotube-like structure ({[K.18-crown-6]Br3}n). Oxidative coupling of thiols and bromination of some aromatic compounds is the first report on the chemistry of this reagent.
- Zolfigol, Mohammad Ali,Chehardoli, Gholamabbas,Salehzadeh, Sadegh,Adams, Harry,Ward, Michael D.
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p. 7969 - 7973
(2008/03/14)
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- Tetrabromo hydrogenated cardanol: Efficient and renewable brominating agent
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(Chemical Equation Presented) 2,4,4,6-Tetrabromo-3-n-pentadecyl-2,5- cyclohexadienone (TBPCO) has been synthesized and used as a new efficient, convenient, and environmentally friendly brominating agent.
- Attanasi, Orazio A.,Berretta, Stefano,Favi, Gianfranco,Filippone, Paolino,Mele, Giuseppe,Moscatelli, Giada,Saladino, Raffaele
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p. 4291 - 4293
(2007/10/03)
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- N-octylquinolinium tribromide: A task specific quinoline based ionic liquid as a new brominating agent
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The N-octylquinolinium tribromide has been synthesized and explored as a new efficient brominating agent. It has high active bromine content per molecule and shows a remarkable reactivity towards various substrates. No organic solvent has been used during any stage of the reaction. The N-octylquinolinium tribromide is stable for months and acts as a safe source of bromine for complete bromination of phenols, aromatic amines, alkenes and alkynes.
- Kaushik,Polshettiwar, Vivek
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p. 2542 - 2545
(2007/10/03)
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- Understanding reactivity patterns of the dialkylaniline radical cation
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N,N-Dimethylaniline and N,N-diethylaniline react with Cu2+ to form the corresponding amine radical cations. The radical cations were characterized by their absorption spectra. In the absence of any nucleophiles, the radical cations dimerize to give tetraalkylbenzidines, and this reaction can be monitored by absorption spectroscopy, In the presence of nucleophiles such as Cl, Br, or SCN, the radical cations undergo nucleophilic substitution to give para-substituted dialkylanilines in good yields.
- Kirchgessner, Micha,Sreenath, Kesavapillai,Gopidas, Karical R.
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p. 9849 - 9852
(2007/10/03)
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- Bis(triarylmethylium)-mediated diaryl ether synthesis: Oxidative arylation of phenols with N,N-dialkyl-4-phenylthioanilines
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Various aryl 4-dialkylaminophenyl ethers were readily synthesized without heating in good yield from phenols and N,N-dialkyl-4-phenylthioanilines. This oxidative arylation of phenols was successfully promoted by a bis(diphenylmethylium)naphthalenediyl dication via ipso-substitution of the phenylthio group in the anilines through a radical process. Copyright
- Saitoh, Terunobu,Ichikawa, Junji
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p. 9696 - 9697
(2007/10/03)
-
- Mild and regioselective bromination of aromatic compounds with N,N,N′,N′-Tetrabromobenzene-1,3-disulfonylamide and poly(N-bromobenzene-1,3-disulfonylamide)
-
N,N,N′,N′-Tetrabromobenzene-1,3-disulfonylamide (TBBDA) and poly[N-bromobenzene-1,3-disulfonylamide] (PBBS) can be used for the regioselective bromination of aromatic compounds in excellent yields under mild conditions.
- Ghorbani-Vaghei, Ramin,Jalili, Hamid
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p. 1099 - 1102
(2007/10/03)
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- Regioselective synthesis of para-bromo aromatic compounds
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Reaction of substituted benzenerings with N-bromophthalimide, underneutral conditions, gave the corresponding bromo derivatives with a preference for the formation of the para bromoisomer over the ortho isomer. The sim pie work-up procedure minimizes loss of product and the yields are good.
- Khazaei, Ardeshir,Manesh, Abbas Amini,Safi, Vahid Reza
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p. 559 - 562
(2007/10/03)
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- Use of 1-halo derivatives of the 2,2,6,6-tetramethylpiperidine series as oxidants and halogenating agents
-
1-Halo derivatives of the 2,2,6,6-tetramethylpiperidine series oxidize sterically hindered phenols to form dimers and p-quinones.
