- First aromatic ring acetamidation by anodic oxidation
-
Anodic oxidation of 1-(trifluoromethyl)benzene in dry acetonitrile/Bu4NBF4under constant potential conditions led to 2-(trifluoromethyl) acetanilide in 86% yield. Other experimental conditions, as the use of constant current or the c
- Barba, Fructuoso,Barba, Isidoro,Batanero, Belen
-
-
Read Online
- Acetonitrile and benzonitrile as versatile amino sources in copper-catalyzed mild electrochemical C-H amidation reactions
-
A mild, efficient electrochemical approach to the site-selective direct C-H amidation of benzene and its derivatives with acetonitrile and benzonitrile has been developed. It has been shown that joint electrochemical oxidation of various arenes in the presence of a copper salt as a catalyst and nitriles leads to the formation of N-phenylacetamide from benzene and N-benzylacetamides from benzyl derivatives (up to 78% yield). A favorable feature of the process is mild conditions (room temperature, ambient pressure, no strong oxidants) that meet the criteria of green chemistry.
- Budnikova, Yulia,Kononov, Alexander,Rizvanov, Ildar,Strekalova, Sofia
-
p. 37540 - 37543
(2021/12/07)
-
- Fungicidal Properties of Some Novel Trifluoromethylphenyl Amides
-
Trifluoromethylphenyl amides (TFMPAs) were designed and synthesized as potential pesticides. Thirty-three structures were evaluated for fungicidal activity against three Colletotrichum species using direct bioautography assays. Active compounds were subsequently tested against C. fragariae, C. gloeosporioides, C. acutatum, Phomopsis obscurans, P. viticola, Botrytis cinerea and Fusarium oxysporum. The study identified 2-chloro-N-[2,6-dichloro-4-(trifluoromethyl)phenyl]acetamide (7a) as showing the strongest antifungal activity, and the broadest activity spectrum in this set against Colletotrichum acutatum (at 48 and 72 h) and Phomopsis viticola (at 144 h). The presence of triethylamine in its complex with N-[2,6-dichloro-4-(trifluoromethyl)phenyl]-2,2,3,3,3-pentafluoropropanamide (7b′) played an important role in the bioactivity, and depending on the concentration or fungal species it showed higher or lower activity than the parent amide. X-Ray crystallography has shown that the complex (7b′) is an ion pair, (C10H2Cl2F8NO)? (C6H16N)+, where a proton is transferred from the amide nitrogen to the triethylamine nitrogen and then connected by hydrogen bonding to the acyl oxygen (N?H 0.893 ?; H???O 1.850 ?; N???O 2.711 ?; N?H???O 161.2(13)°). Although none of these compounds were better than standards, this work revealed some potential lead structures for further development of active novel compounds.
- Tsikolia, Maia,Bernier, Ulrich R.,Wedge, David E.,Tabanca, Nurhayat,Abboud, Khalil A.,Linthicum, Kenneth J.
-
-
- Visible-light-induced Pd-catalyzed: Ortho -trifluoromethylation of acetanilides with CF3SO2Na under ambient conditions in the absence of an external photocatalyst
-
A visible-light-induced Pd-catalyzed ortho-trifluoromethylation of acetanilides with CF3SO2Na was developed. The reaction proceeded smoothly at room temperature in air without any external photocatalyst or additive, providing the desired products in moderate to good yields with good functional group tolerance and regioselectivity.
- Zou, Long,Li, Pinhua,Wang, Bin,Wang, Lei
-
supporting information
p. 3737 - 3740
(2019/04/01)
-
- Visible-Light Mediated ortho-Trifluoromethylation of Aniline Derivatives
-
A general visible-light mediated ortho-C-H trifluoromethylation of aniline derivatives by using a low-cost and stable Langlois reagent (CF3SO2Na) as the "CF3" source has been developed. In contrast to previous reports, this strategy allowed access to elusive trifluoromethyl lactams. Furthermore, mechanism experiments revealed that a copper/photoredox dual catalytic mechanism enabled general trifluoromethylation of aniline derivatives.
