- Substituted conformationally restricted guanidine derivatives: Probing the α2-adrenoceptors’ binding pocket
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In this paper we report the design, synthesis and pharmacological evaluation of new N-substituted 2-amino-1,4-dihydroquinazolines, 2-amino-1,4-dihydropyridopyrimidines and 2-amino-4,5-dihydro-1,3-benzodiazepines as α2-adrenoceptors ligands. Computational studies show that the proposed substitutions and guanidine-containing ring size will probe an extensive area of the active site. Preparation of these molecules involved novel routes than those previously utilised in our laboratory for the preparation of the acyclic aryl-guanidine counterparts. Compounds 8b and 18c showed the highest affinity and antagonistic activity, within their series, towards the α2-adrenoceptor in human brain tissue in?vitro experiments. Structure-activity relationships have been established for the design and biological evaluation of novel α2-adrenoceptor ligands.
- McMullan, Michela,García-Bea, Aintzane,Miranda-Azpiazu, Patricia,Callado, Luis F.,Rozas, Isabel
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Read Online
- Mediator-Enabled Electrocatalysis with Ligandless Copper for Anaerobic Chan-Lam Coupling Reactions
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Simple copper salts serve as catalysts to effect C-X bond-forming reactions in some of the most utilized transformations in synthesis, including the oxidative coupling of aryl boronic acids and amines. However, these Chan-Lam coupling reactions have historically relied on chemical oxidants that limit their applicability beyond small-scale synthesis. Despite the success of replacing strong chemical oxidants with electrochemistry for a variety of metal-catalyzed processes, electrooxidative reactions with ligandless copper catalysts are plagued by slow electron-transfer kinetics, irreversible copper plating, and competitive substrate oxidation. Herein, we report the implementation of substoichiometric quantities of redox mediators to address limitations to Cu-catalyzed electrosynthesis. Mechanistic studies reveal that mediators serve multiple roles by (i) rapidly oxidizing low-valent Cu intermediates, (ii) stripping Cu metal from the cathode to regenerate the catalyst and reveal the active Pt surface for proton reduction, and (iii) providing anodic overcharge protection to prevent substrate oxidation. This strategy is applied to Chan-Lam coupling of aryl-, heteroaryl-, and alkylamines with arylboronic acids in the absence of chemical oxidants. Couplings under these electrochemical conditions occur with higher yields and shorter reaction times than conventional reactions in air and provide complementary substrate reactivity.
- Walker, Benjamin R.,Manabe, Shuhei,Brusoe, Andrew T.,Sevov, Christo S.
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supporting information
p. 6257 - 6265
(2021/05/07)
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- CuSO4-Catalyzed dual annulation to synthesize O, S or N-containing tetracyclic heteroacenes
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In this work, CuSO4 is utilized as a practical redox catalyst for tandem dual annulation in the synthesis of indole-fused tetracyclic heteroacenes, which are important skeletons in both medicinal chemistry and materials chemistry. The preparation of such skeletons in a convenient and efficient manner is in high demand. This method realizes the modular synthesis of benzofuro-, benzothieno-, and indoloindoles from abundant feedstocks such as 2-halobenzyl halides and nitrile derivatives in up to 99% yields, providing a rapid access to diverse indole-fused heteroacenes with biological or optoelectronic properties.
- Kang, Yan-Biao,Qu, Jian-Ping,Shan, Xiang-Huan,Yang, Bo
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supporting information
p. 4063 - 4066
(2020/04/20)
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- Synthesis method of N-phenyl aminobenzoic acid
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The invention belongs to the technical field of organic intermediate synthesis, and particularly relates to a synthesis method of N-phenyl aminobenzoic acid. The method comprises the following steps:(1) dissolving 2-chlorobenzonitrile and aniline in a solvent, adding K2CO3 and NaOH while stirring, and heating to carry out primary reflux reaction; (2) after the reflux reaction is finished, recovering the solvent under reduced pressure, then cooling the residual liquid, adding water, and heating to carry out secondary reflux reaction; and (3) cooling the reaction solution after the secondary reflux reaction in the step (2) to room temperature, extracting excessive aniline, adding diluted hydrochloric acid for neutralization while stirring a water phase, separating out a solid, filtering, and recrystallizing to obtain the target product N-phenyl aminobenzoic acid. According to the method, a one-pot process is adopted, under the condition that a catalyst is not used, 2-chlorobenzonitrileand aniline are used as raw materials for reaction, the target product with high purity (larger than 99%) and high yield (larger than 90%) is obtained, operation is easy, the raw materials are easy toobtain, the reaction is mild and easy to control, and aftertreatment is simple.
