- Selective recognition of acetate ion by perimidinium-based receptors
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The first perimidinium-based receptors 1 and 2 have been designed and synthesized. The anion binding properties of the receptors were evaluated in DMSO by UV-vis, fluorescence spectroscopy, and 1H NMR methods. The results demonstrate that both receptors 1 and 2 exhibit good selectivity to acetate. The (C- H)+· · ·X- type ionic hydrogen bonding between the perimidinium moieties and acetate is the key interaction for the recognition.
- Feng, Meiyun,Jiang, Xiaozhi,Dong, Zhiyun,Zhang, Dawei,Wang, Binshen,Gao, Guohua
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- Converting a perimidine derivative to a cationic N-heterocyclic carbene
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The synthesis and reactivity of the new cationic N-heterocyclic carbene 6 comprising a Cp*Ru+ fragment attached to the aromatic backbone of 1,3-dimethylperimidin-2-ylidene is reported. Carbene 6 forms Rh and Ir complexes of the type [(cod)ClM(6)]+ and [(CO)2ClM(6)] +. The analogous complexes of the neutral perimidin-2-ylidene 9 were prepared for comparison purposes. TEP values for both NHCs were calculated from the IR spectra of the carbonyl complexes. The TEP of the cationic carbene 6 (2062 cm-1) is shifted to higher wavenumbers compared to the neutral derivative 9 (2057 cm-1) indicating that the former ligand is a poorer overall donor. In addition, DFT calculations revealed a reduced HOMO-LUMO gap for the cationic system suggesting an increased π-acceptor character. Crystal structures of the related complexes [IrCl(cod)NHC(L)] with L = 6 and 9 were determined by X-ray diffraction and show only marginal differences in the geometrical parameters.
- Verlinden, Kathrin,Ganter, Christian
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- Synthesis of 1H-1,3-benzimidazoles, benzothiazoles and 3H-imidazo[4,5-c]pyridine using DMF in the presence of HMDS as a reagent under the transition-metal-free condition
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An operationally simple method for synthesis of benzimidazole and 3H-imidazo[4,5-c]pyridine from o-phenylenediamine or pyridine-3, 4-diamine and N,N-dimethylformamide (DMF) in the presence of hexamethyldisilazane (HMDS) as a reagent is described. To evaluate the scope of application of this reagent, it was also used to prepare benzothiazole, 1H-perimidine, and benzoxazole, which was successful for benzothiazole and 1H-perimidine but benzoxazole was not formed. This reaction complies with the principles of green chemistry as it does not use toxic solvents, transition metals, or strong acids. The products are obtained in moderate to excellent yields.
- Mostafavi, Hamid,Islami, Mohammad Reza,Ghonchepour, Ehsan,Tikdari, Ahmad Momeni
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- peri-Naphthylenediamines 31.* Study of interconversions of 2,3-dihydroperimidines and 1,8-bis(dialkylamino)naphthaienes. Convenient synthesis of 1,2,2,3-tetramethyl-2,3-dihydroperimidine and a monoisopropyl analog of the "proton sponge"
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Efficient procedures were developed for the two-step synthesis of 1,2,2,3-tetramethyl-2,3-dihydroperimidines and for the one-step synthesis of 1,3-dimethyl-2,3-dihydroperimidines starting from 1,8-diaminonaphthalenes. New possibilities of the use of 2,3-dihydroperimidinium salts in the synthesis of 1,8-bis(dialkylamino)naphthalenes ("proton sponges") containing the N-isopropyl group along with the N-methyl groups were demonstrated. The 1,1,2,2,3-pentamethyl-2,3-dihydroperimidinium cation exists in the acyclic iminium form responsible for its high reactivity.
