- Diverse reactivity of rhodium β-(tetraphenyl)tetraphenyl porphyrin chlorides with benzonitrile: Formation of Rh porphyrin arene and imine complexes
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The reaction of rhodium trichloride with β-(tetraphenyl)tetraphenyl porphyrin, H2(tpp)(Ph)4, and β-(tetraphenyl)tetrakismesityl porphyrin, H2(tmp)(Ph)4, in refluxing benzonitrile gave novel rhodium porphyrin chl
- Zhou, Xiang,Tse, Man Kin,Wu, De-Dong,Mak, Thomas C.W.,Chan, Kin Shing
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- Metalation of 2-Methyl-N-phenylbenzamide with n-Butyllithium. Formation of N,3-Diphenyl-1-isoquinolinamine by Subsequent Reaction with Benzonitrile
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2-Methyl-N-phenylbenzamide was metalated with two equivalents of n-butyllithium.Benzonitrile was allowed to react with the organomethallic intermediate thus formed to yield N,3-diphenyl-1-isoquinolinamine. - Keywords: Benzamide, iminophenylethyl-phenyl; Cyclodehydratation; Isoquinolinamine, diphenyl; Lithiation
- Abraham, Tonson
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- Direct Synthesis of a Covalent Triazine-Based Framework from Aromatic Amides
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There have been extensive efforts to synthesize crystalline covalent triazine-based frameworks (CTFs) for practical applications and to realize their potential. The phosphorus pentoxide (P2O5)-catalyzed direct condensation of aromatic amide instead of aromatic nitrile to form triazine rings. P2O5-catalyzed condensation was applied on terephthalamide to construct a covalent triazine-based framework (pCTF-1). This approach yielded highly crystalline pCTF-1 with high specific surface area (2034.1 m2 g?1). At low pressure, the pCTF-1 showed high CO2 (21.9 wt % at 273 K) and H2 (1.75 wt % at 77 K) uptake capacities. The direct formation of a triazine-based COF was also confirmed by model reactions, with the P2O5-catalyzed condensation reaction of both benzamide and benzonitrile to form 1,3,5-triphenyl-2,4,6-triazine in high yield.
- Yu, Soo-Young,Mahmood, Javeed,Noh, Hyuk-Jun,Seo, Jeong-Min,Jung, Sun-Min,Shin, Sun-Hee,Im, Yoon-Kwang,Jeon, In-Yup,Baek, Jong-Beom
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- Domino reaction of lithiated allenes with nitriles
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Addition of nitriles to dilithiated allenes results in a unique domino cyclization which involves the so far highest number of nitrile molecules added to an organolithium reagent to form unambiguously characterized oligomers.
- Langer, Peter,Doering, Manfred,Seyferth, Dietmar
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- Butyllithium-induced Cyclotrimerisation Reactions of Organic Nitriles: Solvent Dependency, Crystal and Solution Structures of Lithio Triazine Intermediates and an Unexpected Rearrangement of Dihydrotriazino Anions
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Sequential addition of ButCN and PhCN (2 equiv.) to BunLi in the presence of tetrahydrofuran (THF) produces an isolable lithio 1,4-dihydrotriazine tris(THF) solvate, characterised by both NMR spectroscopic and X-ray crystallographic methods, which converts to a 1,2-dihydro arrangement on methanolysis.
- Armstrong, David R.,Clegg, William,MacGregor, Murray,Mulvey, Robert E.,O'Neil, Paul A.
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- Direct synthesis of covalent triazine-based frameworks (CTFs) through aromatic nucleophilic substitution reactions
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Despite extensive efforts, only three main strategies have been developed to synthesize covalent triazine-based frameworks (CTFs) thus far. We report herein a totally new synthetic strategy which allows C-C bonds in the CTFs to be formed through aromatic nucleophilic substitution reactions. The as-synthesized CTF-1 and CTF-2 exhibited photocatalytic water splitting activity comparable to the CTFs made using ionothermal or Br?nsted acid-catalyzed polymerization. Interestingly, CTF-2 distinguished itself by its two-photon fluorescence (emission at ～530 nm under irradiation at either 400 nm or 800 nm).
- Chen, Tao,Li, Wen-Qian,Hu, Wei-Bo,Hu, Wen-Jing,Liu, Yahu A.,Yang, Hui,Wen, Ke
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- Functionalized fluorenes via dicationic electrophiles
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Dicationic fluorenyl cations are shown to react with nitriles to provide amide-functionalized fluorenes. A similar reaction with alcohols gives ether derivatives. The chemistry is initiated by the reactions of N-heterocyclic ketones in a superacidic solution. This leads to cyclizations involving 2-biphenyl groups and formation of the reactive fluorenyl cations.
- Stentzel, Michael R.,Klumpp, Douglas A.
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- Reactions of rac-(ebthi)M(η2-Me3SiC2SiMe3) (M=Ti, Zr) with Aryl Nitriles
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The reactions of the Group 4 metallocene alkyne complexes rac-(ebthi)M(η2-Me3SiC2SiMe3) (1 a: M=Ti, 1 b: M=Zr; rac-(ebthi)=rac-1,2-ethylene-1,1′-bis(η5-tetrahydroindenyl)) with Ph C N were investigated. For 1 a, an unusual nitrile–nitrile coupling to 1-titana-2,5-diazacyclopenta-2,4-diene (2) at ambient temperature was observed. At higher temperature, the C C coupling of two nitriles resulted in the formation of a dinuclear complex with a four-membered diimine bridge (3). The reaction of 1 b with Ph C N afforded dinuclear compound 4 and 2,4,6-triphenyltriazine. Additionally, the reactivity of 1 b towards other nitriles was investigated.
- Becker, Lisanne,Arndt, Perdita,Spannenberg, Anke,Rosenthal, Uwe
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- Synthetic and theoretical MO calculational studies of lithiotriazine intermediates produced during alkyllithium-induced cyclotrimerisation reactions of organic nitriles, and comparison of their structures with that of a methylmagnesiotriazine derivative
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Benzonitrile can be readily cyclotrimerised by treatment with a suitable alkyllithium to give a simple triazine or to a solvated lithiodihydrotriazine derivative.Which cyclic product dominates depends mainly on the source of the active Li+ cation (n-butyllithium, t-butyllithium and tetramethylguanidinolithium are considered here), and on the solvent employed.X-ray crystallographic studies on a representative compound show that the lithio species exists as a mononuclear, contact ion pair structure, with the triazine ring in a 1,4-dihydro state.On reaction with theGrignard reagent, MeMgCl, this compound gives a methylmagnesiodihydrotriazine, which has also been crystallographically characterised and found to closely resemble its lithio precursor.Ab initio MO calculations on model systems reveal that the 1,4-dihydrotriazine arrangements is energetically preferred to the 1,2-dihydro alternative irrespective of the counterion (Li+ or H+) present.A theoretical investigation of the methanolysis of the lithio species indicates that the formation of an intermediate MeOH complex, with the alcohol attached to a ring N atom and not to Li+, directs the reaction towards ultimate formation of a 1,2-dihydrotriazine.Keywords: Triazine; Lithium; Magnesium; Ab initio; Crystal structure
- Armstrong, David R.,Henderson, Kenneth W.,MacGregor, Murray,Mulvey, Robert E.,Ross, Michael J.,et al.