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Paragraph 0007; 0027-0030; 0033-0036; 0039-0042; 0045-0047
(2021/01/11)
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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF
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The present invention relates to a device for emitting light. Provided are a novel mixture capable of improving stability and longevity, an organic electronic element using the same, and an electronic device thereof. (by machine translation)
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Paragraph 0335; 0437-0443
(2020/08/28)
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- Reductive Molybdenum-Catalyzed Direct Amination of Boronic Acids with Nitro Compounds
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The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C?N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. Moreover, this general and step-economical synthesis of aromatic secondary amines showcases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.
- Suárez-Pantiga, Samuel,Hernández-Ruiz, Raquel,Virumbrales, Cintia,Pedrosa, María R.,Sanz, Roberto
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supporting information
p. 2129 - 2133
(2019/01/25)
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- CoII immobilized on an aminated magnetic metal-organic framework catalyzed C-N and C-S bond forming reactions: A journey for the mild and efficient synthesis of arylamines and arylsulfides
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In this work, we report a simple and versatile method for the modification of a metal-organic framework (NH2-MIL53(Al)) in a step-wise manner. To characterize the synthesized nanostructured catalyst, a variety of spectroscopic and microscopic techniques including FT-IR, XRD, BET, TEM, FE-SEM, EDX, EDX-mapping, TGA, XPS, VSM, ICP-OES and CHN have been employed. Fe3O4@AMCA-MIL53(Al)-NH2-CoII NPs, which benefit from small nanocrystalline size (10-30 nm, according to the XRD and TEM data) in combination with the coexistence of magnetic nanoparticles, a metal-organic framework, and cobalt species, were found to be an excellent environment catalyst to promote the C-N and C-S cross coupling reactions. A wide range of functional substrates including electron-withdrawing and electron-donating aryl halides underwent the coupling reaction with aromatic/heteroaromatic/benzylic and aliphatic amines and sulfides. The results demonstrated that the yields of the target products were good to excellent and the catalyst can be recycled for at least seven recycling runs without a discernible decrease in its catalytic activity. Furthermore, the heterogeneity studies (such as hot filtration and poisoning tests) efficiently confirmed that the as-synthesized nanostructured catalyst is heterogeneous and completely stable under the reaction conditions. We hope that our study inspires more interest in designing novel catalysts based on using low-cost metal ions (such as cobalt) in the field of cross coupling reactions.
- Mohammadinezhad, Arezou,Akhlaghinia, Batool
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p. 15525 - 15538
(2019/10/19)
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- A Copper-Catalyzed Tandem C–H ortho-Hydroxylation and N–N Bond-Formation Transformation: Expedited Synthesis of 1-(ortho-Hydroxyaryl)-1H-indazoles
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A facile, one-pot synthesis of 1H-indazoles featuring a Cu-catalyzed C–H ortho-hydroxylation and N–N bond-formation sequence with the use of pure oxygen as the terminal oxidant was developed. The reaction of readily available 2-arylaminobenzonitriles with
- Chen, Cheng-Yi,He, Fengxian,Tang, Guangrong,Ding, Han,Wang, Zhaobin,Li, Dawei,Deng, Lujiang,Faessler, Roger
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supporting information
p. 6604 - 6608
(2017/12/04)
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- Pd/AlO(OH): A Heterogeneous, Stable and Recyclable Catalyst for N-Arylation of Aniline Under Ligand-Free Aerobic Condition
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Abstract: Many synthetic methods have been reported to construct an aryl-nitrogen bond. But they mainly suffer from the usage of expensive ligands. Herein, we report highly effective, heterogeneous, reusable and ligand-free nanocatalyst for the Buchwald-Hartwig coupling reaction under aerobic condition. Wafer-like structure with nano-porous nature of AlO(OH) was identified with TEM and BET surface area analyses. Zero valent Pd nanoparticles (with less than 10?nm crystallite size which strongly evident from TEM analysis) were observed in XRD pattern, which was further confirmed by XPS studies. The reaction conditions were optimized and the scope of the reaction was extended with various aryl halides and aniline using low amount of Pd (0.31?mol%) based heterogeneous catalyst. Heterogeneity, reusability and stability (confirmed by XRD) were found to be reasonable. Use of meagre amount of Pd and the ligand-free aerobic condition make this system economically as well as environmentally feasible. Graphical Abstract: [Figure not available: see fulltext.].
