cas 626-17-5, 1,3-Dicyanobenzene | Articles data

Articles about 626-17-5Total 98 be found

Article title
Article abstract
Author
Journal number and time
Download

Catalytic activity of vanadium-substituted molybdophosphoric acid supported on titania for the vapor-phase synthesis of isophthalonitrile
Different wt% of vanadium-substituted molybdophosphoric acid H4PMo11VO40 loaded on titania (TiO2) are prepared by wet impregnation method. The catalytic activity of PMoV-supported titania catalyst for the vapor-phase ammoxidation of m-xylene at different temperatures is reported here. The synthesized catalysts were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, N2 adsorption–desorption, thermogravimetric/differential thermal analysis, temperature programmed desorption (TPD), temperature programmed reduction (TPR) scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX), and transmission electron microscopy?(TEM). FTIR studies confirmed that the Keggin structure of PMoV does not change even up to 460°C when loaded on TiO2 surface. Among all the PMoV-supported TiO2 catalysts, 1.7% PMoV/TiO2 showed excellent activity for vapor-phase ammoxidation of m-xylene with 85.4% yield of isophthalonitrile.
Senapati,Dutta,Rana, Surjyakanta,Parida,Sahu,Sarkar
p. 1429 - 1435
(2017)
Read Online

Nitrile Synthesis via Desulfonylative-Smiles Rearrangement
Herein, we designed a simple nitrile synthesis from N-[(2-nitrophenyl)sulfonyl]benzamides via base-promoted intramolecular nucleophilic aromatic substitution. The process features redox-neutral conditions as well as no requirement of toxic cyanide species and transition metals. Our process shows broad scope and various functional group compatibility, affording a variety of (hetero)aromatic nitriles in good to excellent yields.
Abe, Masahiro,Nitta, Sayasa,Miura, Erina,Kimachi, Tetsutaro,Inamoto, Kiyofumi
p. 4460 - 4467
(2022/03/15)

Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
Pd(OAc)2/XPhos–SO3Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly efficient catalyst for the cyanation of aryl chlorides with potassium ferrocyanide. The reaction proceeded smoothly at 100 or 120?oC with K2CO3 or KOAc as base, delivering a variety of aromatic nitriles in good to excellent yields. The isolation of the crude products is facilely performed by extraction with cyclohexane and more importantly, both expensive Pd(OAc)2 and XPhos–SO3Na in PEG-400/H2O system could be easily recycled and reused at least six times without any apparent loss of catalytic efficiency. Graphical Abstract: Palladium-catalyzed cyanation of aryl chlorides with potassium ferrocyanide leading to aryl nitriles by using Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O as a highly efficient and recyclable catalytic system is described.[Figure not available: see fulltext.]
Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
(2021/12/03)

Thermally stable imidazole/heteropoly acid composite as a heterogeneous catalyst for m-xylene ammoxidation
Ammoxidation of m-xylene is evaluated in the presence of a customized heteropoly acid catalyst as an imidazole/molybdovanadophosphoric acid (imidazole/PMoV). Imidazole is employed to maintain its heterogeneous phase during the ammoxidation reaction and to provide the thermal stability of PMoV with the expectation that imidazole can generate strong electronic interactions with terminal molybdenum-oxygen on PMoV. The characterizations of the prepared catalysts are performed using SEM–EDX, XRD, FT-IR, Raman, XPS, and TGA to prove the physical and chemical changes by incorporating imidazole to PMoV, respectively. Also, the thermal stability of the developed catalyst is confirmed by the means of heat treatment test at relatively high temperature. The composite catalyst, imidazole/PMoV, shows an excellent conversion rate of over 98% with high selectivity of isophthalonitrile in m-xylene ammoxidation. Moreover, while the imidazole-free PMoV catalyst is deactivated and washed out during the reaction, the catalyst durability of the imidazole/PMoV is preserved without significant activity loss after 5 reaction cycles at 380 °C.
Jeon, Yukwon,Lee, Chanmin,Lee, Gicheon,Kwon, Ohchan,Kim, Jinsol,Park, Sang Sun,Oh, Kyeongseok,Shul, Yong-Gun
p. 287 - 302
(2021/02/02)

Visible-Light-Promoted Metal-Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)?H Bonds**
The metal-free activation of C(sp3)?H bonds to value-added products is of paramount importance in organic synthesis. We report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as l-menthol, amino acids, and cholesterol derivatives. Furthermore, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments, and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.
Murugesan, Kathiravan,Donabauer, Karsten,K?nig, Burkhard
supporting information
p. 2439 - 2445
(2020/12/07)

