- Catalytic Beckmann rearrangement of ketoximes in ionic liquids
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Under mild conditions and without any additional organic solvents, Beckmann rearrangements of several ketoximes were performed in the catalytic media consisting of room temperature ionic liquid based on 1,3-dialkylimidazolium or alkylpyridinium salts and
- Peng, Jiajian,Deng, Youquan
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- A convenient procedure for the preparation of alkyl nitriles from alkyl halides. Acetone cyanohydrin as an in situ source of cyanide ion
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A convenient preparation of alkyl nitriles from alkyl halides is described. Acetone cyanohydrin is employed as the source of cyanide ion.
- Dowd,Wilk,Wlostowski
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- Alkyllithium Compounds Bearing Electrophilic Functional Groups: A Flash Chemistry Approach
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Flash chemistry based on flow microreactor systems allowed alkyllithiums bearing electrophilic functional groups to be successfully generated and used for subsequent reactions. The series of reactions with high reactivity was achieved by extremely accurate control over residence time in a controlled and selective manner.
- Nagaki, Aiichiro,Yamashita, Hiroki,Hirose, Katsuyuki,Tsuchihashi, Yuta,Yoshida, Jun-ichi
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- Deprotonation-alkylation of alkyl cyanides under sonochemical conditions
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Deprotonation-alkylation of n-alkyl cyanides can be readily effected by an alkyl halide in the presence of sodium in a one pot procedure. Yields are generally better than in the usual methods, and the overall reaction conditions have important advantages
- Berlan,Delmas,Duee,Luche,Vuiglio
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- Palladium-Catalyzed Isomerization/(Cyclo)carbonylation of Pentenamides: a Mechanistic Study of the Chemo- and Regioselectivity
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A new isomerizing ring-closing amidocarbonylation reaction is reported using Pd catalysis with bulky diphosphane ligands. From terminal as well as internal pentenamide isomers (PAs), cyclic imides were obtained in good yield (92 %) with cationic Pd catalysts supported by bis-PCg ligands (PCg=6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-6-yl). An excess of strong acid is required to obtain high selectivity for imide products. From a low-temperature NMR study it was deduced that N coordination of the amide moiety is responsible for a high selectivity to cyclic imide products. In weakly acidic conditions, O coordination of the amide functionality leads to the formation of cyanoacids (i.e., 5-cyanovaleric acid, 2-methyl-4-cyanobutyric acid and 2-ethyl-3-cyanopropionic acid). It is proposed that the formation of these cyanoacids occurs through a novel intramolecular tandem dehydrating hydroxycarbonylation reaction of PAs. This reaction also occurs in intermolecular versions of amidocarbonylation with mixtures of alkene and amide substrates. Experiments with N-alkylated amides have been instrumental in developing mechanistic models. The strong acid co-catalyst ensures double-bond isomerization to occur faster than product formation, resulting in the same product mixture, irrespective of the use of terminal or internal pentenamides. The remaining challenge is to arrive at the desired adipimide by overcoming the undesirable regioselectivity caused by chelation of the amide.
- Limburg, Bart,Gloaguen, Yann,de Bruijn, Hans M.,Drent, Eite,Bouwman, Elisabeth
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- New catalytic properties of iron porphyrins: Model systems for cytochrome P450-catalyzed dehydration of aldoximes
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Various iron porphyrin systems were found to catalyze the dehydration of aldoximes, such as heptanaldoxime or phenylacetaldoxime, into the corresponding nitriles under mild conditions (t = 20 °C, neutral or slightly acidic pH). In all these systems, the presence of both the iron porphyrin catalyst and a reducing agent is required, indicating that the active species is the iron(II) porphyrin. The most efficient systems used either an organosoluble iron porphyrin, such as Fe(OEP), in the presence of a carboxylic acid and zinc amalgam as reducing agent, or a water-soluble heme fragment of cytochrome c (microperoxidase MP-11) in the presence of dithionite. The catalytic activity of the systems was greatly increased when using electron-rich iron porphyrins bearing an electron-donating axial ligand, such as imidazole, and a carboxylic acid cocatalyst in close proximity to the iron center. The activity of the best systems was comparable to that of microsomal cytochromes P450 (between 1 and 10 turnovers per rain). The intermediate (porphyrin)iron-aldoxime complex formed in those dehydration reactions was isolated in the case of Fe(meso-tetra(2,6-dichlorophenyl)-β- octachloroporphyrin) [meso-tetra(2,6-dichlorophenyl)-β-octachloroporphyrin = TDCPCl8P] and characterized by elemental analysis and UV-visible and 1H NMR spectroscopy. Comparison of the 1H NMR spectra of Fe(TDCPCl8P)(CH3- CHNOH)2 and Fe(TDCPCl8P)(pyridine)2 strongly indicates that acetaldoxime is bound to iron(II) via its nitrogen atom in the former. A mechanism for iron porphyrin-catalyzed dehydration of aldoximes based on all these results is proposed. It involves a partial charge transfer from electron-rich Fe(II) to the aldoxime C=NOH moiety, which favors the departure of its OH group assisted by an acid cocatalyst. This illustrates the potential of iron porphyrins as catalysts for new reactions very different from the redox transformations for which they are well-known.
