- One-step selective synthesis of 2-chlorobenzonitrile from 2-chlorotoluene: Via ammoxidation
-
A series of V2O5/Al2O3 catalysts were prepared by a wet impregnation method and employed for a one-step synthesis of 2-chlorobenzonitrile from 2-chlorotoluene via ammoxidation in a fixed bed reactor at atmospheric pressure. The catalysts were characterized by BET-SA, XRD, FT-IR, TPR, UV-Vis DRS and NH3-TPD to identify the molecular structural changes of the catalysts. The characterization results revealed that the addition of V2O5 to Al2O3 amplified the crystallinity of alumina and also resulted in the formation of an interactive species i.e. AlVO4. Most of the V2O5 existed in the form of isolated surface and polymeric tetrahedral vanadia species in a highly dispersed state and/or having a strong interaction with the support. The formation of different kinds of vanadia species was entirely dependent on the content of vanadia present in the catalyst. A 10 wt% V2O5/Al2O3 catalyst was found to be the best and the high selectivity for 2-CBN was presumably due to the formation of the isolated surface and polymeric tetrahedral vanadia species along with aluminum vanadate species.
- Hari Babu,Venkateswara Rao,Suh,Sai Prasad,Lingaiah
-
-
Read Online
- A DFT-assisted mechanism for evolution of the ammoxidation of 2-chlorotoluene (2-CLT) to 2-chlorobenzonitrile (2-CLBN) over alumina-supported V2O5 catalyst prepared by a solution combustion method
-
Ammoxidation of 2-chlorotoluene (2-CLT) has been carried out over vanadates and supported vanadates in the temperature range 350–450 °C. The catalysts were characterized by XRD, XPS, FT-IR, and Raman and surface area measurement. A maximum yield of 76% of 2-CLBN was obtained at a temperature of 425 °C and a 2-CLT:NH3:air mole ratio of 1:8:22. DFT computations suggest that the reaction follows a Mars–van Krevelen (MVK) type of redox mechanism. The catalyst is first reduced by ammonia, producing an imine species. The 2-CLT molecule is also adsorbed through a vanadyl oxygen to produce a CH2[dbnd]C6H5 species. This moiety is adsorbed over the catalyst through an imine formed on the surface to produce 2-chlorobenzonitrile. XPS spectra of fresh and spent catalysts confirm reduction of the catalyst during ammoxidation.
- Dwivedi, Ritambhara,Sharma, Prabhakar,Sisodiya, Akrati,Batra, Manohar Singh,Prasad, Rajendra
-
-
Read Online
- Cyanide-Free Cyanation of Aryl Iodides with Nitromethane by Using an Amphiphilic Polymer-Supported Palladium Catalyst
-
A cyanide-free aromatic cyanation was developed that uses nitromethane as a cyanide source in water with an amphiphilic polystyrene poly(ethylene glycol) resin-supported palladium catalyst and an alkyl halide (1-iodobutane). The cyanation proceeds through the palladium-catalyzed cross-coupling of an aryl halide with nitromethane, followed by transformation of the resultant (nitromethyl)arene intermediate into a nitrile by 1-iodobutane.
- Niimi, Ryoko,Suzuka, Toshimasa,Uozumi, Yasuhiro
-
supporting information
p. 40 - 44
(2021/11/30)
-
- Synthetic method of o-chlorobenzonitrile
-
The invention discloses a synthesis method of o-chlorobenzonitrile, which comprises the following steps: by using one or more than two of o-chlorobenzyl alcohol, o-chlorobenzaldehyde and o-chlorobenzoic acid as raw materials, carrying out ammoxidation reaction in an ammonia gas and oxygen atmosphere under the actions of a copper-manganese composite catalyst and a cooxidant to synthesize the o-chlorobenzonitrile. By adopting the copper-manganese composite catalyst, one or more than two of the raw materials of o-chlorobenzyl alcohol, o-chlorobenzaldehyde and o-chlorobenzoic acid are subjected toammoxidation reaction to generate o-chlorobenzonitrile in the atmosphere of ammonia gas and oxygen under the synergistic action of the oxidant, so that the generation of byproducts is reduced, the difficulty of subsequent separation and purification is reduced, and the yield of o-chlorobenzonitrile is improved. The yield and purity of o-chlorobenzonitrile are improved, and the problems of low yield and high cost of o-chlorobenzonitrile caused by difficult separation and purification of products in the prior art are avoided.