Nickel-Catalyzed Cyanation of Aryl Thioethers
A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
supporting information
p. 7018 - 7022
(2021/09/13)

METHOD FOR PREPARING PHTHALONITRILE COMPOUND
One embodiment of the present invention relates to a method for preparing a phthalonitrile-based compound, including the steps of: (a) preparing a mixture including a phthalic acid-based compound and a nitrile-based compound; and (b) reacting the mixture, wherein the step (b) is performed under supercritical conditions of the nitrile-based compound.
-
Paragraph 0042-0049

(2021/08/17)

An overview on the progress and development on the palladium catalyzed direct cyanation
Generation of the positive CN ion and the corresponding direct cyanation are both extremely important for cyanation of aromatic compounds. Hereby, we would like to report the simultaneous use of the new Pd nano-catalyst as well as the three types of the N-arylsulfonyl cyanamides (A, B and C) as potent reagents for the in situ generation of the positive CN ion for the direct cyanation of phenylboronic acids in acetonitrile at reflux conditions.
Heydari, Somayyeh,Habibi, Davood,Reza Faraji, Ali,keypour, Hassan,Mahmoudabadi, Masoumeh
(2020/10/02)

A Versatile VMPO Catalyst Prepared In Situ for Oxidative Ammonolysis of Isomeric Picolines and Xylenes
Abstract: The V2O5–MoO3–P2O5 (VMPO) catalyst has been prepared in situ by thermal decomposition of vanado-molybdophosphoric acid (PMoV) on TiO2 support at 475°C. The TiO2 supported VMPO catalysts are characterized by FT–IR, XRD, BET surface area, NH3–TPD, and H2–TPR. Morphology of the catalyst has been studied by TEM. The accumulated data indicate decomposition of PMoV and presence of phosphate and pyrophosphate phases of molybdenum and vanadium after calcination. TPD and TPR studies exhibit the moderate acidity and presence of V4+ in the material, respectively. The VMPO catalyst has been used for ammoxidation of six different compounds including three isomeric picolines and three isomeric xylenes to the corresponding nitriles with the yield of 90–96%.
Dutta, P.,Pathak, D. D.,Senapati, Rabinarayan
p. 292 - 298
(2020/04/17)

Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy
Nickel-catalyzed transformation of alkene-tethered oxime ethers to nitriles using a traceless directing group strategy has been developed. A series of alkene-tethered oxime ethers derived from benzaldehyde and cinnamyl aldehyde derivatives were converted into the corresponding benzonitriles and cinnamonitriles in 46-98% yields using the nickel catalyst system. Control experiments showed that the alkene group tethered to an oxygen atom on the oximes via one methylene unit plays a key role as a traceless directing group during the catalysis.
Takahashi, Yoshiyuki,Tsuji, Hiroaki,Kawatsura, Motoi
p. 2654 - 2665
(2020/02/04)

Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
(2020/08/19)

Organic molecular material based on benzene ring unit and having long-afterglow effect and preparation method thereof
The invention discloses an organic molecular material based on benzene ring unit and having long-afterglow effect and a preparation method thereof. The structural formula of the organic material is represented as the specification, wherein Y1 to Y4 are respectively one or two of hydrogen atom and cyano group. By introducing the cyano groups in different number to different sites as electron withdrawing groups, the material has high synthetic efficiency and small molecule. When an excitation source is turned off, the material holds durable luminescence for a couple of seconds and has high fluorescent quantum efficiency. The material has an extensive potential application value in the fields such as anti-counterfeiting, bio-imaging, optic-electronic materials and the like.
-
Paragraph 0048-0052

(2020/04/17)

Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
p. 1397 - 1405
(2020/02/04)

Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
Fang, Wan-Yin,Qin, Hua-Li
p. 5803 - 5812
(2019/05/14)

A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
supporting information
p. 3190 - 3194
(2019/05/21)

Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
supporting information
p. 19257 - 19262
(2019/12/02)

