- Manipulating magnetism: Ru25+ paddlewheels devoid of axial interactions
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Variable-temperature magnetic and structural data of two pairs of diruthenium isomers, one pair having an axial ligand and the formula Ru 2(DArF)4Cl (where DArF is the anion of a diarylformamidine isomer and Ar = p-anisyl or m-anisyl
- Chiarella, Gina M.,Cotton, F. Albert,Murillo, Carlos A.,Ventura, Karen,Villagrán, Dino,Wang, Xiaoping
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- Ionic liquid-functionalized mesoporous silica nanoparticles ([pmim]FeCl4/MSNs): Efficient nanocatalyst for solvent-free synthesis of N,N′-diaryl-substituted formamidines
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We report the synthesis of ionic liquid-functionalized mesoporous silica nanoparticles ([pmim]FeCl4/MSNs) via a method of post-grafting on parent MSNs. This hybrid material was characterized using scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, nitrogen adsorption–desorption analysis, Fourier transform infrared spectroscopy, powder X-ray diffraction and thermal analyses. The material was utilized as an efficient heterogeneous catalyst for the synthesis of N,N′-diaryl-substituted formamidines through the reaction of triethyl orthoformate with arylamines under solvent-free conditions. The catalyst was recovered easily and reused several times without significant loss of its catalytic activity.
- Nasresfahani, Zahra,Kassaee, Mohammad Zaman,Eidi, Esmaiel
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- Ultrasound promoted expeditious, catalyst-free and solvent-free approach for the synthesis of N,N′-diarylsubstituted formamidines at room temperature
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An effortless and efficient protocol was developed for the synthesis of N,N′-diarylsubstituted formamidines under environment-friendly conditions. Ultrasonic energy was employed to obtain the desired products in excellent yields with high purity under solvent-free and catalyst-free conditions. Products were purified by the crystallization technique to avoid excess utilization of organic solvents.
- Dar, Bashir Ahmad,Ahmad, Syed Naseer,Wagay, Mohammad Arif,Hussain, Altaf,Ahmad, Nisar,Bhat, Khursheed Ahmad,Khuroo, Mohammad Akbar,Sharma, Meena,Singh, Baldev
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- Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu4(μ4-S) Model Compounds of the CuZ Active Site of Nitrous Oxide Reductase (N2OR)
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Model compounds have been widely utilized in understanding the structure and function of the unusual Cu4(μ4-S) active site (CuZ) of nitrous oxide reductase (N2OR). However, only a limited number of model compounds that mimic both structural and functional features of CuZ are available, limiting insights about CuZ that can be gained from model studies. Our aim has been to construct Cu4(μ4-S) clusters with tailored redox activity and chemical reactivity via modulating the ligand environment. Our synthetic approach uses dicopper(I) precursor complexes (Cu2L2) that assemble into a Cu4(μ4-S)L4 cluster with the addition of an appropriate sulfur source. Here, we summarize the features of the ligands L that stabilize precursor and Cu4(μ4-S) clusters, along with the alternative products that form with inappropriate ligands. The precursors are more likely to rearrange to Cu4(μ4-S) clusters when the Cu(I) ions are supported by bidentate ligands with 3-atom bridges, but steric and electronic features of the ligand also play crucial roles. Neutral phosphine donors have been found to stabilize Cu4(μ4-S) clusters in the 4Cu(I) oxidation state, while neutral nitrogen donors could not stabilize Cu4(μ4-S) clusters. Anionic formamidinate ligands have been found to stabilize Cu4(μ4-S) clusters in the 2Cu(I):2Cu(II) and 3Cu(I):1Cu(II) states, with both the formation of the dicopper(I) precursors and subsequent assembly of clusters being governed by the steric factor at the ortho positions of the N-aryl substituents. Phosphaamidinates, which combine a neutral phosphine donor and an anionic nitrogen donor in the same ligand, form multinuclear Cu(I) clusters unless the negative charge is valence-trapped on nitrogen, in which case the resulting dicopper precursor is unable to rearrange to a multinuclear cluster. Taken together, the results presented in this study provide design criteria for successful assembly of synthetic model clusters for the CuZ active site of N2OR, which should enable future insights into the chemical behavior of CuZ
- Hsu, Chia-Wei,Iniguez, Sarah J.,Johnson, Brittany J.,Mankad, Neal P.,Rathnayaka, Suresh C.
