- Preparation method of o-trifluoromethylbenzamide
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The present invention discloses a method for preparing o-trifluoromethyl benzamide. The preparation method comprises the following steps: (1) in an organic solvent, the 2-nitrobenzotrifluoride and fluorinated salts are denitrified as shown below to obtain o-fluorobenzotrifluoride; (2) in an organic solvent, the o-fluortrifluorotoluene and cyanidylation reagent are defluoride cyanidation reaction as shown below to obtain o-trifluoromethylbenzonitrile; (3) in the presence of alkali, the o-trifluoromethylbenzonitrile, hydrogen peroxide hydrolysis reaction as shown below. The preparation method is simple to treat, the product purity is high, the impurities are small, and the yield is high.
- -
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Paragraph 0067; 0072-0075
(2022/01/12)
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- Synthesis method 2 - trifluoromethyl benzamide
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The invention discloses a synthesis method of 2 -trifluoromethylbenzamide, which comprises the following steps of 2, 3 -dichloro-trifluorotoluene serving as a raw material and fluorinating. The preparation 2 -trifluoro -6 -cyano-trifluorotoluene is prepared by cyano substitution, 2 -fluoro -6 -cyanobenzotrifluoride is subjected to hydrogenation and dehydrochlorination, and 2 -trifluoromethylbenzamide is prepared by first hydrolyzing and dehydrochlorinating and dechlorinating. 2 - Trifluoromethylbenzamide is synthesized by simple reaction, and the method has the characteristics of cheap and easily available raw materials, no participation of the isomer 2 - fluorine -3 - chlorine - trifluorotoluene isomers in subsequent reaction and easy removal. In each reaction step, flammable and explosive, highly toxic or non-volatile agents commonly used in the existing synthetic method are not used, and harm to operating personnel and in the environment is avoided. , The total yield of the product reaches above 67%, and the purity is 97% or more.
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Paragraph 0028; 0035; 0040-0041; 0055; 0060-0061
(2021/11/27)
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- Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
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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.]
- Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
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-
- Development and Molecular Understanding of a Pd-Catalyzed Cyanation of Aryl Boronic Acids Enabled by High-Throughput Experimentation and Data Analysis
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A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.
- De Jesus Silva, Jordan,Bartalucci, Niccolò,Jelier, Benson,Grosslight, Samantha,Gensch, Tobias,Schünemann, Claas,Müller, Bernd,Kamer, Paul C. J.,Copéret, Christophe,Sigman, Matthew S.,Togni, Antonio
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- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
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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
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
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supporting information
p. 4161 - 4164
(2020/07/14)
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- SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
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A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.
- Ding, Chengrong,Ge, Shuting,Wei, Junjie,Zhang, Guofu,Zhao, Yiyong
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p. 17288 - 17292
(2020/05/18)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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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.
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-
Paragraph 0034-0039; 0178-0183
(2020/09/16)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
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p. 5803 - 5812
(2019/05/14)
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- Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides
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Ni-catalyzed decarbonylative cyanation of acyl chlorides with trimethylsilyl cyanide has been achieved. This transformation is applicable to the synthesis of an array of nitrile compounds bearing a wide range of functional groups under neutral conditions. The step-by-step experimental studies revealed that the reaction sequences of the present catalytic reaction are oxidative addition, transmetalation, decarbonylation, and reductive elimination.
- Wang, Zhenhua,Wang, Xiu,Ura, Yasuyuki,Nishihara, Yasushi
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supporting information
p. 6779 - 6784
(2019/08/26)
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- Visible-Light photoredox decarboxylation of perfluoroarene iodine(III) Trifluoroacetates for C-H trifluoromethylation of (Hetero)arenes
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A scalable and operationally simple decarboxylative trifluoromethylation of (hetero)arenes with easily accessible C6F5I(OCOCF3)2 under photoredox catalysis has been developed. This method is tolerant of various (hetero)arenes and functional groups. Notably, C6F5I is recycled from the decarboxylation reaction and further used for the preparation of C6F5I(OCOCF3)2. The combination of photoredox catalysis and hypervalent iodine reagent provides a practical approach for the application of trifluoroacetic acid in trifluoromethylation reactions.