One-Pot Anodic Conversion of Symmetrical Bisamides of Ethylene Diamine to Unsymmetrical gem-Bisamides of Methylene Diamine
Symmetrical bisamides of ethylene diamine of type ArCONHCH2CH2NHCOAr undergo anodic C-C bond cleavage in acetonitrile-LiClO4 under controlled-potential electrolysis. The electrogenerated carbocation intermediates react with the solvent acetonitrile to afford unsymmetrical gem-bisamides of type ArCONHCH2NHCOMe in a one-pot reaction. The yields of the latter products are moderate (up to 60%). Other minor products involve two symmetrical gem-bisamides of type ArCONHCH2NHCOAr and MeCONHCH2NHCOMe and fragmentation products (e.g., ArCONHCHO, ArCONH2, and ArCN).
Golub, Tatiana,Dou, Gui-Yuan,Zeng, Cheng-Chu,Becker, James Y.
supporting information
p. 7961 - 7964
(2019/10/11)

Biosynthesis of Pd/MnO2 nanocomposite using Solanum melongena plant extract and its application for the one-pot synthesis of 5-substituted 1H-tetrazoles from aryl halides
In this work, for the first time, Solanum melongena plant extract was used for the green synthesis of Pd/MnO2 nanocomposite via reduction osf Pd(II) ions to Pd(0) and their immobilization on the surface of manganese dioxide (MnO2) nanoparticles (NPs) as an effective support. The synthesized nanocomposite were characterized by various analytical techniques such as Fourier transform infrared (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and UV–Vis spectroscopy. The catalytic activity of Pd/MnO2 nanocomposite was used as a heterogeneous catalyst for the one-pot synthesis of 5-substituted 1H-tetrazoles from aryl halides containing various electron-donating or electron-withdrawing groups in the presence of K4[Fe (CN)6] as non-toxic cyanide source and sodium azide. The products were obtained in good yields via a simple methodology and easy work-up. The nanocatalyst can be recycled and reused several times with no remarkable loss of activity.
Nasrollahzadeh, Mahmoud,Ghorbannezhad, Fatemeh,Sajadi, S. Mohammad
(2018/12/14)

Corresponding amine nitrile and method of manufacturing thereof
The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
-
Paragraph 0132; 0133; 0134; 0136; 0140

(2018/05/24)

HETEROGENEOUS COPPER-CATALYZED AEROBIC OXIDATIVE CONVERSION OF AROMATIC ALDEHYDES TO CORRESPONDING NITRILES
The present invention relates to a method of aerobic oxidative converting aromatic aldehyde to nitrile. More specifically, the present invention relates to a method of aerobic oxidative conversion of an aromatic aldehyde to nitrile using a heterogeneous copper catalyst, and optimization of reaction conditions applied thereto. The method can obtain nitrile at high yield with respect to various substrates by synthesizing nitrile, e.g., benzonitrile from aromatic aldehyde, e.g., benzaldehyde and an ammonia source, e.g., ammonia water under an oxygen condition by using TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and a heterogeneous copper catalyst (Cu@C) obtained by pyrolyzing HKUST-1, i.e., a type of a metal-organic framework, and enables the heterogeneous copper catalyst to be reused at least three or more times without significant loss of catalytic activities since the heterogeneous copper catalyst maintains structure thereof even under the presence of the ammonia source.COPYRIGHT KIPO 2018
-
Paragraph 0090-0110; 0134; 0135

(2018/07/31)

HETEROGENEOUS COPPER-CATALYZED AEROBIC OXIDATIVE CONVERSION OF ALCOHOLS TO CORRESPONDING NITRILES
The present invention refers to a method relates to knight reel aerobic oxidation conversion to alcohol (Aerobic oxidative conversion), metal - organic framework is provided electromagnetic wave is pyrolytically cracking using non-uniform copper catalyst (Cu ? C) and TEMPO HKUST-a 1, alcohol (e.g., benzyl alcohol) aromatic aldehyde (e.g., benzaldehyde) aromatic 1 difference after conversion into ammonia source (e.g., ammonia) manner won - port (One-a pot) aromatic aldehydes (e.g., benzo knight reel) added into knight reel by switching, high yield various substrate results in obtaining uniform copper catalyst in the presence of ammonia source knight reel and said holding structure even a significant catalyst activity may be reused without loss to at least 3 or more times, using alcohol knight reel aerobic to non-uniform copper catalyzed oxidative cycle, and applied to the optimization of the reaction conditions are disclosed. (by machine translation)
-
Paragraph 0115-0124; 0155; 0181

(2018/10/03)

Corresponding amine nitrile and method of manufacturing thereof
The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
-
(2018/05/24)