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- Investigation of the reaction of 3,5-diamidino-4-nitropyrazole with amines
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The interaction of 3,5-bis(N,N-dimethylaminomethylene)amino-1-methyl-4-nitropyrazole with amines proceeds regioselectively with the formation of 3-amino-5-(N,N-dimethylaminomethylene)amino-1- methyl-4-nitropyrazole. Amines are converted in this way into N
- Makarov,Ryabova,Alekseeva,Chernyshev,Granik
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- Formation of Amidines from Aryliminodimagnesium and N,N-Dimethylformamide. Novel Catalytic Mediation by Single Electron Transfer with Use of Nitrobenzenes
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N,N'-Diarylformamidines were obtained in good yields by the reaction of aryliminodimagnesium (ArN(MgBr)2) with N,N-dimethylformamide in the presence of nitrobenzene.Novel catalytic mediation by single electron transfer was disclosed.
- Okubo, Masao,Tanaka, Mikio,Matsuo, Koji
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- N-Heterocyclic Carbene Catalyzed Concerted Nucleophilic Aromatic Substitution of Aryl Fluorides Bearing α,β-Unsaturated Amides
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Concerted nucleophilic aromatic substitution (CSNAr) has emerged as a powerful mechanistic manifold, in which nucleophilic aromatic substitution can proceed in one step without the need to form a Meisenheimer intermediate. However, all of the CSNAr reactions reported thus far require a stoichiometric strong base or activating reagent, and no catalytic variants have yet been reported. Herein, we report an N-heterocyclic carbene (NHC)-catalyzed intramolecular cyclization of acrylamides that contain a 2-fluorophenyl group on the nitrogen through a CSNAr reaction. By using this catalytic method, it is possible to synthesize an array of quinolin-2-one derivatives, which are common structural motifs in pharmaceuticals and organic materials. DFT calculations unambiguously revealed that this reaction proceeds through the concerted nucleophilic aromatic substitution of aryl fluorides, in which a stereoelectronic σ (Cipso-Cβ)→ σ*(Cipso-F) interaction critically contributes to the stabilization of the transition state for the cyclization.
- Kamitani, Miharu,Tobisu, Mamoru,Yasui, Kosuke
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supporting information
p. 14157 - 14161
(2019/08/30)
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- Nanoporous TiO2 containing an ionic liquid bridge as an efficient and reusable catalyst for the synthesis of: N, N ′-diarylformamidines, benzoxazoles, benzothiazoles and benzimidazoles
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In this work, a green and efficient procedure is reported for the preparation of N,N'-diarylformamidines, benzoxazoles, benzothiazoles, and benzimidazoles using nanoporous TiO2 containing an ionic liquid bridge. This reagent is prepared via the modification of nanoporous TiO2 with bis-3-(trimethoxysilylpropyl)-ammonium hydrogen sulfate (TiO2-[bip]-NH2+ HSO4-). The procedure gave the products in excellent yields in very short reaction times under solvent-free conditions. The reusability of the catalyst is the other important feature of the reported method.
- Mazloumi,Shirini,Goli-Jolodar,Seddighi
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p. 5742 - 5752
(2018/04/23)
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- Catalyst-Free Synthesis of Aryl Diamines via a Three-Step Reaction Process
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The formation of C-N bonds with aryl amines is one of the most widely studied reactions in organic chemistry. Despite this, it is still highly challenging, often requiring expensive, precious metal-based catalysts. Here we report an easy catalyst-free methodology for constructing C-N bonds. The method, which proceeds via the in situ formation of closed ring amidinium ions, allows the preparation of a series of symmetrical and/or unsymmetrical aryl diamines in notably high yields (82-98%) and purity and with a variety of different substituents. The methodology is shown successful for the preparation of aryl diamines having para- and/or meta-substituted carboxyl, nitro, bromo, methoxy, or methyl groups. This green synthetic pathway, which is catalyst free, requires only three steps, and proceeds without the need for purification. Further, it is a new sustainable, economically viable method to achieve an otherwise challenging bond formation.
- Bulut, Safak,Queen, Wendy L.