- Hart-Davis, Jason,Battioni, Pierrette,Boucher, Jean-Luc,Mansuy, Daniel
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- Zinc Oxide/Graphene Oxide as a Robust Active Catalyst for Direct Oxidative Synthesis of Nitriles from Alcohols in Water
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In this work, without using any linker or chemical modification of graphene oxide, a zinc oxide immobilized graphene oxide-based catalyst was used for the direct aerobic oxidative conversion of alcohols to the nitriles in water. In the first step, graphene oxide was prepared and then zinc ions were electrostatically adsorbed onto the surface of graphene oxide. In the following step, zinc oxide nanoparticles were generated via in-situ growth in presence of NaOH. It was illustrated that graphene oxide layers can control the size of in-situ generated zinc oxide nanoparticles. Various aromatic/aliphatic/heteroaromatic primary alcohols converted to the nitriles in high yields under O2 balloon with ZnO/GO catalyst. This catalyst can be used for 7 successful consecutive runs without significant loss of activity. Graphic Abstract: [Figure not available: see fulltext.]
- Sarvi, Iraj,Zahedi, Ehsan
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- Conversion of Dinitrogen into Nitrile: Cross-Metathesis of N2-Derived Molybdenum Nitride with Alkynes
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The direct synthesis of nitrile from N2 under mild conditions is of great importance and has attracted much interest. Herein, we report a direct conversion of N2 into nitrile via a nitrile–alkyne cross-metathesis (NACM) process involving a N2-derived Mo nitride. Treatment of the Mo nitride with alkyne in the presence of KOTf afforded an alkyne-coordinated nitride, which was then transformed into MoV carbyne and the corresponding nitrile upon 1 e? oxidation. Both aryl- and alkyl-substituted alkynes underwent this process smoothly. Experiments and DFT calculations have proved that the oxidation state of the Mo center plays a crucial role. This method does not rely on the nucleophilicity of the N2-derived metal nitride, offering a novel strategy for N2 fixation chemistry.
- Hong, Xin,Jin, Li,Liao, Qian,Mézailles, Nicolas,Song, Jinyi
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supporting information
p. 12242 - 12247
(2021/04/05)
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- Method for preparing valeronitrile through hydrogenation of pentenenitrile
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The invention relates to a method for preparing valeronitrile through hydrogenation of pentenenitrile, and belongs to the technical field of chemical engineering. The method comprises the following steps: adding pentenenitrile, ethanol, a novel catalyst and an amorphous Fe-Mo-Ni-Al catalyst into a hydrogenation reaction kettle, starting stirring, carrying out nitrogen replacement for 3 times, then carrying out hydrogen replacement for 3 times, controlling the hydrogen pressure to be 0.2 Mpa, heating the reactants to 60 DEG C, and performing a reaction for 2 hours or determining that the hydrogen is not absorbed any more, continuously maintaining the hydrogen pressure, carrying out stirring reaction for half an hour, and then ending the reaction. The novel catalyst is a high-molecular palladium complex prepared from poly-gamma-(m-diphenylphosphinophenyl) propyl siloxane palladium with silicon dioxide as a carrier and sodium chloropalladite tetrahydrate through the interaction thereof.
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Paragraph 0032-0036
(2021/07/21)
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- Cavity-promotion by pillar[5]arenes expedites organic photoredox-catalysed reductive dehalogenations
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The efficiency of the photo-induced electron transfer in photoredox catalysis is limited by the diffusional collision of the excited catalyst and the substrate. We herein present cavity-bound photoredox catalysts, which preassociate the substrates, leading to significantly shortened reaction times. A pillar[5]arene serves as the cavity and phenothiazine as a catalyst in the reductive dehalogenation of aliphatic bromides as a proof of concept reaction.
- Esser, Birgit,Schmidt, Maximilian
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supporting information
p. 9582 - 9585
(2021/09/28)
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- NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
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Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
- Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
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supporting information
p. 575 - 578
(2020/01/29)
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- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
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We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
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supporting information
p. 4161 - 4164
(2020/07/14)
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- Photocatalytic selective aerobic oxidation of amines to nitriles over Ru/γ-Al2O3: The role of the support surface and the strong imine intermediate adsorption
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Hydroxyl coordinated ruthenium dispersed on the surface of γ-Al2O3 can be applied to the selective oxidation of amines with light irradiation and an atmospheric pressure of O2 at room temperature. Sunlight is also an effective light source for the selective aerobic oxidation of primary amines to corresponding nitriles. The high photocatalytic activity and selectivity over Ru/γ-Al2O3 originate from the adsorption of amines and imine intermediates on the abundant surface OH groups of the photocatalyst and further formation of Ru-amide species by ligand exchange of adsorbed amines and imine intermediates with adjacent exposed active Ru sites. Light is introduced to the system successfully via the formation of Ru-amide species, which are used as the light absorption sites of the photocatalytic selective oxidation of amines. Primary amines are directly converted to corresponding nitriles via a two-step oxidative dehydrogenation process.
