cas 456-71-3, 4-(TRIFLUOROMETHOXY)BENZAMIDE

Articles about 456-71-3Total 25 be found

Article title
Article abstract
Author
Journal number and time
Download

Radical C?H Trifluoromethoxylation of (Hetero)arenes with Bis(trifluoromethyl)peroxide
Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro- and medicinal chemistry. Radical C?H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing .OCF3 radical sources make them unsuitable for the large-scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF3OOCF3) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one-step synthesis of valuable pyridine derivatives, which have been previously prepared via multi-step approaches.
Dix, Stefan,Golz, Paul,Schmid, Jonas R.,Riedel, Sebastian,Hopkinson, Matthew N.
supporting information
p. 11554 - 11558
(2021/07/09)

Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
p. 6299 - 6308
(2020/07/21)

Base-Mediated Amination of Alcohols Using Amidines
Novel and efficient base-mediated N-alkylation and amidation of amidines with alcohols have been developed, which can be carried out in one-pot reaction conditions, which allows for the synthesis of a wide range of N-alkyl amines and free amides in good to excellent yields with high atom economy. In contrast to borrowing hydrogen/hydrogen autotransfer or oxidative-type N-alkylation reactions, in which alcohols are activated by transition-metal-catalyzed or oxidative aerobic dehydrogenation, the use of amidines provides an effective surrogate of amines. This circumvents the inherent necessity in N-alkylation of an oxidant or a catalyst to be stabilized by ligands.
Chen, Jianbin,Fang, Yanchen,Jia, Xiaofei,Jiang, Shaohua,Li, Zehua,Liang, Zuyu,Lu, Fenghong,Qi, Shuo,Ren, Chaoyu,Yu, Shuangming,Zhang, Chunyan,Zhang, Guoying,Zhang, Sheng
p. 7728 - 7738
(2020/07/15)

Photocatalytic trifluoromethoxylation of arenes and heteroarenes in continuous-flow
The first example of photocatalytic trifluoromethoxylation of arenes and heteroarenes under continuous-flow conditions is described. Application of continuous-flow microreactor technology allowed to reduce the residence time up to 16 times in comparison t
Cendón, Borja,Gulías, Moisés,Ho, Michelle,No?l, Timothy,Nyuchev, Alexander V.,Sambiagio, Carlo,Struijs, Job J. C.,Wan, Ting,Wang, Ying
supporting information
p. 1305 - 1312
(2020/07/10)

(Ar-tpy)RuII(ACN)3: A Water-Soluble Catalyst for Aldehyde Amidation, Olefin Oxo-Scissoring, and Alkyne Oxygenation
The synthetic chemists always look for developing new catalysts, sustainable catalysis, and their applications in various organic transformations. Herein, we report a new class of water-soluble complexes, (Ar-tpy)RuII(ACN)3, utilizing designed terpyridines possessing electron-donating and -withdrawing aromatic residues for tuning the catalytic activity of the Ru(II) complex. These complexes displayed excellent catalytic activity for several oxidative organic transformations including late-stage C-H functionalization of aldehydes with NH2OR to valuable primary amides in nonconventional aqueous media with excellent yield. Its diverse catalytic power was established for direct oxo-scissoring of a wide range of alkenes to furnish aldehydes and/or ketones in high yield using a low catalyst loading in the water. Its smart catalytic activity under mild conditions was validated for dioxygenation of alkynes to highly demanding labile synthons, 1,2-diketones, and/or acids. This general and sustainable catalysis was successfully employed on sugar-based substrates to obtain the chiral amides, aldehydes, and labile 1,2-diketones. The catalyst is recovered and reused with a moderate turnover. The proposed mechanistic pathway is supported by isolation of the intermediates and their characterization. This multifaceted sustainable catalysis is a unique tool, especially for late-stage functionalization, to furnish the targeted compounds through frequently used amidation and oxygenation processes in the academia and industry.
Joarder, Dripta De,Gayen, Subrata,Sarkar, Rajarshi,Bhattacharya, Rajarshi,Roy, Sima,Maiti, Dilip K.
p. 8468 - 8480
(2019/07/03)