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- Reactions of benzene derivatives containing C≡N and C≡CH groups with atomic chromium
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Reactions of benzonitrile and phenylacetylene with atomic chromium were studied. Products of the trimerization and polymerization of the initial aromatic compounds form in considerable amounts along with bisarenechromium complexes. Mechanisms of the reactions were suggested. The possibility of increasing the yields of the bisarenechromium complexes was considered.
- Vasil'kov,Pribytkov,Peregudov
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- One-pot synthesis of new heterocycles: 2,4-disubstituted 6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-d]pyrimidines
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The reaction of 1-benzosuberone with nitriles in the presence of triflic anhydride affords in good yields 2,4-diaryl substituted 6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-d]pyrimidines, a new class of heterocycle.
- Herrera, Antonio,Martínez-Alvarez, Roberto,Chioua, Rachid,Chioua, Mourad
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- Solvothermal Reactions in and with Nitriles
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Solvothermal reactions and in situ reductions in nitriles yield a variety of new metal complexes and organometallic compounds including ligands of dimers, trimers, and tetramers of the organic solvent upon (oxidative) C-C and/or C-N bond formation and destruction.
- Thiele, Günther,Wagner, Bettina,Dehnen, Stefanie
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- Non-doped thermally activated delayed fluorescent organic light-emitting diodes using an intra- and intermolecular exciplex system with a: Meta -linked acridine-triazine conjugate
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We report OLEDs utilizing non-doped TADF emitters, 10-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine (AmT) and 10-(3′-(4,6-diphenyl-1,3,5-triazin-2-yl)-[1,1′-biphenyl]-3-yl)-9,9-dimethyl-9,10-dihydroacridine (AmmT). These two emitters are composed of electron donor (acridine) and acceptor (triphenyltriazine) moieties, which are connected at the meta positions so that intra- and intermolecular charge transfer (CT) states can be induced through exciplex-like interactions between the same emitters. A neat film of AmmT forms intermolecular CT state-induced exciplexes more favorably than AmT because of the packing benefits and relatively shorter radiative lifetime of AmmT. Electroluminescent devices using AmmT as an emitter exhibit an external quantum efficiency (EQE) over 18%, which is much better than the EQE value for devices using AmT. This is the first example of a non-doped TADF system using a single molecule-based exciplex as a dominant exciton source.
- Jeong, Seongjin,Lee, Youngnam,Kim, Joon Ki,Jang, Du-Jeon,Hong, Jong-In
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- Sustainable and recyclable magnetic nanocatalyst of 1,10-phenanthroline Pd(0) complex in green synthesis of biaryls and tetrazoles using arylboronic acids as versatile substrates
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A magnetic nanocatalyst was purveyed as a heterogeneous recoverable palladium-based catalyst anchored on green, sustainable and phosphine free support. Resulted Fe3O4@SiO2-Phen-Pd(0) nanocatalyst bearing powerful phenanthroline ligand was thoroughly characterized by physicochemical approaches like UV–vis, FT-IR, EDX, XRD, TGA, ICP, VSM, DLS, FESEM, and TEM analyses. After finding trustable data, the obtained magnetic catalyst was considered to be applied in the Suzuki-Miyaura type C-C couplings and getting corresponding tetrazoles using arylboronic acid derivatives as alternate precursors of aromatic halides and stupendous data were observed.
- Bagherzadeh, Nastaran,Sardarian, Ali Reza,Eslahi, Hassan
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- Preparation method of multipurpose compound s-triazine derivative
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The invention provides a preparation method of a s-triazine derivative, which is characterized in that an aryl nitrile compound is used as a substrate, lithium bis (trifluoromethanesulfonimide) is used as a catalyst, and the s-triazine derivative is obtained through a cyclopolymerization reaction. Compared with the prior art, the method has the advantages that a catalytic system is simple and easy to obtain, too high or too low rigorous reaction temperature is not needed, the reaction condition is mild, the reaction time is short, the post-treatment is simple, and the obtained s-triazine derivative has very high yield and is suitable for large-scale production.
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Paragraph 0043-0050
(2021/06/26)
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- Iron-Catalyzed Alkyne-Based Multicomponent Synthesis of Pyrimidines under Air
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An iron-catalyzed sustainable, economically affordable, and eco-friendly synthetic protocol for the construction of various trisubstituted pyrimidines is described. A wide range of trisubstituted pyrimidines were prepared using a well-defined, easy to prepare, bench-stable, and phosphine-free iron catalyst featuring a redox-noninnocent tridentate arylazo pincer under comparatively mild aerobic conditions via dehydrogenative functionalization of alcohols with alkynes and amidines.
- Chakraborty, Gargi,Guin, Amit Kumar,Mondal, Rakesh,Paul, Nanda D.,Sarkar, Susmita
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p. 13186 - 13197
(2021/10/01)
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- Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
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Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature). It was found that the obtained Se,S,N-CNs-1000 was very selective and efficient for oxidative cyanation of various aldehydes including those containing other oxidizable groups into the corresponding nitriles using ammonia as the nitrogen resource below 100 °C. Detailed investigations revealed that the excellent performance of Se,S,N-CNs-1000 originated mainly from the graphitic-N species with lower electron density and synergistic effect between the Se, S, N, and C in the catalyst. Besides, the hierarchically porous structure could also promote the reaction. Notably, the unique feature of this metal-free catalyst is that it tolerated other oxidizable groups, and showed no activity on further reaction of the products, thereby resulting in high selectivity. As far as we know, this is the first work for the synthesis of nitriles via oxidative cyanation of aldehydes over heterogeneous metal-free catalysts.
- Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
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supporting information
p. 21479 - 21485
(2021/08/23)
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- Multifunctional aggregation-induced emission material and preparation method thereof
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The invention belongs to the technical field of photoelectric display devices, and particularly relates to a multifunctional aggregation-induced emission material and a preparation method thereof. The invention provides a multifunctional aggregation-induced emission material. The structure of the multifunctional aggregation-induced emission material is shown as a formula (I). The invention also provides a preparation method of the multifunctional aggregation-induced emission material, and the preparation method comprises the step of carrying out substitution reaction on 2, 4, 6-tri (4-bromophenyl)-1, 3, 5-triazine and the compound as shown in the formula (II) to prepare the compound as shown in the formula (I). The invention solves the technical problems that the efficiency of the existing TADF micromolecule red light emitting material and the electroluminescent device thereof is not high, and the aggregation quenching luminescence effect is easy to generate.
