- Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
-
Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
- Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
-
-
- SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
-
A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.
- Ding, Chengrong,Ge, Shuting,Wei, Junjie,Zhang, Guofu,Zhao, Yiyong
-
p. 17288 - 17292
(2020/05/18)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
-
We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- Nitrosation of Cyanamide: Preparation and Properties of the Elusive E- and Z-N'-Cyanodiazohydroxides
-
Nitrosation of cyanamide leads to unstable E/Z-cyanodiazohydroxides that easily deprotonate to E/Z-cyanodiazotates. Pursuing observations of E. Drechsel 145 years ago, the structure and reactivity of those products was determined, mainly in aqueous solution. Depending on the pH, three different thermal decomposition pathways give either N2O + HCN or N2 + HNCO. They were evaluated experimentally and by quantum mechanical calculations.
- Guethner, Thomas,Huber, Evi,Sans, Juergen,Thalhammer, Franz
-
supporting information
(2020/04/29)
-
- Photocatalytic Conversion of Benzyl Alcohols/Methyl Arenes to Aryl Nitriles via H-Abstraction by Azide Radical
-
This report presents the visible-light-assisted synthesis of aryl nitriles from easily accessible alcohols or methyl arenes in the presence of O2. Organic photoredox catalyst, 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), induces single electron transfer (SET) from azide N3? and generates azide radical N3?.The photogenerated N3? abstracts H atom from α-C?H bond of benzylic system, which provides aldehyde and hydrazoic acid (HN3) in situ. This reaction subsequently forms azido alcohol intermediate that transforms into nitrile with the assistance of triflic acid (Br?nsted acid). A range of alcohols and methyl arenes successfully underwent cyanation at room temperature with good to excellent yields and showed good functional group tolerance.
- Shee, Maniklal,Shah, Sk. Sheriff,Singh, N. D. Pradeep
-
supporting information
p. 14070 - 14074
(2020/10/12)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
-
The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
- -
-
Paragraph 0034-0039; 0130-0135
(2020/09/16)
-
- 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
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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)
-
- Transition-metal-free addition reaction for the synthesis of 3-(aminobenzylidene/aminoalkylidene)indolin-2-ones and its synthetic applications
-
A novel and efficient transition-metal-free approach for the exclusive synthesis of Z-3-(aminobenzylidene/aminoalkylidene)indolin-2-ones in high yield from 2-oxindole and aryl/alkyl nitrile in the presence of LiOtBu and 2,2′-bipyridine system is described. In addition, we disclosed a new approach towards the metal-free fluorination using selectfluor and the C=C bond cleavage using CuI and environmentally benign O2.
- Bisht, Girish Singh,Gnanaprakasam, Boopathy
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p. 13516 - 13527
(2019/10/19)
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- Green synthesis of benzonitrile using ionic liquid with multiple roles as the recycling agent
-
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)
-
- Enhanced catalytic activity of cobalt nanoparticles encapsulated with an N-doped porous carbon shell derived from hollow ZIF-8 for efficient synthesis of nitriles from primary alcohols in water
-
A cobalt catalyst derived from a unique core-shell structure based on hollow ZIF-8 and ZIF-67 (ZIF-67@ZIF-8) is prepared, which exhibits excellent catalytic efficiency for the synthesis of nitriles from alcohols in water under mild conditions (1 atm O2, 50 °C) owing to its large BET surface area, high pore volume, high basicity and hydrophilicity.
- Sun, Kang-Kang,Sun, Jia-Lin,Lu, Guo-Ping,Cai, Chun
-
supporting information
p. 4334 - 4340
(2019/08/21)
-
- Catalytic Promiscuity of Galactose Oxidase: A Mild Synthesis of Nitriles from Alcohols, Air, and Ammonia
-
We report an unprecedented catalytically promiscuous activity of the copper-dependent enzyme galactose oxidase. The enzyme catalyses the one-pot conversion of alcohols into the related nitriles under mild reaction conditions in ammonium buffer, consuming ammonia as the source of nitrogen and dioxygen (from air at atmospheric pressure) as the only oxidant. Thus, this green method does not require either cyanide salts, toxic metals, or undesired oxidants in stoichiometric amounts. The substrate scope of the reaction includes benzyl and cinnamyl alcohols as well as 4- and 3-pyridylmethanol, giving access to valuable chemical compounds. The oxidation proceeds through oxidation from alcohol to aldehyde, in situ imine formation, and final direct oxidation to nitrile.