- Ozeryanskii,Filatova,Sorokin,Pozharskii
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- A chemical-biological evaluation of rhodium(I) n-heterocyclic carbene complexes as prospective anticancer drugs
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Rhodium(I) complexes bearing N-heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry, but there are very few reports of biological properties of these organometallics. A series of RhI-NHC derivatives with 1,5-cyclooctadiene and CO as secondary ligands were synthesized, characterized, and biologically investigated as prospective antitumor drug candidates. Pronounced antiproliferative effects were noted for all complexes, along with moderate inhibitory activity of thioredoxin reductase (TrxR) and efficient binding to biomolecules (DNA, albumin). Biodistribution studies showed that the presence of albumin lowered the cellular uptake and confirmed the transport of rhodium into the nuclei. Changes in the mitochondrial membrane potential (MMP) were observed as well as DNA fragmentation in wild-type and daunorubicin- or vincristine-resistant Nalm-6 leukemia cells. Overall, these studies indicated that RhI-NHC fragments could be used as partial structures of new antitumor agents, in particular in those drugs designed to address resistant malignant tissues. No resistance to special agents: Rhodium(I) N-heterocyclic carbene (NHC) derivatives with 1,5-cyclooctadiene (COD) and CO as secondary ligands were synthesized, characterized, and biologically investigated as prospective antitumor drug candidates. Pronounced antiproliferative effects were noted for all complexes, along with efficient binding to biomolecules. RhI-NHC fragments could be used as partial structures of new antitumor agents, particularly in drugs designed to address daunorubicin- (DNR) and vincristine (VCR)-resistant malignant tissues (see figure). Copyright
- Oehninger, Luciano,Kuester, Laura Nadine,Schmidt, Claudia,Munoz-Castro, Alvaro,Prokop, Aram,Ott, Ingo
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- METHOD OF CARBON MONOXIDE FIXATION AND METHOD OF AMINE FORMYLATION
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The present invention relates to a method for fixing carbon monoxide in a metal-free condition and a method for formating amine using the same.
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Paragraph 0078; 0081-0085; 0100-0102
(2021/02/19)
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- In Situ Formation of Frustrated Lewis Pairs in a Water-Tolerant Metal-Organic Framework for the Transformation of CO2
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Frustrated Lewis pairs (FLPs) consist of sterically hindered Lewis acids and Lewis bases, which provide high catalytic activity towards non-metal-mediated activation of “inert” small molecules, including CO2 among others. One critical issue of homogeneous FLPs, however, is their instability upon recycling, leading to catalytic deactivation. Herein, we provide a solution to this issue by incorporating a bulky Lewis acid-functionalized ligand into a water-tolerant metal-organic framework (MOF), named SION-105, and employing Lewis basic diamine substrates for the in situ formation of FLPs within the MOF. Using CO2 as a C1-feedstock, this combination allows for the efficient transformation of a variety of diamine substrates into benzimidazoles. SION-105 can be easily recycled by washing with MeOH and reused multiple times without losing its identity and catalytic activity, highlighting the advantage of the MOF approach in FLP chemistry.
- Shyshkanov, Serhii,Nguyen, Tu N.,Ebrahim, Fatmah Mish,Stylianou, Kyriakos C.,Dyson, Paul J.
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supporting information
p. 5371 - 5375
(2019/03/17)
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- Metal-free Carbon Monoxide (CO) Capture and Utilization: Formylation of Amines
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The capture and utilization of CO by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the absence of transition-metal complexes. The reaction of TBD with CO afforded TBD-CO adducts, which were converted to formylated TBD (TBD-CHO). TBD-CO adducts may include an interaction of CO with positively charged species based on NMR and IR analysis. In the presence of amines, CO was transferred from TBD-CO to amines, producing formylated amines with good yields. The reaction mechanism involving TBD-CO adducts is presented based on theoretical calculations. (Figure presented.).
- Noh, Hyeong-Wan,An, Youngjoon,Lee, Seulchan,Jung, Jaehoon,Son, Seung Uk,Jang, Hye-Young
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- Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex
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The selective mono-N-methylation of anilines derivatives was achieved under mild conditions using inexpensive methanol as C1 source. Under hydrogen borrowing conditions, using a tridentate PN3P manganese pre-catalyst (5?mol%), a catalytic amount of base (20?mol%), for 24?h at 120?°C, a large variety of anilines derivatives was methylated in good to excellent yield. Mechanistic investigations allowed us to isolate and characterize by X-ray diffraction studies a de-aromatized manganese intermediate.
- Bruneau-Voisine, Antoine,Wang, Ding,Dorcet, Vincent,Roisnel, Thierry,Darcel, Christophe,Sortais, Jean-Baptiste
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- Carbon Dioxide Mediated Novel Synthesis of Quinazoline-2,4(1H,3H)-dione in Water
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A novel, efficient, and scalable CO2 mediated synthesis of quinazoline-2,4(1H,3H)-dione was developed by a simple cyclization of 2-aminobenzonitrile with DMF in water as the solvent. This is the first report of its kind. DMF was used as the necessary carbon source in the synthesis of quinazoline-2,4(1H,3H)-dione. This synthetic protocol is very efficient; it gives >99% conversion with excellent selectivity. The product was isolated by filtration because of the highly insoluble nature of quinazoline-2,4(1H,3H)-dione in water. The co-product, dimethyl amine, also has industrial importance, and the CO2 that is used can be recycled. This protocol has wide-spread applications in the syntheses of benzimidazole and benzothiazole.
- Rasal, Kalidas B.,Yadav, Ganapati D.
