1003-31-2Relevant articles and documents
DMF-catalysed thermal dehydration of aldoximes: A convenient access to functionalized aliphatic and aromatic nitriles
Supsana, Paraskevi,Liaskopoulos, Theodoras,Tsoungas, Petros G.,Varvounis, George
, p. 2671 - 2674 (2007)
N,N-Dimethylformamide was found to act as solvent and catalyst in the dehydration of aldoximes to nitriles. The reaction required heating at 135°C and yields of nitriles were moderate to good. (Benzylideneaminooxy)formaldehyde was detected as an intermediate in one of the reactions. Georg Thieme Verlag Stuttgart.
Palladium nanoparticles stabilized by a copolymer of N-vinylimidazole with N-vinylcaprolactam as efficient recyclable catalyst of aromatic cyanation
Beletskaya,Selivanova,Tyurin,Matveev,Khokhlov
, p. 157 - 161 (2010)
A new recyclable catalytic system was developed based on palladium nanoparticles and a copolymer of N-vinylimidazole and N-vinylcaprolactam for cyanation of aromatic bromides. The source of the cyanide ion was a nontoxic potassium hexacyanoferrate.
Direct Conversion of Benzyl Ethers into Aryl Nitriles
Tian, Xinzhe,Ren, Yun-Lai,Ren, Fangping,Cheng, Xinqiang,Zhao, Shuang,Wang, Jianji
, p. 2444 - 2448 (2018)
A direct method was developed for the conversion of benzyl ethers into aryl nitriles by using NH 4 OAc as the nitrogen source and oxygen as the terminal oxidant with catalysis by TEMPO/HNO 3; the method is valuable for both the synthesis of aromatic nitriles and for the deprotection of ether-protected hydroxy groups to form nitrile groups in multistep organic syntheses.
Metal-free one-pot conversion of electron-rich aromatics into aromatic nitriles
Ushijima, Sousuke,Togo, Hideo
, p. 1067 - 1070 (2010)
Various electron-rich aromatics could be smoothly converted into the corresponding aromatic nitriles in good to moderate yields by treatment of electron-rich aromatics with POCl3 and DMF, followed by treatment with molecular iodine in aqueous ammonia. The present reaction is a novel metal-free one-pot method for the preparation of aromatic nitriles from electron-rich aromatics.
A clean conversion of aldehydes to nitriles using a solid-supported hydrazine
Baxendale, Ian R.,Ley, Steven V.,Sneddon, Helen F.
, p. 775 - 777 (2002)
A polymer-supported hydrazine reagent has been applied to the conversion of a range of aldehydes to nitriles, providing a clean and efficient route to more diverse building blocks for combinatorial chemistry programmes.
NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
, p. 885 - 889 (2018)
Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
New applications of Ph3P=N-Li in organic synthesis and heteroatom chemistry
Taillefer, Marc,Rahier, Nicolas,Minta, Ewelina,Cristau, Henri-Jean
, p. 1847 - 1850 (2002)
The lithium triphenylaminophosphonium azayldiide 1 proved again to be a very good tool in organic synthesis, allowing further synthesis of various compounds such as vinyl nitriles, aromatic or heteroaromatic nitriles, and mono-, bis-, and trisphosphinimines.
CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source
Ren, Yun-Lai,Shen, Zhenpeng,Tian, Xinzhe,Xing, Ai-Ping,Zhao, Zhe
, (2021)
Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.
Pd/Mn Bimetallic Relay Catalysis for Aerobic Aldoxime Dehydration to Nitriles
Zhang, Dongliang,Huang, Yaping,Zhang, Erlei,Yi, Rong,Chen, Chao,Yu, Lei,Xu, Qing
, p. 784 - 790 (2018)
A Pd/Mn bimetal system was found to be an effective catalyst for dehydration of aldoximes to the useful nitriles under mild aerobic conditions. Different to the known metal-catalyzed aldoxime dehydration reactions, this reaction very possibly proceeded via an alternative mechanism of Pd/Mn bimetal relay catalysis involving a Mn-catalyzed aerobic oxidation of aldoximes to nitrile oxides by air and a Pd-catalyzed oxygen transfer from the nitrile oxides to the solvent acetonitrile. This method tolerates a variety of substrates including sterically bulky ones and also the natural product derivative. (Figure presented.).