- Vilím, Jan,Knaus, Tanja,Mutti, Francesco G.
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supporting information
p. 14240 - 14244
(2018/10/15)
-
- Copper-Catalyzed Unstrained C-C Single Bond Cleavage of Acyclic Oxime Acetates Using Air: An Internal Oxidant-Triggered Strategy toward Nitriles and Ketones
-
A copper-catalyzed aerobic oxidative C-C single bond cleavage of acyclic unstrained oxime acetates is reported, providing various aryl nitriles and ketones in good yields. Mechanistic studies indicate a radical procedure is involved in this transformation, and the oxygen atom in the ketone products is originated from O2 in the air. Oxime acetates as an internal oxidant have been proved to be an initiator, which may promote the discovery of novel protocol for C-C bond cleavage and dioxygen activation.
- Zhu, Chuanle,Chen, Fulin,Liu, Chi,Zeng, Hao,Yang, Zhiyi,Wu, Wanqing,Jiang, Huanfeng
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p. 14713 - 14722
(2018/12/14)
-
- [1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination
-
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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- Method for synthesizing aromaticnitrile by using metalloporphyrin to catalyze aromatic olefin
-
The invention discloses a method for synthesizing aromaticnitrile by using metalloporphyrin to catalyze aromatic olefin. The method is characterized in that an aromatic alkene compound or an aromaticheterocyclic alkene compound and nitrite are reacted to generate an aromaticnitrile compound or an aromatic heterocyclic nitrile compound under the catalyzing function of the metalloporphyrin by a one-step method in air atmosphere and an acid solution system. The method has the advantages that (1) the reaction conditions are moderate, the operation is simple, the control is easy, and the yield rate is higher; (2) the high-efficiency metalloporphyrin catalyst is used, but the poisonous CN (carbon-nitrogen) negative ion reagent is not used, so that the pollution to the environment is decreased;(3) the prices of raw materials, nitrogen sources, acid reagents and the like are low, the obtaining is easy, the production cost is obviously reduced, and the method can be popularized and applied toindustrialized production.
- -
-
Paragraph 0115-0119
(2018/03/01)
-
- Preparation method for aromatic nitriles compound
-
The invention discloses a preparation method for an aromatic nitriles compound. The preparation method comprises the following steps: using a methylbenzene derivative as shown in formula (I) as a rawmaterial, using nano ferrovanadium as a catalyst, and using hydrogen peroxide as a promoter, adding a ligand and an ammonia source, at a temperature of 80-180 DEG C, in an oxygen atmosphere, reactingfor 6-24 h in a condition that a working pressure is 0.1-1.5 MPa, to obtain a reaction mixture, after post-treatment, to obtain a target product of the aromatic nitriles compound as shown in a formula(II). The method is capable of realizing the conversion from methyl aromatics to the aromatic nitriles compound in a mild condition, and high in reaction yield, and has the industrialized applicationprospect. Oxygen is used as a cleaning oxidant, so the generation of poisonous and harmful by-products is reduced in a traditional inorganic salt oxidant reaction process. The preparation method is an environment-friendly strategy.
- -
-
Paragraph 0041; 0042; 0043
(2018/11/03)
-
- PROCESS FOR THE PREPARATION OF ORGANIC HALIDES
-
The present invention provides a halo-de-carboxylation process for the preparation of organic chlorides, organic bromides and mixtures thereof, from their corresponding carboxylic acids, using a chlorinating agent selected from trichloroisocyanuric acid (TCCA), dichloroisocyanuric acid (DCCA), or combination thereof, and a brominating agent.
- -
-
Paragraph 00143
(2017/08/01)
-
- One-Pot, Metal-Free Conversion of Anilines to Aryl Bromides and Iodides
-
A metal-free synthesis of aryl bromides and iodides from anilines via halogen abstraction from bromotrichloromethane and diiodomethane is described. This one-pot reaction affords aryl halides from the corresponding anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, a simple workup, and insensitivity to moisture and air and avoids excess halogenation. DFT calculations support a SRN1 mechanism. This method represents a convenient alternative to the classic Sandmeyer reaction.
- Leas, Derek A.,Dong, Yuxiang,Vennerstrom, Jonathan L.,Stack, Douglas E.
