- Changes in the conformational parameters of 1-allylbenzotriazole in a mixed halide π-complex [CuCl0.85Br0.15(C6H 4N3CH2CH=CH2)] under the action of bromine atoms
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Single crystals of [CuCl0.85Br0.15(C 6H4N3CH2=CH2)] (I) were obtained by alternating current electrochemical synthesis; their X-ray structural investigation has been carried out (DARCh automatic diffractometer, MoK α radiation, θ/2θ scanning; 1460 reflections with F ≥ 4σ(F), R = 0.0517). The crystals are monoclinic, their space group is P21/c, a = 7.292(3) A, b = 17.947(8) A, c = 7.398(4) A, β = 93.56(4)°, V = 966(1) A3, Z = 4). Complex I is close in structure to the previously investigated compound [CuCl(C6H4N3CH2=CH2)] (II). In both structures, the trigonal-pyramidal surroundings of the copper atom include two halide atoms (one is apical), a nitrogen atom, and a C=C group. The Cu2X2 dimers are associated into {[Cu2X 2(C6H5N3CH2=CH 2)]}n layers due to the bridging function of the 1-allylbenzotriazole molecule. In spite of the similar coordination polyhedra of the metal atoms and identical bridging function of the ligand molecule in I and II, the differences in the conformation parameters of the allyl group π-coordinated by the copper(I) atom (trans-like in I and cis-like in II) caused by the presence of bromine atoms in the coordination sphere predetermine different structures of the organometallic [Cu2X2(C 6H5N3CH2=CH2)] 4 tetramer subunits in the layers and, as a consequence, formation of different crystal structures.
- Goreshnik,Mykhalichko,Davydov
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Read Online
- Sustainable Palladium-Catalyzed Tsuji-Trost Reactions Enabled by Aqueous Micellar Catalysis
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Palladium-catalyzed allylic substitution, or "Tsuji-Trost"reactions, can be run under micellar catalysis conditions featuring not only chemistry in water but also numerous combinations of reaction partners that require low levels of palladium, typically on the order of 1000 ppm (0.1 mol %). These couplings are further characterized by especially mild conditions, leading to a number of cases not previously reported in an aqueous micellar medium. Inclusion of diverse nucleophiles, such as N-H heterocycles, alcohols, dicarbonyl compounds, and sulfonamides is described. Intramolecular cyclizations further illustrate the broad utility of this process. In addition to recycling studies, a multigram scale example is reported, indicative of the prospects for scale up.
- Braga, Felipe C.,Gallou, Fabrice,Lee, Nicholas R.,Lippincott, Daniel J.,Lipshutz, Bruce H.,Moghadam, Farbod A.,Zhu, Bingchun
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supporting information
(2020/07/15)
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- Synthesis of Structurally Diverse Benzotriazoles via Rapid Diazotization and Intramolecular Cyclization of 1,2-Aryldiamines
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An operationally simple method has been developed for the preparation of N-unsubstituted benzotriazoles by diazotization and intramolecular cyclization of a wide range of 1,2-aryldiamines under mild conditions, using a polymer-supported nitrite reagent and p-tosic acid. The functional group tolerance of this approach was further demonstrated with effective activation and cyclization of N-alkyl, -aryl, and -acyl ortho-aminoanilines leading to the synthesis of N1-substituted benzotriazoles. The synthetic utility of this one-pot heterocyclization process was exemplified with the preparation of a number of biologically and medicinally important benzotriazole scaffolds, including an α-amino acid analogue.