- Zhu, Pengqi,Zhang, Jin,Wang, Jie,Kong, Peng,Wang, Yunwei,Zheng, Zhanfeng
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p. 440 - 449
(2020/02/04)
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- Solvent-Tailored Pd3P0.95 nano catalyst for amide-nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the CO bond
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For the first time, a one pot thermolysis of [Pd(PPh3)2Cl2] prepared by reacting Ph3P with PdCl2 in a 2:1 molar ratio in MeOH at 280 °C in a trioctylphosphine (TOP) and oleylamine(OA)-octadecane(ODE) mixture (1:1) was used to prepare quantum dots (QDs; size ~2-3 nm) and nanoparticles (NPs; size ~13-14 nm), respectively, of composition Pd3P0.95. TEM, SEM-EDX, powder-XRD and XPS (for QDs only) were used to authenticate the two nanophases. 31P{1H}NMR experiments performed to monitor the progress of thermolysis reactions revealed that the phosphorus present in the Pd3P0.95 QDs had come from TOP, whereas in Pd3P0.95 NPs, its source is triphenylphosphine. The nature of the solvent did not affect the chemical composition of the nano-phase but controlled its size. Probably, solvent dependent, unique, single source precursors (SSPs) of palladium were generated in situ, and controlled the size. The catalytic activity of both Pd3P0.95 QDs and NPs was explored. The QDs were found to be efficient as a catalyst for the amide-nitrile interconversion at room temperature (yield up to 92% in 4 h), hydration of nitriles and transfer hydrogenation (TH) of carbonyl compounds with yields up to 96% in 3-4 h. The yields and reaction rates of amide-nitrile inter-conversion and TH when catalyzed by Pd3P0.95 QDs were found to be higher compared to the ones observed with the Pd/C catalyst. The binding energy of Pd(3d) in the X-ray photoelectron spectrum (XPS) of Pd3P0.95 indicated an electron transfer from the metal to phosphorus, resulting in electron deficient palladium, which facilitates the coordination of a substrate to Pd and drives the reaction. The reusability of Pd3P0.95 QDs for the interconversion was found to be up to 4-Times, while for the transfer hydrogenation of carbonyl compounds it was up to 6-Times, but with a diminished yield. Pd3P0.95 NPs were found to be less active (yield up to 36% in optimized reaction conditions) in comparison to Pd3P0.95 QDs. The mercury poisoning test suggested that the catalysis predominantly proceeded heterogeneously on the surface of the QDs. The PXRD and XPS results did not suggest a significant variation in the phase of QDs after the third catalytic cycle. The bleeding of Pd during catalysis (determined by flame AAS) and the agglomeration of QDs as supported by the SEM-EDX and TEM results are probably responsible for the reduction in the catalytic activity of QDs after reusing three times.
- Sharma, Alpesh K.,Joshi, Hemant,Bhaskar, Renu,Singh, Ajai K.
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supporting information
p. 10962 - 10970
(2019/07/31)
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- Green synthesis of benzonitrile using ionic liquid with multiple roles as the recycling agent
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Preparation of benzonitrile from benzaldehyde and hydroxylamine hydrochloride is one of the most advantageous approaches. Nevertheless, it suffers from various constraints such as longer reaction time, corrosion and recovery of hydrochloric acid, the use of metal salt catalysts and their separation. For these reasons, a novel green benzonitrile synthetic route was proposed with ionic liquid as the recycling agent in this study. The results indicated that hydroxylamine 1-sulfobutyl pyridine hydrosulfate salt ((NH2OH)2·[HSO3-b-Py]·HSO4) was an expert alternative to hydroxylamine hydrochloride. Meanwhile, the ionic liquid [HSO3-b-Py]·HSO4 exhibited the multiple roles of co-solvent, catalysis and phase separation, thus the use of metal salt catalyst was eliminated, and no additional catalyst was needed. Hence, the separation process was greatly simplified. When the molar ratio of benzaldehyde to (NH2OH)2·[HSO3-b-Py]·HSO4 was 1:1.5, the volume ratio of paraxylene to [HSO3-b-Py]·HSO4 was 2:1, the benzaldehyde conversion and benzonitrile yield were both 100% at 120 °C in 2 h. Even better, the ionic liquid could be recovered easily by phase separation, and recycled directly after reaction. Additionally, this novel route is applicable to the green synthesis of a variety of aromatic, heteroaromatic and aliphatic nitriles with excellent yields.
- Li, Zhihui,Wang, Tingting,Qi, Xudong,Yang, Qiusheng,Gao, Liya,Zhang, Dongsheng,Zhao, Xinqiang,Wang, Yanji
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p. 17631 - 17638
(2019/06/24)
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- Method for preparing nitrile by reacting acetone cyanohydrin with haloalkane
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The invention provides a method for preparing nitrile by reacting acetone cyanohydrin with haloalkane. According to the invention, by using acetone cyanohydrin as a cyaniding reagent, the problems, such as long reaction time, low yield, strict reaction conditions and the like enchanted in an existing preparation method in which highly toxic sodium cyanide or potassium cyanide or expensive trimethylsilyl cyanide is used as a cyanogen source, are solved. The method comprises the following steps: dissolving acetone cyanohydrin in a mixed solvent of a high boiling point dipolar aprotic solvent anda low boiling point aprotic solvent, adding a catalyst lithium hydroxide, stirring at 25-50 DEG C for one hour and then adding a haloalkane for continuous reaction for 2-3 hours; next, adding saturated saline water for washing twice, separating out an organic layer, and boiling off the solvent after drying, thereby obtaining a nitrile compound. The method for preparing a nitrile compound disclosed in the invention is characterized by low reaction toxicity, simple process, easy of operation, low production cost, and a yield of more than 95%.
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Paragraph 0043-0049; 0051-0057; 0068
(2019/08/20)
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- A method of synthesizing fatty nitrile by the aliphatic aldehyde
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The invention relates to a method of synthesizing fatty nitrile by the aliphatic aldehyde. The method comprises the following steps: the aliphatic aldehyde, ionic liquid regenerating and ionic liquid in the reactor, to join the two toluene, stirring, of the reflux condensation, in the normal pressure, 90 - 120 °C reaction under 0.5 - 2 h, to obtain the product fatty nitrile; wherein said ionic liquid is 1 - sulfobutyl pyridine bisulphate ionic liquid; ion liquid hydroxylamine salt is 1 - sulfobutyl pyridine bisulphate ion liquid hydroxylamine salt. The invention in one reactor to achieve the fat [...] and fat aldoxime dehydration integrated two-step reaction, the process is simple, easy to operate; to ionic liquid as catalyst and a co-solvent, without the addition of metal salt catalyst and corrosive solvent, environment-friendly.