- -
-
Paragraph 0029-0036; 0053-0065; 0077-0084; 0093-0132
(2021/03/18)
-
- Unprecedented Catalysis of Cs+Single Sites Confined in y Zeolite Pores for Selective Csp3-H Bond Ammoxidation: Transformation of Inactive Cs+Ions with a Noble Gas Electronic Structure to Active Cs+Single Sites
-
We report the transformation of Cs+ ions with an inactive noble gas electronic structure to active Cs+ single sites chemically confined in Y zeolite pores (Cs+/Y), which provides an unprecedented catalysis for oxidative cyanation (ammoxidation) of Csp3-H bonds with O2 and NH3, although in general, alkali and alkaline earth metal ions without a moderate redox property cannot activate Csp3-H bonds. The Cs+/Y catalyst was proved to be highly efficient in the synthesis of aromatic nitriles with yields >90% in the selective ammoxidation of toluene and its derivatives as test reactions. The mechanisms for the genesis of active Cs+ single sites and the ammoxidation pathway of Csp3-H bonds were rationalized by density functional theory (DFT) simulations. The chemical confinement of large-sized Cs+ ions with the pore architecture of a Y zeolite supercage rendered the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap reduction, HOMO component change, and preferable coordination arrangement for the selective reaction promotion, which provides a trimolecular assembly platform to enable the coordination-promoted concerted ammoxidation pathway working closely on each Cs+ single site. The new reaction pathway without involvement of O2-dissociated O atom and lattice oxygen differs from the traditional redox catalysis mechanisms for the selective ammoxidation.
- Acharyya, Shankha S.,Ghosh, Shilpi,Iwasawa, Yasuhiro,Kaneko, Takuma,Sasaki, Takehiko,Yoshida, Yusuke
-
p. 6698 - 6708
(2021/06/25)
-
- Dehydration of aldoximes to nitriles using trichloroacetonitrile without catalyst
-
Trichloroacetonitrile has been found to be an efficient dehydrating agent for a range of aldoximes including aromatic and heterocyclic aldoxime yielding the corresponding nitriles in moderate to good yields. The dehydration reactions can take place in non-acetonitrile media without the aid of a metal catalyst. In addition, it has been confirmed that trichloroacetonitrile was converted into trichloroacetamide in the reaction.
- Ma, Xiaoyun,Liu, Dan,Chen, Zhengjian
-
p. 3261 - 3266
(2021/06/30)
-
- One pot synthesis of aryl nitriles from aromatic aldehydes in a water environment
-
In this study, we found a green method to obtain aryl nitriles from aromatic aldehyde in water. This simple process was modified from a conventional method. Compared with those approaches, we used water as the solvent instead of harmful chemical reagents. In this one-pot conversion, we got twenty-five aryl nitriles conveniently with pollution to the environment being minimized. Furthermore, we confirmed the reaction mechanism by capturing the intermediates, aldoximes.
- Chen, Qingqing,Han, Hongwei,Lin, Hongyan,Ma, Xiaopeng,Qi, Jinliang,Wang, Xiaoming,Yang, Yonghua,Zhou, Ziling
-
p. 24232 - 24237
(2021/07/29)
-
- Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
-
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.
- 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)
-
- 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
-
-
- Biomass chitosan-derived nitrogen-doped carbon modified with iron oxide for the catalytic ammoxidation of aromatic aldehydes to aromatic nitriles
-
Nitrogen-doped carbon catalysts have attracted increasing research attention due to several advantages for catalytic application. Herein, cost-effective, renewable biomass chitosan was used to prepare a N-doped carbon modified with iron oxide catalyst (Fe2O3@NC) for nitrile synthesis. The iron oxide nanoparticles were uniformly wrapped in the N-doped carbon matrix to prevent their aggregation and leaching. Fe2O3@NC-800, which was subjected to carbonization at 800 °C, exhibited excellent activity, selectivity, and stability in the catalytic ammoxidation of aromatic aldehydes to aromatic nitriles. This study may provide a new method for the fabrication of an efficient and cost-effective catalyst system for synthesizing nitriles.
- Wang, Wei David,Wang, Fushan,Chang, Youcai,Dong, Zhengping
-
-
- Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
-
The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.
- Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
-
-
- Bis-morpholinophosphorylchloride, a novel reagent for the conversion of primary amides into nitriles
-
Bis-morpholinophosphorylchloride (Bmpc), in the presence of a base, is an efficient dehydrating agent for both aromatic and aliphatic primary amides, and gives corresponding nitriles under mild conditions in god yields and purity. During the reaction the enantiomeric integrity remains intact.
- Rao, P. Purnachandra,Nowshuddin, Shaik,Jha, Anjali,Rao, B. Leela Maheswara,Divi, Murali K.,Rao
-
supporting information
(2021/01/21)
-
- 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
-
p. 378 - 385
(2020/10/02)
-
- Ruthenium(II)-Complex-Catalyzed Acceptorless Double Dehydrogenation of Primary Amines to Nitriles
-
Acceptorless dehydrogenative oxidation of primary amines into nitriles using an in situ complex derived from commercially available dichloro(1,5-cyclooctadiene) ruthenium(II) complex and simple hexamethylenetetramine has been demonstrated. The synthetic protocol is highly selective and yields the nitrile compounds in moderate to excellent yields and produces hydrogen as the sole byproduct.
- Kannan, Muthukumar,Muthaiah, Senthilkumar
-
supporting information
p. 1073 - 1076
(2020/07/04)
-
- Acceptorless dehydrogenation of amines and alcohols using simple ruthenium chloride
-
A highly efficient, economic and environmental friendly catalyst system has been developed for the dehydrogenation of alcohols and amines using simple RuCl3·nH2O and N-benzylhexamethylenetetramine. The in situ catalyst system efficiently oxidized the primary and secondary amines and secondary alcohols into nitrile, imine and ketone products, respectively in moderate to excellent yields. The developed catalyst system was also found to be efficient for the dehydrogenation of N-heterocyles. A detailed mechanism study revealed the first example of N-benzylhexamethylenetetramine (HMTA-Bz) being simultaneously acting as base, reducing agent and hydride source to generate the [Ru(II)(H)2] species as the active catalyst. The mechanism studies also revealed both the alcohol and amine oxidation involves dehydrogenative pathway with the evolution of hydrogen as the only by-product. The developed catalyst system also provides possible platform for the release of hydrogen from liquid organic hydrogen carriers (LOHCs).
- Barteja, Parul,Devi, Preeti,Kannan, Muthukumar,Muthaiah, Senthilkumar
-
-
- Synthetic method of substituted benzoyl isocyanate
-
The invention discloses a preparation method of substituted benzoyl isocyanate, and belongs to the field of pesticide/medicine intermediates. Substituted benzoyl chloride and cyanate react in an organic solvent in the presence of a composite catalyst composed of a Lewis acid and p-toluene sulfonic acid to generate substituted benzoyl isocyanate. The method avoids the use of expensive oxalyl chloride, highly toxic phosgene, and the like, inhibits the generation of side reaction and byproduct namely cyanobenzene, selects the reaction conditions suitable for commercialization, enhances the selectivity and yield of the reaction, and reduces the generation of wastes, production cost, and environmental pollution.
- -
-
Paragraph 0029-0030
(2020/04/22)
-
- Efficient dehydration of primary amides to nitriles catalyzed by phosphorus-chalcogen chelated iron hydrides
-
A series of phosphorus-chalcogen chelated hydrido iron (II) complexes 1–7, (o-(R'2P)-p-R-C6H4Y)FeH (PMe3)3 (1: R = H, R' = Ph, Y = O; 2: R = Me, R' = Ph, Y = O; 3: R = H, R' = iPr, Y = O; 4: R = Me, R' = iPr, Y = O; 5: R = H, R' = Ph, Y = S; 6: R = Me, R' = Ph, Y = S; 7: R = H, R' = Ph, Y = Se), were synthesized. The catalytic performances of 1–7 for dehydration of amides to nitriles were explored by comparing three factors: (1) different chalcogen coordination atoms Y; (2) R' group of the phosphine moiety; (3) R substituent group at the phenyl ring. It is confirmed that 5 with S as coordination atom has the best catalytic activity and 7 with Se as coordination atom has the poorest catalytic activity among complexes 1, 5 and 7. Electron-rich complex 4 is the best catalyst among the seven complexes and the dehydration reaction was completed by using 2 mol% catalyst loading at 60 °C with 24 hr in the presence of (EtO)3SiH in THF. Catalyst 4 has good tolerance to many functional groups. Among the seven iron complexes, new complexes 3 and 4 were obtained via the O-H bond activation of the preligands o-iPr2P(C6H4)OH and o-iPr2P-p-Me-(C6H4)OH by Fe(PMe3)4. Both 3 and 4 were characterized by spectroscopic methods and X-ray diffraction analysis. The catalytic mechanism was experimentally studied and also proposed.