Immobilization of an Aminobisphosphine–PdII Complex over Graphene Oxide: An Efficient and Reusable Catalyst for Suzuki–Miyaura, Ullmann Coupling and Cyanation Reactions
The grafting of an aminobis(phosphine)–PdII complex (PNP–PdII) [PdCl2{(Ph2P)2N(CH2)3Si(OMe)3}] (2) on graphene oxide (GO) has been carried out by a condensation reaction between methoxysilane groups of 2 and hydroxyl groups of GO. The composite material was characterized by FTIR spectroscopy, solid-state 31P NMR spectroscopy, SEM, TEM, XPS and ICP-AES techniques. All these tools support the clean immobilization of compound 2 on GO. The composite material showed high catalytic activity in Suzuki–Miyaura, Ullmann coupling and cyanation reactions. The heterogeneity of the composite was confirmed by a hot filtration test. The immobilized PNP–PdII shows comparable activity to its homogeneous analogue 2. The recycling ability of the catalyst was examined for five consecutive runs, which showed little or no reduction in its catalytic efficiency.
Sengupta, Debasish,Pandey, Madhusudan K.,Mondal, Dipanjan,Radhakrishna, Latchupatula,Balakrishna, Maravanji S.
p. 3374 - 3383
(2018/05/08)

A method for producing methyl benzoic acid, methyl benzonitrile and phthalonitrile method (by machine translation)
The invention discloses a method for producing methyl benzoic acid, methyl benzonitrile and phthalonitrile method, including: (1) to the oxidation reactor is injected continuously xylene, catalyst and an oxygen-containing gas to the reaction, oxidation reaction solution obtained; (2) the oxidation reaction solution into the initial steaming tower to separate rectification, when methyl methanol content in the [...] 0.01 - 0.15 wt % stop rectification, a low boiling point component and [...]; (3) will be [...] enter the rectifying tower for rectification, when the rectifying tower in [...] methyl benzoic acid content of 30 - 90 wt % stop rectification, to obtain the methyl benzoic acid products and rectifying tower [...]; (4) the spiral [...] mixed with ammonia, nitrile reaction solution obtained; (5) the nitrile reaction liquid to separate rectification, to respectively obtain the methyl benzonitrile and phthalonitrile product. The invention has simple process, equipment investment, environmental protection, integrated and good economic benefits. (by machine translation)
-
Paragraph 0121-0171

(2018/12/13)

Catalytic Cyanation Using CO2 and NH3
Li and co-workers describe the catalytic cyanation of organic halides with CO2 and NH3. In the presence of Cu2O/DABCO as the catalyst, a variety of aromatic bromides and iodides were transformed to the desired nitrile products with broad functional-group tolerance. Both 13C- and/or 15N-labeled nitriles were obtained conveniently with appropriately isotope-labeled CO2 and NH3. Construction of functionalized chemical compounds from small molecules in a highly selective and efficient manner is crucial for sustainable development. The chemical-based manufacturing sector of the future should aim to produce chemicals from very simple and abundant resources, just as nature uses CO2 and N2 to generate sugars, amino acids, and so forth. In practice, however, the utilization of CO2 for the generation of industrial products, such as drugs and related intermediates, still remains a major challenge. Here, we describe the facile cyanide-free production of high-value nitriles with CO2 and NH3 as the sole sources of carbon and nitrogen, respectively. This practical and catalytic methodology provides a unique strategy for the utilization of small molecules for sustainable and cost-effective applications. Selective cyanation of aryl halides was achieved with CO2 and NH3 as the only sources of carbon and nitrogen, respectively. In the presence of Cu catalysts under low pressure (3 atm), a variety of aromatic iodides and bromides were transformed to the desired nitrile products without the use of toxic metal cyanides. Notably, olefins, esters, amides, alcohols, and amino groups were tolerated. Mechanistic studies suggest that Cu(III)-aryl insertion by isocyanate intermediates is involved. [13C,15N]-labeled nitriles were conveniently accessible from the respective isotope-labeled CO2 and NH3 via this methodology.
Wang, Hua,Dong, Yanan,Zheng, Chaonan,Sandoval, Christian A.,Wang, Xue,Makha, Mohamed,Li, Yuehui
supporting information
p. 2883 - 2893
(2019/01/05)

Nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine
A nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine (TCT) using aminoacetonitrile as the cyanating agent is described. This catalytic system delivered the desired products in moderate to good yields with good substrate compatibility. The readily available starting materials, cost-effective nickel catalyst and metal-free cyanating agent are the major features of the present method.
Wang, Liang,Wang, Yaoyao,Shen, Jun,Chen, Qun,He, Ming-Yang
supporting information
p. 4816 - 4820
(2018/07/13)

Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues
The use of Pd(DPEPhos)Cl2 (P26) as a catalyst for the formation of benzonitriles and their heterocyclic analogues provides excellent complementarity to existing catalysts, allowing highly electron-deficient heterocyclic aryl halides to be effic
Richardson, Jeffery,Mutton, Simon P.
p. 4922 - 4931
(2018/05/22)

Pd-Catalyzed Cyanation of (Hetero)Aryl Halides by Using Biphosphine Ligands
Tetraadamantylbiphosphine (TABP; L1), which showed superior activity in the palladium-catalyzed cyanation of 4-chloroanisole compared to standard phosphines, was synthesized as a new ligand. The generality of the new catalytic system was shown by the cyanation reaction of approximately 30 (hetero)aryl halides including hindered, electron-rich, and electron-poor aryl chlorides. These reactions constitute the first examples of using biphosphine ligands in Pd-catalyzed coupling reactions.
Zhang, Shaoke,Neumann, Helfried,Beller, Matthias
supporting information
p. 67 - 70
(2017/11/27)

Corresponding amine nitrile and method of manufacturing thereof (by machine translation)
The invention relates to a method of manufacturing one kind of nitrile, compared with the prior art, has significantly reduced the amount of ammonia, the environmental pressure of the small, low energy consumption, low production cost, nitrile product purity and yield and the like, and can obtain more complex structure of the nitriles. The invention also relates to the corresponding amine by the nitrile manufacture method. (by machine translation)
-
Paragraph 0134; 0140-0141

(2017/10/22)

Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate
An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH4OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.
Kim, Myeong Jin,Mun, Junyoung,Kim, Jinho
supporting information
p. 4695 - 4698
(2017/11/17)

AEROBIC OXIDATIVE CONVERSION OF AROMATIC ALDEHYDES TO NITRILES USING A NITROXYL/NOx CATALYST SYSTEM
The present invention relates to an aerobic oxidative conversion method for converting aromatic aldehydes into nitriles and, more particularly to, an aerobic oxidative conversion method for converting aromatic aldehydes into nitriles using a nitroxyl/NO_x catalyst system, which replaces an existing transition metal by converting aromatic aldehydes into nitriles through the oxidative conversion under oxygenic conditions by using a non-metal catalyst system including nitroxyl and NO_x to selectively acquire high-yield nitriles with respect to various substrates and meet the green chemistry, and optimization of reaction conditions applied thereto.COPYRIGHT KIPO 2017
-
Paragraph 0113; 0114

(2017/11/08)

Photoinduced Copper(I)-Catalyzed Cyanation of Aromatic Halides at Room Temperature
The first photoinduced copper(I)-catalyzed cyanation of aromatic halides at room temperature has been developed. The sp2 cyanation reaction exhibits outstanding tolerance to functional groups including primary amines and carboxylic acids, and chemoselectivity to SN2-reactive alkyl chlorides. Mechanistic investigations indicate that the reaction occurs via a single-electron transfer (SET) between the aryl halide and an excited copper(I) cyanide catalytic intermediate. (Figure presented.).
Kim, Kicheol,Hong, Soon Hyeok
supporting information
p. 2345 - 2351
(2017/07/22)

Pd Catalysis in Cyanide-Free Synthesis of Nitriles from Haloarenes via Isoxazolines
A method to obtain aryl nitriles from the corresponding halides by Pd catalysis, in the absence of any cyanide source, is reported. The reaction of an aryl halide, ethyl nitroacetate, and an olefin readily delivers an aromatic nitrile. A variety of aryl iodides/bromides have been converted into the corresponding cyanoarenes in fair to excellent yields. The reaction likely involves the following steps: (a) Pd-catalyzed α-arylation of ethyl nitroacetate; (b) nitrile oxide formation; (c) [3 + 2]-cycloaddition with an olefin to provide an isoxazoline; (d) isoxazoline cleavage to benzonitrile formation.
Maestri, Giovanni,Ca?eque, Tatiana,Della Ca, Nicola,Derat, Etienne,Catellani, Marta,Chiusoli, Gian Paolo,Malacria, Max
supporting information
p. 6108 - 6111
(2016/12/09)