Influence of alkyl side chain on the crystallinity and trap density of states in thiophene and thiazole semiconducting copolymer based inkjet-printed field-effect transistors
Lee, Jiyoul,Chung, Jong Won,Jang, Jaeman,Kim, Do Hwan,Park, Jeong-Il,Lee, Eunkyung,Lee, Bang-Lin,Kim, Joo-Young,Jung, Ji Young,Park, Joon Seok,Koo, Bonwon,Jin, Yong Wan,Kim, Dae Hwan
, p. 1927 - 1934 (2013)
The influence of alkyl side chains on the crystallinity of semiconducting copolymer films and their sub-bandgap density-of-states (DOS), the latter being closely related to the stability and the device performance of organic field-effect transistors (OFETs), is investigated. Three different poly(hexathiophene-alt-bithiazole) (PHTBTz) based polymer semiconductors, with identical backbones but different side chain positions and lengths, were synthesized. The crystallinity examined by grazing incidence X-ray diffraction (GIXRD) strongly depends on the number, position, and length of each type of alkyl side chain attached to the thiophene and thiazole copolymer backbones. Also, the sub-bandgap trap DOS distributions were extracted by performing multiple-frequency capacitance-voltage (MF-CV) spectroscopy on the field effect devices. The relationship between film crystallinity and trap DOS in the field-effect transistors can be interpreted in terms of the complex interplay between the number, position, and length of each alkyl side chain for efficient π-π stacking. In particular, the number and position of the alkyl side chain attached to the polymer backbone significantly affects the device performance. Poly(tetryloctylhexathiophene-alt-dioctylbithiazole) (PHTBTz-C8) exhibits the best electrical performance among the different semiconductors synthesized, with a relatively low bulk trap density of ～2.0 × 10 20 cm-3 eV-1 as well as reasonable hole mobility of ～0.25 cm2 V-1 s-1. The microstructural analyses of this organic material strongly suggest that the short π-π stacking distance induces strong interaction between adjacent polymer backbones, which in turn results in enhanced electrical properties.
A mild and efficient method for the conversion of aldehydes into nitriles and thiols into disulfides using an ionic liquid oxidant
Hosseinzadeh, Rahman,Golchoubian, Hamid,Nouzarian, Mahboobe
, p. 4713 - 4725 (2015)
A simple, mild and high yielding method for the conversion of various aldehydes to nitriles has been developed using an ionic liquid reagent, hexamethylene bis(N-methylimidazolium) bis(dichloroiodate) (HMBMIBDCI), in combination with aqueous ammonia in CH3CN at room temperature. Moreover, the treatment of aromatic and aliphatic thiols with HMBMIBDCI resulted in the corresponding disulfides in solvent-free condition at room temperature.
AlCl3·6H2O/KI/H2O/CH3CN: A new alternate system for dehydration of oximes and amides in hydrated media
Boruah, Monalisa,Konwar, Dilip
, p. 7138 - 7139 (2002)
Dehydration of oximes and amides to nitriles was carried out using the AlCl3·6H2O/KI/H2O/CH3CN system. It produced isoquinoline derivatives 8a-c (Bischler Naperialski reaction) when reacted with amides 7a-c in hydrated media. Also, the keto oximes produced anilides (Beckmann rearrangement) with the system under the same reaction conditions.
Microwave-induced conversion of aldoximes to nitriles by DBU
Sabitha, Gowravaram,Syamala
, p. 4577 - 4580 (1998)
Aldoximes (1) can be rapidly converted into corresponding nitriles (2) in good yields with a novel reagent DBU under microwave irradiation.
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Wentrop
, p. 1027,1031 (1971)
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Postsynthesis-Treated Iron-Based Metal-Organic Frameworks as Selective Catalysts for the Sustainable Synthesis of Nitriles
Rapeyko, Anastasia,Climent, Maria J.,Corma, Avelino,Concepci?n, Patricia,Iborra, Sara
, p. 3270 - 3282 (2015)
The dehydration of aldoximes to the corresponding nitriles can be performed with excellent activity and selectivity by using iron trimesate as a homogeneous catalyst. Iron trimesate has been heterogenized by synthesizing metal-organic frameworks (MOFs) from iron trimesate, that is, Fe(BTC), and MIL-100 (Fe). These materials were active and selective aldoxime dehydration catalysts, and postsynthesis-treated MIL-100 (Fe) produced the desired nitriles with 100 conversion and selectivities >90 under mild reaction conditions and in short reaction times. X-ray photoelectron spectroscopy showed the presence of different Fe species in the catalyst, and in situ IR spectroscopy combined with catalytic results indicates that the catalytic activity is associated with Fe framework species. The postsynthesis-treated MIL-100 (Fe)-NH4F can be recycled several times and has an excellent reaction scope, which gives better catalytic results than other solid acid or base catalysts.
A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
, p. 7176 - 7185 (2021)
The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.