- Li, Kai,Sun, Hongjian,Yang, Wenjing,Wang, Yajie,Xie, Shangqing,Li, Xiaoyan,Fuhr, Olaf,Fenske, Dieter
-
-
- Iron-Promoted Decarboxylation of Arylacetic Acids for the Synthesis of Aromatic Nitriles with Sodium Nitrite as the Nitrogen Source
-
A new and effective method was developed for the synthesis of aromatic nitriles from arylacetic acids by using NaNO 2as the nitrogen source and Fe(OTf) 3as the promoter at 50 °C. A series of arylacetic acids underwent this transformation to give the targeted products in yields of 51-90%. Because of the mild conditions, the reaction is compatible with a broad range of functional groups, including ester, carboxy, hydroxy, acetamido, halo, nitro, cyano, methoxy, and even highly reactive formyl groups.
- Shen, Zhenpeng,Liu, Wenbo,Tian, Xinzhe,Zhao, Zhe,Ren, Yun-Lai
-
supporting information
p. 1805 - 1808
(2020/11/02)
-
- 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; 0166-0171
(2020/09/16)
-
- Lewis acid promoted dehydration of amides to nitriles catalyzed by [PSiP]-pincer iron hydrides
-
The dehydration of primary amides to their corresponding nitriles using four [PSiP]-pincer hydrido iron complexes 1–4 [(2-Ph2PC6H4)2MeSiFe(H)(PMe3)2 (1), (2-Ph2PC6H4)2HSiFe(H)(PMe3)2 (2), (2-(iPr)2PC6H4)2HSiFe(H)(PMe3)2 (3) and (2-(iPr)2PC6H4)2MeSiFe(H)(PMe3)2 (4)] as catalysts in the presence of (EtO)3SiH as dehydrating reagent was explored in the good to excellent yields. It was proved for the first time that Lewis acid could significantly promote this catalytic system under milder reaction conditions than other Lewis acid-promoted system, such as shorter reaction time or lower reaction temperature. This is also the first example that dehydration of primary amides to nitriles was catalyzed by silyl hydrido iron complexes bearing [PSiP]-pincer ligands with Lewis acid as additive. This catalytic system has good tolerance for many substituents. Among the four iron hydrides 1 is the best catalyst. The effects of substituents of the [PSiP]-pincer ligands on the catalytic activity of the iron hydrides were discussed. A catalytic reaction mechanism was proposed. Complex 4 is a new iron complex and was fully characterized. The molecular structure of 4 was determined by single crystal X-ray diffraction.
- Chang, Guoliang,Li, Xiaoyan,Zhang, Peng,Yang, Wenjing,Li, Kai,Wang, Yajie,Sun, Hongjian,Fuhr, Olaf,Fenske, Dieter
-
-
- An Air-Stable N-Heterocyclic [PSiP] Pincer Iron Hydride and an Analogous Nitrogen Iron Hydride: Synthesis and Catalytic Dehydration of Primary Amides to Nitriles
-
An air-stable N-heterocyclic PSiP pincer iron hydride FeH(PMe3)2(SiPh(NCH2PPh2)2C6H4) (4) was synthesized by Si-H activation of a Ph-substituted [PSiP] pincer ligand. The analogous strong electron-donating iPr-substituted [PSiP] pincer ligand was prepared and introduced into iron complex to give an iron nitrogen complex FeH(N2)(PMe3)(SiPh(NCH2PiPr2)2C6H4) (6). Both 4 and 6 showed similar high efficiency for catalytic dehydration of primary amides to nitriles. Air-stable iron hydride 4 was the best catalyst for its stabilization and convenient preparation. A diverse range of cyano compounds including aromatic and aliphatic species was obtained in moderate to excellent yields. A plausible catalytic reaction mechanism was proposed.