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Paragraph 0027; 0028; 0043; 0044
(2019/05/28)
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- Cyaniding method for preparing nitrile compound
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The invention provides a cyaniding method for preparing a nitrile compound. Organic halide or pseudohalide, CO2 and NH3 which are low in price and are easily obtained and a reducing agent react, a selective cyaniding reaction is conducted in the presence of a transition metal catalyst, and the target product namely organic the nitrile compound is obtained. According to the cyaniding method for preparing the nitrile compound, a new reaction route is used, through a CO2 and NH3 reaction of metal catalysis, dehalogenation cyaniding or quasi halide cyaniding of halide or pseudohalide is directly achieved through a one-pot method, the problem is solved that a traditional cyanation reaction needs equivalent toxic cyanide, a new direct and convenient method for preparing isotope-labeled nitrile compounds is provided at the same time, and the method can be applied to medicine, tracing, biology and medicine research and development.
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Paragraph 0113-015
(2018/05/30)
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- [1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination
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A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids.
- Kanchupalli, Vinaykumar,Katukojvala, Sreenivas
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p. 5433 - 5437
(2018/04/09)
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- Trinuclear complexes of palladium(II) with chalcogenated N-heterocyclic carbenes: Catalysis of selective nitrile-primary amide interconversion and Sonogashira coupling
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3-Methyl-1-(2-(phenylthio/seleno)ethyl)-1H-benzo[d]imidazol-3-ium iodide (L1/L2), a precursor of sulfated/selenated N-heterocyclic carbene, was synthesized by the reaction of benzimidazole with 1,2-dichloroethane followed by treatment with PhS/SeNa and MeI. The reaction of L1/L2 with Ag2O followed by treatment with [Pd(CH3CN)2Cl2] (metal to ligand ratio 3:2), i.e. transmetallation, resulted in trinuclear palladium(ii) complexes [Pd3(L1/L2-HI)2(CH3CN)Cl6] (1-2). The complexes were characterized with 1H, 13C{1H} and 77Se{1H} NMR (2 only), elemental analyses, HR-MS and single-crystal X-ray diffraction. The geometry of three Pd atoms in each complex is nearly square planar. The Pd-S/Se, Pd-C, Pd-N and Pd-Cl bond distances (?) in 1/2 are 2.3179(19)/2.4312(10), 1.968(7)/1.952(4), 2.073(8)/2.079(4) and 2.2784(19)-2.298(2)/2.292(2)-2.3003(15), respectively. In both the complexes, all Cl are trans to each other. For the central Pd atom, two benzimidazole rings are also trans to each other. The C-H?Cl non-covalent interactions result in a three-dimensional network. The moisture and air insensitive trinuclear Pd(ii) complexes 1 and 2 are thermally stable and efficient as a catalyst for nitrile-amide interconversion and amine-free Sonogashira C-C coupling (in the presence of CuI). The optimum temperature is 80 °C for the interconversion and 110 °C for the coupling. The catalytic protocols are applicable to both aliphatic and aromatic amides/nitriles. The optimum catalyst loading is 1 mol% for the C-C coupling and 0.5 to 1 mol% for the interconversion. K2CO3 as a base gives the best result for Sonogashira C-C coupling. In the conversion of nitriles to amides, the formation of an acid was not detected. After using once, 1/2 can carry out the conversion of ten fresh lots of nitriles to amides with almost the same efficiency. The real catalytic species for the interconversion and coupling appear to be based on Pd(ii) and Pd(0), respectively.
- Dubey, Pooja,Gupta, Sonu,Singh, Ajai K.
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p. 13065 - 13076
(2017/10/13)
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- Synthesis of new N-glycosides based on Valproic acid analogs tetrazole derivatives
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New N-glycosides based on valproic acid analogs tetrazole derivatives were synthesized. The bis-tetrazole derived from 1,6-hexandiol was also connected to acetylated glucose and formed bis-N-glycoside. Structures characterizations have been performed using FT IR, 1H and 13C NMR spectroscopy.
- Noroozi Pesyan, Nader,Ebrahimi, Marziyeh
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p. 1059 - 1067
(2017/03/11)
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- Direct synthesis of nitriles from aldehydes with hydroxylamine-O-sulfonic acid in acidic water
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Herein is reported the selective transformation of aldehydes to nitriles in the presence of hydroxylamine-O-sulfonic acid (NH2OSO3H) as a source of the N atom and acidic water. The reaction works with high yields for a large array of aromatic and aliphatic aldehydes, as well as hindered aldehydes and conjugated aldehydes without purification. The reaction conditions are very mild and tolerate a wide array of functional groups. In principle, the reaction can be completed in vinegar.
- Quinn, Dylan J.,Haun, Graham J.,Moura-Letts, Gustavo
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supporting information
p. 3844 - 3847
(2016/08/02)
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- Reactivity of aminophosphonic acids. Oxidative dephosphonylation of 1-aminoalkylphosphonic acids by aqueous halogens
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The reactions of 1-aminoalkylphosphonic acids with bromine-water, chlorine-water and iodine-water were investigated. The formation of phosphoric(v) acid, as a result of a halogen-promoted cleavage of the Cα-P bond, accompanied by nitrogen release, was observed. The dephosphonylation of 1-aminoalkylphosphonic acids was found to occur quantitatively. In the reactions of 1-aminoalkylphosphonic acids with other halogen-water reagents investigated by 31P NMR, scission of the Cα-P bond was also observed, the reaction rates being comparable for bromine and chlorine, but much slower for iodine.
- Drabowicz, Józef,Jordan, Frank,Kudzin, Marcin H.,Kudzin, Zbigniew H.,Stevens, Christian V.,Urbaniak, Pawe?