- Yang, Bin,Yu, Donghai,Xu, Xiu-Hua,Qing, Feng-Ling
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p. 2839 - 2843
(2018/04/14)
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- Phosphovanadomolybdic acid catalyzed direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 as the CF3 source and O2 as the terminal oxidant
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A direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 (Langlois' reagent) as the CF3 source and O2 as the terminal oxidant has been developed. In the presence of catalytic amounts of phosphovanadomolybdic acids, such as H6PV3Mo9O40, various kinds of substituted benzenes and heteroaromatic compounds could be converted into the corresponding trifluoromethylated products.
- Li, Chifeng,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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supporting information
p. 1417 - 1420
(2017/02/23)
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- A pharmaceutical intermediate trifluoromethyl substituted arene the synthetic method of the compound of
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The invention relates to a method for synthesizing a medical intermediate trifluoromethyl substituted aromatic compound shown in a formula (I). The structural formula is as shown in the specification. The method comprises the following steps: adding a formula shown in a formula (II), a formula shown in a formula (III), a catalyst and alkali into an organic solvent at room temperature in a shading mode, heating to the temperature of 30-40 DEG C, and stirring for 20-30 minutes; adding an accelerant, heating to the temperature of 70-80 DEG C, carrying out heat preservation reaction and stirring reaction for 3-5 hours, thereby obtaining the compound shown in the formula (I), wherein the structural formula is as shown in the specification, and R refers to C1-C6 alkyl, cyano, halogens or ester groups. According to the trifluoromethylation method of the aromatic compound, the specific reaction substrate, catalyst, alkali, accelerant and organic solvent are adopted in the method, and good area location property is obtained by virtue of mutual coordination of the factors, so that the trifluoromethyl is introduced into a specific position (ortho-position of the substituted aromatic compound) at high yield, high yield is achieved, and the method has good research value and application potential.
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-
Paragraph 0035-0038
(2017/03/08)
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- Trifluoromethylation of (hetero)aryl iodides and bromides with copper(i) chlorodifluoroacetate complexes
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A new copper-mediated trifluoromethylation reaction using copper(i) chlorodifluoroacetate complexes as reagents is reported. The complex [L2Cu][O2CCF2Cl] (L = bpy, dmbpy, phen) reacted with (hetero)aryl iodides and bromides in the presence of CsF in DMF at 75 °C to afford the trifluoromethylarenes in good to excellent yields. High compatibility with various chemical functions or (hetero)cycles was also observed in the reaction. A reaction mechanism involving a difluorocarbene intermediate, along with a subsequent formation of a -CF3 anion was proposed.
- Lin, Xiaoxi,Li, Zhengyu,Han, Xiaoyan,Weng, Zhiqiang
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p. 75465 - 75469
(2016/08/24)
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- Trifluoromethylation of haloarenes with a new trifluoro-methylating reagent Cu(O2CCF2SO2F)2
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A new trifluoromethylating reagent Cu(O2CCF2SO2F)2, which easily decomposes to generate active CuCF3 species in DMF at room temperature, has been conveniently prepared from inexpensive starting materials on a large scale. This new reagent can be applied to efficiently trifluoromethylate a variety of haloarenes under mild conditions, providing good-to-excellent yields of the desired products.
- Zhao, Gang,Wu, Hao,Xiao, Zhiwei,Chen, Qing-Yun,Liu, Chao
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p. 50250 - 50254
(2016/06/15)
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- A method for preparing of the benzonitrile derivatives
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The invention discloses a preparation method of a cyanobenzene derivative. The cyanobenzene derivative is prepared by taking phenylacetic acid or the derivative thereof as well as urea as raw materials, copper salt as a catalyst and oxygen as an oxidizing agent. According to the preparation method disclosed by the invention, by adopting copper salt as the catalyst and oxygen as the oxidizing agent without an extra cocatalyst, the raw materials phenylacetic acid or the derivative thereof are easy to purchase in the market, low in cost and various in type, and urea as the source of cyanogen is low in toxicity, low in price, mild in reaction condition and environmentally friendly, and has a good functional group compatibility.