- Fenske, Dieter,Fuhr, Olaf,Li, Xiaoyan,Sun, Hongjian,Wang, Yajie,Xie, Shangqing,Zhang, Hua
-
-
- NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
-
Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
- Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
-
supporting information
p. 575 - 578
(2020/01/29)
-
- Method for continuous preparation of nitriles by amides (by machine translation)
-
The method comprises the following steps: preparing a lead salt supported by a molecular sieve by a lead salt and a molecular sieve through an impregnation method; and filling a molecular sieve-loaded lead catalyst into a fixed bed reactor. The amide or amide solution is sent into a fixed bed reactor from the top of the fixed bed to be subjected to catalytic dehydration, and the obtained reaction product is led out from the bottom of the fixed bed. The reaction product is separated to obtain the crude product of the nitrile corresponding to the amide. A fixed bed continuous production process is adopted, the reaction process is simple, the production efficiency is high, the product post-treatment is simple, and industrial production is easy to realize. (by machine translation)
- -
-
Paragraph 0033-0054; 0061-0065
(2020/12/15)
-
- Extending the Chemistry of Hexamethylenetetramine in Ruthenium-Catalyzed Amine Oxidation
-
A very efficient, highly atom economical, and environmentally benign oxidation of primary and secondary amines using an in situ catalyst system generated from commercially available ruthenium(II) benzene dichloride dimer and hexamethylenetetramine has been demonstrated. Mechanistic studies revealed that hexamethylenetetramine acted as a source of hydride to generate the active ruthenium hydride catalyst and amine oxidation involves a dehydrogenative pathway. In comparison to reported catalyst systems for the dehydrogenative oxidation of amines, this synthetic protocol makes use of a simple ruthenium precursor and a cheaper additive; it is very selective, leading to the exclusive formation of nitrile/imine compounds. Further, it releases hydrogen as the only side product, suggesting the potential application of the developed catalyst system in hydrogen storage.
- Kannan, Muthukumar,Muthaiah, Senthilkumar
-
supporting information
p. 3560 - 3567
(2019/11/13)
-
- Selectivity-tunable amine aerobic oxidation catalysed by metal-free N,O-doped carbons
-
Herein, we present a series of N,O-doped mesoporous carbons obtained at different pyrolysis temperatures as the first metal-free catalysts which successfully switch between imine and nitrile products for amine oxidation. Systematic characterization studies and control experiments revealed that the C-O group on the surface could function as a catalytically active site for nitrile synthesis and the N-doping environment was essential.
- Li, Yingguang,Shang, Sensen,Wang, Lianyue,Lv, Ying,Niu, Jingyang,Gao, Shuang
-
supporting information
p. 12251 - 12254
(2019/10/21)
-
- Cyanation of Anilines to Aryl Nitriles Using tert-Butyl Isocyanide: A Simple and Copper-free Procedure
-
In this manuscript, a simple and copper-free procedure for the synthesis of aryl nitrile derivatives from anilines is described. Under the improved protocol, the anilines were reacted with tert-butyl isocyanide under a mild reaction condition without the use of solvents and copper catalyst to synthesize benzonitriles. This copper-free Sandmeyer-type reaction could tolerate a range of anilines bearing different functional groups and also can be conducted even without the exclusion of air. In addition, this method has afforded the aryl nitriles in moderate to good yields (52–81%). The obtained results in this study reveal that the tert-butyl isocyanide as a potential cyanide source for the cyanation reaction.
- Chia, Poh Wai,Yong, Fu Siong Julius,Mohamad, Habsah,Kan, Su-Yin
-
supporting information
p. 939 - 942
(2019/08/21)
-
- Method for preparing nitrile
-
The invention provides a method for preparing nitrile. Aldoxime carboxylic ester is used as a reactant to prepare a nitrile compound. The aldoxime carboxylic ester can be completely converted into corresponding nitrile under common catalysis of ferric salt and phenol within a few minutes. The method for preparing the nitrile has the advantages of gentle reaction conditions, simple and easy-to-getused reagents, cheap and environment-friendly catalyst, wide substrate application range, simple operation, rapid reaction and the like.
- -
-
Paragraph 0015
(2019/06/13)
-
- Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
-
A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
- Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
-
p. 4617 - 4623
(2019/07/15)
-
- Ni-Mediated Generation of "cN" Unit from Formamide and Its Catalysis in the Cyanation Reactions
-
The in situ generation of a "cyano" unit from readily available organic precursors is of high interest in synthetic chemistry. Herein, we report the first example of Ni-mediated dehydration of formamide to form "CN" and its subsequent catalytic applications in the hydrocyanation of alkynes and cyanation of aryl halides. Formamide can serve as a convenient source for the nitrile unit, in that it releases water as the only byproduct.