- Tian, Chao,Wang, Qiyue,Wang, Xueqi,An, Guanghui,Li, Guangming
-
p. 14241 - 14247
(2019/10/16)
-
- Acetanilide and bromoacetyl-lysine derivatives as activators for human histone deacetylase 8
-
In the current study, seven compounds (i.e. 1–7) were found to be novel activators for the Nε-acetyl-lysine deacetylation reaction catalyzed by human histone deacetylase 8 (HDAC8). When assessed with the commercially available HDAC8 peptide substrate Fluor-de-Lys-HDAC8 that harbors the unnatural 7-amino-4-methylcoumarin (AMC) residue immediately C-terminal to the Nε-acetyl-lysine residue to be deacetylated, our compounds exhibited comparable activation potency to that of TM-2-51, the strongest HDAC8 activator reported in the current literature. However, when assessed with an AMC-less peptide substrate derived from the native HDAC8 non-histone substrate protein Zinc finger protein ZNF318, while our compounds were all found to be able to activate HDAC8 deacetylation reaction, TM-2-51 was found not to be able to. Our compounds also seemed to be largely selective for HDAC8 over other classical HDACs. Moreover, treatment with the strongest activator among our compounds (i.e. 7) was found to decrease the KM of the above AMC-less HDAC8 substrate, while nearly maintaining the kcat of the HDAC8-catalyzed deacetylation on this substrate.
- Mukhtar, Yusif M.,Huang, Yajun,Liu, Jiajia,Chen, Di,Zheng, Weiping
-
supporting information
p. 2319 - 2323
(2017/05/09)
-
- 2-fluoro-6-trifluoromethylbenzenesulfonyl chloride synthesis method
-
The present invention provides a 2-fluoro-6-trifluoromethylbenzenesulfonyl chloride synthesis method. According to the reaction formula defined in the specification, o-trifluoromethylaniline is used as a raw material, and acylation, alkylation, nitration, dealkylation, reduction, diazotization fluorination, hydrolysis and sulfonylation are performed to synthesize an intermediate 2-fluoro-6-trifluoromethylbenzenesulfonyl chloride. According to the present invention, the target is that the synthesis process is suitable for the industrial production, the starting raw material is easy to obtain, the raw material cost is low, the process operating condition is mild, and the method is suitable for industrial production.
- -
-
Paragraph 0035-0036; 0050-0052
(2017/08/30)
-
- Silver-catalysed trifluoromethylation of arenes at room temperature
-
A variety of heteroarenes and electron rich arenes can be trifluoromethylated at room temperature with TMSCF3, catalytic silver and PhI(OAc)2.
- Seo, Sangwon,Taylor, John B.,Greaney, Michael F.
-
supporting information
p. 6385 - 6387
(2013/08/23)
-
- Palladium-catalyzed trifluoromethylation of aromatic C-H bond directed by an acetamino group
-
The first palladium-catalyzed ortho-trifluoromethylation of the aromatic C-H bond directed by an acetamino group is reported. This method provides an efficient and green approach to synthesize the highly biological potential key structure of ortho-CF3 acetanilides and anilines.
- Zhang, Li-Sheng,Chen, Kang,Chen, Guihua,Li, Bi-Jie,Luo, Shuang,Guo, Qing-Yun,Wei, Jiang-Bo,Shi, Zhang-Jie
-
-
- Quantitative insights into energy contributions of intermolecular interactions in fluorine and trifluoromethyl substituted isomeric N-phenylacetamides and N-methylbenzamides
-
The presence of the C-F bond in organic molecules, particularly in the context of generating different intermolecular interactions of the type C-F...F-C, C-H...F and C-F...π is of extreme significance in the realm of structural chemistry. These interactions generate different packing motifs in the formation of the crystal. It is of interest to evaluate the energetic contributions of such weak interactions to evaluate their important role in crystal packing. In this respect, a library of twelve compounds containing a strong donor and acceptor, along with the presence of a C-F bond in different electronic environments (fluorine atom connected to C(sp2) and C(sp3) carbon atom) have been synthesized and characterized using single crystal X-ray diffraction studies at low temperature. In addition, the non-fluorinated counterpart has also been synthesized. These crystal structures have been analyzed to understand the contribution of weak interactions involving organic fluorine in the crystal packing. Furthermore, the stabilizing-destabilizing roles of such interactions in terms of favourable energetics have been quantified with inputs from calculations performed using PIXEL. It is observed that most of the interactions involving fluorine are of a dispersive character, and in some cases the interaction is also coulombic in origin. These results have been compared with ab initio quantum-chemical calculations (DFT-D3/B-97D level) performed using TURBOMOLE. In addition, the lattice energies of all the compounds have been evaluated, and the total contribution partitioned into the corresponding coulombic, polarization, dispersion and exchange contributions using the CLP module. The results correlate well with thermochemical data experimentally determined for these compounds.
