- 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; 0061-0066
(2020/12/15)
-
- Dehydrogenation of Primary Alkyl Azides to Nitriles Catalyzed by Pincer Iridium/Ruthenium Complexes
-
Pincer metal complexes exhibit superior catalytic activity in the dehydrogenation of plain alkanes, but find limited application in the dehydrogenation of functionalized organic molecules. Starting from easily accessible primary alkyl azides, here we report an efficient dehydrogenation of azides to nitriles using pincer iridium or ruthenium complexes as the catalysts. This method offers a route to cyanide-free preparation of nitriles without carbon chain elongation and without the use of strong oxidants. Both benzyl and linear aliphatic azides can be dehydrogenated with tert-butylethylene as the hydrogen acceptor to afford nitriles in moderate to high yields. Various functional groups can be tolerated, and the H?C?C?H bond dehydrogenation does not occur for linear alkyl azide substrates. Furthermore, the pincer Ir catalytic system was found to catalyze the direct azide dehydrogenation without the use of a sacrificial hydrogen acceptor.
- Gan, Lan,Jia, Xiangqing,Fang, Huaquan,Liu, Guixia,Huang, Zheng
-
p. 3661 - 3665
(2020/06/02)
-
- Synthesis, characterization, catalytic and biological application of half-sandwich ruthenium complexes bearing hemilabile (κ2-: C, S)-thioether-functionalised NHC ligands
-
A series of cationic Ru(ii)(η6-p-cymene) complexes with thioether-functionalised N-heterocyclic carbene ligands have been prepared and fully characterized. Steric and electronic influence of the R thioether substituent on the coordination of the sulfur atom was investigated. The molecular structure of three of them has been determined by means of X-ray diffractrometry and confirmed the bidentate (κ2-C,S) coordination mode of the ligand. Interestingly, only a single diastereomer, as an enantiomeric couple, was observed in the solid state for complexes 1c, 1i and 1j. DFT calculations established a low energy inversion barrier between the two diastereomers through a sulfur pyramidal inversion pathway with R donating group while a dissociative/associative mechanism is more likely with R substituents that contain electron withdrawing group, thus suggesting that the only species observed by the 1H-NMR correspond to an average resonance position of a fluxional mixtures of isomers. All these complexes were found to catalyse the oxydant-free double dehydrogenation of primary amine into nitrile. Ru complex bearing NHC-functionalised S-tBu group was further investigated in a wide range of amines and was found more selective for alkyl amine substrates than for benzylamine derivatives. Finally, preliminary results of the biological effects on various human cancer cells of four selected Ru complexes are reported.
- Achard, Thierry,Bellemin-Laponnaz, Stéphane,Chen, Weiguang,Egly, Julien,Maisse-Francois, Aline,Poblador-Bahamonde, Amalia I.
-
supporting information
p. 3243 - 3252
(2020/03/19)
-
- Fatty Amidine as Copper Corrosion Inhibitor
-
The development of green and sustainable corrosion inhibitors for copper in a corrosive marine environment is highly desired. Herein, we studied the fatty acid-based amidine as the new type of renewable corrosion inhibitor. Stearamidine salt was used as a model inhibitor, and it was synthesized through stearonitrile intermediate with an excellent isolated yield of 88%. We used electrochemical (potentiodynamic polarization) and morphological (scanning electron microscopy) measurements to assess the corrosion inhibition efficiency of stearamidine in 3.0 wt.% NaCl at 300 K. We show that, in such a condition, the optimum inhibition efficiency of 96% was achieved using only 0.2 mM stearamidine. The results suggested the fatty amidine is a promising corrosion inhibitor for copper that is suitable in the saltwater ecosystem. The thermodynamic parameters of the interaction between the stearamidine and the copper surface were determined, and the result suggests that the adsorption process occurred accordingly with the Langmuir adsorption isotherm and involved both physisorption and chemisorption.