-
supporting information
p. 2518 - 2521
(2017/05/24)
-
- Green method for catalyzing alcohols and ammonia to prepare nitriles by using heterogeneous mesoporous cobalt catalyst
-
The invention provides a novel green method for catalyzing alcohols and ammonia to prepare nitriles by using a heterogeneous mesoporous cobalt catalyst. According to the method, cobalt acetate and nitrogen-containing ligands are taken as precursors, the novel heterogeneous mesoporous cobalt catalyst is prepared through high-temperature calcinations by using a hard template agent method, and catalyzed synthesis of various nitriles is realized in non-halogen solvents, particularly synthesis of aromatic and heterocyclic nitriles can be realized. The catalytic system has the characteristics that the novel and high-efficiency mesoporous cobalt catalyst is used; safe and green oxygen serves as an oxidizing agent; extra aids do not need to be added; the reaction is easy to operate; particularly the synthesis of aromatic and heterocyclic nitriles can be efficiently realized, and the nitriles can be repeatedly recycled. The novel heterogeneous mesoporous cobalt catalyst is used in the invention and has excellent research and industrial application prospects.
- -
-
Paragraph 0043-0045
(2017/07/20)
-
- PROCESS FOR THE PREPARATION OF ORGANIC BROMIDES
-
The present invention provides a process for the preparation of organic bromides, by a radical bromodecarboxylation of carboxylic acids with a bromoisocyanurate.
- -
-
Paragraph 00139; 00150
(2017/07/28)
-
- Design, synthesis and in vitro activity of phidianidine B derivatives as novel PTP1B inhibitors with specific selectivity
-
A series of phidianidine B derivatives were synthesized by introducing various heterocyclic rings. Their inhibitory effects on PTP1B and other PTPs (TCPTP, SHP1, SHP2 and LAR) were evaluated. A majority of them displayed significant inhibitory potency and specific selectivity over PTP1B. The SAR and molecular docking analysis were also described.
- Zhang, Li,Jiang, Cheng-Shi,Gao, Li-Xin,Gong, Jing-Xu,Wang, Zhong-Hua,Li, Jing-Ya,Li, Jia,Li, Xu-Wen,Guo, Yue-Wei
-
supporting information
p. 778 - 781
(2016/05/24)
-
- Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles
-
Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products.
- Lambert, Kyle M.,Bobbitt, James M.,Eldirany, Sherif A.,Kissane, Liam E.,Sheridan, Rose K.,Stempel, Zachary D.,Sternberg, Francis H.,Bailey, William F.
-
supporting information
p. 5156 - 5159
(2016/04/09)
-
- Synthesis of nitriles from aldehydes with trimethylphenylammonium tribromide and ammonium acetate
-
Various aromatic and heterocyclic aldehydes were easily converted to respective nitriles with the combination of trimethylphenylammonium tribromide and ammonium acetate in good yields at room temperature.
- Sayama, Shinsei
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p. 1796 - 1802
(2016/11/06)
-
- Synthesis, Cycloaddition, and Cycloreversion Reactions of Mononuclear Titanocene-oxo Complexes
-
Titanocene-oxo complexes of the type Cpx2Ti=O(L) (Cpx = pentamethylcyclopentadienyl; tetramethylcyclopentadienyl; L = pyridine or derivatives) are synthesized from the corresponding titanocene-ethylene complexes via oxidation with pyridine N-oxides or styrene oxide. These oxo complexes react with alkynes, nitriles, and α,β-unsaturated carbonyls to form titanacycles, which undergo exchange reactions with organic substrates or react with 4-dimethylaminopyridine to regenerate the titanocene-oxo. Mechanistic experiments support a dissociative mechanism in which the first step is rate-determining retrocycloaddition followed by trapping of the reactive [Cpx2Ti=O] species. In the case of the retro-[4+2]-cycloaddition from dioxatitanacyclohexene complexes, a Hammett study gives ρ values of -1.18 and -1.04 for substituents on two different phenyl rings on the metallacycles, suggesting positive charge buildup and a slightly asynchronous cycloreversion in the rate-determining step.
- Nguyen, Trang T.,Kortman, Gregory D.,Hull, Kami L.