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p. 2067 - 2073
(2016/12/24)
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- Gold-Catalyzed Ring Expansion of Alkynyl Heterocycles through 1,2-Migration of an Endocyclic Carbon-Heteroatom Bond
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A mild and efficient gold-catalyzed oxidative ring-expansion of a series of alkynyl heterocycles using pyridine-N-oxide as the oxidant has been developed, which affords highly valuable six- or seven-membered heterocycles with wide functional group toleration. The reaction consists of a regioselective oxidation and a chemoselective migration of an endocyclic carbon-heteroatom bond (favored over C-H migration) with the order of migratory aptitude for carbon-heteroatom bonds being C-S>C-N>C-O. In the absence of an oxidant, polycyclic products are readily constructed through a ring-expansion/Nazarov cyclization reaction sequence.
- Chen, Ming,Sun, Ning,Xu, Wei,Zhao, Jidong,Wang, Gaonan,Liu, Yuanhong
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supporting information
p. 18571 - 18575
(2016/01/26)
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- N-Substituted Formamides as C1-Sources for the Synthesis of Benzimidazole and Benzothiazole Derivatives by Using Zinc Catalysts
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An efficient and convenient one-pot protocol has been developed for the synthesis of a variety of benzimidazole, benzoxazole, and benzothiazole derivatives. This novel approach uses various o-phenylenediamines and N-substituted formamides (C1 sources) in a zinc-catalyzed cyclization in the presence of poly(methylhydrosiloxane) to afford the corresponding derivatives as sole products in moderate to excellent yields.
- Nale, Deepak B.,Bhanage, Bhalchandra M.
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p. 2835 - 2842
(2015/12/18)
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- Method For Preparing Nitrogen Compounds
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The present invention relates to a method for preparing nitrogen compounds using carbon dioxide, and to the use of the method in the production of vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, pesticides, herbicides, antifungal agents and fertilisers. The invention also relates to a method for producing vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, pesticides, herbicides, antifungal agents and fertilisers, which includes a step of preparing nitrogen compounds using the method of the invention. The invention further relates to a method for preparing labelled nitrogen compounds using carbon dioxide and to the uses thereof.
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Paragraph 0.201
(2015/06/03)
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- Tolerance of base pair size and shape in postlesion DNA synthesis
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The influence of base pair size and shape on the fidelity of DNA polymerase-mediated extension past lesion-containing mispairs was examined. Primer extension analysis was performed with synthetic nucleosides paired opposite the pro-mutagenic DNA lesion O6-benzylguanine (O 6-BnG). These data indicate that the error-prone DNA polymerase IV (Dpo4) inefficiently extended past the larger Peri:O6-BnG base pair, and in contrast, error-free extension was observed for the smaller BIM:O 6-BnG base pair. Steady-state kinetic analysis revealed that Dpo4 catalytic efficiency was strongly influenced by the primer:template base pair. Compared to the C:G pair, a 1.9- and 79 000-fold reduction in Dpo4 efficiency was observed for terminal C:O6-BnG and BIM:G base pairs respectively. These results demonstrate the impact of geometrical size and shape on polymerase-mediated mispair extension.
- Gahlon, Hailey L.,Schweizer, W. Bernd,Sturla, Shana J.
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supporting information
p. 6384 - 6387
(2013/06/04)
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- A new and green synthesis of formamidines by γ-Fe2O 3@SiO2-HBF4 nanoparticles as a robust and magnetically recoverable catalyst
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A series of Bronsted acids (HA) were immobilized on superparamagnetic γ-Fe2O3@SiO2. The synthesized [γ-Fe2O3@SiO2-HA] nanocrystallites were fully characterized by spectroscopic techniques (FT-IR, XRD, SEM, EDX) and used as solid acid catalysts in the synthesis of biologically important formamidines. The results were excellent in yield and time of reaction. Activity of various Bronsted acids on superparamagnetic support as catalyst were also evaluated and among them immobilized HBF4 showed the best catalytic properties.
- Sheykhan, Mehdi,Mohammadquli, Mohsen,Heydari, Akbar
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p. 156 - 161
(2013/01/14)
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- A new method for pyrrole peri-annulation: synthesis of 1H-1,5,7-triazacyclopenta[c,d]phenalenes from 1H-perimidines
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New methods for the synthesis of 1H-1,5,7-triazacyclopenta[c,d]phenalenes have been developed based on a sequence involving Schmidt reaction of keto-perimidines and acylation of the intermediate amides with 1,3,5-triazines or carboxylic acids. The same synthetic sequence starting from the corresponding alkylperimidine includes acylation with acetic acid as the first step.