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-
Paragraph 0021; 0022; 0023; 0054; 0055; 0056; 0057
(2016/10/17)
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- Silver-Catalyzed C-H Trifluoromethylation of Arenes Using Trifluoroacetic Acid as the Trifluoromethylating Reagent
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Direct trifluoromethylation of arenes using TFA as the trifluoromethylating reagent was achieved with Ag as the catalyst. This reaction not only provides a new protocol for aryl C-H trifluoromethylation, but the generation of CF3· from TFA may prove useful in other contexts and could potentially be extended to other trifluoromethylation reactions. (Chemical Equation Presented).
- Shi, Guangfa,Shao, Changdong,Pan, Shulei,Yu, Jingxun,Zhang, Yanghui
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supporting information
p. 38 - 41
(2015/07/28)
-
- Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
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An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct. (Chemical Equation Presented).
- Reeves, Jonathan T.,Malapit, Christian A.,Buono, Frederic G.,Sidhu, Kanwar P.,Marsini, Maurice A.,Sader, C. Avery,Fandrick, Keith R.,Busacca, Carl A.,Senanayake, Chris H.
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supporting information
p. 9481 - 9488
(2015/08/11)
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- Copper-mediated trifluoromethylation using phenyl trifluoromethyl sulfoxide
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A new method for the generation of trifluoromethylcopper ( CuCF3 ) species from readily available phenyl trifluoromethyl sulfoxide has been developed. The CuCF3 reagent can be applied in efficient trifluoromethylations of aryl iodides and activated aryl bromides in the absence of additional ligands. Furthermore, the CuCF3 species can also undergo oxidative cross-coupling with terminal alkynes and arylboronic acids.
- Li, Xinjin,Zhao, Jingwei,Zhang, Liang,Hu, Mingyou,Wang, Limin,Hu, Jinbo
-
supporting information
p. 298 - 301
(2015/03/04)
-
- 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU)-promoted decomposition of difluorocarbene and the subsequent trifluoromethylation
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Difluorocarbene derived from various carbene precursors could be effectively decomposed by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). This decomposition process was successfully applied in the subsequent trifluoromethylation of a variety of (hetero)aryl iodides without the addition of an external fluoride ion. Mechanistic investigation revealed the detailed difluorocarbene conversion process in which the decomposed difluorocarbene is finally transformed into a fluoride ion and carbon monoxide.
- Zheng, Jian,Lin, Jin-Hong,Deng, Xiao-Yun,Xiao, Ji-Chang
-
supporting information
p. 532 - 535
(2015/03/04)
-
- Mechanism of trifluoromethylation of aryl halides with CuCF3and the ortho effect
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A combined experimental (radical clock, kinetic, Hammett) and computational (DFT, MM) study of the trifluoromethylation reaction of aryl halides with CuCF3 reveals a nonradical mechanism involving Ar-X oxidative addition to the Cu(I) center as the rate determining step. The reaction is second order, first order in each reactant with ΔG? ≈ 24 kcal/mol for PhI (computed ΔG? = 21.9 kcal/ mol). An abrupt change in the gradient on the Hammett plot of log(kR/ kH) versus σp for 11 p-RC6H4I substrates produces two correlations (ρ = +0.69 and +1.83), which is temptingly suggestive of two different reaction pathways. Only one mechanism is operational, however, as advocated by a single linear correlation with σp- (ρ = +0.91), analysis of the experimental ρ values, close similarity of the transition states varying in R and displaying clear signs of -M interactions, and excellent reproduction of the plot by DFT. The long-known yet previously uncomprehended ortho effect has been quantified, for the first time, using the reaction of CuCF3 with a series of o-RC6H4Br: R(kR/kH) = H (1) 2Me (850) 2 (4300) 2H (150 000). With minor contributions from electronic factors, the ortho effect is largely determined by (i) the stabilizing coordination of the o-substituent to Cu in the transition state with the Cu?O distance varying directly with the barrier and (ii) the steric bulk of the o-substituent that raises the ground state free energy of the haloarene (Go ortho - Go H or Go ortho - Go para) by inflicting molecular strain and consequently weakening the Ar-X bond.