- Yang, Luo,Liu, Yu-Ting,Park, Yoonsu,Park, Sung-Woo,Chang, Sukbok
-
p. 3360 - 3365
(2019/03/26)
-
- Dual Ligand-Enabled Nondirected C-H Cyanation of Arenes
-
Aromatic nitriles are key structural units in organic chemistry and, therefore, highly attractive targets for C-H activation. Herein, the development of an arene-limited, nondirected C-H cyanation based on the use of two cooperatively acting commercially available ligands is reported. The reaction enables the cyanation of arenes by C-H activation in the absence of directing groups and is therefore complementary to established approaches.
- Chen, Hao,Mondal, Arup,Wedi, Philipp,Van Gemmeren, Manuel
-
p. 1979 - 1984
(2019/02/19)
-
- Palladium-Catalyzed Late-Stage Direct Arene Cyanation
-
Methods for direct benzonitrile synthesis are sparse, despite the versatility of cyano groups in organic synthesis and the importance of benzonitriles for the dye, agrochemical, and pharmaceutical industries. We report the first general late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance. The reaction is enabled by a dual-ligand combination of quinoxaline and an amino acid-derived ligand. The method is applicable to direct cyanation of several marketed small-molecule drugs, common pharmacophores, and organic dyes. Benzonitriles are some of the most versatile building blocks for organic synthesis, in particular in the pharmaceutical industry, but general methods to make them by direct C–H functionalization are unknown. In this issue of Chem, Ritter and coworkers describe a late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance, enabled by a palladium-dual-ligand catalyst system. The reaction may serve for the late-stage modification of drug candidates. Aryl nitriles constitute an important class of organic compounds that are widely found in natural products, pharmaceuticals, agricultural chemicals, dyes, and materials. Moreover, nitriles are versatile building blocks to access numerous other important molecular structure groups. However, no general method for direct aromatic C–H cyanation is known. All approaches to date require either an appropriate directing group or reactive electron-rich substrates, such as indoles, which limit their synthetic applications. Here we describe an undirected, palladium-catalyzed late-stage aryl C–H cyanation reaction for the synthesis of complex aryl nitriles that would otherwise be more challenging to produce. The wide substrate scope and good functional-group tolerance of this reaction provide direct and quick access to structural diversity for pharmaceutical and agrochemical development.
- Zhao, Da,Xu, Peng,Ritter, Tobias
-
supporting information
p. 97 - 107
(2019/01/21)
-
- Ligand-Promoted Non-Directed C?H Cyanation of Arenes
-
This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
- Liu, Luo-Yan,Yeung, Kap-Sun,Yu, Jin-Quan
-
supporting information
p. 2199 - 2202
(2019/01/24)
-
- Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions
-
A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl2]2 with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.
- Achard, Thierry,Egly, Julien,Sigrist, Michel,Maisse-Fran?ois, Aline,Bellemin-Laponnaz, Stéphane
-
supporting information
p. 13271 - 13274
(2019/10/21)
-
- A carboxamide is the cyanogen source of aromatic nitrile to the preparation method of the (by machine translation)
-
The invention discloses a method for preparing aromatic nitrile, is under the action of the nickel catalyst, in order to carboxamide is the cyanogen source, and with various substituents haloarene coupled reactions, preparing aromatic nitrile. The reaction temperature is 100 - 160 °C, the reaction time is 6 - 24 hours. It overcomes the traditional aromatic nitrile of the synthesis method operation of complex steps, requires the use of a toxic, more expensive, functionalization of the cyanogen source as the reaction raw material and the like. Compared with the traditional method, this method is simple to use cheap, green non-toxic of the formamide is cyano sources; without the need of external dehydrating agent, formamide in the nickel catalyst of the catalytic dehydration at the same time, with a nickel catalyst in coordination with the halogenated aromatic hydrocyanation, more economic, high-efficiency, environmental protection; at the same time the method exhibits good substrate universality, to air, moisture, light are not sensitive, high yield, product separation and purification is simple, with wide application. (by machine translation)
- -
-
Paragraph 0015; 0016; 0017; 0018-0024; 0116; 0117-0119
(2019/05/08)
-
- Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
-
A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
- Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
-
supporting information
p. 1434 - 1436
(2019/05/01)
-
- Dehydration of primary amides to nitriles catalyzed by [CNC]-pincer hydrido cobalt(III) complexes
-
The dehydration reactions from primary amides to nitriles were catalyzed by the [CNC]-pincer hydrido cobalt(III) complexes [(ortho-F4C6–CH[dbnd]N–C10H6)Co(III)(H)(PMe3)2] (1), [(2,5-F2C6H2–CH[dbnd]N–C10H6)Co(III)(H)(PMe3)2] (2) and [(2,4,5-F3C6H–CH[dbnd]N–C10H6)Co(III)(H)(PMe3)2] (3) as catalysts with (EtO)3SiH as an efficient reducing agent. These hydrido cobalt(III) complexes as catalysts are suitable for many substrates and have good functional group tolerance. Among the three cobalt hydrides, complex 2 is the best catalyst. This is the first hydrido cobalt complex-catalyzed dehydration of primary amides to nitriles.