Aryl Nitriles from Alkynes Using tert -Butyl Nitrite: Metal-Free Approach to C≡C Bond Cleavage
Alkyne C≡C bond breaking, outside of alkyne metathesis, remains an underdeveloped area in reaction discovery. Recently, nitrogenation has been reported to allow nitrile formation from alkynes. A new protocol for the metal-free C≡C bond cleavage of terminal alkynes to produce nitriles is reported. This method provides an opportunity to synthesize a vast range of nitriles containing aryl, heteroaryl, and natural product derivatives (38 examples). In addition, the potential of tBuONO to act as a powerful nitrogenating agent for terminal aryl alkynes is demonstrated. (Figure Presented).
Dutta, Uttam,Lupton, David W.,Maiti, Debabrata
supporting information
p. 860 - 863
(2016/03/01)

Synthesis of 5-substituted 1H-tetrazoles from aryl halides using nanopolymer-anchored palladium(II) complex as a new heterogeneous and reusable catalyst
Abstract: This paper reports on the preparation and use of chloromethylated polystyrene-anchored palladium(II) complex, [Ps-ttet-Pd(II)], as a separable nanocatalyst for the synthesis of 5-substituted 1H-tetrazoles by treating aryl halides with K4[Fe(CN)6] as non-toxic cyanide source, to generate in situ the corresponding aryl nitriles which then react through [2?+?3] cycloaddition with sodium azide. High yields of the products, simple methodology, easy work-up procedure, high catalytic activity, and superior cycling stability of the catalyst are the main advantages of this protocol. The structure of the catalyst was characterized using the powder XRD, SEM, TG-DTA, EDS, AAS, and FT-IR spectroscopy techniques. Graphical abstract: [Figure not available: see fulltext.]
Tajbakhsh, Mahmood,Alinezhad, Heshmatollah,Nasrollahzadeh, Mahmoud,Kamali, Taghi A.
p. 2135 - 2142
(2016/11/17)

Palladium/N-Heterocyclic carbene catalyzed mono- and double-cyanation of aryl halides using potassium ferrocyanide trihydrate under aerobic conditions
Abstract A practical palladium/N-heterocyclic carbene catalyzed procedure for the mono- and double-cyanation of aryl halides is described using inexpensive, easy-to-handle and nontoxic potassium ferrocyanide trihydrate {K4[Fe(CN)6]·3H2O} as the cyanating agent. The reaction does not require an anhydrous solvent, or the exclusion of air or moisture. A variety of electron-rich and electron-deficient aryl halides are efficiently converted into their corresponding nitriles and dicarbonitriles.
Xu, Zhicheng,Xiao, Yunqing,Ding, Hong,Cao, Changsheng,Li, Haitao,Pang, Guangsheng,Shi, Yanhui
p. 1560 - 1566
(2015/06/02)

An aerobic oxidative synthesis of aryl nitriles and primary aryl amides from benzylic alcohols catalyzed by a polymer supported Cu(II) complex
A new polymer supported Cu(II) complex has been synthesized and characterized. The catalytic performance of the complex has been tested for the direct conversion of benzylic alcohols to aryl nitriles. In this reaction ammonium formate was used as the nitrogen source and O2 as the oxidant. Furthermore, the copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved. The effects of solvents, reaction time and catalyst amount for the aryl nitriles and aryl amides synthesis were reported. This catalyst showed excellent catalytic activity and recyclability. The polymer supported Cu(II) catalyst could be easily recovered by filtration and reused more than five times without appreciable loss of its initial activity.
Molla, Rostam Ali,Ghosh, Kajari,Tuhina,Manirul Islam
p. 921 - 930
(2015/02/19)

Aerobic Oxidative Conversion of Aromatic Aldehydes to Nitriles Using a Nitroxyl/NOx Catalyst System
The first transition-metal-free aerobic oxidative conversion of aldehyde catalyzed by a nitroxyl radical/NOx system is presented for the synthesis of nitrile. In the presence of a catalytic amount of 4-AcNH-TEMPO (4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl), NaNO2, and HNO3, benzaldehydes bearing a variety of functional groups underwent condensation with NH4OAc and following aerobic oxidation to produce nitriles selectively under an O2 balloon. Aerobic oxidative conversion of a primary alcohol instead of aldehyde is also achieved by a one-pot sequential strategy.
Noh, Ji-Hyun,Kim, Jinho
p. 11624 - 11628
(2015/12/01)