- Konovalov, Andrey I.,Lishchynskyi, Anton,Grushin, Vladimir V.
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supporting information
p. 13410 - 13425
(2015/03/30)
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- Trifluoromethylation of arenediazonium salts with fluoroform-derived CuCF3 in aqueous media
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A new protocol has been developed for trifluoromethylation of arenediazonium salts with moisture-sensitive CuCF3 (from fluoroform) in aqueous media. The reaction is governed by a radical mechanism, tolerates a broad variety of functional groups, and is applicable to the synthesis of complex, polyfunctionalized molecules. This journal is the Partner Organisations 2014.
- Lishchynskyi, Anton,Berthon, Guillaume,Grushin, Vladimir V.
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supporting information
p. 10237 - 10240
(2014/08/18)
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- Copper-catalyzed decarboxylative C≡N triple bond formation: Direct synthesis of benzonitriles from phenylacetic acids under O2 atmosphere
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A copper-catalyzed reaction of phenylacetic acids with urea was found to afford benzonitriles under an oxygen atmosphere. This reaction proceeds smoothly by a sequence of decarboxylation, dioxygen activation, C-H bond functionalization, and nitrile formation with urea as the nitrogen source. Molecular oxygen was found to play a crucial role in this transformation. This reaction represents a novel protocol for the formation of benzonitriles in an environmental friendly way and with good functional group tolerability.
- Feng, Qiang,Song, Qiuling
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supporting information
p. 1697 - 1702
(2014/06/09)
-
- Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: Scope, limitations, and mechanistic features
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Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the ligandless CuCF3 at 23-50 C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents. Only the most electrophilic chloroarenes can be trifluoromethylated, e.g., 2-chloronicotinic acid. Exceptionally high chemoselectivity of the reactions (no side-formation of arenes, biaryls, and C2F5 derivatives) has allowed for the isolation of a large number of trifluoromethylated products in high yield on a gram scale (up to 20 mmol). The CuCF3 reagent is destabilized by CuX coproduced in the reaction, the magnitude of the effect paralleling the Lewis acidity of CuX: CuCl > CuBr > CuI. While SNAr and SRN1 mechanisms are not operational, there is a well-pronounced ortho effect, i.e., the enhanced reactivity of ortho-substituted aryl halides 2-RC6H4X toward CuCF3. Intriguingly, this ortho-effect is observed for R = NO2, COOH, CHO, COOEt, COCH3, OCH3, and even CH3, but not for R = CN. The fluoroform-derived CuCF3 reagent and its reactions with haloarenes provide an unmatched combination of reactivity, selectivity, and low cost.
- Lishchynskyi, Anton,Novikov, Maxim A.,Martin, Eddy,Escudero-Adan, Eduardo C.,Novak, Petr,Grushin, Vladimir V.
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p. 11126 - 11146
(2013/12/04)
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- Cleavage of carbon-carbon triple bond: Direct transformation of alkynes to nitriles
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A new cleavage reaction of carbon-carbon triple bonds proceeds efficiently with NIS and TMSN3, giving the corresponding nitriles in moderate to good yields.
- Okamoto, Noriko,Ishikura, Minoru,Yanada, Reiko
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supporting information
p. 2571 - 2573
(2013/07/11)
-
- Practical one-pot conversion of aryl bromides and β-bromostyrenes into aromatic nitriles and cinnamonitriles
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Various aryl bromides were efficiently converted into the corresponding aromatic nitriles in good yields by the treatment with Mg turnings and subsequently DMF, followed by treatment with molecular iodine and aq NH 3. The same treatment of aryl bromides, which are weakly reactive to Mg turnings, with iPrMgCl·LiCl and subsequently DMF, followed by the treatment with molecular iodine and aq NH3 also afforded the corresponding aromatic nitriles in good yields. On the other hand, when N-formylpiperidine was used instead of DMF, p-substituted β-bromostyrenes were converted into the corresponding p-substituted cinnamonitriles, i.e., α,β-unsaturated nitriles, in good to moderate yields by the same procedure. The reactions were carried out by means of a simple experimental procedure and did not require any toxic metal cyanides or expensive rare metals. Therefore, the present reactions are practical and environmentally benign one-pot methods for the preparation of aromatic nitriles, cinnamonitriles, and aliphatic nitriles from aryl bromides, β-bromostyrenes, and alkyl bromides, respectively, through the formation of Grignard reagents and their DMF or N-formylpiperidine adducts.
