- Design, synthesis and anticancer evaluation of 3-methyl-1H-indazole derivatives as novel selective bromodomain-containing protein 4 inhibitors
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Bromodomain-containing Protein 4 (BRD4), an ‘epigenetic reader’, regulates chromatin structure and gene expression via recognizing and binding acetylated lysine in histones. BRD4 has become a therapeutic target for cancers because it promotes the expression of the tumor genes, such as c-Myc, NF-κB, and Bcl-2. In this study, a new series of 3-methyl-1H-indazole derivatives were designed via virtual screening and structure-based optimization. All compounds were synthesized and evaluated for their inhibitory activities to BRD4-BD1 and their antiproliferative effects in cancer cell lines. Among them, several compounds (such as 9d, 9u and 9w) exhibited strong BRD4-BD1 affinities and inhibition activities, and potently suppressed MV4;11 cancer cell line proliferation. Among them, compound 9d showed excellent selectivity for BRD4 and effectively suppressed c-Myc, the downstream protein of BRD4. This study provided new lead compounds for further biological evaluation on BRD4.
- Dong, Ru,Zhang, Cheng,Wang, Chao,Zhou, Xin,Li, Wen,Zhang, Jin-Yang,Wang, Min,Xu, Yong,Sun, Li-Ping
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- Acid-catalyzed chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines
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Chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines were described, which were established on the basis of either a C[sbnd]C bond cleavage or a rearrangement process of a reaction intermediate. These reactions proceeded in a condition-determined manner with good functional group tolerance. In the first model, 2,2-dimethoxyacetaldehyde reacted with aniline to form a new C[sbnd]N bond, in the presence of O2, via a C[sbnd]C bond cleavage reaction. However, in the second model, by performing the reaction in the absence of O2, Heyns rearrangement occurred and generated a new C[sbnd]O bond to form methyl phenylglycinate. Such condition-determined reactions not only offered the new way for value-added conversion of biomass-derived platform molecule, 2, 2-dimethoxyacetaldehyde, but also provided efficient methods for the synthesis of N-arylformamides and methyl phenylglycinates.
- Guo, Luxia,Chen, Zihao,Zhu, Hongmei,Li, Minghao,Gu, Yanlong
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supporting information
p. 1419 - 1422
(2020/11/12)
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- HCl-mediated transamidation of unactivated formamides using aromatic amines in aqueous media
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We report transamidation protocol to synthesize a range of secondary and tertiary amides from weakly nucleophilic aromatic and hetero-aryl amines with low reactive formamide derivatives, utilizing hydrochloric acid as catalyst. This current acid mediated strategy is beneficial because it eliminates the need for a metal catalyst, promoter or additives in the reaction, simplifies isolation and purification. Notably, this approach conventionally used to synthesize molecules on gram scales with excellent yields and a high tolerance for functional groups.
- Dhawan, Sanjeev,Girase, Pankaj Sanjay,Kumar, Vishal,Karpoormath, Rajshekhar
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p. 3729 - 3739
(2021/10/14)
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- Palladium supported on MRGO@CoAl-LDH catalyzed reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as liquid CO and H2 source
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In the present study, a heterogeneous palladium catalyst system, Pd nanoparticles supported on MRGO@CoAl-LDH, was synthesized and employed in reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as CO and H2 source. The as-obtained heterogeneous catalyst was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The nanocatalyst was reused for 5 cycles with a negligible reduction in the yield of products. All reactions were carried out with high yields and under suitable and safe conditions. Also, we have successfully applied formic acid as a good and safe alternative to CO and H2 gases.
- Jadidi Nejad, Masoumeh,Heydari, Akbar
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- Copper promoted aerobic oxidative c(sp3)-c(sp3) bond cleavage of n-(2-(pyridin-2-yl)-ethyl)anilines
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A strategy of aerobic oxidative C(sp3)-C(sp3) bond cleavage of N-ethylaniline derivatives bearing azaarenes for the synthesis of N-aryl formamides has been developed. This approach was carried out smoothly with the CuI/TEMPO/air system to give N-aryl formamides in yields of 50-90%. With this methodology, a mutagenically active compound was constructed in 90% yield. Moreover, the reaction also provided a one-pot synthetic tool for accessing a promoter of hematopoietic stem cells by difunctionalization in 61% yield.