- Ganesh Babu, Sundaram,Emayavaramban, Balakumar,Jerome, Peter,Karvembu, Ramasamy
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p. 2619 - 2629
(2017/09/06)
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- A Synthesis of 1H-Indazoles via a Cu(OAc)2-Catalyzed N-N Bond Formation
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A facile synthesis of 1H-indazoles featuring a Cu(OAc)2-catalyzed N-N bond formation using oxygen as the terminal oxidant is described. The reaction of readily available 2-aminobenzonitriles with various organometallic reagents led to o-aminoar
- Chen, Cheng-Yi,Tang, Guangrong,He, Fengxian,Wang, Zhaobin,Jing, Hailin,Faessler, Roger
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supporting information
p. 1690 - 1693
(2016/04/26)
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- Rhodium(III)-Catalyzed Direct Cyanation of Aromatic C-H Bond to Form 2-(Alkylamino)benzonitriles Using N-Nitroso As Directing Group
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2-(Alkylamino)benzonitriles were synthesized via a rhodium-catalyzed cyanation on the aryl C-H bond and subsequent denitrosation of N-nitrosoarylamines using a removable nitroso as the directing group, in which N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS) was used as the "CN" source. Various substituents on the aryl ring and amino group of N-nitrosoarylamines tolerated the reaction, and the corresponding products were achieved in moderate to good yields.
- Dong, Jiawei,Wu, Zhongjie,Liu, Zhengyi,Liu, Ping,Sun, Peipei
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p. 12588 - 12593
(2016/01/09)
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- HISTONE DEMETHYLASE INHIBITORS
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The present invention relates generally to compositions and methods for treating cancer and neoplastic disease. Provided herein are substituted amidopyridine or amidopyridazine derivative compounds and pharmaceutical compositions comprising said compounds. The subject compounds and compositions are useful for inhibition histone demethylase. Furthermore, the subject compounds and compositions are useful for the treatment of cancer, such as prostate cancer, breast cancer, bladder cancer, lung cancer and/or melanoma and the like.
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Paragraph 00260
(2014/07/08)
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- Deproto-metallation using a mixed lithium-zinc base and computed CH acidity of 1-aryl 1H-benzotriazoles and 1-aryl 1H-indazoles
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1-Aryl-1H-benzotriazoles and -1H-indazoles were synthesized, and their deproto-metallation using the base prepared by mixing LiTMP with ZnCl 2·TMEDA (1/3 equiv.) was studied. In the indazole series, reactions occurring at the 3 position were fo
- Nagaradja, Elisabeth,Chevallier, Floris,Roisnel, Thierry,Dorcet, Vincent,Halauko, Yury S.,Ivashkevich, Oleg A.,Matulis, Vadim E.,Mongin, Florence
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p. 1475 - 1487
(2014/03/21)
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- Aminocyanation by the addition of N-CN bonds to arynes: Chemoselective synthesis of 1,2-bifunctional aminobenzonitriles
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An efficient aminocyanation by the direct addition of aryl cyanamides to arynes is described, enabling incorporation of highly useful amino and cyano groups synchronously via cleavage of inert N-CN bonds, affording synthetically useful 1,2-bifunctional aminobenzonitriles. The postsynthetic functionalization of the aminocyanation products allows diverse formation of synthetically important derivatives such as drug molecule Ponstan and fused heterocycles.
- Rao, Bin,Zeng, Xiaoming
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p. 314 - 317
(2014/01/23)
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- NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
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The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device containing the same. The organic electroluminescent compounds according to the present invention have high luminescent efficiency and a lo
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Paragraph 100; 101; 102; 103; 173; 174; 175; 176
(2014/01/07)
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- Efficient palladium-catalyzed amination of aryl chlorides using di(dicyclohexylamino)phenylphosphine as a PN2 ligand
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The palladium-catalyzed amination of a variety of aryl chlorides has been accomplished by using di(dicyclohexylamino)phenylphosphine (1) as a bulky electron-rich monoaryl phosphine ligand. The optimized condition for the palladium-catalyzed amination of aryl chloride is the followings: aniline (3.0 mmol, 1.0 equiv), chlorobenzene (3.15 mmol, 1.05 equiv), ligand 1 (1 mol %, 0.03 mmol), KOtBu (4.5 mmol, 1.5 equiv), Pd2(dba)3 (1 mol %, 0.03 mmol), and toluene as solvent at reflux temperature. We report on couplings of various amines or chloroamines with chlorobenzenes and heteroaryl chloride.
- Kim, Bo Ram,Cho, Su-Dong,Kim, Eun Jung,Lee, In-Hye,Sung, Gi Hyeon,Kim, Jeum-Jong,Lee, Sang-Gyeong,Yoon, Yong-Jin
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experimental part
p. 287 - 293
(2012/01/05)
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- Air-stable and highly efficient indenyl-derived phosphine ligand: Application to Buchwald-Hartwig amination reactions
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2-Mesitylindenyl phosphine ligand (1) and [(2-mesitylindenyl)dicyclohexyl- phosphine]PdCl2 (2) have been synthesized and fully characterized by NMR and elemental analysis, as well as by X-ray crystallography for 2. A Highly active catalyst system derived from a palladium precatalyst and bulky 2-mesitylindenyl phosphine ligand (1) for the Buchwald-Hartwig amination reaction of aryl halides with primary and secondary amines has been developed. This method allows for the preparation of a wide variety of amines in moderate to excellent yields and displays a high level of activity for the coupling of aryl chlorides as well as hindered aryl bromides.