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p. 2308 - 2317
(2016/02/09)
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- Nitrilation of carboxylic acids with acetonitrile catalyzed by molybdenum and vanadium complexes
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Various carbonitriles were synthesized by reaction of the corresponding carboxylic acids with acetonitrile in carbon tetrachloride in the presence of VO(acac)2and Mo(CO)6in 6 h at 150–170°C.
- Khusnutdinov,Shchadneva,Bayguzina,Mayakova, Yu. Yu.
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p. 1282 - 1286
(2016/10/26)
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- Mechanistic insights into the oxidative dehydrogenation of amines to nitriles in continuous flow
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The oxidative dehydrogenation of various aliphatic amines to their corresponding nitrile compounds using RuO2/Al2O3 catalysts in air was successfully applied to a continuous flow reaction. Conversions of amines (up to >99%) and yields of nitriles (up to 77%) varied depending on reaction conditions and the amine utilised. The presence of water was found to be important for the activity and stability of the RuO2/Al2O3 catalyst. The Hammett relationship and in situ infrared spectroscopy were applied to divulge details about the catalytic mechanism of the oxidative dehydrogenation of amines over RuO2/Al2O3 catalysts.
- Corker, Emily C.,Ruiz-Martínez, Javier,Riisager, Anders,Fehrmann, Rasmus
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p. 5008 - 5015
(2015/11/03)
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- Ametoctradin is a Potent Qo Site Inhibitor of the Mitochondrial Respiration Complex III
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Ametoctradin is a new Oomycete-specific fungicide under development by BASF. It is a potent inhibitor of the bc1 complex in mitochondrial respiration. However, its detailed action mechanism remains unknown. In the present work, the binding mode of ametoctradin was first uncovered by integrating molecular docking, MD simulations, and MM/PBSA calculations, which showed that ametoctradin should be a Qo site inhibitor of bc1 complex. Subsequently, a series of new 1,2,4-triazolo[1,5-a]pyrimidine derivatives were designed and synthesized to further understand the substituent effects on the 5- and 6-position of 1,2,4-triazolo[1,5-a]pyrimidine. The calculated binding free energies (ΔGcal) of newly synthesized analogues as Qo site inhibitors correlated very well (R2 = 0.96) with their experimental binding free energies (ΔGexp). Two compounds (4a and 4c) with higher inhibitory activity against porcine SQR than ametoctradin were successfully identified. The structural and mechanistic insights obtained from the present study will provide a valuable clue for future designing of a new promising bc1 inhibitor.
- Zhu, Xiaolei,Zhang, Mengmeng,Liu, Jingjing,Ge, Jingming,Yang, Guangfu
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p. 3377 - 3386
(2015/04/14)
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- Preparation of novel magnetic dicationic ionic liquid polymeric phase transfer catalyst and their application in nucleophilic substitution reactions of benzyl halides in water
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PEG-based magnetic dicationic ionic liquid was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions of benzyl halides for the synthesis of benzyl azides and cyanides from good to excellent yields at 90 °C in water. The reactions occur in water and furnish the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.
- Godajdar, Bijan Mombani,Ansari, Bita
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- Visible-Light-Driven Aerobic Oxidation of Amines to Nitriles over Hydrous Ruthenium Oxide Supported on TiO2
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Aerobic oxidation of amines to nitriles under visible light irradiation was catalyzed by supported hydrous ruthenium oxide catalyst. Both LED (blue, green, or red) and the Sun were effective light sources for the transformation of benzylic and aliphatic amines to the corresponding nitriles under atmospheric pressure of O2. Water can be used as a solvent instead of toluene without the loss of activity and selectivity. (Figure Presented).
- Ovoshchnikov, Daniil S.,Donoeva, Baira G.,Golovko, Vladimir B.
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- Ruthenium-catalyzed aerobic oxidative decarboxylation of amino acids: A green, zero-waste route to biobased nitriles
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Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent. This journal is
- Claes, Laurens,Verduyckt, Jasper,Stassen, Ivo,Lagrain, Bert,De Vos, Dirk E.
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supporting information
p. 6528 - 6531
(2015/04/14)
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- Addition reactions of organometallic reagents to nitrogen trifluoride and enhanced alkyl-alkyl coupling by NF3
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A survey of the reaction of nitrogen trifluoride (NF3) with various organometallic reagents finds that organomagnesium (Grignard) reagents are the most useful for producing N,N-difluoroaminoalkanes. Alkyl-alkyl coupling is a persistant side reaction. Organolithiums are marginally effective. Organocopper, organozinc reagents undergo primarily alkyl-alkyl coupling catalyzed by the presence of NF3. Organocalcium and organoaluminum reagents are unreactive.
- Belter, Randolph K.
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p. 110 - 113
(2015/04/27)
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- Bio-based nitriles from the heterogeneously catalyzed oxidative decarboxylation of amino acids
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The oxidative decarboxylation of amino acids to nitriles was achieved in aqueous solution by in situ halide oxidation using catalytic amounts of tungstate exchanged on a [Ni,Al] layered double hydroxide (LDH), NH4Br, and H2O2 as the terminal oxidant. Both halide oxidation and oxidative decarboxylation were facilitated by proximity effects between the reactants and the LDH catalyst. A wide range of amino acids was converted with high yields, often > 90%. The nitrile selectivity was excellent, and the system is compatible with amide, alcohol, and in particular carboxylic acid, amine, and guanidine functional groups after appropriate neutralization. This heterogeneous catalytic system was applied successfully to convert a pro-tein-rich byproduct from the starch industry into useful biobased N-containing chemicals.
- Claes, Laurens,Matthessen, Roman,Rombouts, Ine,Stassen, Ivo,De Baerdemaeker, Trees,Depla, Diederik,Delcour, Jan A.,Lagrain, Bert,De Vos, Dirk E.