One-Flask Conversion of Aldehydes into Nitriles
Saednya, Akbar
, p. 190 - 191 (1982)
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One-pot oxidative conversion of alcohols into nitriles by using a TEMPO/PhI(OAc)2/NH4OAc system
Vatèle, Jean-Michel
, p. 1275 - 1278 (2014)
A direct conversion of alcohols into nitriles with 2,2,6,6- tetramethylpiperidine-1-oxyl (TEMPO), iodosobenzene diacetate, and ammonium acetate as a nitrogen source is reported. This transformation, which proceeds through an oxidation-imination-aldimine oxidation sequence in situ, has been applied to a range of aliphatic, benzylic, heteroaromatic, allylic, and propargyl alcohols. Highly chemoselective ammoxidation of primary alcohols in the presence of secondary alcohols was also achieved. Georg Thieme Verlag Stuttgart New York.
NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
, p. 575 - 578 (2020)
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.
Polyethylene glycol supported phosphorus chloride: An efficient and recyclable catalyst for the preparation of nitriles from aldoximes
Zhang, Xiao-Lan,Sheng, Shou-Ri,Wei, Mei-Hong,Liu, Xiao-Ling
, p. 513 - 517 (2017)
Polyethylene glycol (PEG) supported phosphorus chloride has been developed and used as an efficient and recyclable catalyst for dehydration of various aldoximes into the corresponding nitriles. This protocol has many advantages such as high conversion, high selectivity, short reaction time, mild reaction conditions, and simple experimental procedure.
Supported monomeric vanadium catalyst for dehydration of amides to form nitriles
Sueoka, Shoichiro,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
, p. 8243 - 8245 (2010)
Monomeric vanadium oxide species is created on the surface of hydrotalcite (V/HT), which acts as a reusable solid catalyst for the highly efficient dehydration of amides into the corresponding nitriles.
Copper-catalyzed cyanation of heteroaryl bromides: A novel and versatile catalyst system inspired by nature
Schareina, Thomas,Zapf, Alexander,M?gerlein, Wolfgang,Müller, Nikolaus,Beller, Matthias
, p. 555 - 558 (2007)
An improved copper catalyst system for the cyanation of heteroaryl halides leading to substituted heteroaryl nitriles is described. The catalyst system consists of simple CuI and N-alkylimidazoles, and mimics known Cu-containing metalloproteins. It is stable, commercially available, cheap and easily tunable. By using inexpensive and non-toxic K4[Fe(CN)6] and the novel Cu catalysts we were able to cyanate both activated and non-activated heteroarenes with high yield and selectivity. The generality of the procedure is demonstrated by a variety of different examples, some of which did not react under other known methods. Georg Thieme Verlag Stuttgart.
High-throughput synthesis of symmetrically 3,5-disubstituted 4-amino-1,2,4-triazoles from aldehydes using microwave
Koshima, Hideko,Hamada, Mitsuo,Tani, Makiko,Iwasaki, Shunsuke,Sato, Fumika
, p. 2145 - 2148 (2002)
Symmetrically 3,5-substituted 4-amino-1,2,4-triazoles are quickly prepared from aromatic aldehydes via nitriles by two-step reactions without any separation under microwave irradiation for each several minutes.
Straightforward uranium-catalyzed dehydration of primary amides to nitriles
Enthaler, Stephan
, p. 9316 - 9319 (2011)
Easy for U! The efficient uranium-catalyzed dehydration of a variety of primary amides, using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as a dehydration reagent, to the corresponding nitriles has been investigated. With this catalyst system, extraordinary catalyst activities and selectivities were feasible (see scheme; DME=dimethoxyethane). Copyright
Metal-free dehydrosulfurization of thioamides to nitriles under visible light
Xu, Tianxiao,Cao, Tianpeng,Feng, Qingyuan,Huang, Shenlin,Liao, Saihu
, p. 5151 - 5153 (2020)
A visible light-mediated, metal-free dehydrosulfurization reaction of thioamides to nitriles is described. This reaction features high yields, mild reaction conditions, and the use of a cheap organic dye as the photoredox catalyst and air as the oxidant.
Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
, (2021/12/03)
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.]
Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
Liu, Si-Zhan,Li, Jing,Xue, Cao-Gen,Xu, Xue-Tao,Lei, Lin-Sheng,Huo, Chen-Yu,Wang, Zhen,Wang, Shao-Hua
supporting information, (2021/02/01)
A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
Iodine Promoted Conversion of Esters to Nitriles and Ketones under Metal-Free Conditions
Xiao, Jing,Guo, Fengzhe,Li, Yinfeng,Li, Fangshao,Li, Qiang,Tang, Zi-Long
, p. 2028 - 2035 (2021/02/03)
We report a novel strategy to prepare valuable nitriles and ketones through the conversion of esters under metal-free conditions. By using the I2/PCl3 system, various substrates including aliphatic and aromatic esters could react with acetonitrile and arenes to afford the desired products in good to excellent yields. This method is compatible with a number of functional groups and provides a simple and practical approach for the synthesis of nitrile compounds and aryl ketones.