- Faggyas, Réka J.,Sloan, Nikki L.,Buijs, Ned,Sutherland, Andrew
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p. 5344 - 5353
(2019/05/21)
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- Isomer-selective complexation of copper(I) ionic salts towards 1- and 2-allylbenzotriazoles. Synthesis and characterization of CuBF 4·2-all-bta·H2O, CuClO4·2- all-bta, CuClO4·1-all-bta·2-all-bta and CuHSO 4·2-all-bta - The first known example of CuHSO4 π-complexes
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The alternating current electrochemical synthesis starting from ethanol solution of Cu(ClO4)2·6H2O, CuSO 4·5H2O and Cu(BF4)2· 6H2O with the equimolar mixture of 1- and 2-allylbenzotriazole (all-bta) has led to a formation of Cu[2-all-bta]ClO4 (I), Cu[2-all-bta]HSO4 (II) and Cu[2-all-bta]BF4·H 2O (III) compounds. The direct interaction between Cu(ClO 4)2·6H2O and the mixture of 1- and 2-allylbenzotriazole in ethanol solution results in an appearance of Cu[(1-all-bta)(2-all-bta)]ClO4 (IV) compound. These results are strikingly different from earlier performed syntheses using the same ligands mixture and copper(II) halides, and producing coordination compounds with 1-allylbenzotriazole only. Compounds I and II are isotypical and crystallize in a monoclinic space group Cc. I: a = 9.5413(10) , b = 12.3171(9) , c = 10.3264(10) , β = 111.155(4)°, V = 1131.78(18) 3, Z = 4. II: a = 9.1707(17) , b = 13.6639(17) , c = 9.4543(17) , β = 105.555(7)°, V = 1141.3(3) 3, Z = 4. The main feature of structures I and II is a chelate-bridging role of the ligand moiety, bonded to one copper ion via CC-bond of the allyl group and nitrogen atom of the triazole core, and to the second Cu+ centre by another N atom. Trigonal-pyramidal copper environment comprises of two nitrogen atoms from different ligand units, CC-bond and oxygen atom at the apical position. The bridging function of both Cu+ cations and 2-all-bta molecules results in the formation of infinite chains. High affinity of BF4- anion to the H2O leads to a formation of compound III including water molecule. It crystallizes in an orthorhombic Pbca space group, a = 13.502(8) b = 11.299(5) c = 16.124(8) , V = 2460(2) 3, Z = 8. The ligand moiety plays the same as in I and II chelate-bridging function, but Cu+, being also bonded to CC group and to two N atoms, is connected with the disordered BF4- anion through the water bridge. In the crystal structure IV the metal ion possesses mixed-isomer surrounding, being bound to N-atom and CC-bond of 2-all-bta molecule, N-atom of 1-all-bta-moiety and O(ClO4 -) atom at apical position. IR spectra confirm rather effective Cu-(CC) bonding.
- Goreshnik,Vakulka,Slyvka, Yu. I.,Mys'Kiv
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experimental part
p. 1 - 5
(2012/06/29)
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- Development of a palladium on boron nitride catalyst and its application to the semihydrogenation of alkynes
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The simple preparative method for a novel palladium supported on boron nitride catalyst (Pd/BN) was accomplished. Pd/BN is widely applicable for the semihydrogenation of mono- as well as disubstituted alkynes to furnish the corresponding alkenes in the presence of diethylenetriamine (DETA), which exhibits both an unprecedented acceleration effect toward the semihydrogenation and a suppression effect with regard to the overhydrogenation to alkanes. Copyright
- Yabe, Yuki,Yamada, Tsuyoshi,Nagata, Saori,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
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supporting information; experimental part
p. 1264 - 1268
(2012/06/15)
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- Green and efficient protocol for N-alkylation of benzotriazole using basic ionic liquid [Bmim]OH as catalyst under solvent-free conditions
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N-Alkylation of benzotriazole bearing an acidic hydrogen atom attached to nitrogen with alkyl halides is accomplished in basic ionic liquid [Bmim]OH (1-butyl-3-methylimidazolium hydroxide) under solvent-free conditions. The procedure is convenient and efficient and generally affords the N-alkylated product. Taylor & Francis Group, LLC.
- Le, Zhang-Gao,Zhong, Tao,Xie, Zong-Bo,Lue, Xue-Xia,Cao, Xia
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experimental part
p. 2525 - 2530
(2010/09/14)
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- Highly selective N-Alkylation of amines promoted on silica: An efficient and recyclable surface
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N-Alkylation of amines suffers from competing over alkylations. At the same time, use of strong base and other harsh conditions greatly limits providing a practical, generalized and selective procedure. Activated silica gel has been found to promote N-alkylations of amines. Here, we studied N-alkylation of amines with various types of alkyl halides, which finally constitute practical, highly selective and eco-friendly conditions for mono- or bis-alkylated amines at ambient temperature with recyclability of silica.