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p. 345 - 352
(2015/01/30)
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- One-step synthesis of nitriles by the dehydrogenation-amination of fatty primary alcohols over Cu/m-ZrO2
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An effective method for one-step synthesis of nitriles employing C 2-C8 fatty primary alcohols and ammonia over 5%Cu/m-ZrO2 has been found. The conversion of alcohols and selectivity of nitriles obtained are > 96 and > 87 wt.%, respectively, and are obviously influenced by the C2-substitution rather than the chain length of fatty primary alcohols. Cu/m-ZrO2 was characterized by XRD, H 2-TPR, CO2-TPD and NH3-TPD. It is revealed that a substantial amount of Cu species over m-ZrO2 is in highly dispersed CuO. A plausible mechanism is proposed and supported by different experiments, and aldehyde generation is an important step in the reaction mechanism.
- Hu, Yunfeng,Jin, Shuhan,Zhang, Zhichao,Zhang, Likun,Deng, Jun,Zhang, Hongsheng
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- One-step synthesis of nitriles by the dehydrogenation-amination of fatty primary alcohols over Cu/m-ZrO2
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An effective method for one-step synthesis of nitriles employing C2-C8 fatty primary alcohols and ammonia over 5%Cu/m-ZrO2 has been found. The conversion of alcohols and selectivity of nitriles obtained are > 96 and > 87 wt.%, respectively, and are obviously influenced by the C2-substitution rather than the chain length of fatty primary alcohols. Cu/m-ZrO2 was characterized by XRD, H2-TPR, CO2-TPD and NH3-TPD. It is revealed that a substantial amount of Cu species over m-ZrO2 is in highly dispersed CuO. A plausible mechanism is proposed and supported by different experiments, and aldehyde generation is an important step in the reaction mechanism.
- Hu, Yunfeng,Jin, Shuhan,Zhang, Zhichao,Zhang, Likun,Deng, Jun,Zhang, Hongsheng
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- Chitosan supported ionic liquid: A recyclable wet and dry catalyst for the direct conversion of aldehydes into nitriles and amides under mild conditions
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A green and highly efficient chitosan supported magnetic ionic liquid (CSMIL) was synthesized with chitosan (the most abundant biopolymer in nature and a cheap industrial waste product), methyl imidazole and anhydrous/hydrous FeCl3. The heterogeneous catalyst thus obtained was used for the direct conversion of aldehydes to the corresponding nitriles in the presence of NH2OH·HCl/dry-CSMIL/MeSO2Cl and amides with NH 2OH·HCl/wet-CSMIL/MeSO2Cl. A highlight of our approach is the easy separation of the catalyst from the reaction medium and thus the recyclability of the catalyst. This simple method can be applied to obtain a wide range of aromatic, heterocyclic, and aliphatic nitriles and amides.
- Khalafi-Nezhad, Ali,Mohammadi, Somayeh
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p. 13782 - 13787
(2014/04/17)
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- Direct transformation of primary nitro compounds into nitriles with sodium-dithionite
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A new and practical direct transformation of primary nitro compounds into nitriles with sodium dithionite is described. The reaction is simple, convenient and eliminates the use of expensive and moisture-sensitive reagents. Georg Thieme Verlag Stuttgart New York.
- Temelli, Baris,Unaleroglu, Canan
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p. 1407 - 1412
(2014/06/09)
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- Base-catalyzed N -N bond cleavage of hydrazones: Synthesis of α-amino ketones
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An efficient Cs2CO3-promoted synthesis of α-amino ketones using hydrazines, aldehydes, and α-haloketones as starting materials through a cascade condensation/nucleophilic substitution/N -N bond cleavage route is developed. The carbonyl group plays a key role in this novel N -N bond cleavage process. Breaking good: A novel method of base-catalyzed N -N bond cleavage of hydrazones has been discovered. A variety of α-amino ketones was synthesized using hydrazines, α-haloketones, and benzaldehyde as starting materials through a cascade condensation/ nucleophilic substitution/N -N bond cleavage sequence.
- Tang, Hai-Tao,Zhou, Yun-Bing,Zhu, Yu,Sun, Hong-Chao,Lin, Min,Zhan, Zhuang-Ping
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p. 1278 - 1281
(2014/05/06)
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- Ac2O/K2CO3/DMSO: An efficient and practical reagent system for the synthesis of nitriles from aldoximes
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The transformation of aldoximes to nitriles using acetic anhydride as dehydration agent under mild reaction conditions is reported. The reaction, which proceeds under weak alkaline condition, allows for the conversion of a range of aldoximes including aromatic aldoximes, alphatic aldoximes, and heterocyclic aldoximes in good to excellent yields. This method has also been successfully applied to the synthesis of calcium channel blocker nilvadipine in pilot scale.
- Song, Yaoping,Shen, Dongguo,Zhang, Qinghua,Chen, Bo,Xu, Guangyu
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p. 639 - 641
(2014/01/23)
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- Direct synthesis of nitriles from aldehydes using chloramine-T/KI in aqueous ammonia
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A convenient method for direct conversion of aldehydes into nitriles has been developed using chloramine-T/KI in aqueous ammonia.
