Xn:Harmful;
110-61-2Relevant articles and documents
Photochemical Production of Ethane from an Iridium Methyl Complex
Pitman, Catherine L.,Miller, Alexander J. M.
, p. 1906 - 1914 (2017)
An iridium methyl complex, [Cp?Ir(bpy)(CH3)]+, was prepared by electrophilic methylation of Cp?Ir(bpy) with CH3I and characterized electrochemically, photophysically, crystallographically, and computationally. Irradiation of the MLCT transition of [Cp?Ir(bpy)(CH3)]+ in the presence of CH3I in acetonitrile produces ethane, methane, propionitrile, and succinonitrile. A series of mechanistic studies indicates that C-C bond formation is mediated by free methyl radicals produced through monometallic photochemical homolysis of the Ir-CH3 bond.
Reactions in water: Alkyl nitrile coupling reactions using Fenton's reagent
Keller, Christopher L.,Dalessandro, James D.,Hotz, Richard P.,Pinhas, Allan R.
, p. 3616 - 3618 (2008)
(Chemical Equation Presented) The coupling reaction of water-soluble alkyl nitriles using Fenton's reagent (Fe(II) and H2O2) is described. The best metal for the reaction is iron(II), and the greatest yields are obtained when the concentration of the metal is kept low. Hydrogen-atom abstraction is selective, preferentially producing the radical α to the nitrile. In order to increase the production of dinitrile, in situ reduction of iron(III) to iron(II), using a variety of reducing agents, was investigated.
Combined preparation method of 2-cyano-3-chloro-5-trifluoromethylpyridine and succinonitrile
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Paragraph 0024-0036, (2021/02/24)
The invention discloses a combined preparation method of 2-cyano-3-chloro-5-trifluoromethylpyridine and succinonitrile, and belongs to the field of organic chemistry. The method comprises the following steps: taking 2-fluoro-3-chloro-5-trifluoromethylpyridine and dichloroethane as raw materials, reacting in a potassium cyanide/sodium solution under the action of a phase transfer catalyst to obtaina mixed solution of 2-cyano-3-chloro-5-trifluoromethylpyridine and succinonitrile, layering, washing with water, and rectifying to obtain the 2-cyano-3-chloro-5-trifluoromethylpyridine with the content of more than 99% and the succinonitrile with the content of more than 99.9%. According to the method, the yield is high, the wastewater treatment is simple, byproducts are fully utilized, the yieldof the 2-cyano-3-chloro-5-trifluoromethylpyridine can reach 93%, and the yield of the succinonitrile can reach 95%.
Photocatalytic C-H activation and the subtle role of chlorine radical complexation in reactivity
Yang, Qiaomu,Wang, Yu-Heng,Qiao, Yusen,Gau, Michael,Carroll, Patrick J.,Walsh, Patrick J.,Schelter, Eric J.
, p. 847 - 852 (2021/05/28)
The functionalization of methane, ethane, and other alkanes derived from fossil fuels is a central goal in the chemical enterprise. Recently, a photocatalytic system comprising [CeIVCl5(OR)]2- [CeIV, cerium(IV); OR, -OCH3 or -OCCl2CH3] was disclosed. The system was reportedly capable of alkane activation by alkoxy radicals (RO·) formed by CeIV-OR bond photolysis. In this work, we present evidence that the reported carbon-hydrogen (C-H) activation of alkanes is instead mediated by the photocatalyst [NEt4]2[CeCl6] (NEt4+, tetraethylammonium), and RO· are not intermediates. Spectroscopic analyses and kinetics were investigated for C-H activation to identify chlorine radical (Cl·) generation as the ratelimiting step. Density functional theory calculations support the formation of [Cl·][alcohol] adducts when alcohols are present, which can manifest a masked RO· character. This result serves as an important cautionary note for interpretation of radical trapping experiments.
Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
, (2020/12/09)
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.
Method for continuous preparation of nitriles by amides (by machine translation)
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Paragraph 0033-0054; 0061-0066, (2020/12/15)
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)
HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
supporting information, p. 4161 - 4164 (2020/07/14)
We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
Copper(II)-Photocatalyzed N-H Alkylation with Alkanes
Donabauer, Karsten,K?nig, Burkhard,Narobe, Rok,Yakubov, Shahboz,Zheng, Yi-Wen
, p. 8582 - 8589 (2020/09/23)
We report a practical method for the alkylation of N-H bonds with alkanes using a photoinduced copper(II) peroxide catalytic system. Upon light irradiation, the peroxide serves as a hydrogen atom transfer reagent to activate stable C(sp3)-H bonds for the reaction with a broad range of nitrogen nucleophiles. The method enables the chemoselective alkylation of amides and is utilized for the late-stage functionalization of N-H bond containing pharmaceuticals with good to excellent yields. The mechanism of the reaction was preliminarily investigated by radical trapping experiments and spectroscopic methods.
Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
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Paragraph 0036-0047; 0056; 0058, (2020/12/14)
The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)
Method for preparing nitrile by reacting acetone cyanohydrin with haloalkane
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Paragraph 0043-0049; 0051-0058, (2019/08/20)
The invention provides a method for preparing nitrile by reacting acetone cyanohydrin with haloalkane. According to the invention, by using acetone cyanohydrin as a cyaniding reagent, the problems, such as long reaction time, low yield, strict reaction conditions and the like enchanted in an existing preparation method in which highly toxic sodium cyanide or potassium cyanide or expensive trimethylsilyl cyanide is used as a cyanogen source, are solved. The method comprises the following steps: dissolving acetone cyanohydrin in a mixed solvent of a high boiling point dipolar aprotic solvent anda low boiling point aprotic solvent, adding a catalyst lithium hydroxide, stirring at 25-50 DEG C for one hour and then adding a haloalkane for continuous reaction for 2-3 hours; next, adding saturated saline water for washing twice, separating out an organic layer, and boiling off the solvent after drying, thereby obtaining a nitrile compound. The method for preparing a nitrile compound disclosed in the invention is characterized by low reaction toxicity, simple process, easy of operation, low production cost, and a yield of more than 95%.