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Paragraph 0020; 0021; 0022
(2021/08/19)
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- Synthesis method of cyanoacrylate compound
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The method comprises the following reaction steps: a compound (1) reacts with a compound (2) to directly prepare a compound (3), and is characterized in that the reaction is carried out in a molten state. Compound (1). Compound (2). Compound (3).
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- Method for synthesizing 2, 4, 6-trisubstituted 1, 3, 5-triazine compound from aromatic aldehyde and ammonium iodide
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The invention discloses a method for synthesizing a 2, 4, 6-trisubstituted 1, 3, 5-triazine compound from aromatic aldehyde and ammonium iodide, and belongs to the field of organic synthesis. According to the method, aromatic aldehyde and ammonium iodide undergo a one-pot reaction under the catalytic action of a ferric salt, so that the 2, 4, 6-trisubstituted 1, 3, 5-triazine compound is obtained.According to the present invention, the small molecule aryl aldehyde raw material and the iron salt catalyst are used, such that the cost is low, the reaction conditions are mild, the symmetric 2, 4,6-trisubstituted 1, 3, 5-triazine compound can be highly selectively obtained, and the brand-new synthesis idea is provided for the triazine ring construction.
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Paragraph 0053-0097; 0101-0104
(2020/08/06)
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- Atom-efficient synthesis of 2,4,6-trisubstituted 1,3,5-triazinesviaFe-catalyzed cyclization of aldehydes with NH4I as the sole nitrogen source
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An atom-efficient, straightforward method for the synthesis of 2,4,6-triaryl-1,3,5-triazinesviairon-catalyzed cyclization of aldehydes with NH4I as the sole nitrogen source is demonstrated. This strategy works smoothly under air atmosphere, and affords symmetrical 2,4,6-trisubstituted and unsymmetrical 1,3,5-triazines with yields from 18% to 72%. Compared to other methods, the present protocol provides a straightforward and atom-efficient approach to 2,4,6-trisubstituted 1,3,5-triazines using an inexpensive, easily available ammonium salt as the sole nitrogen source. Research into the preliminary mechanism indicates thatN-benzylidenebenzimidamides are involved in this cyclization reaction.
- Liu, Qiang,Ren, Shuang,Xiao, Jiang
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p. 22230 - 22233
(2020/07/03)
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- Band Gap Modification of TiO2 Nanoparticles by Ascorbic Acid-Stabilized Pd Nanoparticles for Photocatalytic Suzuki–Miyaura and Ullmann Coupling Reactions
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In this study, synthesis, characterization and photocatalytic performance of surface-modified TiO2 nanoparticles with ascorbic acid-stabilized Pd nanoparticles are presented. The structure, composition and morphology of as-prepared nanophotocatalyst were characterized by UV-DRS, FT-IR, ICP-AES, TEM and XPS analysis. Ascorbic acid-stabilized Pd nanoparticles induced visible light driven photocatalytic property on the surface of TiO2 which are otherwise insensitive to visible light owing to the wide band gap. The catalytic system worked well for the Suzuki–Miyaura cross-coupling and Ullmann homocoupling under compact fluorescent light as a visible source with significant activity, selectivity and recyclability. Good to excellent yields of biaryl products were obtained for various aryl halides having different electronic demands and even aryl chlorides. Our results proposed that the improved photoactivity predominantly benefits from the synergistic effects of ascorbic acid-stabilized Pd nanoparticles on TiO2 nanoparticles that cause efficient separation and photoexcited charge carriers and photoredox capability of nanocatalyst. Thus, tuning of band gap of TiO2 making a visible light sensitive photocatalyst, demonstrates a significant advancement in the photocatalytic Suzuki–Miyaura and Ullmann coupling reactions. Graphical Abstract: [Figure not available: see fulltext.].
- Feizpour, Fahimeh,Jafarpour, Maasoumeh,Rezaeifard, Abdolreza
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- MANUFACTURING METHOD OF TRIAZINES FROM NITRILE COMPOUND USING MIXED CATALYST
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PROBLEM TO BE SOLVED: To provide a method for simply and effectively manufacturing a triazine compound from aromatic cyclic nitrile by a mild manufacturing condition using a metal catalyst. SOLUTION: The invention relates to a manufacturing method of a triazine compound by reacting aromatic cyclic nitrile in a halogenated polar solvent in presence of a Group V metal compound, a mixed catalyst containing a halogenated compound of one metal of iron, copper or aluminum, a halogenated inorganic compound or a halogenated inorganic metal salt. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0049; 0052-0058
(2019/10/01)
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- Synthesis of novel racemic 3,4-dihydroferroceno[c]pyridines via the Ritter reaction
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A new approach for the synthesis of functionalized racemic 3,4-dihydroferroceno[c]pyridines via the Ritter reaction of 2-methyl-1-ferrocenylpropan-1-ol with nitriles in the presence of methansulfonic acid was developed. The scope and limitations of the reaction were evaluated. Selected racemic 3,4-dihydroferroceno[c]pyridines were successfully separated by preparative HPLC on a Chiralcel OD-H column. The absolute configuration of the enantiomers was determined by X-ray crystal structure analysis.
- Rozhkova, Yuliya S.,Plekhanova, Irina V.,Gorbunov, Alexey A.,Stryapunina, Olga G.,Chulakov, Evgeny N.,Krasnov, Victor P.,Ezhikova, Marina A.,Kodess, Mikhail I.,Slepukhin, Pavel A.,Shklyaev, Yurii V.
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supporting information
p. 768 - 772
(2019/02/13)
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- Base-free synthesis of 1,3,5-triazines via aerobic oxidation of alcohols and benzamidine over a recyclable OMS-2 catalyst
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By using 4Na2SO4·2H2O2·NaCl as a reductant, manganese oxide octahedral molecular sieve (OMS-2)with enhanced surface area and mixed valence was prepared successfully. OMS-2 showed excellent catalytic ability towards aerobic oxidative synthesis of 1,3,5-triazines from benzyl alcohols and benzamidine. Methyl benzenes, DMF and DMSO could also be employed as substrates to react with benzamidine offering triazines under the heterogeneous conditions. The catalytic system features base-free conditions, broad substrate scope, high chemoselectivity, operational simplicity, catalyst recyclability and utilization of O2 as the green oxidant.
- Shen, Jian,Meng, Xu
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- Method for synthesizing a 1,3,5-triazine derivative
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A method for synthesizing a 1,3,5-triazine derivative specifically includes the following steps: dissolving a benzyl chloride compound and an amidine hydrochloride compound in an organic solvent, wherein the amount-of-substance ratio of the benzyl chloride compound to the amidine hydrochloride compound is 1:(1-2); adding an oxidizing agent and an alkaline medium, and stirring at 100-130 DEG C for12-24 hours for reaction to obtain a 1,3,5-s-triazine derivative; and subjecting the 1,3,5-s-triazine derivative to cooling, extracting, drying and column chromatography isolation to obtain a pure product. The method has the advantages that reaction conditions are mild, the reaction activity is high, the reaction yield reaches 90%, the product selectivity is high, and the substrate expansion rangeis wide; transition metals, especially precious metal compounds, are avoided in a catalytic system, the cost is low, the method is safe and convenient, and the reaction system has less environmentalpollution.