- Zhu, Yi-Zhong,Zhang, Xi-Quan,Liu, Fei,Gu, Hong-Mei,Zhu, Hai-Liang
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supporting information
p. 2943 - 2948
(2013/09/02)
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- Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage
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Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright
- Shen, Tao,Wang, Teng,Qin, Chong,Jiao, Ning
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supporting information
p. 6677 - 6680
(2013/07/25)
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- Rhodium-cobalt bimetallic nanoparticles: A catalyst for selective hydrogenation of unsaturated carbon-carbon bonds with hydrous hydrazine
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Our studies on the effect of metal compositions on the catalytic activity of the rhodium-based bimetallic nanocatalysts revealed that the nanoparticles with a 4:1 ratio of rhodium to cobalt, were more active than the rhodium monometallic nanoparticles in the selective hydrogenation of unsaturated carbon-carbon bonds with hydrous hydrazine as a hydrogen source. The nanocatalysts effected this hydrogenation process in good-to-excellent yields with high functional group tolerance, and could be reused 10 times without the loss of catalytic activity. The catalyst characterization by X-ray photoelectron spectroscopy, transmission electron microscopy and line-scanning analysis suggested that the coexistence of metallic rhodium and cobalt plays an important role in the enhancement of catalytic activity. Copyright
- Lin, Jin,Chen, Jing,Su, Weiping
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supporting information
p. 41 - 46
(2013/03/14)
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- Molecular iodine in aqueous ammonia: Oxidative fragmentation of oxiranes to nitriles
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Oxiranes undergo oxidative fragmentation, when treated with iodine in aqueous ammonia, to give nitriles. The reaction goes via formation of 1,2-amino alcohols as intermediates followed by CC bond cleavage. Advantages of the method are use of off-the-shelf nonexplosive, unlike previously used potentially explosive o-iodoxybenzoic acid, reagents, mild reaction conditions, and easy work-up procedure.
- Jadhav, Ravindra R.,Akamanchi, Krishnacharya G.
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p. 162 - 164
(2013/03/28)
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- One pot synthesis of nitriles from aldehydes and hydroxylamine hydrochloride using ferrous sulphate in DMF under reflux condition
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A rapid and facile one pot synthesis of nitrile has been carried out in high yields from the corresponding aldehydes and hydroxylamine hydrochloride in the presence of anhydrous ferrous sulphate and DMF under reflux condition.
- Patil, Dinanath D.,Wadhava, Gurumeet C.,Deshmukh, Arun K.
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experimental part
p. 1401 - 1402
(2012/08/28)
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- Selective conversion of aldehydes into nitriles and primary amides in aqueous media
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A simple and selective conversion of aldehydes into the corresponding nitriles and primary amides in aqueous ammonia has been developed. The aldehydes were efficiently converted to the corresponding nitriles in moderate to excellent yields using tetrabutylammonium iodide/tert-butyl hydroperoxide system. The primary amides, however, can be selectively synthesised only in the presence of tert-butyl hydroperoxide.
- Wang, Liang,Shen, Chen,Wang, Hai-Ping,Zhou, Wei-You,Sun, Fu-An,He, Ming-Yang,Chen, Qun
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p. 460 - 462
(2012/10/29)
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- 8-Bromocaffeine (8-BC): A new versatile reagent for conversion of aldoximes into nitriles
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A rapid and highly convenient synthesis of nitriles from the corresponding aldoximes using 8-bromocaffeine (8-BC) is described. In this protocol, aldoximes react with 8-BC in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and N,N-dimethylformamide (DMF) to furnish the corresponding nitriles under both microwave-assisted and/or conventional heating (reflux) conditions in short times and in good to excellent yields. This methodology is highly efficient for structurally diverse aldoximes including aliphatic, aromatic, and heteroaromatic oximes. Georg Thieme Verlag Stuttgart · New York.
- Soltani Rad, Mohammad Navid,Behrouz, Somayeh,Nekoei, Abdo-Reza
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experimental part
p. 1191 - 1198
(2012/06/04)
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- Vapor-phase Beckmann rearrangement of cyclohexanone oxime over halide cluster catalysts
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When a silica gel-supported tungsten halide cluster with an octahedral metal framework, (H3O)2[(W6Cl 8)Cl6]·6H2O/SiO2, is treated in a helium stream in the temperature range 250-350 °C, catalytic activity for the Beckmann rearrangement of cyclohexanone oxime develops. Niobium and tantalum clusters with the same metal framework also catalyze the reaction. Cyclopentanone oxime and acetone oxime also undergo Beckmann rearrangements over the tungsten cluster. The weak Br?nsted acidity (H0 ≈ +1.5) of the hydroxo ligand, which is developed on the activated cluster, is favorable for the rearrangement.
- Nagashima, Sayoko,Kamiguchi, Satoshi,Ohguchi, Satoshi,Chihara, Teiji
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experimental part
p. 135 - 138
(2012/02/03)
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- Oxidative fragmentation of oxiranes to nitriles with hypervalent iodine(V) reagents in aqueous ammonia
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Oxiranes undergo oxidative fragmentation when treated with hypervalent iodine(V) reagents particularly o-iodoxybenzoic acid in aqueous ammonia to give nitriles. The reaction goes via the formation of 1, 2-amino alcohols as intermediates followed by C-C bond cleavage.
- Deshmukh, Swapnil S.,Huddar, Sameerana N.,Jadhav, Ravindra R.,Akamanchi, Krishnacharya G.
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experimental part
p. 4533 - 4536
(2011/09/20)
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- A one-pot conversion of carboxylic acids into nitriles catalysed by PEG400 under microwave irradiation
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A new efficient method for the synthesis of nitriles is reported. Carboxylic acids were converted into nitriles by a onepot reaction with hydroxylamine sulfate and zinc catalysed by PEG400 under microwave irradiation in excellent yields. The most suitable condition was 20 minutes under the microwave power of 231 W with 5 mol% PEG400.
- Cao, Yu-Qing,Qu, An-Li,Liu, Rui-Yan,Duan, Chun-Ming
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experimental part
p. 414 - 415
(2010/12/19)
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- Direct synthesis of nitriles from aldehydes using tetrabutylammonium tribromide in aqueous ammonia
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A convenient method for direct conversion of aldehydes into nitriles has been developed by using tetrabutylammonium tribromide in aqueous ammonia. Springer-Verlag 2010.