- Ishii, Genki,Harigae, Ryo,Moriyama, Katsuhiko,Togo, Hideo
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p. 1462 - 1469
(2013/02/25)
-
- Hydrosiloxane-Ti(OiPr)4: An efficient system for the reduction of primary amides into primary amines as their hydrochloride salts
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A simple and useful method for the reduction of primary amides into the corresponding amines using a polymethylhydrosiloxane (PMHS)-Ti(OiPr)4 reducing system is described. Aromatic as well as aliphatic primary amides are reduced in high selectivity and excellent yields. The reduction could proceed via dehydration of the primary amide group into the corresponding nitrile which is then reduced into the corresponding primary amine.
- Laval, Stéphane,Dayoub, Wissam,Pehlivan, Leyla,Métay, Estelle,Favre-Réguillon, Alain,Delbrayelle, Dominique,Mignani, Gérard,Lemaire, Marc
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scheme or table
p. 4072 - 4075
(2011/09/12)
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- Highly efficient Pd-catalyzed cyanation of aryl chlorides and arenesulfonates with potassium ferrocyanide in aqueous media
-
A highly improved Pd-catalyzed cyanation of aryl chlorides to corresponding benzonitriles was demonstrated in aqueous media. Moreover, Pd-catalyzed cyanation of aryl tosylates and benzenesulfonates with K4[Fe(CN) 6] was developed under the similar conditions, which extended application scope of the cyanation. Graphical Abstract: [Figure not available: see fulltext.]
- Zhang, Junli,Chen, Xiaorong,Hu, Tongjie,Zhang, Yuan,Xu, Kunling,Yu, Yanpeng,Huang, Jun
-
experimental part
p. 56 - 60
(2011/01/12)
-
- A novel synthesis of N-unsubstituted β-enamino thioesters from 3-arylisoxazoles and 3-aryl-5-phenylthio-2-isoxazolines
-
A novel procedure for the synthesis of N-unsubstituted β-enamino thioesters, (Z)-S-phenyl 3-amino-3-arylprop-2-enethioates, from 3-arylisoxazoles or 3-aryl-5-phenylthio-2-isoxazolines is described and a plausible mechanism for the reaction is proposed. Some examples of conversion of one β-enamino thioester [(Z)-S-phenyl 3-amino-3-phenylprop-2-enethioate] into N-unsubstituted β-enaminoacyl derivatives (β-enamino esters, β-enamino amides, and β-keto amides) are also reported. Georg Thieme Verlag Stuttgart - New York.
- Vitale, Paola,Di Nunno, Leonardo,Scilimati, Antonio
-
experimental part
p. 3195 - 3203
(2010/10/21)
-
- Process for catalytically preparing aromatic or heteroaromatic nitriles
-
The present invention relates to a process for preparing optionally substituted aromatic or heteroaromatic nitriles starting from haloaromatics. These are reacted in a copper-catalysed reaction with potassium hexacyanoferrate(II) or potassium hexacyanoferrate(III) in the presence of heteroaromatic amines.
- -
-
Page/Page column 3
(2009/04/24)
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- A bio-inspired copper catalyst system for practical catalytic cyanation of aryl bromides
-
A general and environmentally improved protocol for the cyanation of aryl halides with the nontoxic cyanide source potassium hexacyanoferrate(II) {K 4[Fe(CN)6]} using copper catalysis and a ligand system based on 1-alkyl-1H-imidazoles is presented. The advantages of this system are a wide substrate range, high selectivity, easy handling, and inexpensive reagents.