- Basu, Basudeb,Paul, Susmita,Nanda, Ashis K.
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experimental part
p. 1115 - 1120
(2010/05/02)
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- Organic reactions in ionic liquids: A simple highly regioselective or regiospecific substitutions of benzotriazole
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In the absence of any added base in ionic liquids [Bmim][BF4], benzotriazole replaces the halogen atom of an α-halogenated ketone or α-halogenated carboxylic ester to give the corresponding N-1-substituted benzotriazole as the only isomer, and
- Le, Zhang-Gao,Chen, Zhen-Chu,Hu, Yi,Zheng, Qin-Guo
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p. 1077 - 1081
(2007/10/03)
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- Aqueous micellar medium in organic synthesis: Alkylations and Michael reactions of benzotriazole
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The feasibility of aqueous micelles of cetyltrimethylammonium bromide in catalyzing C-N bond formation has been studied with respect to N-alkylations of benzotriazole (Bt). Alkylations with various alkylating agents and the addition of Bt across activated double bonds in the Michael fashion occurred successfully in fair-to-good yields in the aqueous micellar regime. These reactions provided a mixture of N-1 and N-2 alkylated products, with a marked preference for N-1 over N-2 isomers. Micellar catalysis has been evaluated experimentally to indicate over a 50% micellar contribution to these alkylations in contrast to their aqueous counterparts. Since, N-alkyl benzotriazoles are of potential biological interest, the present micellar procedure offers a convenient alternative to other available methods.
- Mashraqui, Sabir Hussain,Kumar, Sukeerthi,Mudaliar, Chandrasekhar Dayal
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p. 2133 - 2138
(2007/10/03)
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- Synthesis and crystal structure of copper(I) chloride π-complex with 1-allylbenzotriazole of CuCl·C6H4N3(C3H5) composition
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By alternating-current electrochemical synthesis crystals of CuCl·C6H4N3(C3H5) π-complex (I) have been obtained and structurally investigated. Due to the coordination of Cu(I) atoms through the nitrogen atom and olefinic group of the same molecule, organometallic chains appear. Bridged Cl atoms combine these chains into a three-dimensional framework. The trigonal-pyramidal copper environment involves two Cl atoms (one of them occupies the apical position), nitrogen atom and C=C group.
- Goreshnik
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p. 1253 - 1258
(2007/10/03)
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- The Mitsunobu reaction: An alternative synthesis of 1-(primary alkyl)benzotriazoles
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1-(Primary alkyl)benzotriazoles are obtained in convenient yields by treating the corresponding alcohol with triphenylphosphine, N-bromosuccinimide and benzotriazole. Under these conditions, the alcohols gave exclusively the corresponding 1-alkyl-benzotriazoles. Allyl and propargyl alcohols also reacted regiospecifically in a typical S(N)2 manner, and no products derived from prototropic rearrangement were found.
- Katritzky, Alan R.,Oniciu, Daniela C.,Ghiviriga, Ion
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p. 1613 - 1621
(2007/10/03)
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- 1-(1-Alkenyl)benzotriazoles: Novel α-hydroxyacyl anion equivalents for the synthesis of α-hydroxy ketones
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α-Lithiated 1-(1-alkenyl)benzotriazoles, generated from the reactions of 1-(1-alkenyl)benzotriazoles with n-BuLi, react with a variety of electrophiles to afford α-substituted 1-(1-alkenyl)benzotriazoles which undergo epoxidation with m-CPBA followed by h
- Katritzky, Alan R.,Heck, Kenneth A.,Li, Jianqing,Wells, Adam,Garot, Catherine
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p. 2657 - 2670
(2007/10/03)
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- A new indole synthesis via [3 + 3] annulation of 2-(benzotriazol-1-ylmethyl)pyrroles with α,β-unsaturated aldehydes and ketones
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Poly-substituted indoles are readily accessible from substituted 2-(benzotriazol-1-ylmethyl)pyrroles by lithiation, reaction with α,β-unsaturated aldehydes and ketones, and subsequent facile dehydrobenzotriazolylation-cyclodehydration. The substituted 2-(
- Katritzky, Alan R.,Levell, Julian R.,Li, Jianqing
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p. 5641 - 5644
(2007/10/03)
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- Selective Allylation and Propargylation of Azoles by Phase Transfer Catalysis in the Absence of Solvent
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Phase transfer catalysis without solvent allows the selective preparation of N-allyl- and N-propargylazoles or N-(1-propenyl)- and N-(1,2-propadienyl)azoles by reaction of the parent azole with allyl or propargyl bromides.Small variations in the reaction conditions, base or temperature, afford the desired selectivity.