- Kashparova,Kagan,Zhukova,Ivakhnenko
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p. 964 - 967
(2007/10/03)
-
- Alkylation of aromatic amines and related compounds using a copper(II)-aluminum(III) couple
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Copper(II)-mediated alkylation of amines and related compounds (e.g. hydrazines, hydrazones, hydroxylamines) using an alkyl aluminum reagent is described. The reaction proceeds selectively and in good yield, utilizing a metal-metal exchange as the key step.
- Barton, Derek H.R.,Doris, Eric
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p. 3295 - 3298
(2007/10/03)
-
- para-Bromination of Anilinium Ions in the Presence of Nitrosonium Hydrogen Sulfate in Concentrated Sulfuric Acid
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Aniline and its o-, m-, and N-substituted derivatives are converted to corresponding 4-bromo derivatives in concentrated sulfuric acid under the action of bromine and nitrosonium hydrogen sulfate; in the absence of the latter, no bromination occurs.
- Gorelik, M. V.,Lomzakova, V. I.,Khamidova, E. A.,Shteiman, V. Ya.,Kuznetsova, M. G.,Andrievskii, A. M.
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p. 508 - 512
(2007/10/03)
-
- Surfactant Control of the Ortho/Para Ratio in the Bromination of Anilines. 2.
-
We report the bromination of some N,N-disubstituted anilines (N-ethyl-N-methylaniline, N,N-diethylaniline, N-butyl-N-methylaniline, 1-phenylpyrrolidine, 1-phenylpiperidine) both in aqueous suspension of cetyltrimethylammonium tribromide (CTAB3) and in homogeneous solution (CHCl3).In the presence of surfactant we observed a regioselectivity different from that observed in homogeneous conditions.The regioselectivity seems to depend on the nature of the substituents on the nitrogen of the aniline as well as on the temperature.An explanation based on specific interactions between the aniline and the packed structure of the aggregate is proposed.
- Cerichelli, Giorgio,Mancini, Giovanna,Luchetti, Luciana
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p. 3797 - 3802
(2007/10/02)
-
- Novel 11β-substituted-19-nor-steroids
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Novel 19-nor-steroids of the formula STR1 wherein R1 is an organic group of 1 to 18 carbon atoms optionally containing at leat one heteroatom with the atom immediately adjacent the 11-carbon atom being carbon, R2 is a hydrocarbon of 1 to 8 carbon atoms, X is the remainder of a pentagonal or hexagonal ring optionally substituted and optionally containing one unsaturated bond, the A and B rings are selected from the group consisting of STR2 R' and R" are individually selected from the group consisting of hydrogen, --CN and alkyl of 1 to 4 carbon atoms, Rx is selected from the group consisting of hydrogen and ORe, Re is selected from the group consisting of hydrogen, optionally substituted alkyl of 1 to 6 carbon atoms and acyl, Ra may be in the E or Z positions as indicated by the wavy line and is selected from the group consisting of STR3 and acyloxy, Ra ' and Ra " are alkyl of 1 to 4 carbon atoms or taken together with the nitrogen atom form a heterocycle of 5 to 6 chain members optionally containing another heteroatom with the proviso that when A and B are STR4 wherein R' and R" are both hydrogen, R1 contain at least one nitrogen, phosphorus or silicium atom and when A and B are STR5 R1 is not a linear alkyl and their non-toxic, pharmaceutically acceptable acid addition salts having a remarkable antiglucocorticoid activity, their preparation and novel intermediates.
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-
- Bromation regioselective en serie aromatique. I: Monobromation en position para de phenols et d'amines aromatiques par le tribromure de tetrabutylammonium
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The reaction of tetrabutylammonium tribromide (TBABr3) with phenols and aromatic amines in aprotic and non-basic solvents at 20 deg C gives exclusively the corresponding para-brominated compounds in high yields.A mechanism involving electrophilic substitution by the tribromide anion Br3- itself is suggested to account for the results, especially the regioselective para bromination.Key words: bromination, tetrabutylammonium tribromide, phenols, aromatic amines.
- Berthelot, Jacques,Guette, Catherine,Desbene, Paul-Louis,Basselier, Jean-Jacques,Chaquin, Patrick,Masure, Daniel
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p. 2061 - 2066
(2007/10/02)
-
- Oxybromination Catalysed by the Heteropolyanion Compound H5PMo10V2O40 in an Organic Medium: Selective para-Bromination of Phenol
-
Selective bromination of phenol and its derivatives and the bromination of ketones and alkenes have been achieved by oxybromination at ambient conditions catalysed by the mixed addenda heteropolyanion compound H5PMo10V2O40, which is dissolved in a nonpolar chlorohydrocarbon solvent by complexation with tetraglyme.