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Paragraph 0022-0027
(2019/08/07)
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- An alternatively metal-free synthesis of 1,3,5-triazines or 1,2,4-thiadiazoles from benzyl chlorides and benzylamines mediated by elemental sulfur
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An elemental sulfur mediated reaction of benzyl chlorides with benzylamines is developed, which allows the practical synthesis of valuable 1,3,5-triazines. This protocol that is metal free, ligand free, and uses inexpensive elemental sulfur as oxidant or raw material displays mild reaction conditions, a broad substrate scope and moderate to good yields. Moreover, the modified sulfur-mediated reaction system can also be used to synthesize 1,2,4-thiadiazoles, by simply switching the stoichiometry of sulfur powder from 0.75 equivalents to 5 equivalents.
- Zhang, Yurong,Liu, Yafei,Zhang, Jun,Gu, Ren,Han, Shiqing
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supporting information
(2019/11/11)
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- Synthesis, characterization, and cycloaddition reactivity of a monocyclic aromatic 1,2,3,5-tetrazine
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Herein we disclose the synthesis and full characterization of the first monocyclic aromatic 1,2,3,5-tetrazine, 4,6-diphenyl-1,2,3,5-tetrazine. Initial studies of its cycloaddition reactivity, mode, regioselectivity, and scope illustrate that it participates as the 4π-component of well-behaved inverse electron demand Diels-Alder reactions where it preferentially reacts with electron-rich or strained dienophiles. It was found to exhibit an intrinsic reactivity comparable to that of the isomeric 3,6-diphenyl-1,2,4,5-tetrazine, display a single mode of cycloaddition with reaction only across C4/N1 (no N2/N5 cycloaddition observed), proceed with a predictable regioselectivity (dienophile most electron-rich atom attaches to C4), and manifest additional reactivity complementary to the isomeric 1,2,4,5-tetrazines. It not only exhibits a remarkable cycloaddition reactivity, surprisingly good stability (e.g., stable to chromatography, long-term storage, presence of H2O even as reaction co-solvent), and broad cycloaddition scope, but it also displays powerful orthogonal reactivity with the 1,2,4,5-tetrazines. Whereas the latter reacts at extraordinary cycloaddition rates with strained dienophiles (tetrazine ligation), the new and isomeric 1,2,3,5-tetrazine displays similarly remarkable cycloaddition rates and efficiencies with amidines (1,2,3,5-tetrazine/amidine ligation). The crossover reactivities (1,2,4,5-tetrazines with amidines and 1,2,3,5-tetrazines with strained dienophiles) are sufficiently low to indicate they may be capable of use concurrently without competitive reactions.
- Wu, Zhi-Chen,Boger, Dale L.
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p. 16388 - 16397
(2019/10/16)
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- New Strategy for the Synthesis of Heterocycles via Copper-Catalyzed Oxidative Decarboxylative Amination of Glyoxylic Acid
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A copper-catalyzed oxidative decarboxylative amination of glyoxylic acid with substrates having two nitrogen-nucleophilic sites was first demonstrated. Using this novel approach, 1,3,5-triazines, quinazolinones and quinazolines were obtained in up to 93 % yields. Notably, glyoxylic acid was employed as the C1 synthon for heterocycles. This strategy enriches the application of glyoxylic acid for the synthesis of valuable heterocycles.
- Niu, Bin,Li, Shaoqing,Cui, Chang,Yan, Yizhe,Tang, Lin,Wang, Jianyong
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supporting information
p. 7800 - 7803
(2019/11/28)
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- Palladium Niacin Complex Immobilized on Starch-Coated Maghemite Nanoparticles as an Efficient Homo- and Cross-coupling Catalyst for the Synthesis of Symmetrical and Unsymmetrical Biaryls
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Abstract: In this work, catalytic efficiency of palladium niacin complex immobilized on starch-coated maghemite nanoparticles successfully exploited for homo- and cross-coupling reactions such as Suzuki–Miyaura, Sonogashira-, and Ullmann coupling reactions. The solid catalyst characterized by different methods such as FT-IR, TGA, XPS, EDS and ICP-AES. TEM images revealed a nanosize structure for catalyst and vibrating sample magnetometer (VSM) demonstrated its magnetic property. The reactions proceeded well in the absence of commonly used additives with high selectivity. Potential reusability of magnetically separable palladium catalyst and performing the reactions at environmentally conditions are notable features of the present methods making great potential for practical applications. Graphical Abstract: [Figure not available: see fulltext.].
- Rezapour, Elham,Jafarpour, Maasoumeh,Rezaeifard, Abdolreza
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p. 3165 - 3177
(2018/08/22)
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- Oxidative Coupling with Zr(IV) Supported by a Noninnocent Anthracene-Based Ligand: Application to the Catalytic Cotrimerization of Alkynes and Nitriles to Pyrimidines
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We report the synthesis and reactivity of Zr complexes supported by a 9,10-anthracenediyl-linked bisphenoxide ligand, L. ZrIVLBn2 (1) undergoes facile photolytic reduction with concomitant formation of bibenzyl and ZrIVL(THF)3 (2), which displays a two-electron reduced anthracene moiety. Leveraging ligand-stored reducing equivalents, 2 promotes the oxidative coupling of internal and terminal alkynes to isolable zirconacyclopentadiene complexes, demonstrating the reversible utilization of anthracene as a redox reservoir. With diphenylacetylene under CO, cyclopentadienone is formed stoichiometrically. 2 is competent for the catalytic formation of pyrimidines from alkynes and nitriles. Mechanistic studies suggest that selectivity for pyrimidine originates from preferred formation of an azazirconacyclopentadiene intermediate, which reacts preferentially with nitriles over alkynes.
- Low, Choon Heng,Rosenberg, Jeffrey N.,Lopez, Marco A.,Agapie, Theodor
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supporting information
p. 11906 - 11910
(2018/09/25)
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- Crystalline Covalent Triazine Frameworks by In Situ Oxidation of Alcohols to Aldehyde Monomers
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Covalent triazine frameworks (CTFs) with aromatic triazine linkages have recently received increasing interest for various applications because of their rich nitrogen content and high chemical stability. Owing to the strong aromatic C=N bond and high chemical stability, only a few CTFs are crystalline, and most CTFs are amorphous. Herein we report a new general strategy to give highly crystalline CTFs by in situ formation of aldehyde monomers through the controlled oxidation of alcohols. This general strategy allows a series of crystalline CTFs with different monomers to be prepared, which are shown to have higher thermal stability and enhanced performance in photocatalysis as compared with the less crystalline or amorphous CTFs. This open-system approach is very simple and convenient, which presents a potential pathway to large-scale industrial production of crystalline CTFs.