- Schareina, Thomas,Zapf, Alexander,Cotte, Alain,Mueller, Nikolaus,Beller, Matthias
-
experimental part
p. 3351 - 3355
(2009/06/06)
-
- Effect of the aryl group substituent in the dimerization of 3-arylisoxazoles to syn 2,6-diaryl-3,7-diazatricyclo[4.2.0.02,5]octan-4,8-diones induced by LDA
-
3-Arylisoxazoles react with LDA in THF at 0 °C affording syn-2,6-diaryl-3,7-diazatricyclo[4.2.0.02,5]octan-4,8-diones (bis-azetidinones), via stereoselective dimerization of an azetinone anion intermediate. A?fragmentation reaction affording arylnitriles may compete with electronic and steric effects of the substituent present in the aryl group being pivotal in determining the outcome of this reaction. An interesting behaviour with LDA of arylnitriles arising from the fragmentation reaction of some 3-arylisoxazoles was also observed. N,N-Diisopropylaminobenzonitriles were in fact formed (plausibly via a benzyne mechanism) from 3-(4-chlorophenyl)isoxazole and 3-(2-chlorophenyl)isoxazole, whereas 3-(2-methylphenyl)isoquinolin-1-amine was isolated starting from 3-(2-methylphenyl)isoxazole and LDA.
- Di Nunno, Leonardo,Vitale, Paola,Scilimati, Antonio
-
experimental part
p. 11198 - 11204
(2009/04/11)
-
- A new palladium catalyst system for the cyanation of aryl chlorides with K4[Fe(CN)6]
-
The development of a novel Pd-catalyzed synthesis of (hetero)aromatic nitriles from the corresponding aryl chlorides and potassium hexacyanoferrate(II) is described. This novel protocol avoids the use of highly toxic alkali cyanides and proceeds in the presence of small amounts of palladium catalysts. High yields and selectivities of the corresponding aryl nitriles were achieved applying di(1-adamantyl)-1-butylphosphine (cataCXium A) as the ligand.
- Schareina, Thomas,Zapf, Alexander,M?gerlein, Wolfgang,Müller, Nikolaus,Beller, Matthias
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p. 1087 - 1090
(2008/01/27)
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- A state-of-the-art cyanation of aryl bromides: A novel and versatile copper catalyst system inspired by nature
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A general protocol for the cyanation of aryl halides with the nontoxic cyanide source K4[Fe(CN)6] using copper catalysis and a ligand system based on 1-alkylimidazoles is presented. The advantages of this system are the high selectivity, a unique substrate range, easy handling, and inexpensive reagents.
- Schareina, Thomas,Zapf, Alexander,Maegerlein, Wolfgang,Mueller, Nikolaus,Beller, Matthias
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p. 6249 - 6254
(2008/02/13)
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- Electron attachment and detachment: Electron affinities of isomers of trifluoromethylbenzonitrile
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Rate constants for electron attachment to the three isomers of trifluoromethylbenzonitrile [(CF3)(CN)C6H4, or TFMBN] were measured over the temperature range of 303-463 K in a 133-Pa He buffer gas, using a flowing-afterglow Langmuir-probe apparatus. At 303 K, the measured attachment rate constants are 9.0×10-8 (o-TFMBN), 5.5× 10-8 (m-TFMBN), and 8.9 × 10-8 cm 3 s-1 (p-TFMBN), estimated accurate to ±25%. The attachment process formed only the parent anion in all three cases. Thermal electron detachment was observed for all three anion isomers, and rate constants for this reverse process were also measured. From the attachment and detachment results, the electron affinities of the three isomers of TFMBN were determined to be 0.70(o-TFMBN), 0.67(m-TFMBN), and 0.83 eV (p-TFMBN), all ±0.05 eV. G3(MP2) [Gaussian-3 calculations with reduced Moller-Plesset orders (MP2)] calculations were carried out for the neutrals and anions. Electron affinities derived from these calculations are in good agreement with the experimental values.