- Neumann, Ronny,Assael, Igal
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p. 1285 - 1287
(2007/10/02)
-
- Steroid derivatives
-
Novel 19-nor steroids and 19-nor-D-homo-steroids of the formula STR1 wherein R 1 is an organic radical of 1 to 18 carbon atoms containing at least one atom selected from the group consisting of nitrogen, phosphorous and silicon with the atom immediately adjacent to the 11-carbon atom being carbon, R 2 is a hydrocarbon of 1 to 8 carbon atoms, X is selected from the group consisting of a pentagonal ring and a hexagonal ring optionally substituted and optionally containing a double bond, B and C together form a double bond or an epoxy group, the C A group at position 3 is selected from the group consisting of C O, ketal, which may be open or closed STR2 are selected from the group consisting of alkyl of 1 to 8 carbon atoms and aralkyl of 7 to 15 carbon atoms and their non-toxic, pharmaceutically acceptable acid addition salts having anti-glucocorticoid activity and a process for their preparation.
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-
-
- REGIOSELECTIVE MONOBROMINATION OF AROMATIC AMINES WITH TETRABUTYLAMMONIUM TRIBROMIDE
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A simple and efficient method for monobromination of aromatic amines predominantly in the para position is reported.Tetrabutylammonium tribromide is used at 20 deg C and yields of parabromoanilines are higher than 90percent.
- Berthelot, J.,Guette, C.,Essayegh, M.,Desbene, P.L.,Basselier, J.J.
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p. 1641 - 1646
(2007/10/02)
-
- Steroid derivatives
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Novel 19-nor steroids and 19-nor-D-homo-steroids of the formula STR1 wherein R1 is an organic radical of 1 to 18 carbon atoms containing at least one atom selected from the group consisting of nitrogen, phosphorous and silicon with the atom immediately adjacent to the 11-carbon atom being carbon, R2 is a hydrocarbon of 1 to 8 carbon atoms, X is selected from the group consisting of a pentagonal ring and a hexagonal ring optionally substituted and optionally containing a double bond, B and C together form a double bond or an epoxy group, the C=A group at position 3 is selected from the group consisting of C--O, ketal, which may be open or closed STR2 --C=NOH, --C--NOAlK3 and C--CH2, AlK1, AlK2 and AlK3 are selected from the group consisting of alkyl of 1 to 8 carbon atoms and aralkyl of 7 to 15 carbon atoms and their non-toxic, pharmaceutically acceptable acid addition salts having anti-glucocorticoid activity and a process for their preparation.
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- Novel steroids
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Novel 19-nor steroids and 19-nor-D-homo-steroids of the formula STR1 wherein R1 is an organic radical of 1 to 18 carbon atoms containing at least one atom selected from the group consisting of nitrogen, phosphorous and silicon with the atom immediately adjacent to the 11-carbon atom being carbon, R2 is a hydrocarbon of 1 to 8 carbon atoms, X is selected from the group consisting of a pentagonal ring and a hexagonal ring optionally substituted and optionally containing a double bond, B and C together form a double bond or an epoxy group, the C=A group at position 3 is selected from the group consisting of C=O, ketal, STR2 --C=NOH, --C=NOAlK3 and =CH2, AlK1, AlK2 and AlK3 are selected from the group consisting of alkyl of 1 to 8 carbon atoms and aralkyl of 7 to 15 carbon atoms and their non-toxic, pharmaceutically acceptable acid addition salts having anti-glucocorticoid activity and a process for their preparation.
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- PALLADIUM-CATALYZED AROMATIC AMINATION OF ARYL BROMIDES WITH N,N-DIETHYLAMINO-TRIBUTYLTIN
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The reaction of N,N-diethylamino-tributyltin with aryl bromides in the presence of a catalytic amount of PdCl2(o-tolyl3P)2 gave N,N-diethylaminobenzene derivatives.The reaction is a new kind of amination different from ones through aryne or SRN1 mechanism.
- Kosugi, Masanori,Kameyama,Masayuki,Migita, Toshihiko
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p. 927 - 928
(2007/10/02)
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