- Liu, Manying,Huang, Qi,Wang, Shaolei,Li, Ziyong,Li, Buyi,Jin, Shangbin,Tan, Bien
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supporting information
p. 11968 - 11972
(2018/09/06)
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- An I2-mediated aerobic oxidative annulation of amidines with tertiary amines: Via C-H amination/C-N cleavage for the synthesis of 2,4-disubstituted 1,3,5-triazines
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An iodine-mediated formal oxidative cycloaddition of amidines with tertiary amines was first demonstrated in air. Both symmetrical and unsymmetrical 2,4-disubstituted 1,3,5-triazines were obtained in up to 85% yields. It is noted that a tertiary amine was employed as a one carbon synthon of 1,3,5-triazines and two C-N bonds were formed in one pot. Control experiments revealed that the reaction underwent a radical pathway promoted by I+. The method is transition-metal-free, peroxide-free, and operationally simple to implement with a wide scope of substrates.
- Yan, Yizhe,Li, Zheng,Cui, Chang,Li, Hongyi,Shi, Miaomiao,Liu, Yanqi
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supporting information
p. 2629 - 2633
(2018/04/27)
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- Synthesis, Spectra, and Theoretical Investigations of 1,3,5-Triazines Compounds as Ultraviolet Rays Absorber Based on Time-Dependent Density Functional Calculations and three-Dimensional Quantitative Structure-Property Relationship
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A series of 1,3,5-triazines were synthesized and their UV absorption properties were tested. The computational chemistry methods were used to construct quantitative structure-property relationship (QSPR), which was used to computer aided design of new 1,3,5-triazines ultraviolet rays absorber compounds. The experimental UV absorption data are in good agreement with those predicted data using the Time-dependent density functional theory (TD-DFT) [B3LYP/6–311 + G(d,p)]. A suitable forecasting model (R > 0.8, P 0.0001) was revealed. Predictive three-dimensional quantitative structure-property relationship (3D-QSPR) model was established using multifit molecular alignment rule of Sybyl program, which conclusion is consistent with the TD-DFT calculation. The exceptional photostability mechanism of such ultraviolet rays absorber compounds was studied and confirmed as principally banked upon their ability to undergo excited-state deactivation via an ultrafast excited-state proton transfer (ESIPT). The intramolecular hydrogen bond (IMHB) of 1,3,5-triazines compounds is the basis for the excited state proton transfer, which was explored by IR spectroscopy, UV spectra, structural and energetic aspects of different conformers and frontier molecular orbitals analysis.
- Wang, Xueding,Xu, Yilian,Yang, Lu,Lu, Xiang,Zou, Hao,Yang, Weiqing,Zhang, Yuanyuan,Li, Zicheng,Ma, Menglin
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p. 707 - 723
(2018/05/05)
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- Transition Metal-Free sp3 C–H Functionalization of Arylacetic Acids for the Synthesis of 1,3,5-Triazines
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A one-pot simple, efficient and practically viable protocol for the synthesis of substituted 1,3,5-triazines has been reported from arylacetic acids and benzamidine hydrochloride. In addition, we demonstrated first transition metal-free conversion of phenylacetic acid to benzaldehyde which on condensation with two equivalents of benzamidine hydrochloride offered 2,4,6-trisubstituted 1,3,5-triazines. This protocol is environmentally benign and economically viable which makes it feasible for gram scale synthesis.
- Pardeshi, Sachin D.,Sathe, Pratima A.,Pawar, Balu V.,Vadagaonkar, Kamlesh S.,Chaskar, Atul C.
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p. 2098 - 2102
(2018/05/31)
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- Tautomer-selective derivatives of enolate, ketone and enaminone by addition reaction of picolyl-type anions with nitriles
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We describe an efficient for the synthesis of compounds of tautomeric β-pyridyl/quinolyl-enol, -ketone, -enaminone, which were finally characterized by standard methods like NMR, IR or SCXRD. The addition reaction of lithiated intermediates of picoline, 2-ethylpyridine and 2-methylquinoline, respectively, with nitriles followed by acid hydrolysis afforded the corresponding tautomeric compounds of enol, ketone and emaminone. Interestingly, treatment of 2-methylpyridine or 2-ethylpyridine with nitriles, respectively, yielded mostly β-pyridyl ketone and enol tautomers without enaminones, while 2-methylquinoline with nitriles gave β-quinolyl ketone and enaminone tautomers without enols. The reaction of 2-benzylpyridine with nitriles was not available under the same conditions.
- Bai, Jianliang,Wang, Peng,Cao, Wei,Chen, Xia
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p. 645 - 652
(2016/09/28)
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- A 1, 3, 5 - triazine derivative synthesis method
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The invention relates to a synthesis method of 1,3,5-triazine derivatives. The synthesis method comprises the steps of mixing amidine hydrochloride, alcohol, hydrated copper acetate and sodium carbonate, adding a solvent, reacting for 12 hours-24 hours in air at the temperature of 110 DEG C-120 DEG C to obtain a product, purifying the product, extracting, drying, concentrating and separating by virtue of column chromatography to obtain the 1,3,5-triazine derivatives. The synthesis method of the 1,3,5-triazine derivatives, which is disclosed by the invention has the advantages of low cost, available raw materials, high synthesis efficiency and wide application range and is suitable for reaction of a plurality of substrates.
- -
-
Paragraph 0040-0042
(2018/11/03)
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- Aminocarbonylation of Aryl Halides to Produce Primary Amides by Using NH4HCO3 Dually as Ammonia Surrogate and Base
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An efficient and clean protocol was developed for rapid production of primary aromatic amides by aminocarbonylation with NH4HCO3. Without addition of auxiliary base, the use of solid and cheap NH4HCO3 dually as ammonia surrogate and base not only promoted aminocarbonylation over subsequent dehydration and hydrolysis of amides owing to its weak basicity, and it also made the reaction manipulation clean and simplified without the presence of stinky NH3 or organic amines. The Xantphos ligand with relatively intensive π-acceptor character (1J31P–77Se=758 Hz) and wide natural bite angle (βn=111°) was found to be indispensable for the high efficiency of this reaction.
- Wang, Dong-Liang,Liu, Huan,Yang, Da,Wang, Peng,Lu, Yong,Liu, Ye
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p. 4206 - 4211
(2017/12/02)
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- Covalent Triazine Frameworks via a Low-Temperature Polycondensation Approach
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Covalent triazine frameworks (CTFs) are normally synthesized by ionothermal methods. The harsh synthetic conditions and associated limited structural diversity do not benefit for further development and practical large-scale synthesis of CTFs. Herein we report a new strategy to construct CTFs (CTF-HUSTs) via a polycondensation approach, which allows the synthesis of CTFs under mild conditions from a wide array of building blocks. Interestingly, these CTFs display a layered structure. The CTFs synthesized were also readily scaled up to gram quantities. The CTFs are potential candidates for separations, photocatalysis and for energy storage applications. In particular, CTF-HUSTs are found to be promising photocatalysts for sacrificial photocatalytic hydrogen evolution with a maximum rate of 2647 μmol h?1 g?1 under visible light. We also applied a pyrolyzed form of CTF-HUST-4 as an anode material in a sodium-ion battery achieving an excellent discharge capacity of 467 mAh g?1.