Radical Trifluoromethoxylation of Arenes Triggered by a Visible-Light-Mediated N?O Bond Redox Fragmentation
A simple trifluoromethoxylation method enables non-directed functionalization of C?H bonds on a range of substrates, providing access to aryl trifluoromethyl ethers. This light-driven process is distinctly different from conventional procedures and occurs through an OCF3 radical mechanism mediated by a photoredox catalyst, which triggers an N?O bond fragmentation. The pyridinium-based trifluoromethoxylation reagent is bench-stable and provides access to synthetic diversity in lead compounds in an operationally simple manner.
Jelier, Benson J.,Tripet, Pascal F.,Pietrasiak, Ewa,Franzoni, Ivan,Jeschke, Gunnar,Togni, Antonio
supporting information
p. 13784 - 13789
(2018/09/14)

Tandem synthesis of aromatic amides from styrenes in water
An expedient one-pot synthesis of aromatic amides has been reported from styrenes in the presence of N-bromosuccinimide and iodine by using aqueous ammonia in water. The reaction proceeds through the formation of α-bromoketone as an intermediate in the pr
Sathe, Pratima A.,Karpe, Aniket S.,Parab, Aniket A.,Parade, Babasao S.,Vadagaonkar, Kamlesh S.,Chaskar, Atul C.
supporting information
p. 2820 - 2823
(2018/06/25)

Highly Selective Ruthenium-Catalyzed Direct Oxygenation of Amines to Amides
Reports on aerobic oxidation of amines to amides are rare, and those reported suffer from several limitations like poor yield or selectivity and make use of pure oxygen under elevated pressure. Herein, we report a practical and an efficient ruthenium-catalyzed synthetic protocol that enables selective oxidation of a broad range of primary aliphatic, heterocyclic and benzylic amines to their corresponding amides, using readily available reagents and ambient air as the sole oxidant. Secondary amines instead, yield benzamides selectively as the sole product. Mechanistic investigations reveal intermediacy of nitriles, which undergo hydration to afford amide as the final product.
Ray, Ritwika,Hazari, Arijit Singha,Chandra, Shubhadeep,Maiti, Debabrata,Lahiri, Goutam Kumar
supporting information
p. 1067 - 1071
(2018/01/03)

Metal-Free Thermal Activation of Molecular Oxygen Enabled Direct α-CH2-Oxygenation of Free Amines
Direct oxidation of α-CH2 group of free amines is hard to achieve due to the higher reactivity of amine moiety. Therefore, oxidation of amines involves the use of sophisticated metallic reagents/catalyst in the presence or absence of hazardous oxidants under sensitive reaction conditions. A novel method for direct C-H oxygenation of aliphatic amines through a metal-free activation of molecular oxygen has been developed. Both activated and unactivated free amines were oxygenated efficiently to provide a wide variety of amides (primary, secondary) and lactams under operationally simple conditions without the aid of metallic reagents and toxic oxidants. The method has been applied to the synthesis of highly functionalized amide-containing medicinal drugs, such as O-Me-alibendol and -buclosamide.
Ghosh, Santanu,Jana, Chandan K.
p. 260 - 266
(2018/02/19)

Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
supporting information
p. 266 - 273
(2018/01/12)

A Brevibacterium process for synthesizing amide
The invention discloses a method for synthesizing amide through nitrile hydrolysis. The method comprises the following steps: adding nitrile, acetaldoxime, water, a water-soluble rhodium complex to a reaction vessel, and cooling to room temperature after reaction of a reaction mixture for several hours at the temperature of 50-80 DEG C; and adding ethyl acetate for extraction so as to obtain an organic layer, and carrying out rotary evaporation to remove a solvent, thus obtaining a target product. Compared with a method for synthesizing amide through nitrile hydrolysis by using oxime as a water source in a transition metal catalysis process, the method has the advantages that a used catalyst is low in loading and does not contain a phosphine ligand seriously polluting environments, synthesis can be performed in air, and nitrogen protection is not needed; and therefore, the method meets the green chemistry requirements and has a wide development prospect.
-
Paragraph 0060; 0061; 0062; 0063

(2017/04/29)

Highly efficient synthesis of primary amides: Via aldoximes rearrangement in water under air atmosphere catalyzed by an ionic ruthenium pincer complex
The transformation of aldoximes to primary amides has been evaluated using pincer ruthenium complexes a-c, among which the ionic Ru catalyst a proved to be the most efficient in water under air atmosphere. A variety of (hetero)arene aldoximes proceeded smoothly to afford amides in high yields with good functional group compatibilities. Furthermore, a direct synthetic route of amides from aldehydes, hydroxylamine hydrochloride and sodium carbonate was also described with broad substrates including conjugated and aliphatic aldehydes. This protocol is operationally simple and proceeds with a low catalyst loading (0.5 mol%).
Yang, Fa-Liu,Zhu, Xinju,Rao, Dun-Kang,Cao, Xiao-Niu,Li, Ke,Xu, Yan,Hao, Xin-Qi,Song, Mao-Ping
p. 37093 - 37098
(2016/05/24)