-
supporting information
p. 1713 - 1725
(2016/07/06)
-
- High catalytic activity of mesoporous Co-N/C catalysts for aerobic oxidative synthesis of nitriles
-
A high-efficiency and atom-economic synthetic strategy for nitriles by aerobic ammoxidation of alcohols is developed using a novel mesoporous cobalt-coordinated nitrogen-doped carbon catalyst (meso-Co-N/C) fabricated from a cobalt-coordinating polymer, which manifests superior activity towards the target reaction. The catalytic system features a broad substrate scope for various benzylic, allylic as well as heterocyclic alcohols, providing good to excellent yields of the target products with high selectivities, albeit with 0.5 mol% Co catalyst loading. 11,11′-Bis(dipyrido[3,2-a:2′,3′-c]phenazinyl) (bidppz) with extreme thermostability is selected as a robust ligand bridge between cobalt ions, resulting in the homogeneous distribution of active sites at the atomic or subnanoscale level and high catalyst yield. Silica colloid or ordered mesoporous silica SBA-15 is employed to realize the mesoporous structure. The unprecedented performance of the meso-Co-N/C catalyst is attributed to its high Brunauer-Emmett-Teller (BET) surface area (up to 680 m2 g-1) with a well-controlled mesoporous structure and homogeneous distribution of active sites. Kinetic analysis demonstrates that the catalytic oxidation of benzyl alcohol to benzaldehyde is the turnover-limiting step and that the apparent activation energy for benzonitrile synthesis is 61.5 kJ mol-1 and cationic species are involved in the reaction.
- Shang, Sensen,Wang, Lianyue,Dai, Wen,Chen, Bo,Lv, Ying,Gao, Shuang
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p. 5746 - 5753
(2016/07/21)
-
- Visible light catalysis synthesis method of aryl cyanide
-
The invention discloses a visible light catalysis synthesis method of aryl cyanide. The method comprises the following steps: putting aryl halide, potassium ferrocyanide and alkali in an organic solvent; in the condition of magnetic stirring, starting a visible light source with power of 100-500W; irradiating with light intensity of 0.2-0.8W/cm until the reaction is over while controlling the reaction temperature at 25-85 DEG C; and carrying out a catalytic reaction for 1-12h by using a nano precious metal supported photocatalyst to synthesize the aryl cyanide. The photocatalysis cyaniding process can be shown by a general formula (I), wherein the X group is Br or I; and the R group is selected from electron attracting groups such as nitryl, acetyl and carboxyl and electron donating groups such as methoxy and methyl. In the invention, nontoxic green potassium ferrocyanide is used as a cyanogen source for synthesizing aryl cyanide, the highly toxic cyanides widely used in original methods are replaced, and thus the problem of environmental pollution in the aryl cyanide synthesis is reduced. The photocatalysis cyaniding reaction has the advantages of mild reaction conditions, stability and high efficiency, simplicity in operation, environmental friendliness, high product conversion rate and good selectivity.
- -
-
Paragraph 0034; 0035
(2017/02/28)
-
- Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the nitrogen source and oxidant
-
The transformation of the C=C bond of olefin to nitriles has been developed, using easily available NaNO2 as both the nitrogen source and oxidant. Several aryl, heterocyclic nitriles with various substituting groups could be successfully prepared in good to high yields. Based upon experimental observations, a possible reaction mechanism is proposed.
- Liu, Qiang,Fang, Bao,Bai, Xiaohui,Liu, Yuan,Wu, Yao,Xu, Guiming,Guo, Cancheng
-
supporting information
p. 2620 - 2623
(2016/06/01)
-
- A method for preparing of the benzonitrile derivatives
-
The invention discloses a preparation method of a cyanobenzene derivative. The cyanobenzene derivative is prepared by taking phenylacetic acid or the derivative thereof as well as urea as raw materials, copper salt as a catalyst and oxygen as an oxidizing agent. According to the preparation method disclosed by the invention, by adopting copper salt as the catalyst and oxygen as the oxidizing agent without an extra cocatalyst, the raw materials phenylacetic acid or the derivative thereof are easy to purchase in the market, low in cost and various in type, and urea as the source of cyanogen is low in toxicity, low in price, mild in reaction condition and environmentally friendly, and has a good functional group compatibility.
- -
-
Paragraph 0021; 0022; 0023; 0054; 0055; 0056; 0057
(2016/10/17)
-
- Cobalt/nitrophenolate-catalyzed selective conversion of aldoximes into nitriles or amides
-
A novel cobalt/nitrophenolate complex has been synthesized, characterized and studied for their catalytic activities. Conversion of aldoximes to nitriles can be performed via in situ conditions from cobalt(II) acetate and 2,4-dinitrophenol. The rearrangement of aldoximes to amides via cobalt(II) acetate and 2-nitro-1-naphthol has also been demonstrated. A complete reversal of transformation was accomplished by modifying the cobalt salt and careful choice of both the nitrophenol ligand and reaction conditions.