- Diez-Barra, Enrique,Hoz, Antonio de la,Loupy, Andre,Sanchez-Migallon, Ana
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p. 1367 - 1374
(2007/10/02)
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- STUDIES ON THE THERMAL DECARBOXYLATION OF 1-ALKOXYCARBONYLBENZOTRIAZOLES
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1-Alkoxycarbonylbenzotriazoles on thermolysis lose carbon dioxide; the decarboxylation is accompanied by the formation of a mixture of 1- and 2-alkylbenzotriazoles, with the N-1 isomer predominating over the N-2 isomer in all cases.A cross-over experiment
- Katritzky, Alan R.,Zhang, Gui-Fen,Fan, Wei-Qiang,Wu, Jing,Pernak, Juliusz
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p. 567 - 573
(2007/10/02)
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- N-Vinyl-, N-Allyl-, N-Propenyl- and N-Propargyl-benzotriazoles: Reactions of Their Lithium Derivatives
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1-Vinylbenzotriazole undergoes lithiation at the α-carbon and subsequent reactions with electrophiles to afford 1-(1-substituted vinyl)benzotriazoles (3a-d).Similarly, 1-(1-substituted propylenyl)- (9a-c, 9e, 10a-c, 10e) and 2-(1-methylpropyl)benzotriazol
- Katritzky, Alan R.,Li, Jianqing,Malhotra, Nageshwar
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p. 843 - 854
(2007/10/02)
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- N-Alkylation of Pyrrole, Indole, and Several Other Nitrogen Heterocycles Using Potassium Hydroxide as a Base in the Presence of Polyethylene Glycols or Their Dialkyl Ethers
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The alkylation of pyrrole and indole in aqueous potassium hydroxide-organic two-phase systems in the presence of polyethylene glycols (PEG) or their dialkyl ethers (PEG-ether) as phase transfer catalysts (PTC) gave substantial quantities of the C-alkylated and C,N-polyalkylated products as well as the N-alkylated products.This fact is similar to that obtained in the presence of quaternary ammonium salts as PTC.In powdered potassium hydroxide-organic two-phase system, the yields of the N-alkylated products were generally high.Especially, when PEG-ether were employed as solvents, the N-alkylated products were obtained in excellent yields under mild conditions.Imidazole, benzimidazole, carbazole, 2-methylindole, and benzotriazole were similarly N-alkylated in high yields by this method.
- Sukata, Kazuaki
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p. 280 - 284
(2007/10/02)
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- ETUDE DANS LA SERIE DES ORGANOSILYLAZOLES I. ACTION DES HALOGENURES D'ALKYLE, DES CHLORURES D'ACIDE ET DES CETONES HALOGENEES
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The reactivity of organosilylamines of imidazole, pyrazole, 1,2,4-triazole and benzotriazole towards alkyl halides, acidic chlorides and halogenated ketones has been studied.Except for 1-trimethylsilylimidazole, which gives a mixed quaternary salt, reactions with primary halides lead to the corresponding 1-alkylated heterocyclic compounds in high yields; in each case only one isomer is obtained (1-alkyl-1,2,4-triazole and 1-alkylbenzotriazole).Similarly acidic chlorides give 1-acylated derivatives in quantitative yields.Finally α- or β-halogenated ketones show different behaviour and give the addition or substitution products.
- Gasparini, J. P.,Gassend, R.,Maire, J. C.,Elguero, J.
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p. 141 - 150
(2007/10/02)
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