A method of from [...] amide
The invention discloses a method for synthesizing amides from oxime. The method is characterized by adding oxime, water and a water-soluble iridium complex catalyst to a reaction vessel, cooling a reactant to the room temperature after the reaction mixture reacts at 80-120 DEG C for several hours, removing water through selective evaporation, and obtaining a target product through column separation. Compared with existing methods for synthesizing amides through oxime rearrangement in water through transition metal catalysis, the method has the advantages that the used catalyst is low in load and does not contain phosphine ligands severely polluting the environment, so that the reaction can be carried out in the air, without nitrogen protection; therefore the reaction meets the green chemical requirements and has an extensive development prospect.
-
Paragraph 0094-0098

(2017/01/31)

An aerobic oxidative synthesis of aryl nitriles and primary aryl amides from benzylic alcohols catalyzed by a polymer supported Cu(II) complex
A new polymer supported Cu(II) complex has been synthesized and characterized. The catalytic performance of the complex has been tested for the direct conversion of benzylic alcohols to aryl nitriles. In this reaction ammonium formate was used as the nitrogen source and O2 as the oxidant. Furthermore, the copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved. The effects of solvents, reaction time and catalyst amount for the aryl nitriles and aryl amides synthesis were reported. This catalyst showed excellent catalytic activity and recyclability. The polymer supported Cu(II) catalyst could be easily recovered by filtration and reused more than five times without appreciable loss of its initial activity.
Molla, Rostam Ali,Ghosh, Kajari,Tuhina,Manirul Islam
p. 921 - 930
(2015/02/19)

A facile manganese dioxide mediated oxidation of primary benzylamines to benzamides
A high yielding manganese dioxide mediated oxidation of benzylamines to the corresponding amides has been developed under mild reaction conditions. The mechanism for the conversion has been explored by 1H NMR spectroscopy and the role of both manganese dioxide and molecular sieves in the reaction elucidated. This journal is the Partner Organisations 2014.
Poeschl,Mountford
supporting information
p. 7150 - 7158
(2014/10/15)

Rearrangement of aldoximes to amides in water under air atmosphere catalyzed by water-soluble iridium complex [Cp*Ir(H2O) 3][OTf]2
In the presence of the water-soluble iridium complex [Cp*Ir(H 2O)3][OTf]2, a variety of aldoximes, including aromatic, aliphatic, conjugated unsaturated and non-conjugated unsaturated, were converted into their corresponding amides in water with good to excellent yields. Further, the one-pot synthesis of amides from aldehydes, hydroxylamine hydrochloride and sodium carbonate via a tandem condensation-rearrangement reaction in water was also accomplished. Compared with the reported organometallic catalysts for the rearrangement of aldoximes to amides in water, the present catalyst exhibited some advantages such as being phosphorus ligand-free, having low catalyst loading, and operational convenience under air atmosphere. This journal is the Partner Organisations 2014.
Sun, Chunlou,Qu, Panpan,Li, Feng
p. 988 - 996
(2014/04/03)

The direct synthesis of N-alkylated amides via a tandem hydration/N-alkylation reaction from nitriles, aldoximes and alcohols
A novel strategy for the direct synthesis of N-alkylated amides from nitriles, aldoximes and alcohols was proposed and accomplished in the presence of a Cp*Ir complex. This journal is the Partner Organisations 2014.
Wang, Nana,Zou, Xiaoyuan,Ma, Juan,Li, Feng
supporting information
p. 8303 - 8305
(2014/07/22)

A general and practical oxidation of alcohols to primary amides under metal-free conditions
A general procedure for oxidation of both benzyl alcohols and alkyl alcohols to primary amides under catalyst free conditions has been developed. 34 examples of primary amides were produced from their corresponding alcohols in moderate to excellent yields. This is a practical procedure for primary amides synthesis; water and tert-butanol are the only by-products. A commercial drug, Piracetam, was prepared in one step with 73% yield as well.
Wu, Xiao-Feng,Sharif, Muhammad,Feng, Jian-Bo,Neumann, Helfried,Pews-Davtyan, Anahit,Langer, Peter,Beller, Matthias
p. 1956 - 1961
(2013/09/24)