- Wang, Kewei,Yang, Li-Ming,Wang, Xi,Guo, Liping,Cheng, Guang,Zhang, Chun,Jin, Shangbin,Tan, Bien,Cooper, Andrew
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supporting information
p. 14149 - 14153
(2017/10/17)
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- IEDDA Reaction of the Molecular Iodine-Catalyzed Synthesis of 1,3,5-Triazines via Functionalization of the sp3 C-H Bond of Acetophenones with Amidines: An Experimental Investigation and DFT Study
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The present work reports an inverse electron demand Diels-Alder (iEDDA)-type reaction to synthesize 1,3,5-trizines from acetophenones and amidines. The use of molecular iodine in a catalytic amount facilitates the functionalization of the sp3 C-H bond of acetophenones. This is a simple and efficient methodology for the synthesis of 1,3,5-triazines in good to excellent yields under transition-metal-free and peroxide-free conditions. The reaction is believed to take place via an in situ iodination-based oxidative elimination of formaldehyde. DFT calculations at the M062X/6-31+G(d,p) level were employed to investigate the reaction mechanism. Reaction barriers for the cycloaddition as well as a formaldehyde expulsion steps were computed, and a multistep mechanism starting with the nucleophilic attack by benzamidine on an in situ generated imine intermediate has been proposed. Both local and global reactivity descriptors were used to study the regioselectivity of the addition steps.
- Tiwari, Abhishek R.,Nath, Shilpa R.,Joshi, Kaustubh A.,Bhanage, Bhalchandra M.
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p. 13239 - 13249
(2017/12/26)
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- Polythene glycol (PEG) as a reusable solvent system for the synthesis of 1,3,5-triazines via aerobic oxidative tandem cyclization of benzylamines and N-substituted benzylamines with amidines under transition metal-free conditions
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A green and highly efficient protocol for the synthesis of 1,3,5-triazines from benzylamines and N-substituted benzylamines with amidines in PEG-600 has been developed. This protocol is transition-metal free, phosphine ligand free and uses inexpensive, easily available molecular oxygen (O2) as an oxidant. A series of 1,3,5-triazines derivatives were synthesized in good to excellent yields in a shorter reaction time. The ease of the product separation and reusability of PEG-600 makes it more environmentally benign and economically affordable for gram-scale synthesis.
- Tiwari, Abhishek R.,Bhanage, Bhalchandra M.
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supporting information
p. 144 - 149
(2015/12/31)
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- Iridium-catalyzed cascade dehydrogenation, ring-closure reaction leading to 2,4,6-triaryl-1,3,5-triazines
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An efficient iridium-catalyzed dehydrogenation, ring-closure reaction, has been developed via a cascade sequence, in which [Cp?IrI2]2/Xantphos proved to be the most efficient catalyst for the synthesis of 2,4,6-triaryl-1,3,5-triazines from stable aryl-substituted alcohols and amidines. It was the first case of iridium catalyst successful application in such transformation.
- Shi, Gang,He, Fei,Che, Youxin,Ni, Caihua,Li, Ying
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p. 380 - 386
(2016/04/20)
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- Magnetically-recoverable Schiff Base Complex of Pd (II) Immobilized on Fe3O4@SiO2 Nanoparticles: An Efficient Catalyst for Mizoroki-Heck and Suzuki-Miyaura Coupling Reactions
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The activity of Pd(II)-Schiff base complexmolecules grafted on the surface of Fe3O4@SiO2 particles were investigated in the palladium-catalyzed coupling reactions of aryl halides with alkenes (Mizoroki-Heck reaction) and phenylboronic acids (Suzuki-Miyaura reaction) in the absence of phosphorous ligands. This method shows notable advantages such as heterogeneous nature of the catalyst, excellent yields, short reaction times, easy preparation, simplicity of operation, and cleaner reaction profiles. The catalyst can be separated from the reaction mixture by applying a permanent magnet externally and can be reused for several times without significant loss of activity. Also, the amount of palladium leaching has been determined by ICP analysis.
- Esmaeilpour, Mohsen,Javidi, Jaber
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p. 614 - 626
(2018/01/18)
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- Synthesis of 1,3,5-triazines via Cu(OAc)2-catalyzed aerobic oxidative coupling of alcohols and amidine hydrochlorides
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Cu(OAc)2 was found to be an efficient catalyst for dehydrogenative synthesis of 1,3,5-triazine derivatives via oxidative coupling reaction of amidine hydrochlorides and alcohols in air. Both aromatic and aliphatic alcohols can be involved in the reaction and thirty-three products were obtained with good to excellent yields. Moreover, the use of a ligand, strong base and organic oxidant is unnecessary.
- You, Qing,Wang, Fei,Wu, Chaoting,Shi, Tianchao,Min, Dewen,Chen, Huajun,Zhang, Wu
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supporting information
p. 6723 - 6727
(2015/06/25)
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- NIS-catalyzed oxidative cyclization of alcohols with amidines: A simple and efficient transition-metal free method for the synthesis of 1,3,5-triazines
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An efficient method for the synthesis of 1,3,5-triazines by NIS-catalyzed oxidative cyclization of alcohols with amidines has been developed. The reaction works smoothly under transition-metal free and phosphine-free conditions to afford a wide range of 1,3,5-triazine derivatives in moderate to good yields. The synthetic methodology was achieved via in situ oxidation of alcohols to aldehydes.
- Tiwari, Abhishek R.,Akash,Bhanage, Bhalchandra M.
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supporting information
p. 10973 - 10976
(2015/11/25)
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- Direct oxidative coupling of amidine hydrochlorides and methylarenes: TBHP-mediated synthesis of substituted 1,3,5-triazines under metal-free conditions
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Various 2,4,6-trisubstituted 1,3,5-triazines were smoothly formed via TBHP-mediated direct oxidative coupling of amidine and methylarenes. This tandem oxidation-imination-cyclization transformation exhibits a straightforward protocol to prepare 1,3,5-triazines from easily available starting materials and green oxidants under metal-free conditions.
- Guo, Wei
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supporting information
p. 10285 - 10289
(2015/10/28)
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- A novel straightforward synthesis of 2,4,6-triaryl-1,3,5-triazines via copper-catalyzed cyclization of N-benzylbenzamidines
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A novel, straightforward method for the synthesis of 2,4,6-triaryl-1,3,5-triazines via copper-catalyzed cyclization of N-benzylbenzamidines in DMSO has been developed. Compared to other methods, the present protocol has a number of advantages such as - cost-effectiveness, avoidance of aldehydes or alcohols as reaction partners, and easy accessibility of starting materials, making it a highly practical approach to access various 2,4,6-triaryl-1,3,5-triazines.