Mild palladium-catalyzed cyanation of (hetero)aryl halides and triflates in aqueous media
A mild, efficient, and low-temperature palladium-catalyzed cyanation of (hetero)aryl halides and triflates is reported. Previous palladium-catalyzed cyanations of (hetero)aryl halides have required higher temperatures to achieve good catalytic activity. This current reaction allows the cyanation of a general scope of (hetero)aryl halides and triflates at 2-5 mol % catalyst loadings with temperatures ranging from rt to 40 °C. This mild method was applied to the synthesis of lersivirine, a reverse transcriptase inhibitor.
Cohen, Daniel T.,Buchwald, Stephen L.
supporting information
p. 202 - 205
(2015/01/30)

Ammoxidation of 2-picoline catalyzed by modified V2O 5/TiO2
A vanadium-titanium catalyst was used in the preparation of aromatic nitriles by ammoxidation in a fixed-bed reactor. The catalyst prepared by the mixing method showed high conversion (91 %) and selectivity (95 %) in the ammoxidation of 2-picoline. The effect of varied conditions on the ammoxidation of 2-picoline was also explored, including LHSV, H2O/NH3 molar ratio, reaction temperature, and the catalyst calcination temperature. This catalyst was also used in the ammoxidation of 3-picoline, 4-picoline, and toluene derivatives.
Pan, Jiong-Bin,Huang, Jia-Min,Li, Jia-Xu,Jiang, Zeng-Yang,Lan, Jia-Long,Qian, Chao,Chen, Xin-Zhi
p. 1365 - 1369
(2014/07/22)

One-pot transformation of methylarenes into aromatic nitriles with inorganic metal-free reagents
Various methylarenes were transformed into the corresponding aromatic nitriles in good to moderate yields by the treatment with aq. HBr and aq. H 2O2, followed by reaction with molecular iodine and aq. ammonia in a one-pot procedure. The present reaction is a useful, practical, transition-metal-free, and organic-reagent-free method for the preparation of aromatic nitriles from methylarenes. Various methylarenes were treated with aq. HBr and aq. H2O2 under warming conditions and/or irradiation conditions, followed by the reaction with molecular iodine and aq. ammonia, to provide the corresponding aromatic nitriles, in a one-pot procedure. The present reaction was carried out under metal-free and organic-reagent-free conditions. Copyright
Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
p. 4115 - 4122
(2014/07/08)

Method for producing compounds comprising nitrile functions
The present invention concerns the production of compounds comprising nitrite functions and cyclic imide compounds. More specifically, the invention relates to the production of compounds comprising nitrile functions from compounds comprising carboxylic functions, advantageously of natural and renewable origin, and from methyl-2 glutaronitrile (MGN) or a mixture N of dinitriles comprising methyl-2 glutaronitrile (MGN), ethyl-2 succinonitrile (ESN) and adiponitrile (AdN).
-
Paragraph 0086-0088

(2014/12/09)

Ultrasounds in melted poly(ethylene glycol) promote copper-catalyzed cyanation of aryl halides with K4[Fe(CN)6]
Melted poly(ethylene glycols) (PEGs) were used for the first time as solvent for the sonochemically promoted cyanation of aryl halides employing inexpensive and safe K4[Fe(CN)6] and a relatively low amount of Cu-based catalyst. The Mw (weight-average polymer molecular weight) of PEG proved to notably influence the substrate conversion, which is indicative of a strong dependence of the sonication efficacy on solvent properties. Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) contributed to the characterization of the polymer and the elucidation of the catalytic system. Off the PEG: Melted poly(ethylene glycol)s (PEG)s were used for the first time as solvent for the sonochemical cyanation of aryl halides using K 4[Fe(CN)6] and a relatively low amount of Cu catalyst (5 %). The weight-average molecular weight of PEG was proven to exert a notable influence on conversion, and CuI proved to be the most efficient catalyst, affording good results within short reaction times with the use of aryl iodides and activated aryl bromides as substrates.
Giachi, Guido,Frediani, Marco,Oberhauser, Werner,Lamaty, Frederic,Martinez, Jean,Colacino, Evelina
p. 919 - 924
(2014/03/21)