- Apriliyanto, Yusuf Bramastya,Darmawan, Noviyan,Dawolo, Januari,Mas'Ud, Zainal Alim
-
-
- Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis
-
The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.
- Jamil, Md. A. R.,Siddiki, S. M. A. Hakim,Touchy, Abeda Sultana,Rashed, Md. Nurnobi,Poly, Sharmin Sultana,Jing, Yuan,Ting, Kah Wei,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
-
p. 3115 - 3125
(2019/04/26)
-
- 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)
-
- Ru@UiO-66(Ce) catalyzed acceptorless dehydrogenation of primary amines to nitriles: The roles of Lewis acid-base pairs in the reaction
-
UiO-66(Ce)-encapsulated ruthenium nanoparticles (Ru@UiO-66(Ce)) was designed and used for dehydrogenation of primary amines to nitriles in water without any hydrogen acceptors and additives. Introduction of metal Ru to UiO-66(Ce) contributes to the formation of Lewis acid-base pairs on the catalyst owing to the metal-support interaction, acting as active sites for activation of amines and transfer of hydrogen. Ab initio calculation results further confirm the roles of Lewis acid-base pairs in the reaction.
- Lu, Guo-Ping,Li, Xinxin,Zhong, Lixiang,Li, Shuzhou,Chen, Fei
-
supporting information
p. 5386 - 5393
(2019/10/11)
-
- Highly Active and Selective Ru-PNH Catalyst in Aerobic Oxidation of Benzyl Amines
-
Set of [Ru(η6-cymene)(R)XCl] (R=L1SnCl, L1GeCl L2PPh2, X=Cl or SnCl3, L1=[2-(CH2NEt2)-4,6-(tBu)2C6H2]?, L2=2,6-iPr2-C6H3-NH?) catalysts was tested in aerobic oxidations of primary amines. The activity of studied catalysts depends on the charge of the Ru atom that has been influenced either by donating ligands R or by character of X. Typical Ru/P catalyst [Ru(η6-cymene)(L2PPh2)Cl2] (3) with least negative charge on the Ru atom has been observed as the most effective. The design of the phosphine ligand L2 containing amino-phosphine PNH moiety provided efficient anchoring of complex 3 to silica gel via hydrogen bonding of the PNH functional group to SiO2 to give heterogeneous catalyst 3-silica. This complex has been also efficiently tested in aerobic oxidation as recyclable catalyst with cumulative TON up to 6930.
- Aman, Michal,Tremmel, Jakub,Dostál, Libor,Erben, Milan,Tydlitát, Ji?í,Jansa, Josef,Jambor, Roman
-
p. 4624 - 4630
(2019/08/16)
-
- Corresponding amine nitrile and method of manufacturing thereof
-
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
- -
-
Paragraph 0153; 0154; 0155; 0156; 0157
(2018/05/07)
-
- Graphene oxide as a metal-free catalyst for oxidation of primary amines to nitriles by hypochlorite
-
Graphene oxide catalyzes oxidation by NaClO of primary benzyl and aliphatic amines to a product distribution comprising nitriles and imines. Nitriles are the sole product for long chain aliphatic amines. Spectroscopic characterization suggests that percarboxylic and perlactone groups could be the active sites of the process.
- Primo, Ana,Puche, Marta,Pavel, Octavian D.,Cojocaru, Bogdan,Tirsoaga, Alina,Parvulescu, Vasile,García, Hermenegildo
-
p. 1839 - 1842
(2016/02/12)
-
- Catalytic Hydrogen Production by Ruthenium Complexes from the Conversion of Primary Amines to Nitriles: Potential Application as a Liquid Organic Hydrogen Carrier
-
The potential application of the primary amine/nitrile pair as a liquid organic hydrogen carrier (LOHC) has been evaluated. Ruthenium complexes of formula [(p-cym)Ru(NHC)Cl2] (NHC=N-heterocyclic carbene) catalyze the acceptorless dehydrogenation of primary amines to nitriles with the formation of molecular hydrogen. Notably, the reaction proceeds without any external additive, under air, and under mild reaction conditions. The catalytic properties of a ruthenium complex supported on the surface of graphene have been explored for reutilization purposes. The ruthenium-supported catalyst is active for at least 10 runs without any apparent loss of activity. The results obtained in terms of catalytic activity, stability, and recyclability are encouraging for the potential application of the amine/nitrile pair as a LOHC. The main challenge in the dehydrogenation of benzylamines is the selectivity control, such as avoiding the formation of imine byproducts due to transamination reactions. Herein, selectivity has been achieved by using long-chain primary amines such as dodecylamine. Mechanistic studies have been performed to rationalize the key factors involved in the activity and selectivity of the catalysts in the dehydrogenation of amines. The experimental results suggest that the catalyst resting state contains a coordinated amine.