- Panini, Piyush,Chopra, Deepak
-
p. 3711 - 3733
(2013/07/26)
-
- Lewis basic ionic liquid as an efficient and facile catalyst for acetylation of alcohols, phenols, and amines under solvent-free conditions
-
The Lewis basic ionic liquid 1,8-diazabicyclo[5.4.0]undec-7-en-8-ium acetate was employed for the acetylation of various phenols, alcohols, and amines in good-to-excellent yields at 50 C under solvent-free conditions in a short time. Compared with existing methods based on conventional catalysts and toxic solvents, the reported method is simple, mild and environmentally viable. Furthermore, the ionic liquid was conveniently separated from the products and easily recycled to catalyze other acetylation reactions with excellent yields. .
- Ji, Li,Qian, Chao,Chen, Xin-Zhi
-
p. 369 - 374
(2013/05/21)
-
- Antiviral Compounds
-
Novel compounds, methods, and compositions for treating various viral infections are described. In some embodiments the novel compounds of the invention are 3-oxo-phenothiazine derivatives; more specific embodiments include 3-oxo-phenothiazine derivatives having substituents at the 1-, 7-, and 9-positions of the phenothiazine parent ring. In other embodiments, the invention provides compositions and methods for treating viral infections, especially HIV.
- -
-
Page/Page column 14
(2012/09/25)
-
- Zinc oxide (ZnO) as a new, highly efficient, and reusable catalyst for acylation of alcohols, phenols and amines under solvent free conditions
-
Zinc oxide (ZnO) is a highly efficient catalyst for the acylation of a variety of alcohols, phenols and amines with acid chlorides or acid anhydrides under solvent free conditions. Primary, secondary, tertiary, allylic and benzylic alcohols, diols and phenols with electron donating or withdrawing substituents can be easily acylated in good to excellent yield.
- Hosseini Sarvari, Mona,Sharghi, Hashem
-
p. 10903 - 10907
(2007/10/03)
-
- Fischer indolization of ethyl pyruvate 2-[2- (trifluoromethyl)phenyl]phenylhydrazone and new insight into the mechanism of the Goldberg reaction. (Fischer indolization and its related compounds. XXVI)
-
The Fischer indolization of ethyl pyruvate 2-[2- (trifluoromethyl)phenyl]phenylhydrazone (5) gave two indolic products, ethyl 7-(trifluoromethyl)-1-phenylindole-2-carboxylate (12) as a minor product and ethyl 1-[2-(trifluoromethyl)phenyl]indole-2-carboxylate (13) as a major product. This result shows that the Fischer indolization occurred on the more electron-rich phenyl group. In the Goldberg reaction to prepare 13 from ethyl indole-2-carboxylate (15) and o- (21) or m-bromo-α,α,α-trifluorotoluene (23), it was found that Goldberg reaction proceeds via a benzyne mechanism, at least in part, in a sterically crowded situation.
- Murakami,Watanabe,Hagiwara,Akiyama,Ishii
-
p. 1281 - 1286
(2007/10/02)
-
- The o-Amino-Trifluoromethyl Functionality as a Novel Synthon for 4-Fluoroquinolines
-
2-Substituted 4-fluoroquinolines 3 are obtained by the reaction of 2-(trifluoromethyl)aniline (1) with lithium enolates 2 derived from methyl ketones.A similar reaction of 1 with lithium enolate of acetaldehyde produces 4-fluoroquinoline. 1-Fluoro-3-phenyl-4,6-phenanthroline (18) is obtained by treatment of lithium enolate of acetophenone with 4-(trifluoromethyl)quinolin-3-amine (17).By contrast, (Z)-N-carboxamides 10 and 12 are the products of the reaction of 1 with the respective enolate ions derived from 3-pentanone and isobutyl phenyl ketone.A unified mechanism for the formation of quinolines and carboxamides is proposed.