- Jang, Wonseok,Kim, Se Eun,Yang, Cheol Mo,Yoon, Sungwoo,Park, Myunghwan,Lee, Junseong,Kim, Youngjo,Kim, Min
-
p. 120 - 123
(2015/02/02)
-
- Direct oxidative conversion of benzylhalides, -amines, -alcohols, and arylaldehydes to nitriles with trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane activated by NH4Br
-
A simple and efficient oxidative conversion of benzyl derivatives of halides, amines, alcohols, and aldehydes into corresponding nitriles is described using trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane in the presence of NH4Br. The reactions proceeded smoothly at room temperature to afford the products in high-to-excellent yields. Graphical Abstract: [Figure not available: see fulltext.]
- Azarifar, Davood,Najminejad, Zohreh
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p. 107 - 111
(2015/01/30)
-
- Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
-
The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.
- Nimnual, Phongprapan,Tummatorn, Jumreang,Thongsornkleeb, Charnsak,Ruchirawat, Somsak
-
p. 8657 - 8667
(2015/09/15)
-
- Copper-catalyzed aerobic conversion of the C=O bond of ketones to a C≡N bond using ammonium salts as the nitrogen source
-
The conversion of the C=O bond of ketones to a C≡N bond is described. This conversion is catalyzed by copper salts with ammonium salts as the nitrogen source in the presence of molecular oxygen. A wide variety of ketones can be converted into the corresponding compounds containing a C≡N bond. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.
- Xu, Bin,Jiang, Qing,Zhao, An,Jia, Jing,Liu, Qiang,Luo, Weiping,Guo, Cancheng
-
supporting information
p. 11264 - 11267
(2015/07/08)
-
- Versatile and chemoselective transformation of aliphatic and aromatic secondary amides to nitriles
-
Triflic anhydride in combination with 2-fluoropyridine effectively dehydrates secondary amides to afford nitriles under mild reaction conditions. The reaction is general in scope and compatible with the use of aliphatic, α,β-unsaturated, aromatic, and heteroaromatic amides bearing either secondary, tertiary, or benzylic N-alkyl groups. The reaction also shows good to excellent chemoselectivity for the secondary amide and tolerates several labile functional groups.
- Geng, Hui,Huang, Pei-Qiang
-
p. 3795 - 3801
(2015/06/02)
-
- Metal-free, one-pot oxidative conversion of aldehydes to primary thioamides in aqueous media
-
One-pot tandem reactions of a variety of aldehydes with aqueous ammonia, molecular iodine, and O,O-diethyl dithiophosphoric acid readily afford the corresponding primary thioamides. This is an inexpensive, practical, and metal-free way of accessing various thioamides from aldehydes in aqueous media. The pure products are obtained simply by filtration followed by successive washing with aqueous sodium thiosulfate and water. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
-
supporting information
p. 408 - 416
(2014/01/06)
-
- Two ways of preparing benzonitriles using BrCCl3-PPh3 as the reagent
-
Benzamides were converted into benzonitriles with BrCCl3- PPh3-Et3N in CH2Cl2 in an Appel-type reaction. Benzaldoximes could be transformed to benzonitriles under identical conditions. It was found that the reaction system BrCCl3-(2 equiv.)PPh3 was also suitable for these transformations with PPh 3 replacing Et3N.
- Jasem, Yosef Al,Barkhad, Mohamed,Khazali, Mona Al,Butt, Hifsa Pervez,El-Khwass, Noha Ashraf,Azani, Mariam Al,Hindawi, Bassam Al,Thiemann, Thies
-
-
- A highly efficient, ligand-free and recyclable SBA-15 supported Cu 2O catalyzed cyanation of aryl iodides with potassium hexacyanoferrate(ii)
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SBA-15 supported Cu2O nanoparticles (Cu2O/SBA-15) have been fabricated and characterized. The as-prepared Cu2O/SBA-15 is a highly effective catalyst for cyanation of aryl iodides using non-toxic K4[Fe(CN)6] as a cyanide source in dimethylformamide (DMF). The approach achieves a high selectivity and an excellent yield without using any ligands and base additives. Moreover, the Cu2O/SBA-15 catalyst shows wide functional group tolerance and reusability with a slight loss of activity. the Partner Organisations 2014.