A general palladium-catalyzed aminocarbonylation of phenols to primary benzamides via in situ generation of aryl nonaflates
Amides in mind! A novel palladium-catalyzed amino-carbonylation of in situ formed aryl nonaflates to give primary amides in moderate to excellent yields has been developed (see scheme). Copyright
Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
experimental part
p. 419 - 422
(2012/02/04)

Ruthenium-catalyzed rearrangement of aldoximes to primary amides in water
The rearrangement of aldoximes to primary amides has been studied using the readily available arene-ruthenium(II) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol %) as catalyst. Reactions proceeded cleanly in pure water at 100 °C without the assistance of any cocatalyst, affording the desired amides in high yields (70-90%) after short reaction times (1-7 h). The process was operative with both aromatic, heteroaromatic, α,β-unsaturated, and aliphatic aldoximes and tolerated several functional groups. Reaction profiles and experiments using 18O-labeled water indicate that two different mechanisms are implicated in these transformations. In both of them, nitrile intermediates are initially formed by dehydration of the aldoximes. These intermediates are then hydrated to the corresponding amides by the action of a second molecule of aldoxime or water. A kinetic analysis of the rearrangement of benzaldoxime to benzamide is also discussed.
Garcia-Alvarez, Rocio,Diaz-Alvarez, Alba E.,Borge, Javier,Crochet, Pascale,Cadierno, Victorio
p. 6482 - 6490
(2012/10/30)

A simple Ru catalyst for the conversion of aldehydes or oximes to primary amides
Ru(DMSO)4Cl2 is catalytically active for converting aldehydes to primary amides via oxime intermediates. This catalyst is readily available, and requires no additional ligands, a great simplification compared to previous work. A Ru(II)/(IV) mechanism is proposed.
Hull, Jonathan F.,Hilton, Sheena T.,Crabtree, Robert H.
experimental part
p. 1243 - 1245
(2010/07/05)

Highly efficient ruthenium-catalyzed oxime to amide rearrangement
A wide range of aldoximes has been converted into the corresponding amides using the ruthenium-based catalyst Ru(PPh3)3(CO)H 2/dppe/ TsOH. The amides are generated in high yield and selectivity, with catalyst loading as low as 0.04 mol %.
Owston, Nathan A.,Parker, Alexandra J.,Williams, Jonathan M. J.
p. 3599 - 3601
(2008/02/12)

Synthesis and anthelmintic activity of 3'-benzoylurea derivatives of 6-phenyl-2,3,5,6-tetrahydroimidazo[2,1-b]thiazole
Reaction of 3-amino derivatives of the nematocides tetramisole and levamisole with variously substituted benzoylisocyanates gave a series of benzoylureas I which were tested for activity against helminths and ectoparasites. Compounds bearing 2,6-difluoro and 4-trifluoromethyl substituents had potent nematocidal activity in both mice and sheep. No antiectoparasitic activity was observed.
Weikert,Bingham Jr.,Emanuel,Fraser-Smith,Loughhead,Nelson,Poulton
p. 1630 - 1633
(2007/10/02)

Chlorination of 4-methoxybenzoyl chloride
An improved process for chlorinating 4-methoxybenzoyl chloride on the methyl group with molecular chlorine is done neat at elevated temperature in the absence of light of radical-forming intensity.
-
(2008/06/13)

4-[-(Alkoxy or polyhaloalkoxy)-benzamido]cyclohexanones
3-R-3-(Ac2 NH)-9-R'-9-(Ac1 NH)-1,5-dioxaspiro[5.5]undecane (I), where R and R' are each hydrogen or lower-alkyl, Ac1 is lower-alkanoyl or 4-Q1 -benzoyl and Ac2 is 4-Q2 -benzoyl where Q1 and Q2 each is lower-alkoxy or polyhalo-lower-alkoxy, are antifertility agents. The compounds are prepared by di-acylating 3-R-9-R'-1,5-dioxaspiro[5.5]undecan-3,9-diamine (II) or mono-acylating 9-(Ac1 NH)-3-R-9-R'-1,5-dioxaspiro[5.5]undecan-3-amine (IV). IV and II are prepared by oxidizing 4-(Ac1 NH)-4-R'-cyclohexanol (VI) to produce 4-(Ac1 NH)-4-R'-cyclohexanone (VII), reacting VII with 2-NO2 -2-R-1,3-propanediol to produce 3-R-3-NO2 -9-(Ac1 NH)-9-R'-1,5-dioxaspiro[5.5]undecane (VIII), reducing VIII to produce the corresponding 3-amine (IV) and hydrolyzing IV to the corresponding 3,9-diamine (II). Methods of preparing VI are shown.
-
(2008/06/13)