- Aksenov, Alexander V.,Lyakhovnenko, Alexander S.,Andrienko, Anna V.,Levina, Irina I.
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scheme or table
p. 2406 - 2408
(2010/06/21)
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- Reaction of 6(7)-acyl-and 6(7)-formylperimidines with 1,3,5-triazines in poly-phosphoric acid
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A method has been developed for the synthesis of 1,3,7-triazapyrenes using the reaction of 6(7)-formyl-and 6(7)-benzoylperimidines with 1,3,5-triazines in PPA. Under these conditions, 6(7)-formylperimidine reacts with 2,4,6-trimethyl-1,3,5-triazine to give 6-hydroxy-1,3-diazapyrene.
- Aksenov,Borovlev,Pisarenko,Aksenova
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scheme or table
p. 868 - 871
(2009/04/08)
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- Heterocyclic analogs of pleiadiene. 75. Formylation of perimidines and 2,2-dimethyl-2,3-dihydroperimidine under Vilsmeier conditions
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The formylation of perimidine, its 2- and 3-methyl derivatives, and 2,2-dimethyl-2,3-dihydroperimidine has been studied under the conditions of the Vilsmeier reaction. In the last case recyclization occurs. The characteristics of the 1H NMR spectra of the aldehydes obtained are discussed. 2006 Springer Science+Business Media, Inc.
- Filatova,Borovlev,Pozharskii,Goncharov,Demidov
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- Hair colorants based on perimidine derivatives
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A method of preparing an oxidation dyestuff comprising the step of: mixing a coupler substance of formula I STR1 wherein R1 is hydrogen, (C1 -C6)-alkyl, hydroxy-(C1 -C6)-alkyl, (C1 -C4)-alkoxy-(C1 -C6)-alkyl, carboxy-(C1 -C6)-alkyl, 2,3-dihydroxypropyl, 2-hydroxy-3-((C1 -C4)-alkoxy)-propyl, cyano-(C1 -C6)-alkyl, carbamoyl-(C1 -C6)-alkyl, ((C1 -C4)-alkoxy) carbonyl-(C1 -C4)-alkyl, benzyl, phenyl or substituted phenyl; R2 is hydrogen, (C1 -C6)-alkyl, hydroxy-(C1 -C6)-alkyl, (C1 -C4)-alkoxy-(C1 -C6)-alkyl, oxo-(C1 -C6)-alkyl, carboxy-(C1 -C6)-alkyl, ((C1 -C4)-alkoxy) carbonyl-(C1 -C6)-alkyl, carbamoyl-(C1 -C6)-alkyl, carboxyl, ((C1 -C4)-alkoxy) carbonyl, carbamoyl, phenyl, substituted phenyl or pyridyl; R3 is (C1 -C6)-alkyl, chlorine or bromine and n is 0, 1 or 2, or of salts thereof; with a developer substance. A Hair coloring composition comprising one or more coupler substances and one or more developer substances, characterized in that it comprises one or more compounds of the general formula I as the coupler substance.
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- Potential Antitumor Agents. 53. Synthesis, DNA Binding Properties, and Biological Activity of Perimidines Designed as "Minimal" DNA-Intercalating Agents
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A series of compounds based on perimidine have been synthesized and evaluated for their DNA-binding properties and antitumor activity.The fused tricyclic perimidine chromophore appears to be the minimal structural requirement for intercalative binding to DNA since the mode of binding could be dictated by the position of attachment of the side chain.The intercalating compounds have DNA association constants (log K = 5.8-6.5) and cytotoxic potencies (IC50 = 500-1500 nM) comparable to those shown by other classes of linear, tricyclic DNA-intercalating antitumor agents (acridinecarboxamides, phenazinecarboxamides), but none of the compounds showed in vivo activity.
- Herbert, John M.,Woodgate, Paul D.,Denny, William A.
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p. 2081 - 2086
(2007/10/02)
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- HETEROCYCLIC ANALOGS OF PLEIADIENE. 48. PYROSULFITE AS A MILD DEHYDROGENATING AGENT IN THE 2,3-DIHYDROPERIMIDINE SERIES. SYNTHESIS OF 2-POLYHYDROXYALKYLPERIMIDINES
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2,3-Dihydroperimidines are dehydrogenated smoothly by sodium pyrosulfite in refluxing aqueous alcohol, as a result of which the corresponding perimidines are formed in high yields.The reaction of 1,8-naphthalenediamine with the aldehydic forms of sugars gives 2-polyhydroxyalkyl-2,3-dihydroperimidines, which are also aromatized by sodium pyrosulfite to give the corresponding 2-polyhydroxyalkylperimidines in high yields.
- Starshikov, N.M.,Pozharskii, A.F.
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