- Strekowski, Lucjan,Kiselyov, Alexander S.,Hojjat, Maryam
-
p. 5886 - 5890
(2007/10/02)
-
- Trifluoromethylation of aromatic compounds with sodium trifluoromethanesulfinate under oxidative conditions
-
Radical trifluoromethylation occurs without Cu(II) but cations are involved with Cu(II). Electron-rich aromatic compounds are triluforomethylated with sodium trifluoromethanesulfinate and t-butyl hydroperoxide. Monotrifluoromethylation predominates in the presence of catalytic amounts of Cu(II) triflate whereas mono- and bis-trifluoromethylated aromatics are obtained in almost equal quantities in the absence of Cu(II).
- Langlois, Bernard R.,Laurent, Eliane,Roidot, Nathalie
-
p. 7525 - 7528
(2007/10/02)
-
- Synthesis and Reactivity of N-Trifluoromethyl-N-nitrosotrifluoromethanesulfonamide as a New Type of Trifluoromethylating Agent
-
N-Trifluoromethyl-N-nitrosotrifluoromethanesulfonamide (TNS-Tf) was synthesized in a 58 percent yield by the reaction of trifluoronitrosomethane with hydroxylamine followed by the treatment with trifluoromethanesulfonyl fluoride in the presence of a base.TNS-Tf was demonstrated to be an effective trifluoromethylating agent photochemically or thermally for aromatics, thiols, disulfides, and uridine derivatives.The insertion reaction by two trifluoromethyl groups of TNS-Tf to the sulfur-sulfur bonds was observed in the reaction with disulfides having electron-withdrawing groups, giving 2 mols of trifluoromethylthio compounds.Furthermore, TNS-Tf served as a good reagent for mild and convenient in situ generation of trifluoromethylcopper complex which converted iodoaromatics to trifluoromethyl-substituted aromatics in good yields.Similarly, N-trifluoromethyl-N-nitrosononafluoro-1-butanesulfonamide (TNS-Nf) was synthesized in a 36 percent yield.The examination of the reactivity indicated that this type of N-nitroso sulfonamides became to be sources of both perfluoroalkyl radicals contained.
- Umemoto, Teruo,Ando, Akira
-
p. 447 - 452
(2007/10/02)
-
- Fluorination of Aromatic Derivatives with Fluoroxytrifluoromethane and Bis(fluoroxy)difluoromethane
-
Fluoroxytrifluoromethane (CF3OF) and bis(fluoroxy)difluoromethane CF2(OF)2 are formed by the reaction of F2 with CO and CO2, respectively, over a CsF catalyst in a continouous-stream process.Both reagents react with aromatic substrates by an electrophilic substitution mechanism to yield fluoro-substituted derivatives.Fluorobenzene is produced in good yield from benzene, and aniline derivatives afford monofluorination products.Acetanilide (1), N-phenylmethanesulfonamide (2), α,α,α-trifluoroacetanilide (3), and 1,1,1-trifluoro(N-phenyl)methanesulfonamide (4) react with either reagent to yield mixtures of o- and p-fluoro-substituted derivatives.Solvent effects and competitive rate experiments demonstrate a preference for ortho substitution, especially in aprotic, nonpolar solvents.With particular substrates, these fluorinating agents are of practical synthetic utility, e.g., 2-fluoro-4-(trifluoromethyl)aniline is produced in high yield by fluorinating the intermediate 4-(trifluoromethyl)acetanilide (6) with CF3OF.Activated substrates such as toluene, xylenes, anisole, and cresols give mixtures of products which reduce the synthetic utility of these reagents.Nitrobenzene is fairly unreactive toward CF3OF and gives low yields of substitution products.
- Fifolt, Michael J.,Olczak, Raymond T.,Mundhenke, Rudolph F.
-
p. 4576 - 4582
(2007/10/02)
-