- Zhu, Yi-Zhong,Cai, Chun
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experimental part
p. 637 - 639
(2011/04/25)
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- Novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and [bis(trifluoroacetoxy)iodo]benzene
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A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and trivalent hypervalent iodine reagent, [bis(trifluoroacetoxy)iodo]benzene, at room temperature is discussed. Advantages of this system are short reaction time, easy workup, and moderate to good yields. Copyright Taylor & Francis Group, LLC.
- Telvekar, Vikas N.,Rane, Rajesh A.,Namjoshi, Tejal V.
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experimental part
p. 494 - 497
(2010/04/04)
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- The influence of carbon laydown on selectivity in the hydrogenation of pentenenitriles over supported-nickel catalysts
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Pentenenitriles contain two-reducible functionalities: a carbon-carbon double bond and a nitrile group, either of which may undergo hydrogenation during reaction. In this work we show how the deposition of hydrocarbonaceous material on the catalyst surface during pentenenitrile hydrogenation over 16 wt.% Ni/Al2O3 and 10 wt.% Ni/SiO2 catalysts has a significant impact on the observed catalytic activity and selectivity. The role of carbon laydown in controlling catalytic performance in this system has been evaluated through activity measurements and mechanistic studies employing a Tapered Element Oscillating Microbalance (TEOM) and a conventional flow-through reactor. TEOM data indicating the deposition of carbonaceous material during reaction are correlated with kinetic analysis which provides a description of catalyst deactivation in terms of the deactivation of groups of active sites. Specifically five distinct active sites are shown to exist on Ni/Al 2O3 including a hydrogenation site on the support, which is not present in the case of Ni/SiO2. The nature and strength of these sites are discussed. Furthermore, deuteration studies provide mechanistic insights suggesting that the hydrogenation reaction proceeds via a cyclic intermediate. The reported data identify a correlation between mass laydown on specific active sites and deactivation, thereby demonstrating the influence of hydrocarbonaceous deposits on selectivity. Both the location and the nature of such deposits are crucial in determining its influence on reaction.
- McGregor, James,Canning, Arran S.,Mitchell, Scott,Jackson, S. David,Gladden, Lynn F.
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experimental part
p. 192 - 200
(2010/11/17)
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- Oxidation of amidoximes with IBX and IBX/TEAB
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Biologically important process of oxidation of amidoximes has been investigated using IBX (oiodoxybenzoic acid) and combination of IBX with TEAB (tetraethylammonium bromide). The reaction proceeds with high % conversion leading to selective formation of amide and nitrile depending upon the combination of reagents. ARKAT USA, Inc.
- Deshmukh, Swapnil S.,Huddar, Sameerana N.,Bhalerao, Dinesh S.,Akamanchi, Krishnacharya G.
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experimental part
p. 118 - 126
(2010/09/05)
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- Oxidation of amines over alumina based catalysts
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Amines were oxidized by molecular oxygen in the vapor phase at atmospheric pressure over alumina and silicotungstic acid/alumina catalysts. The study is focused on the influence of structure of amine and catalyst properties on the composition of the main reaction products and byproducts. Coating of γ-Al2O3 with silicotungstic acid or its semisalt can significantly enhance its catalytic activity in amine oxidation. The adsorption of amine on weak acidic sites of catalyst is essential for its oxidation to main reaction products. Cycloalkylamines are oxidized mainly to cyclic oximes (selectivity up to 64%) and Schiff bases of appropriate cycloalkanone and cycloalkylamine (selectivity up to 38%). Mainly nitriles (selectivity up to 55%) and appropriate Schiff bases (selectivity up to 54%) were observed in the oxidation products of primary alkylamines. Their molar ratio depends on the catalyst acidity and reaction conditions. 1,6-Hexanediamine is oxidized mainly to caprolactam (yield 48%) and other cyclic lactames and Schiff bases as well as to dinitrile (yield 13%).
- Rakottyay, Karol,Kaszonyi, Alexander,Vají?ek, Stanislav
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experimental part
p. 33 - 41
(2010/08/22)
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- Simple and highly efficient procedure for conversion of aldoximes to nitriles using N-(p-Toluenesulfonyl) imidazole
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A facile and efficient method for dehydration of aldoximes into nitriles using N-(p-toluenesulfonyl) imidazole (TsIm) is described. In this method, aldoximes were refluxed with TsIm in the presence of 1,8-diazabicyclo-[5.4.0] undec-7-ene (DBU) in dimethylformamide (DMF) to afford the corresponding nitriles in good yields. This methodology is highly efficient for various structurally diverse aldoximes including aromatic, heteroaromatic, and aliphatic oximes. A plausible mechanism for the conversion of aldoxime into nitriles using TsIm/DBU is explained. Copyright Taylor & Francis Group, LLC.
- Rad, Mohammad Navid Soltani,Khalafi-Nezhad, Ali,Behrouz, Somayeh,Amini, Zohreh,Behrouz, Marzieh
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experimental part
p. 2429 - 2440
(2010/09/05)
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- Bromodimethylsulfonium bromide (BDMS): a useful reagent for conversion of aldoximes and primary amides to nitriles
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An operationally simple and high yielding procedure has been developed for the preparation of nitriles from aldoximes and primary amides using bromodimethylsulfonium bromide (BDMS) as a novel and efficient reagent in the absence of any added base or catal
- Yadav, Lal Dhar S.,Srivastava, Vishnu P.,Patel, Rajesh
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experimental part
p. 5532 - 5535
(2010/01/11)
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