- Yin, Wenzhu,Liu, Rui,He, Guangke,Lv, Wangjie,Zhu, Hongjun
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p. 37773 - 37778
(2014/11/07)
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- A green and efficient access to aryl nitriles via an electrochemical anodic oxidation
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The nitrile functionality is a key building block in synthetic chemistry, and has wide applications in pharmaceuticals. However, traditional methodologies for the synthesis of nitriles are limited to harsh reaction conditions. Herein, we report a new and efficient access to aryl nitriles by an electrochemical synthesis. Compared with the conventional synthetic methods, this electrochemical synthesis is more environmentally friendly and easier to handle.
- Ye, Jia-Qian,Zhang, Zhen-Lei,Zha, Zheng-Gen,Wang, Zhi-Yong
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p. 1112 - 1114
(2014/08/18)
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- Copper-catalyzed decarboxylative C≡N triple bond formation: Direct synthesis of benzonitriles from phenylacetic acids under O2 atmosphere
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A copper-catalyzed reaction of phenylacetic acids with urea was found to afford benzonitriles under an oxygen atmosphere. This reaction proceeds smoothly by a sequence of decarboxylation, dioxygen activation, C-H bond functionalization, and nitrile formation with urea as the nitrogen source. Molecular oxygen was found to play a crucial role in this transformation. This reaction represents a novel protocol for the formation of benzonitriles in an environmental friendly way and with good functional group tolerability.
- Feng, Qiang,Song, Qiuling
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supporting information
p. 1697 - 1702
(2014/06/09)
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- One-pot transformation of methylarenes into aromatic nitriles with inorganic metal-free reagents
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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
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p. 4115 - 4122
(2014/07/08)
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- A clean and efficient conversion of aldehydes into the corresponding nitriles using ionic supported triphenylphosphine and CBr4
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An ionic supported triphenylphosphine and carbon tetrabromide system has been applied to the clean and efficient conversion of various aromatic and aliphatic aldehydes to the corresponding nitriles.
- Huo, Congde,Wang, Cheng,Hu, Dongcheng,Jia, Xiaodong
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p. 442 - 444
(2013/08/23)
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- Schmidt reaction in ionic liquids: Highly efficient and selective conversion of aromatic and heteroaromatic aldehydes to nitriles with [BMIM(SO3H)][OTf] as catalyst and [BMIM][PF6] as solvent
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A mild and selective method is presented for the conversion of aromatic and heteroaromatic aldehydes to nitriles via the Schmidt reaction with TMSN 3 by using [BMIM(SO3H)][OTf] as catalyst and [BMIM][PF6] as solvent. The method offers high yields and simple product isolation, and avoids the use of liquid superacids or corrosive Lewis acids commonly employed for this transformation. It also offers some potential for recycling/reuse of the IL solvent.
- Nandi, Ganesh C.,Laali, Kenneth K.
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p. 2177 - 2179
(2013/04/24)
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- Phenyliodonium diacetate mediated direct synthesis of benzonitriles from styrenes through oxidative cleavage of C=C bonds
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A metal-free PhI(OAc)2 mediated nitrogenation of alkenes through C=C bond cleavage using inorganic ammonia salt as nitrogen source under mild conditions was developed, affording nitriles in moderate to good yields. The advantages of this reaction are mild reaction conditions, operational simplicity, and use of an ammonium salt as nitrogen source. Based upon experimental observations, a plausible reaction mechanism is proposed.
- Xu, Jin-Hui,Jiang, Qing,Guo, Can-Cheng
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p. 11881 - 11886
(2014/01/06)
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- Direct oxidative conversion of methylarenes into aromatic nitriles
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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
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supporting information
p. 4194 - 4197
(2013/09/12)
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- Palladium(II)-catalyzed direct conversion of methyl arenes into aromatic nitriles
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From methyl to nitrile: A mild ammoxidation method, which directly converts methyl arenes into aromatic nitriles, has been developed by using Pd(OAc) 2 and N-hydroxyphthalimide (NHPI) as the catalysts, and tert-butyl nitrite as the nitrogen source and oxidant. Copyright
- Shu, Zhibin,Ye, Yuxuan,Deng, Yifan,Zhang, Yan,Wang, Jianbo
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supporting information
p. 10573 - 10576
(2013/10/21)
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- Ruthenium-catalyzed one-pot synthesis of primary amides from aldehydes in water
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The readily available arene-ruthenium(ii) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol%) proved to be an efficient catalyst for the direct synthesis of primary amides from aldehydes and hydroxylamine hydrochloride (NH2OH· HCl) in water at 100 °C. The process, which requires the presence of NaHCO3 to catch the HCl released during the formation of the key aldoxime intermediates, was operative with both aromatic, heteroaromatic, α,β-unsaturated and aliphatic aldehydes, and tolerated several functional groups. A greener approach using commercially available NH 2OH solution (50 wt.% in water) is also presented.