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p. 3806 - 3818
(2018/04/14)
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- Synthesis, X-ray Structure Analysis and Spectroscopic Characterization of trans-Aquabis(μ-benzoato-κ2 O:O′) bis[μ-N,N′-bis(4-methoxyphenyl) formamidinato-κ2 N:N′] dimolybdenum(II)
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Abstract: The title compound, trans-Mo2(DAniF)2(OOCC6H5)2(H2O) (I) has a quadruply bonded Mo2 4+ unit equatorially coordinated by two N,N′-bis(4-methoxyphenyl)formamidinate (referred as DAniF) ligands and two benzoate (OOCC6H5) groups in transverse, and axially coordinated by one aqua oxygen atom. The compound crystallizes in the space group C2/c with one molecule in the asymmetric unit and features a Mo–Mo bond length of 2.0983(4) ?, which is typical for dimolybdenum quadruple bonds. In the crystal, the offsetstacking between pairs of phenyl rings creating a one-dimensional linear chain perpendicular to the Mo–Mo directions, with a distance between phenyl rings of 3.44?? and the center-to-center distance of 3.83??. The coordinated water oxygen atoms act as donors and uncoordinated methoxyl group oxygen atoms act as acceptors in intermolecular O–H?O hydrogen bonds.stacking between phenyl rings assemble the molecules into a three-dimensional framework. Graphical Abstract: The offsetstacking between phenyl rings of quadruply bonded Mo2 4+ paddle-wheel molecules create a one-dimensional linear chain. [Figure not available: see fulltext.].
- Kong, Ya-Jie,Han, Li-Juan
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p. 208 - 214
(2017/09/06)
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- An efficient method for the synthesis of formamidine and formamide derivatives promoted by sulfonated rice husk ash (RHA-SO3H)
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A mild, simple and efficient method has been developed for the promotion of the preparation of N,N′-diphenylformamidines from various aromatic amines and ethyl orthoformate using sulfonated rice husk ash (RHA-SO3H) solid acid catalyst. This reagent has also been used for the N-formylation of a variety of amines using formic acid under solvent-free conditions. The procedures gave the products in very short reaction times and good-to-high yields. Also this catalyst can be reused for five times without loss of its catalytic activity.
- Seddighi, Mohadeseh,Shirini, Farhad,Mamaghani, Manouchehr
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p. 433 - 439
(2015/02/05)
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- Method For Preparing Formamidines
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A method for preparing formamidines of formula (I) in a single step by reducing ureas of formula (II) using silanes of formula (III), according to reaction (II)+(III)+(I) is provided. The present invention also provides a method for preparing insecticides
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Paragraph 0109; 0110; 0114
(2015/11/09)
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- Pushing back the limits of hydrosilylation: Unprecedented catalytic reduction of organic ureas to formamidines
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Pushing back the limits: A novel catalytic transformation has been designed to prepare formamidine derivatives by reduction of substituted ureas with hydrosilanes. Simple iron catalysts based on commercially available iron salts and phosphine ligands prov
- Pouessel, Jacky,Jacquet, Olivier,Cantat, Thibault
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p. 3552 - 3556
(2014/01/06)
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- Multicomponent synthesis of 1-aryl 1,2,4-triazoles
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A multicomponent (single reactor) process for the synthesis of 1-aryl 1,2,4-triazoles was explored and developed. This transformation prepared the 1,2,4-triazole directly from anilines, amino pyridines, and pyrimidines. The reaction scope was explored with 21 different substrates, and the position of the nitrogen atoms in the newly formed ring was established by 15N labeling and NMR spectroscopy.
- Tam, Annie,Armstrong, Ian S.,La Cruz, Thomas E.
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supporting information
p. 3586 - 3589
(2013/08/23)
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- Biomimetic approach for the synthesis of N,N′-diarylsubstituted formamidines catalyzed by β-cyclodextrin in water
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An environmentally benign and highly efficient biomimetic approach for the synthesis of N,N′-diarylsubstituted formamidines in water catalyzed β-cyclodextrin is described under neutral condition with quantitative yields of products. β-Cyclodextrin has bee
- Patil, Dipak R.,Dalal, Dipak S.
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p. 1125 - 1128
(2012/11/13)
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- Evaluation of electrophilic heteroaromatic substitution: Synthesis of heteroaromatic-fused pyrimidine derivatives via sequential three-component heterocyclization
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A new sequential three-component heterocyclization was developed by reacting aromatic and heterocyclic substrates, including aminobenzenes, 1-aminonaphthalene, 2-aminopyrazines, 5-aminopyrazoles, 3-aminopyridine, 5-aminopyrimidine, 5-aminoquinoline, and 8
- Wong, Fung Fuh,Huang, Yu-Ying,Chang, Chun-Hsi
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p. 8492 - 8500
(2012/11/07)
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- Deep eutectic solvent promoted highly efficient synthesis of N, N'-diarylamidines and formamides
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A deep eutectic solvent was used as a dual catalyst and reaction medium for the efficient N-formylation of aromatic amines without hazardous organic solvent and catalyst. Treatment of aromatic amines with trimethyl orthoformate and formic acid in deep eutectic solvent at 70 °C gives the corresponding N-formyl derivatives in good to excellent yields. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and SnCl2, with 100% atom economy and making it applicable to industry and laboratory. Furthermore, heating the trimethyl orthoformate and aromatic primary amines in the deep eutectic solvent results in formation of the corresponding N,N'-diarylamidines in high yields.