- Yu, Yang,Zhang, Yong,Sun, Chengyu,Shi, Lei,Wang, Wei,Li, Hao
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p. 2725 - 2732
(2020/03/11)
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- Application of Ag/TFPG-DMB COF in carbamates synthesis via CO2 fixation reaction and one-pot reductive N-formylation of nitroarenes under sunlight
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We have designed mesoporous AgNPs decorated COF (Ag/TFPG-DMB COF) nanomaterial which has been formed by an easy ex-situ synthetic method. The synthesized material is characterized by FTIR, PXRD, UV–vis, N2 adsorption–desorption studies, TEM, FESEM and XPS. The material showed the generation of identical mesopore at 3.9 nm. It is observed that the material can perform as both thermally and photochemically active catalyst for carbamate synthesis and one-pot reduction and N-formylation of nitroarenes respectively. The catalytic activity of the Ag/ TFPG-DMB COF nanomaterial is checked for green synthesis of carbamates from different amines and alcohols under 1 atmospheric pressure of CO2 with excellent yield (upto 95 %) as well as with high TOF value (182 h?1) and high selectivity. Additionally, the Ag/ TFPG-DMB COF nanomaterial is also applied as a potentially active photocatalyst for one-pot nitroarene reduction along with N-formylation reaction under sunlight irradiation in green reaction conditions with exceptionally high yield of formylated products upto 99 % as well as with high TOF value (762 h ?1). The catalyst efficiently reduced and formylated para-nitrophenol, a potential water pollutant, which elaborates its scope as an efficient catalyst for water purification also. The catalyst recyclability is also checked for five reaction cycles for both the reactions and the Ag/TFPG-DMB COF material showed outstanding recycling ability without any noticeable leaching of active metal or catalyst degradation.
- Biswas, Surajit,Hazra Chowdhury, Arpita,Hazra Chowdhury, Ipsita,Islam, Sk. Manirul
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- Mesostructure organic-inorganic hybrid ionic liquids based on heteropoly acids: Effect of linkage on the molecular structure and catalytic activity
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The new inorganic–organic hybrids based on SO3H-functionalized ionic liquids (ILs) and Keggin-type heteropoly acids (H3PW12O40, H3PMo12O40, and H4SiW12O40; HPAs) are prepared and characterized by FT-IR, NMR, XRD, CV, SEM/EDX, ICP-OES, BJH and UV. Different molecular structures according to the different inorganic part were also proved. Potentiometric titration showed a good relationship between catalytic activity and acidity of the catalysts. Electrochemical aspects showed electron transfer ability of the compounds. For understanding catalytic activities of the HPA-IL hybrids in N-formylation reaction, effect of catalyst composition, substrate, and reaction conditions were studied. The best SO3H-functionalized ionic liquid catalyst was readily recovered and reused for four runs. Easy preparation of the catalyst, simple and easy work-up, mild reaction conditions, low cost, excellent yields and short reaction times are the key features of this work.
- Shahebrahimi, Shabnam,Rafiee, Ezzat,Sadrjavadi, Komail
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- Visible-light-induced radical cascade cyclization of oxime esters and aryl isonitriles: Synthesis of cyclopenta[: B] quinoxalines
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A visible-light-induced radical cascade cyclization of aryl isonitriles and cyclobutanone oxime esters for the synthesis of cyclopenta[b]quinoxalines has been accomplished for the first time. The key to the success of this process was the integration of the in situ-formed nitrile radical followed by the cascade radical isonitrile/nitrile insertion-cyclization. The easy introduction of substituents for both substrates and the high functional group tolerance of the reaction make it an efficient strategy to give various quinoxaline derivatives in moderate to good yields.
- Yuan, Yao,Dong, Wu-Heng,Gao, Xiao-Shuang,Xie, Xiao-Min,Zhang, Zhao-Guo
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supporting information
p. 11900 - 11903
(2019/10/11)
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- An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
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A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.
- Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
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supporting information
p. 1254 - 1258
(2019/04/10)
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- Modified Graphene Oxide Based Zinc Composite: an Efficient Catalyst for N-formylation and Carbamate Formation Reactions Through CO2 Fixation
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Catalytic fixation of CO2 through chemical reactions is always a challenging task of synthetic chemistry. This paper represents the design and synthesis of an eco-friendly low cost zinc metal containing heterogeneous catalyst of aminically modified Graphene Oxide. Characterization of the catalyst has been carried out by Raman and FTIR spectra, AAS, XRD, TEM, SEM, EDX and N2 adsorption desorption studies. It was found that the catalyst was very proficient for the CO2 fixation through N-formylation and carbamate formation reactions of amines. Catalytic N-formylation reaction of both aromatic and aliphatic amines gave high yield of corresponding formylated products in presence of polymethylhydrosiloxane (PMHS) as reducing agent under 1 bar CO2 pressure and mild temperature. Formation of carbamates from aniline or its derivatives and alkyl/aryl bromide with good product selectivity was also achieved under same CO2 pressure in presence of our synthesized catalyst at room temperature with solvent-free condition. The catalyst is reusable and e?cient even after six cycles.