- Garcia-Alvarez, Rocio,Diaz-Alvarez, Alba E.,Crochet, Pascale,Cadierno, Victorio
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p. 5889 - 5894
(2013/05/09)
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- One-pot transformation of carboxylic acids into nitriles
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A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. This method is useful for the conversion of various aromatic and aliphatic carboxylic acids into the corresponding nitriles in a one-pot procedure. A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. Copyright
- Miyagi, Kotaro,Moriyama, Katsuhiko,Togo, Hideo
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p. 5886 - 5892
(2013/09/23)
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- Synthesis of aryl nitriles using the stable aryl diazonium silica sulfates
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An efficient method for preparation of aryl nitriles is reported using Cu(I) to catalyse the reaction of aryl diazonium silica sulfates with sodium cyanide under mild conditions at room temperature in water. This method has the advantages of high yields,
- Habibi, Davood,Heydari, Somayyeh,Nasrollahzadeh, Mahmoud
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p. 573 - 574,2
(2020/09/16)
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- SO3H-functionalized ionic liquids: Green, efficient and reusable catalysts for the facile dehydration of aldoximes into nitriles
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Easily synthesized aldoximes have been converted to the corresponding nitriles under very mild conditions by a simple reaction using two halogen-free SO3H-functionalized ionic liquids, 3-methyl-1-(4-sulfonic acid)butylimidazolium hydrogen sulfate [MIM(CH2)4SO 3H][HSO4] and 1-(4-sulfonic acid)butylpyridinium hydrogen sulfate [PY(CH2)4SO3H][HSO4], as catalyst and reaction medium without any additional organic solvent. The method was equally effective for aromatic aldoximes bearing electron-donating and electron-withdrawing substituents. Taking into account environmental and economical consideration, the protocol presented here has the merits of environmentally friendly, simple operation, easy work-up and very good yields. The catalysts could be recycled and reused for several times without noticeably decreasing in their catalytic activities.
- Davoodnia, Abolghasem,Khojastehnezhad, Amir,Bakavoli, Mehdi,Tavakoli-Hoseini, Niloofar
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experimental part
p. 978 - 982
(2012/01/04)
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- Efficient dehydration of aldoximes to nitriles catalyzed by a Lewis acid ionic liquid
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A Lewis acid ionic liquid, 1-[4-(chlorosulfonyl)butyl]-3-methylimidazolium chlorosulfate ([CBMIm]SO3Cl), with Lewis acid sites in both the anion and cation was synthesized. This was demonstrated to be an efficient catalyst for dehydration of aldoximes to nitriles. An unexpected self-induced phase separation of the reaction mixture was observed when the reaction was carried out in acetonitrile. This could be attributed to the hydrolysis of [CBMIm]SO3Cl to regenerate 1-(4-sulfobutyl)-3-methylimidazolium hydrogensulfate ([SBMIm]HSO4), which was the Bronsted precursor of [CBMIm]SO3Cl.
- Nakajima, Mizuki,Qiao, Kun,Kobayashi, Nobuhisa,Bao, Quanxi,Tomida, Daisuke,Yokoyama, Chiaki
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experimental part
p. 396 - 397
(2011/05/04)
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- Diethyl chlorophosphate: A new alternative reagent for dehydration of primary amides to nitriles in solvent and solvent-free conditions
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An efficient method for synthesis of nitriles has been developed using diethyl chlorophosphate in solvent and solvent-free conditions. Primary alkyl and aryl amides, efficiently are converted to the corresponding nitriles by heating in the presence of diethyl chlorophosphate in excellent yields. This method works under mild conditions with shorter reaction times.
- Shahsavari-Fard,Sardarian
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experimental part
p. 204 - 208
(2011/12/21)
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