- Debnath, Pradip,Majumdar
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p. 6976 - 6978
(2015/02/19)
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- An efficient ruthenium-catalyzed dehydrogenative synthesis of 2,4,6-triaryl-1,3,5-triazines from aryl methanols and amidines
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By using [RuCl2(p-Cymene)]2/Cs2CO 3 as an efficient catalyst system, the readily available, inexpensive aryl methanols were firstly employed for dehydrogenative synthesis of aryl substituted 1,3,5-triazine derivatives. Due to the inherent stability of alcohols in contrast with aldehydes, our synthetic protocol is adaptable to a broad substrate scope, there is no need for stringent protection during the whole operation process, and it has the potential to prepare valuable products that are currently inaccessible or challenging to prepare using conventional methods. It is a significantly important complement to the conventional synthetic methodologies. This journal is the Partner Organisations 2014.
- Xie, Feng,Chen, Mengmeng,Wang, Xiaoting,Jiang, Huanfeng,Zhang, Min
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supporting information
p. 2761 - 2768
(2014/05/06)
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- Palladium nanoparticles immobilized on nano-silica triazine dendritic polymer (Pdnp-nSTDP): An efficient and reusable catalyst for suzuki-miyaura cross-coupling and heck reactions
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A new catalyst based on palladium nanoparticles immobilized on nano-silica triazine dendritic polymer (Pdnp-nSTDP) was synthesized and characterized by FT-IR spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy dispersive X-ray, transmission electron microscopy and elemental analysis. The size of the palladium nanoparticles was determined to be 3.1±0.5 nm. This catalytic system showed high activity in the Suzuki-Miyaura cross-coupling of aryl iodides, bromides and chlorides with arylboronic acids and also in the Heck reaction of these aryl halides with styrenes. These reactions were best performed in a dimethylformamide (DMF)/water mixture (1:3) in the presence of only 0.006 mol% and 0.01 mol% of the catalyst, respectively, under conventional conditions and microwave irradiation to afford the desired coupling products in high yields. The Pdnp-nSTDP was also used as an efficient catalyst for the preparation of a series of star- and banana-shaped compounds with a benzene, pyridine, pyrimidine or 1,3,5-triazine unit as the central core. Moreover, the catalyst could be recovered easily and reused several times without any considerable loss of its catalytic activity. Copyright
- Isfahani, Amir Landarani,Mohammadpoor-Baltork, Iraj,Mirkhani, Valiollah,Khosropour, Ahmad R.,Moghadam, Majid,Tangestaninejad, Shahram,Kia, Reza
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supporting information
p. 957 - 972
(2013/05/08)
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- DFT studies on the reaction mechanisms of 1,4-dilithio 1,3-dienes with nitriles
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Mechanisms for the reactions of 1,4-dilithio-1,3-butadienes and nitriles are explored through both experiments and DFT calculations. The computational results suggest that the selectivity of these reaction systems is strongly affected by the structures of the substrates. As the first step of all reaction pathways, the addition intermediate of one C-Li bond to the nitrile is formed. When tetraalkyl-substituted 1,4-dilithio 1,3-dienes and 2-cyanopyridine are used, the intermediate gives the cyclopentadienyl amine product as the kinetic product because of the coordination of the pyridyl N atom to the lithium atoms (system B). This addition intermediate also undergoes a second nitrile insertion into the C-Li bond, giving the dilithio ketimine intermediate. When tetraalkyl-substituted 1,4-dilithio 1,3-dienes and aryl nitriles are used, the dilithio ketimine intermediate undergoes a 1,6-cyclization, generating pyridine and triazine products through thermodynamically favored pathways (systems A and B). When cyclic 1,4-dilithiobutadiene and tertiary aliphatic nitriles are used, the dilithio ketimine intermediate undergoes two sequential 1,5-cyclization steps with a lower energy barrier, generating tricyclic Δ1- bipyrrolines (system C). Experimentally, the lithium-containing triazine intermediate 10 and Δ1-bipyrroline intermediate 19 have been isolated and their structures investigated through NMR and quenching experiments. The calculation results clearly show the mechanism details of these reactions and are in good agreement with the experimental observations.
- Zhao, Fei,Zhan, Ming,Zhang, Wen-Xiong,Xi, Zhenfeng
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p. 2059 - 2068
(2013/05/21)
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- One-step synthesis of 2-amino-5h-pyrimido[5,4-b]indoles, substituted 2-(1,3,5-triazin-2-yl)-1h-indoles, and 1,3,5-triazines from aldehydes
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An efficient one-step synthesis of 2-amino-5H-pyrimido[5,4-b]indoles through a copper-catalyzed cascade reaction between 3-haloindole-2-carbaldehydes and guanidine hydrochloride is described. In contrast, the base-mediated reactions of either 3-haloindole-2-carbaldehydes or substituted indole-2-carbaldehydes with substituted amidine hydrochlorides in DMSO result in the formation of 2-(1,3,5-triazin-2-yl)-1H-indole derivatives in one step in excellent yields. Studies toward exploring the utility of the method demonstrate that even substituted benzaldehydes undergo a similar reaction to efficiently yield 2,4,6-trisubstituted 1,3,5-triazines. A plausible mechanism for the formation of substituted 1,3,5-triazines identifies the role of DMSO as an oxidant during the reaction. The synthesis of 2-amino-5H-pyrimido[5,4-b]indoles from 3-haloindole-2-carbaldehyde and guanidine hydrochloride is described. In contrast, 3-haloindole-2-carbaldehydes or indole-2-carbaldehydes react with substituted amidine hydrochlorides to give 2-(1,3,5-triazin-2-yl)-1H-indole derivatives in excellent yields. The latter protocol was used to prepare 2,4,6-trisubstituted 1,3,5-triazines.
- Biswas, Subhasish,Batra, Sanjay
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scheme or table
p. 3492 - 3499
(2012/08/13)
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- Metal oxide-catalyzed ammoxidation of alcohols to nitriles and promotion effect of gold nanoparticles for one-pot amide synthesis
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Transition metal oxides (MnO2, Co3O4, and NiO) are catalytically active for the ammoxidation of alcohols to nitriles. In particular, MnO2 exhibited remarkably high catalytic activity and selectivity for the ammoxidation of alcohols to produce nitriles. Benzyl alcohol could also be directly converted to benzonitrile by MnO2 catalyst by the one-pot ammoxidation and the hydration with water which was formed by the first ammoxidation step. The deposition of gold nanoparticles (Au NPs) onto MnO2 did not enhance the ammoxidation of benzyl alcohol but promoted the hydration of benzonitrile to produce benzamide with high selectivity. In contrast, Au NPs supported on Al2O3, CuO, and CeO 2 catalyzed the ammoxidation of benzyl alcohol, whereas these metal oxides themselves were inactive for the ammoxidation or showed low catalytic activity. These results have demonstrated that gold is intrinsically active as a catalyst for the ammoxidation of alcohols.