METHOD FOR PRODUCING XYLYLENEDIAMINE
Provided is a method for stably and economically producing xylylenediamine with a high yield and long catalyst service life by hydrogenating dicyanobenzene that is obtained by ammoxidating xylene. By bringing an aqueous basic solution into contact with a dicyanobenzene-absorbed liquid, which is obtained by bringing an ammoxidation reaction gas into contact with an organic solvent, under specified temperature conditions, and subjecting a base and a carboxylic acid in the dicyanobenzene-absorbed liquid to a neutralization reaction so as to form an aqueous phase that contains a water-soluble salt, and then subjecting an organic phase and the aqueous phase to liquid-liquid separation so as to remove the aqueous phase, it is possible to remove the carboxylic acid contained in the dicyanobenzene-absorbed liquid with high selectivity while inhibiting loss of the dicyanobenzene. By subjecting the raw material dicyanobenzene, which is obtained by separating low boiling point compounds from the post liquid-liquid separation organic phase by distillation under reduced pressure, to hydrogenation, xylylenediamine is produced with a high yield and the service life of the hydrogenation catalyst is extended.
-
Paragraph 0059

(2013/11/19)

Cu/nitroxyl-catalyzed aerobic oxidation of primary amines into nitriles at room temperature
An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu 2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one-N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope and are effective with benzylic, allylic, and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.
Kim, Jinho,Stahl, Shannon S.
p. 1652 - 1656
(2013/07/26)

Direct oxidative conversion of methylarenes into aromatic nitriles
A variety of methylarenes were successfully converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with NBS or DBDMH in the presence of a catalytic amount of AIBN or BPO, followed by the reaction with molecular iodine in aq NH3 in a one-pot procedure. The present reaction is a useful and practical transition-metal-free method for the preparation of aromatic nitriles from methylarenes.
Tsuchiya, Daisuke,Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
supporting information
p. 4194 - 4197
(2013/09/12)

Simple one-pot conversion of alcohols into nitriles
Various benzylic and primary alcohols were efficiently converted into the corresponding nitriles in good yields at room temperature by treatment with tert-butyl hypochlorite, diiodine, or 1,3-diiodo-5,5-dimethylhydantoin in the presence of (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), followed by treatment with diiodine and aqueous ammonia. The nitriles were obtained in good yields and high purities simply by extraction of the reaction mixture with chloroform and subsequent removal of the solvent.
Shimojo, Hiroyuki,Moriyama, Katsuhiko,Togo, Hideo
p. 2155 - 2164
(2013/08/23)

Practical one-pot conversion of aryl bromides and β-bromostyrenes into aromatic nitriles and cinnamonitriles
Various aryl bromides were efficiently converted into the corresponding aromatic nitriles in good yields by the treatment with Mg turnings and subsequently DMF, followed by treatment with molecular iodine and aq NH 3. The same treatment of aryl bromides, which are weakly reactive to Mg turnings, with iPrMgCl·LiCl and subsequently DMF, followed by the treatment with molecular iodine and aq NH3 also afforded the corresponding aromatic nitriles in good yields. On the other hand, when N-formylpiperidine was used instead of DMF, p-substituted β-bromostyrenes were converted into the corresponding p-substituted cinnamonitriles, i.e., α,β-unsaturated nitriles, in good to moderate yields by the same procedure. The reactions were carried out by means of a simple experimental procedure and did not require any toxic metal cyanides or expensive rare metals. Therefore, the present reactions are practical and environmentally benign one-pot methods for the preparation of aromatic nitriles, cinnamonitriles, and aliphatic nitriles from aryl bromides, β-bromostyrenes, and alkyl bromides, respectively, through the formation of Grignard reagents and their DMF or N-formylpiperidine adducts.
Ishii, Genki,Harigae, Ryo,Moriyama, Katsuhiko,Togo, Hideo
p. 1462 - 1469
(2013/02/25)

AMMOXIDATION CATALYST AND METHOD FOR PRODUCING NITRILE COMPOUND USING THE SAME
The present invention provides an ammoxidation catalyst containing vanadium oxide, titanium oxide and diamond.
-
Page/Page column 7-8; 10

(2012/06/18)

Palladium catalyzed cyanation of o-dichloroarenes with potassium hexacyanoferrate(ii)
Cyanation of o-dichloroarenes with potassium hexacyanoferrate(ii) catalyzed by Pd(OAc)2/PPh3 system gave the corresponding phthalodinitriles in moderate yields. The method of competitive reactions revealed that activation rate of chl
Savicheva,Boyarskiy
p. 980 - 983
(2013/07/25)