- Ventura-Espinosa, David,Marzá-Beltrán, Aida,Mata, Jose A.
-
p. 17758 - 17766
(2016/11/28)
-
- Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP
-
The immobilization of a ruthenium complex (Ru2Cl4(az-tpy)2) within a range of supported ionic liquids ([C4C1im]Cl, [C4C1im][NTf2], [C6C1im]Cl, [C4C1pyrr]Br, [C4C1im]Br, [C4C1pyrr]Cl) dispersed silica (SILP) operates as an efficient heterogeneous catalyst in oxidation of long chain linear primary amines to corresponding nitriles. This reaction follows a "green" route using a cheap and easy to handles oxidant (oxygen or air). The conversion was found to be strongly influenced by the alkyl chain length of the amine substrate and the choice of oxidant. No condensation reaction was observed between the starting amines and the selectivity to nitrile is 100%. Moving from a composition of 20 atm N2/5 atm O2 to 5 atm N2/20 atm O2 led to enhancements in the conversion (n-alkylamines) and selectivity (benzonitrile) which have been correlated with an increase of the solubilized oxygen. This was further supported by using different inert gas (nitrogen, helium, argon)/oxygen mixtures indicating that the O2 solubility in the SILP system, has an important effect on conversions and TON in this reaction using SILP catalysts. Experiments performed in the presence of CO2 led to a different behaviour due to the formation of amine-CO2 adducts. The application of the Weisz-Prater criterion confirmed the absence of any diffusional constraints.
- Pavel, Octavian Dumitru,Goodrich, Peter,Cristian, Liliana,Coman, Simona M.,Parvulescu, Vasile I.,Hardacre, Christopher
-
p. 2696 - 2704
(2015/07/22)
-
- One-pot transformation of carboxylic acids into nitriles
-
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
-
p. 5886 - 5892
(2013/09/23)
-
- Novel ruthenium-terpyridyl complex for direct oxidation of amines to nitriles
-
High catalytic activity and selectivity has been demonstrated for the oxidation of both aliphatic and aromatic amines to nitriles under benign conditions with dioxygen or air using the Ru2Cl4(az-tpy) 2 complex. The conversion was found to be strongly influenced by the alkyl chain length of the reactant with shorter chain amines found to have lower conversions than those with longer chains. Importantly, by using the ruthenium terpyridine complex functionalized with azulenyl moiety at the 4 position of central pyridine core provided a much higher reactivity catalyst compared with a series of ruthenium terpyridine-based ligand complexes reported. Mechanistic studies using deuterated benzylamine demonstrated the importance of RuOH in this reaction.
- Cristian, Liliana,Nica, Simona,Pavel, Octavian D.,Mihailciuc, Constantin,Almasan, Valer,Coman, Simona M.,Hardacre, Christopher,Parvulescu, Vasile I.