- Miller, Thomas M.,Viggiano,Friedman, Jeffrey F.,Van Doren, Jane M.
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p. 9993 - 9998
(2008/01/27)
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- Progress in the palladium-catalyzed cyanation of aryl chlorides
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The development of new palladium catalysts for the cyanation of various aryl and heteroaryl chlorides is described. The combination of amine co-catalysts with chelating phosphine ligands, for example, 1,4-bis(diphenylphosphino)butane (dppb) or 1,5-bis(diphenylphosphino)pentane (dpppe), allows an efficient cyanation of chloroarenes with simple potassium cyanide. General palladium-catalyzed cyanation of nonactivated and deactivated chloroarenes is possible for the first time. Studies of the oxidative addition of aryl halides to palladium triphenylphosphine complexes in the presence and absence of amines suggest that the co-catalyst is capable of preventing catalyst deactivation caused by the presence of excess cyanide ions in solution.
- Sundermeier, Mark,Zapf, Alexander,Mutyala, Sateesh,Baumann, Wolfgang,Sans, Juergen,Weiss, Stefan,Beller, Matthias
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p. 1828 - 1836
(2007/10/03)
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- Process for producing trifluoromethylbenzylamines
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The invention relates to a process for producing a trifluotomethylbenzylamine represented by the following general formula (1), 1where each R independently represents a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, an alkyl group having a carbon atom number of 1-4, an alkoxy group having a carbon atom number of 1-4, an amino group, a hydroxyl group or a trifluoromethyl group, and n represents an integer from 0 to 4. The process includes hydrogenating a trifluoromethylbenzonitrile by hydrogen in an organic solvent in the presence of ammonia and a catalyst containing a platinum group element. This trifluoromethylbenzonitrile is represented by the following general formula (2), 2where R and n are defined as above. With this process, it is possible to obtain the trifluoromethylbenzylamine at an extremely high yield.
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- Process for producing trifluoromethylbenzylamines
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The invention relates to a process for producing a trifluoromethylbenzylamine represented by the following general formula (1). This process includes hydrogenating a trifliuoromethylbenzonitrile represented by the following general formula (2) by hydrogen in an organic solvent in the presence of ammonia, using a Raney catalyst, where each R independently represents a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, an alkyl group having a carbon atom number of 1-4, an alkoxy group having a carbon atom number of 1-4, an amino group, a hydroxyl group or a trifluoromethyl group, and n represents an integer from 0 to 4, where R and n are defined as above. With this process, it is possible to obtain the trifluoromethylbenzylamine easily and inexpensively at an extremely high yield.
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- Aromatic trifluoromethyldenitration and trifluoromethyldecyanation using trifluoromethyltrimethylsilane
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Activation of trifluoromethyltrimethylsilane by potassium fluoride in N,N-dimethylacetamide provides a powerful source of trifluoromethide which is capable of substituting aromatic nitro and cyano groups under nucleophilic conditions, albeit in low yield. The trifluoromethide generated in this system is also a potent base which leads to a number of interesting side reactions via deprotonation of the substrate.
- Adams, Dave J.,Clark, James H.,Hansen, Liv B.,Sanders, Victoria C.,Tavener, Stewart J.
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p. 3081 - 3085
(2007/10/03)
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- Reactivity of Negative Ions with Trifluoromethyl Halides
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The kinetics of the reactions of selected anions (A(-)) with the trifluoromethyl halides CF3X (X = F, Cl, Br, I) in the gas phase were measured at 300 K.Reaction rate constants and product branching fractions were determined using a selected ion flow tube (SIFT) instrument.The chosen anions were C5F5N(-), o-, m-, and p-CF3C6H4CN(-), C6F5Br(-), C6F5Cl(-), C6F5CF3(-), C6F5COCH3(-), Fe(-), FeCO(-), SF6(-), SO(-), SO2(-), NO(-), NO2(-), and NO3(-).The reactivity of these systems varies from unreactive to collisional, and a variety of reaction types was found.The results of our present and previous measurements on A(-) + CF3X reactions show that, in cases where nondissociative electron transfer (NDET) is energetically allowed, the total reactivity tends to be high, approaching collisional.This suggests that reactivity in these cases is initiated and controlled by electron transfer from the anion.In addition, association reactions tend to be preempted when NDET is energetically allowed.A few exceptions to these tendencies were found and are discussed.