- Ren, Shishuai,Wang, Yangyang,Yang, Fei,Sun, Hongjian,Li, Xiaoyan
-
-
- Primary amides to amines or nitriles: A dual role by a single catalyst
-
We report a manganese-catalyzed hydrosilylative reduction of various primary amides to amines (25 examples). On simple modification of the reaction conditions such as in the presence of a catalytic amount of secondary amide, the same catalyst can transform the primary amides into intermediate nitrile compounds (16 examples) in excellent yields. This is the first example where such a controlled catalytic transformation of primary amides to amines or nitriles with a single catalyst has been demonstrated.
- Das, Hari S.,Das, Shyamal,Dey, Kartick,Singh, Bhagat,Haridasan, Rahul,Das, Arpan,Ahmed, Jasimuddin,Mandal, Swadhin K.
-
supporting information
p. 11868 - 11871
(2019/10/11)
-
- Practical CuCl/DABCO/4-HO-TEMPO-catalyzed oxidative synthesis of nitriles from alcohols with air as oxidant
-
A mild and efficient methodology for the direct oxidative synthesis of nitriles from easily available alcohols and aqueous ammonia by employing CuCl/DABCO/4-HO-TEMPO as the catalysts is described. This protocol uses the air as a green oxidant and aqueous ammonia as the nitrogen source at room temperature. A variety of aryl, heterocyclic and allylic alcohols are smoothly converted into the corresponding nitriles in good to excellent yields.
- Hu, Yongke,Chen, Lei,Li, Bindong
-
supporting information
p. 464 - 466
(2017/11/13)
-
- Aerobic Oxidative Dehydrogenation of Amines Catalyzed by a Recoverable Ruthenium Catalyst under Mild Reaction Conditions
-
A highly active catalyst based on perruthenate ions supported inside the channels of periodic mesoporous organosilica with a bridged imidazolium ionic liquid framework (Ru@PMO-IL) was developed. The material was found to be an efficient, durable, and recoverable catalyst for the oxidative dehydrogenation of various types of amines such as benzylic, aliphatic, and cyclic aliphatic amines under mild reaction conditions. The products were obtained in excellent yields with excellent selectivities.
- Karimi, Babak,Yari, Omolbanin,Khorasani, Mojtaba,Vali, Hojatollah,Mansouri, Fariborz
-
p. 1783 - 1787
(2018/01/27)
-
- Cu(OAc)2/malononitrile/water: A simple reaction system for synthesis of aromatic nitriles from aldoximes
-
A simple method for the preparation of nitriles in moderate to good yield has been achieved by treatment of aromatic and heterocyclic aldoximes with malononitrile in water at reflux in the presence of copper acetate as catalyst. Arylaldoximes with an electron-donating group showed the highest reactivity, their conversion being achievable at room temperature.
- Ma, Xiaoyun,He, Daqin,Chen, Zhengjian
-
p. 595 - 597
(2018/12/13)
-
- Pd/Mn Bimetallic Relay Catalysis for Aerobic Aldoxime Dehydration to Nitriles
-
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.).
- Zhang, Dongliang,Huang, Yaping,Zhang, Erlei,Yi, Rong,Chen, Chao,Yu, Lei,Xu, Qing
-
supporting information
p. 784 - 790
(2018/01/04)
-
- 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.