-
p. 2646 - 2653
(2013/09/24)
-
- Fe5C2 nanoparticles: A facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis
-
Iron carbide nanoparticles have long been considered to have great potential in new energy conversion, nanomagnets, and nanomedicines. However, the conventional relatively harsh synthetic conditions of iron carbide hindered its wide applications. In this
- Yang, Ce,Hou, Yanglong,Zhao, Huabo,Ma, Ding
-
supporting information
p. 15814 - 15821,8
(2020/08/24)
-
- Iridium-catalyzed α-alkylation of acetonitrile with primary and secondary alcohols
-
Acetonitrile is successfully alkylated with primary and secondary alcohols in the presence of t-BuOK using [Ir(OH)- (cod)]2 as a catalyst. This method provides a very clean and atom-economical convenient direct route to substituted nitriles, which are very important raw materials in organic and industrial chemistry.
- Sawaguchi, Takuya,Obora, Yasushi
-
supporting information; experimental part
p. 1055 - 1057
(2011/12/05)
-
- Lizard epidermal gland secretions. II. Chemical characterization of the generation gland secretion of the sungazer, cordylus giganteus
-
In lizards, the epidermal glands of the femoral and precloacal regions are involved in the production of semiochemicals. In addition to its femoral glands, the giant girdled lizard, or sungazer, Cordylus giganteus, which is endemic to South Africa, has generation glands as an additional potential source of semiochemicals. These epidermal glands are described as glandular scales that overlay the femoral glands and are included in the normal epidermal profile located in the femoral (thigh) and anterior antebrachial (fore-leg) regions of the male sungazer. GC-MS analysis of the generation gland secretions and the trimethylsilyl derivatives of some of the steroidal constituents was employed to identify 59 constituents, including alkenes, carboxylic acids, alcohols, ketones, aldehydes, esters, amides, nitriles, and steroids. The quantitative differences of the volatile constituents of the fore- and hind-leg generation glands were compared between individuals. This is the first report on the chemical composition of generation glandular material of lizards.
- Louw, Stefan,Burger, Ben V.,Le Roux, Maritha,Van Wyk, Johannes H.
-
supporting information; experimental part
p. 1364 - 1369
(2011/08/09)
-
- Straightforward conversion of alcohols into nitriles
-
The reaction of various alcohols with cyanogen bromide, triphenylphosphine, and a base afforded the corresponding nitrile in satisfactory yields. Copyright
- Tarrade-Matha, Aurelie,Pillon, Florence,Doris, Eric
-
experimental part
p. 1646 - 1649
(2010/07/09)
-
- Catalytic oxidative conversion of alcohols, aldehydes and amines into nitriles using KI/I2-TBHP system
-
The oxidative conversion of alcohols, aldehydes and amines to give corresponding nitriles in excellent yields was easily achieved by the catalytic amount of KI or I2 in combination with TBHP as an external oxidant. This non-transition metal catalyst is cost effective and provides easy work-up and separation of the product.
- Rajender Reddy,Uma Maheswari,Venkateshwar,Prashanthi,Lakshmi Kantam
-
supporting information; experimental part
p. 2050 - 2053
(2009/09/06)
-
- PROCESS FOR PRODUCING ALIPHATIC NITRILES
-
The present invention relates to a process for producing an aliphatic nitrile, including the step of reacting at least one compound selected from the group consisting of an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid and alkyl esters of these acids containing an alkyl group having 1 to 5 carbon atoms, with ammonia in the presence of a compound of at least one metal selected from the group consisting of zinc, cobalt, titanium and aluminum, and a sulfonic acid compound! and a process for producing an aliphatic amine, including the step of subjecting the aliphatic nitrile produced by the above process to hydrogenation reaction in the presence of a hydrogenation catalyst. There are provided an industrially advantageous process for producing an aliphatic nitrile with a high reactivity; and a process for producing an aliphatic amine using the aliphatic nitrile as a raw material.
- -
-
Page/Page column 12
(2008/06/13)
-
- Direct, facile synthesis of acyl azides and nitriles from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride
-
A mild, efficient, and practical method for the one-step synthesis of acyl azides from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding nitriles by the inclusion of phosphorous reagents. The method can be applied to the synthesis of optically active nitriles in high yields, and is compatible with fluorous phosphines.