- Morris, Robert A.,Viggiano, A. A.,Miller, Thomas M.,Seeley, John V.,Arnold, Susan T.,et al.
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p. 10641 - 10645
(2007/10/03)
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- Electrosynthesis of (trifluoromethyl)copper complexes from bromotrifluoromethane: reactivities with various organic halides
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The synthesis of (trifluoromethyl)copper complexes is achieved easily by electroreduction of bromotrifluoromethane in N,N-dimethylformamide, in the presence of a sacrificial copper anode and various potential ligands.Three (trifluoromethyl)copper species are considered; two copper(II) and one copper(I).The mechanism of formation of the (trifluoromethyl)copper species is discussed and a study of their reactivities towards various organic halides is reported. Keywords: Copper; Trifluoromethyl derivatives; Electroreduction; Mechanism; Bromotrifluoromethane; (Trifluoromethyl)copper complexes
- Paratian, J. M.,Labbe, E.,Sibille, S.,Perichon, J.
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p. 137 - 144
(2007/10/02)
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- THE INTRODUCTION OF SCF3 INTO AROMATIC SUBSTRATES USING CuSCF3 AND ALUMINA-SUPPORTED CuSCF3
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Trifluoromethylthiocopper(I) has been readily prepared from the silver analogue, using a metathetical reaction with copper(I) bromide.Homogeneous CuSCF3 and the supported reagent CuSCF3-alumina have been compared in their reactivity towards aryl iodides, in order to form trifluoromethylaryl sulphides in good yields.
- Clark, James H.,Craig, W. Jones,Kybett, Adrian P.,McClinton, Martin A.,Miller, Jack M.,et al.
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p. 249 - 255
(2007/10/02)
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- Electron Affinities of Di- and Tetracyanoethylene and Cyanobenzenes Based on Measurements of Gas-Phase Electron-Transfer Equilibria
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The electron affinities of tetracyanoethylene, trans-1,2-dicyanoethylene, and eleven substituted benzonitriles as well as two naphthonitriles were determined by measurement of the electron-transfer equilibria A-+B=A+B- with a pulsed electron high ion source pressure mass spectrometer.Rate constants for exothermic electron transfer involving the cyano compounds were found to be near unit collision efficiency.The EA (tetracyanoethylene)=3.17 eV obtained in the present work is considerably higher than the 2.3 eV photodetachment value of Palmer and Lyons.The electron affinities of benzene and benzonitrile substituted by CN, CHO, and NO2 increase in the given order, while the order for nitrobenzene is CHO, CN, NO2.This reversal of order is explained on the basis of a larger attenuation of the ?-withdrawing effect relative to the field effect of substituents when the electron density in the ?* single-electron orbital is decreased.
- Chowdhury, Swapan,Kebarle, Paul
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p. 5453 - 5459
(2007/10/02)
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- Cyanation of Aromatic Compounds in a Gaseous Plasma
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Aromatic compounds are directly cyanated by passing cyanogen and the respective compounds through a radio-frequency generated and inductively coupled glow discharge zone.Benzene and a wide variety of substituted benzenes (C6H5X: X = CH3, t-Bu, CF3, OH, F, Cl, Br, CHO) are cyanated providing a good yield of ortho-, meta-, para-, and ipso-substituted products.The relative amount of ipso product increases as the carbon-X bond dissociation energy decreases.The ratio of ortho to meta to para cyanated products demonstrates a slight preference for substitution on electron-rich positions.A plot of the meta/para yield ratio against ?m - ?p gives a ρ value of -0.5.It is proposed that electron impact on cyanogen produces CN., which in turn attacks the aromatic, causing substitution.
- So, Y. H.,Miller, Larry L.
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p. 4204 - 4209
(2007/10/02)
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