- Ishida, Tamao,Watanabe, Hiroto,Takei, Takashi,Hamasaki, Akiyuki,Tokunaga, Makoto,Haruta, Masatake
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experimental part
p. 85 - 90
(2012/07/03)
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- 1,2-Dihydrotriazinyl-N-oxy free radicals
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Triazinyl-N-oxy free radicals, 2-methyl-2,4,6-triphenyl-1,2-dihydro-1,3,5- triazinyl-1-oxy (6 a), 2,2,4,6-tetraphenyl-1,2-dihydro-1,3,5-triazinyl-1-oxy (6 b), 2,2-dimethyl-4,6-diphenyl-1,2-dihydro-1,3,5-triazinyl-1-oxy (13), and 2,6-dimethyl-2,4-diphenyl-1,2-dihydro-1,3,5-triazinyl-1-oxy (14), in which the unpaired electron is delocalized over three nitrogen atoms, have been prepared and characterized. A method has been devised for introducing an N-oxide function into the triazinyl core. Then, by using a Grignard reagent, substitution α to the N-oxide group was achieved and the resulting 1,2-dihydrotriazine- N-oxide oxidized into the corresponding nitroxide. Solution EPR spectra exhibit hyperfine splitting that confirms spin delocalization over the three nitrogen atoms of the triazinyl ring. They also show that spin delocalization diminishes with increasing distance for the coupling and is largest for nitrogen N1 and weakest for N5. Free radicals 6 a and 13 are stable in the solid state and have been characterized by X-ray diffraction, but they tend to gradually degrade in solution. In the solid state, these two free radicals are arranged into antiferromagnetically exchange-coupled pairs, J=-5.2(6) for 6 a and -3.7(4) cm-1 for 13 (H=-2 JS1S2). Copyright
- Brough, Peter,Gambarelli, Serge,Jacquot, Jean-Francois,Grand, Andre,Pecaut, Jacques,Rey, Paul
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experimental part
p. 11250 - 11257
(2011/11/07)
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- Reaction of N-nitro-O-(4-nitrophenyl)hydroxylamine with phosphorus pentoxide in the presence of nitriles. New method for the generation of aryloxenium ion
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A reaction of N-nitro-O-(4-nitrophenyl)hydroxylamine with nitriles RCN (R = Me, Et, Ph) in the presence of P4O10 in excess amount at 0°C leads to the formation of 2-R-5-nitro-1,3-benzoxazoles. The reaction presumably takes place through the intermediate (phenoxy)oxodiazonium ion [NO2C6H4O-N=N=O]+, which eliminates an N2O molecule to form the aryloxenium ion [NO2C 6H4O]+. The latter reacts with nitriles RCN at the ortho-carbon atom of the phenyl ring giving 2-R-5-nitro-1,3-benzoxazoles.
- Klenov, M. S.,Churakov, A. M.,Strelenko, Yu. A.,Tartakovsky, V. A.
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p. 2429 - 2431,3
(2020/08/31)
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- Chemoselectivity diversity in the reaction of LiNC6F 5SiMe3 with nitriles and the synthesis, structure, and reactivity of zirconium mono-and tris[2-(2-pyridyl)tetrafluorobenzimidazolate] complexes
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Unlike the reaction of LiNTMS2· TMEDA (TMS = SiMe 3; TMEDA = tetramethylethylenediamine) with 2-cyanopyridine, which results in the nearly exclusive formation of the amidinate, (Me 3SiNC6F5)Li · TMEDA (1) reacts with 2-cyanopyridine in toluene to yield quantitatively the lithium pyridyltetrafluorobenzimidazolate complex [C6F4N 2C(2-C5H4N)]Li · TMEDA (3). In this work, the reactivity of complex 1 toward aromatic nitriles Ar-CN (Ar = Ph, o-OMeC6H4, C6F5, 2-pyridyl) was examined. Whereas complex 1 fails to react with o-methoxybenzonitrile, its reaction with benzonitrile or pentafluorobenzonitrile gives triphenyl-1,3,5- triazine (4) or the hexacoordinate lithium polymer [LiN(4-NCC6F 4)(C6F5) · THF · TMEDA] n (7), respectively. When 1 is reacted with 2-cyanopyridine in tetrahydrofuran (THF), the benzimidazolate coordination polymer {[C 6F4N2C(2-C5H4N)]Li · THF}n (5) is obtained. Herein we discuss how this diverse chemoselectivity in the reaction of the examined lithium N-silylated amides LiNRTMS · TMEDA (R = TMS, C6F5) with nitriles is influenced by the electronic properties of the nitrile or amide substituents and by the ability of these substituents to interact with the lithium or silicon atoms. Further, we present the syntheses and structures of zirconium tris(pyridyltetrafluorobenzimidazolate) chloride (10) and zirconium bis(dimethylamido)(pyridyltetrafluorobenzimidazolate) chloride · THF (11) complexes. These complexes, the first prepared zirconium mono-and tris(benzimidazolate)s, were crystallographically characterized and examined in the polymerization of propylene with methyl aluminoxane (1:1000 Zr/Al molar ratio).
- Aharonovich, Sinai,Botoshansky, Mark,Waymouth, Robert M.,Eisen, Moris S.
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experimental part
p. 9217 - 9229
(2011/01/11)
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- Reinvestigating the synthesis of N-arylbenzamidines from benzonitriles and anilines in the presence of AlCl3
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The preparation of N-phenylbenzamidine 3a from the reaction between benzonitrile Ia and aniline in the presence of AId3 is reinvestigated with respect to mode of reagent addition, reaction temperature and Lewis acid catalysis. Pre-forming the nitrile-Lewis acid complex prior to the addition of aniline allows for milder reaction conditions, allowing for the higher yielding synthesis of N-phenylbenzamidine 3a (83%). Using these modified conditions several N-(4-substituted phenyl)benzamidines can be prepared including the N-(4-methoxyphenyl)benzamidine 3b (93%) and the previously unobtainable 2-amino-N-(4-methoxyphenyl)benzamidine 31(56%). All new compounds are fully characterised.
- Koutentis, Panayiotis A.,Mirallai, Styliana I.
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experimental part
p. 5134 - 5139
(2010/08/20)
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- Addition of amines to nitriles catalyzed by ytterbium amides: An efficient one-step synthesis of monosubstituted N-arylamidines
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A one-step synthesis of monosubstituted N-arylamidinates via addition of amines to nitriles catalyzed by ytterbium amides is reported. The reactions with various substrates give the products in good to excellent yields with 5 mol % ytterbium at 100 °C under solvent-free conditions.
- Wang, Junfeng,Xu, Fan,Cai, Tao,Shen, Qi
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p. 445 - 448
(2008/09/19)
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