- Kangani, Cyrous O.,Day, Billy W.,Kelley, David E.
-
p. 5933 - 5937
(2008/02/10)
-
- Method of producing aliphatic nitrile
-
The present invention relates to a method of producing an aliphatic nitrile by reacting an aliphatic carboxylic acid, by reacting an aliphatic dicarboxylic acid or their alkyl esters (the alkyl group with 1 to 5 carbon atoms) with ammonia in the presence of a catalyst of titanium oxide supported on solid silica. In addition, the present invention relates to a method of producing an aliphatic amine, including hydrogenating the aliphatic nitrile by using a hydrogenating catalyst and a catalyst for producing an aliphatic nitrile.
- -
-
Page/Page column 4-5
(2008/06/13)
-
- Mild and Efficient Dehydrosulfurization of Thioamides to Nitriles induced by Tellurium or Selenium Tetrachloride with Triethylamine
-
Tellurium tetrachloride or selenium tetrachloride in combination with triethylamine reacts smoothly with primary thioamides at room temperature to give nitriles in very high yields.
- Aso, Yoshio,Omote, Kazushi,Takagi, Seitaro,Otsubo, Tetsuo,Ogura, Fumio
-
p. 152 - 153
(2007/10/03)
-
- A facile synthesis of N-substituted pyrroles
-
Phosphorous pentoxide is the catalyst of choice for the facile conversion of primary amines, aromatic amines, sulfonamides and primary amides into the corresponding N-substituted pyrroles from 2,5-dimethoxytetrahydrofuran.
- Fang,Leysen,Ottenheijm
-
p. 1857 - 1861
(2007/10/02)
-
- Chemoselective Reactions of Tellurium Tetraethoxide towards Thioamides and Amides
-
Tellurium tetraethoxide reacts with primary thioamides at room temperature, forming nitriles in high yields. On the other hand, the reactions with amides are largely temperature-dependent, giving predominantly esters at 80 deg C and nitriles at a higher temperature. Similarly, tellurium tetraethoxide readily induces the C-N bond cleavage of ureas to give carbamates and amines.
- Omote, Kazushi,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
-
p. 1759 - 1761
(2007/10/02)
-
- Polymer-Supported Diaryl Selenoxide and Telluroxide as Mild and Selective Oxidizing Agents
-
Polystyrene-bound diaryl selenoxide and telluroxide have been prepared, which behaved as mild oxidizing agents for thiols to disulfide, phosphines to phosphine oxides, hydroquinone and catechol to p- and o-benzoquinones, and thioketones to oxo compounds.The telluroxide completed these reactions in shorter periods or under milder conditions than the selenoxide.In addition, they effected novel solvent-dependent reactions of thioamides involving thioureas to 1,2,4-thiadiazoles or to nitriles.In nonacidic solvents, the dehydrosulfurization to nitriles occured in preference to the oxidative dimerization to 1,2,4-thiadiazoles, but an acidic solvent such as acetic acid promoted the latter reaction.
- Hu, Nan Xing,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
-
p. 879 - 884
(2007/10/02)
-
- Process for the preparation of organic nitriles from organic carboxylic acid primary amides
-
This invention relates to a process for the preparation of organic nitriles. More particularly, the invention relates to a process for the preparation of organic nitriles by reacting organic carboxylic acid primary amides with a dehydrating agent in the presence of a catalytic amount of a particular quaternary ammonium salt.
- -
-
-
- MILD AND SELECTIVE OXIDATIONS WITH POLYSTYRENE-BOUND DIARYL SELENOXIDE
-
Polystyrene-bound diaryl selenoxide is sohwn to behave as a mild oxidizing agent for thiol to disulfide, sulfide to sulfoxide, phosphine to phosphine oxide, and hydroquinone to benzoquinone.In addition, it effects solvent-dependent reactions of thioamide to nitrile in usual solvent and to thiadiazole in acetic acid.
- Hu, Nan Xing,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
-
p. 603 - 606
(2007/10/02)
-