- Azizi, Najmadin,Gholibeglo, Elham,Babapour, Mahbobe,Ghafuri, Hossein,Bolourtchian, Seyed Mohammad
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p. 768 - 773
(2012/10/30)
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- Facile synthesis of hydroxyformamidines by the N-oxidation of their corresponding formamidines
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The N-oxidation of N,N-disubstituted amidines with MCPBA (m-chloroperoxibenzoic acid) affords a mild, rapid, and efficient route to the corresponding hydroxyamidines This novel synthetic route for the preparation of N,N-disubstituted hydroxyamidines provi
- Cibian, Mihaela,Langis-Barsetti, Sophie,Hanan, Garry S.
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supporting information; experimental part
p. 405 - 409
(2011/04/22)
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- Amine exchange in formamidines: An experimental and theoretical study
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N-H-containing formamidines combine a reasonably strong association to carboxylic acids to form complexes of well-defined geometries with a simultaneous proton-induced electrophilicity enhancement that allows for the exchange of their amine portion. The N
- Capela, Marinha Df.,Mosey, Nicholas J.,Xing, Liyan,Wang, Ruiyao,Petitjean, Anne
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supporting information; experimental part
p. 4598 - 4612
(2011/06/24)
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- DNA photography: An ultrasensitive DNA-detection method based on photographic techniques
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(Figure Presented) All there in black and white: DNA labeled with spectral sensitizers applied to commercially available photopaper allows the detection of oligonucleotides with extreme sensitivity. The detection of the DNA with the help of black and whit
- Hammond, David M.,Manetto, Antonio,Gierlich, Johannes,Azov, Vladimir A.,Gramlich, Philipp M. E.,Burley, Glenn A.,Maul, Melanie,Carell, Thomas
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p. 4184 - 4187
(2008/03/12)
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- Benzamidines, alkamidines and formamidines formed by use of aryl- and alkyliminodimagnesium: Molar ratio and structure of reagent governing the reaction
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In order to extend the the method for preparation of amidines using N-Mg reagents, aryl- and alkyliminodimagnesium [IDMg, ArN(MgBr)2 and RN(MgBr)2] were reacted with esters, amides, ortho- esters, acetals, aminoacetal and arene- and
- Okubo, Masao,Omote, Yasumasa
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p. 212 - 220
(2007/10/03)
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- Reactions of Aryliminodimagnesium with Some N,N-Dimethylcarboxamides and Benzonitriles Affording Various Types of Amidines. Correction of Previous Results on Formamidine Formation from N,N-Dimethylformamide
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Some symmetrical and unsymmetrical form- and benzamidines were prepared by the reaction of ArN(MgBr)2 with Ar'CN, HCONMe2 and related compounds in tetrahydrofuran.
- Okubo, Masao,Tanaka, Mikio,Murata, Yuri,Tsurusaki, Nobuyuki,Omote, Yasumasa,et al.
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p. 1965 - 1968
(2007/10/02)
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- A Convenient Synthesis of N-Substituted Formamidines by Desulfurization of the Corresponding Thioureas
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N,N'-Di- and N,N,N'-trisubstituted thioureas were easily desulfurized by Raney nickel to yield the corresponding formamidines, while N-monosubstituted thioureas gave N,N'-disubstituted formamidines.
- Kashima, Choji,Shimizu, Masao,Eto, Takeshi,Omote, Yoshimori
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p. 3317 - 3319
(2007/10/02)
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- Raney Nickel Desulphuration of 1-Substituted- and 1,3-Disubstituted-thioureas
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Certain 1-aryl-1,3-diaryl- and 1-aryl-3-tetra-O-acetyl-β-D-glucopyranosyl thioureas have been successfully desulphurated into the related mono- and 1,3-di-substituted formamidines with the help of Raney nickel catalyst.A few of them have been converted into the corresponding formamides also.Structure of the products have been established through usual chemical transformations, ir, nmr and mass spectral analysis.
- Ali, M. Umar,Meshram, H. M.,Paranjpe, M. G.
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p. 666 - 669
(2007/10/02)
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- Raney Nickel Desulphuration of Some 1-Arylthioureas
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1-Arylthioureas (I) undergo desulphuration in boiling ethanol in the presence of Raney nickel (W-2) to give the corresponding arylformamides (IV) and arylamines (III).A probable mechanism for the formation of these products has been suggested.
- Ali, M. Umar,Paranjpe, M. G.
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p. 573 - 574
(2007/10/02)
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