- Hao, Xiaowei,Yuan, Jia,Yu, Guang-Ao,Qiu, Ming-Qiang,She, Neng-Fang,Sun, Yue,Zhao, Cui,Mao, Shu-Lan,Yin, Jun,Liu, Sheng-Hua
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experimental part
p. 99 - 105
(2012/06/17)
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- Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)2 and applications in in situ cross coupling reactions
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This study investigates the ability of the mixed-metal reagent [Li(TMP)Zn(tBu)2] 1 to promote direct Zn-H exchange reactions (zincations) of a wide range of N-heterocyclic molecules. The generated metallated intermediates from these reactions are intercepted with I2 and some of them are also employed as precursors in Pd-catalysed Negishi cross-coupling applications. A comparison with recent precedents in metallation chemistry reveals that for some of these heterocycles, 1 allows improved conversions, under milder conditions and in certain cases, even gives unique regioselectivities.
- Blair, Victoria L.,Blakemore, David C.,Hay, Duncan,Hevia, Eva,Pryde, David C.
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supporting information; experimental part
p. 4590 - 4594
(2011/09/30)
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- Novel nickel-carbene, palladium-carbene and platinum-carbene complexes, their produciton and use in catalytic reactions
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The invention relates to novel monocarbene complexes of nickel, palladium or platinum with electron-deficient olefin ligands, to their preparation and to their use in the homogeneous catalysis of organic reactions.
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Page/Page column 9
(2008/06/13)
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- Thermal decomposition of tert-butyl o-(phenoxy)- and o-(anilino)-phenyliminoxyperacetates
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Some o-phenoxy- and o-anilino-substituted aryliminyl radicals have been generated by thermal decomposition of suitable tert-butyl iminoxyperacetates. The iminyls show no disposition to give 7-membered cyclisation on the phenyl group. In some cases, products have been found that can be rationalised through a 1,6-spirocyclisation of the iminyl radicals followed by homolytic 1,5-migration of the phenyl group from the aminic to the iminic nitrogen: this seems to be the first instance of such a process. Evidence has been found for the formation of imines through hydrogen abstraction by the iminyls; with two o-phenoxy-substituted peresters these imines have been unexpectedly isolated. The reactions have also afforded significant - in some cases major - amounts of other products (acridine, quinazolinone and indole derivatives) presumably deriving from carbon radicals: mechanisms are suggested to account for the formation of these compounds. The structure of the quinazolinone compound has been determined by X-ray crystallographic analysis.
- Calestani, Gianluca,Leardini, Rino,McNab, Hamish,Nanni, Daniele,Zanardi, Giuseppe
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p. 1813 - 1824
(2007/10/03)
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- Gas-phase cyclisation reactions of 1-(2-arylaminophenyl)alkaniminyl radicals
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Flash vacuum pyrolysis (FVP) of the oxime ethers 9-11 at 650°C (10-2-10-3 Torr) gives products such as the nitrile 17, carbazoles 19 and 20 and acridines 18 and 21 derived from the corresponding iminyl radicals 13-15. The mechanism proposed for the formation of the acridines involves a key hydrogen abstraction by the iminyl of the adjacent N-H atom. When this route is blocked by an N-methyl group, as in 12, alternative cyclisations ensue, yielding the dihydroquinazoline 26 (via another hydrogen abstraction process) and the benzimidazole 25 (via an iminyl-imidoyl interconversion).
- Leardini, Rino,McNab, Hamish,Nanni, Daniele,Parsons, Simon,Reed, David,Tenan, Anton G.
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p. 1833 - 1838
(2007/10/03)
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- EXLUSIVE ORTHO CYANATION AND ALKYLTHIOCARBONYLATION OF ANILINES AND PHENOLS USING BORON TRICHLORIDE
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Use of boron trichloride with or without an aditional Lewis acid makes possible a one-step synthesis of 2-cyano and 2-alkylthiocarbonyl anilines and phenols.
- Adachi, Makoto,Sugasawa, Tsutomu
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- Reaction of Benzyne with 1,2,5-Thiadiazoles and 2,1-Benzisothiazoles
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1,2,5-Thiadiazoles react with benzyne to give 1,2-benzisothiazole derivatives. 3.4-Diphenyl-1,2,5-selenadiazole with benzyne likewise affords 3-phenyl-1,2-benzisoselenazole, contrary to a previous report.Some reactions of 3-(8-cyano-1-naphthyl)-1,2-benzisothiazole are described.The reaction of benzyne with 3-amino-2,1-benzisothiazole afforded N-phenylated products, including N-phenyl-anthranonitrile.
- Bryce, Martin R.,Dransfield, Trevor A.,Kandeel, Kamal A.,Vernon, John M.
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p. 2141 - 2144
(2007/10/02)
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