-
supporting information
p. 14240 - 14244
(2018/10/15)
-
- 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)
-
- Cyaniding method for preparing nitrile compound
-
The invention provides a cyaniding method for preparing a nitrile compound. Organic halide or pseudohalide, CO2 and NH3 which are low in price and are easily obtained and a reducing agent react, a selective cyaniding reaction is conducted in the presence of a transition metal catalyst, and the target product namely organic the nitrile compound is obtained. According to the cyaniding method for preparing the nitrile compound, a new reaction route is used, through a CO2 and NH3 reaction of metal catalysis, dehalogenation cyaniding or quasi halide cyaniding of halide or pseudohalide is directly achieved through a one-pot method, the problem is solved that a traditional cyanation reaction needs equivalent toxic cyanide, a new direct and convenient method for preparing isotope-labeled nitrile compounds is provided at the same time, and the method can be applied to medicine, tracing, biology and medicine research and development.
- -
-
Paragraph 0074-0076
(2018/05/30)
-
- 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 0103-0107
(2018/03/01)
-
- Synthesis of silyl iron hydride: Via Si-H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides
-
The hydrido silyl iron complex (o-Ph2PC6H4SiMe2)Fe(PMe3)3H (2) was obtained via the activation of the Si-H bond of the bidentate silyl ligand o-Ph2P(C6H4)SiMe2H (1) by Fe(PMe3)4. 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified.
- Ren, Shishuai,Xie, Shangqing,Zheng, Tingting,Wang, Yangyang,Xu, Shilu,Xue, Benjing,Li, Xiaoyan,Sun, Hongjian,Fuhr, Olaf,Fenske, Dieter
-
p. 4352 - 4359
(2018/03/26)
-
- Heterogeneous cobalt catalysts for selective oxygenation of alcohols to aldehydes, esters and nitriles
-
Efficient and green oxygenation of alcohols to the corresponding aldehydes, esters and nitriles was developed with high selectivity. Functional alcohols, including some heterocyclic and allylic alcohols can be oxygenated to the corresponding aldehydes, esters and nitriles respectively. Moreover, the catalyst can be recycled and reused without significant deactivation. Noteworthy, the Co@NC (800-2h) catalyzed oxygenation of alcohols can be regulated easily by changing the reaction conditions, and then the corresponding aldehydes, esters and nitriles can be obtained in high yields respectively.
- Mao, Fei,Qi, Zhengliang,Fan, Haipeng,Sui, Dejun,Chen, Rizhi,Huang, Jun
-
p. 1498 - 1503
(2017/01/18)
-
- Cu(NO3)2-catalysed direct synthesis of 5-substituted 1H-tetrazoles from alcohols or aldehydes
-
A simple, convenient and practical protocol to synthesise 5-substituted 1H-tetrazoles from alcohols or aldehydes is reported. Using ammonia and sodium azide as nitrogen sources and Cu(NO3)2 as catalyst, benzylic alcohols and benzaldehydes were directly converted into 5-substituted 1H-tetrazoles in a one-pot procedure.
- Tao, Chuanzhou,Wang, Bin,Sun, Lei,Yi, Jiuyin,Shi, Dahua,Wang, Jian,Liu, Weiwei
-
-
- Synthesis of nitriles from aerobic oxidation of amines catalyzed by ruthenium supported on activated carbon
-
Nitriles were synthesized from the aerobic oxidation of amines over commercially available catalysts, which were activated carbon-supported ruthenium catalysts (Ru/AC). The 5%Ru/AC catalyst can tolerate a wide range of substrates, such as aromatic, aliphatic, and heterocyclic amines, and afford the target nitriles in good-to-excellent yields. The 5%Ru/AC catalyst was easily recovered and no ruthenium leaking took place in the catalytic run.
- Niu, Baoqiang,Lu, Fei,Zhang, Hong-Yu,Zhang, Yuecheng,Zhao, Jiquan
-
supporting information
p. 330 - 333
(2017/02/23)
-
- A method for the preparation of nitrile compounds amine catalysis oxidation method
-
A method for preparing nitrile compounds by catalytic oxidation of amine can catalyze amine to oxidize and synthesize the nitrile compounds high efficiently and high selectively under the condition of normal pressure and normal temperature by using peroxide as an oxidizing agent. The method for preparing nitrile compounds by catalytic oxidation of amine has mild operation condition. The conversion rate of amine can be reached to 92%, and the selectivity of the nitrile compounds can be reached to 95%.
- -
-
Paragraph 0034; 0035
(2017/07/04)
-