- Khatun, Resmin,Biswas, Surajit,Islam, Sarikul,Biswas, Imdadul Haque,Riyajuddin, Sk,Ghosh, Kaushik,Islam, Sk Manirul
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supporting information
p. 1303 - 1312
(2019/01/25)
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- NH4I-promoted N-acylation of amines via the transamidation of DMF and DMA under metal-free conditions
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An unprecedented NH4I-promoted N-formylation and N-acetylization of various amines with dimethylformamide (DMF)and dimethylacetamide (DMA)has been developed. This protocol shows broad substrate scope for aromatic, aliphatic, and heterocyclic amines, which provides a metal-free strategy for N-acylation featuring mild reaction conditions, as well as inexpensive and readily available starting materials.
- Chen, Jiahui,Jia, Jing,Guo, Ziyi,Zhang, Jitan,Xie, Meihua
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supporting information
p. 1426 - 1429
(2019/05/06)
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- Cobalt nanoparticles anchoring on nitrogen doped carbon with excellent performances for transfer hydrogenation of nitrocompounds to primary amines and N-substituted formamides with formic acid
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Cobalt nanoparticles anchoring on nitrogen doped carbon derived from pyrolysis of a cobalt complex and chitosan were developed for reduction of nitrocompounds with neat formic acid to their corresponding amines or N-substituted formamides by switch of solvents. Characterization results revealed that most of the nitrogen atoms are present as graphitic N and pyridinic N as anchoring sites, and the cobalt nanoparticles are wrapped by nitrogen doped carbon layers, endowing the catalyst with excellent activity and superior reusability.
- Zhang, Yuecheng,Cao, Pengwei,Zhang, Hong-Yu,Yin, Guohui,Zhao, Jiquan
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- Mesoporous silica SBA-15 functionalized with acidic deep eutectic solvent: A highly active heterogeneous N-formylation catalyst under solvent-free conditions
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Mesoporous silica SBA-15 functionalized with N-methylpyrrolidonium-zinc chloride based deep eutectic solvent (DES) is found to be a more efficient and reusable catalyst for a convenient N-formylation of a variety of amines at room temperature. N-Formylation of primary, secondary as well as heterocyclic amines have been carried out in good to excellent yields by treatment with formic acid in low loading of DES/SBA-15 an environmentally benign catalyst for the first time. The DES/SBA-15 catalyst, which possesses both Br?nsted and Lewis acidities as well as an active SBA-15 support, makes this procedure quite simple, reusable, more convenient and practical. This catalyst was tolerant of a wide range of functional groups, and it can be reused for four runs without obvious deactivation.
- Azizi, Najmedin,Edrisi, Mahtab,Abbasi, Faezeh
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- Magnesium oxide as an efficient catalyst for CO2 fixation and N-formylation reactions under ambient conditions
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Chemical fixation of CO2 into fine chemicals is one of the key areas of research today to mitigate greenhouse gas CO2 and its successful utilization as C1 building block. Nanocrystalline MgO has been synthesized by simple precipitation method followed by calcination at 450 °C. The materials are characterized thoroughly by several instrumental tools, which suggested the presence of mesoscopic void space and excellent catalytic activity for the synthesis of organic cyclic carbonates by chemical fixation of CO2 on a wide range of epoxides at atmospheric pressure and room temperature within a short reaction time. Maximum product yields upto 99% for the cyclic carbonates are observed. It also displayed a high catalytic activity in the N-formylation of various amines by using formic acid as reagent (acts both as carbon source and reducing agent) at room temperature with excellent product yields upto 99.5%. This nanocrystalline MgO material showed high recycling efficiency for the cycloaddition of CO2 onto the epoxides and no sign of catalyst deactivation.
- Chowdhury, Arpita Hazra,Bhanja, Piyali,Salam, Noor,Bhaumik, Asim,Islam, Sk. Manirul
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- Mild Access to N-Formylation of Primary Amines using Ethers as C1 Synthons under Metal-Free Conditions
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A new synthetic protocol has been developed for the synthesis of N-formamide derivatives using ethers as a C1 synthon under metal-free reaction conditions. The reaction is proposed to proceed through C?H functionalization, C?O cleavage, and C?N bond formation. This protocol is applicable to a variety of primary amines resulting in N-formamides in moderate to good yields. 1,4-dioxane was chosen as best C1 synthon after screening with various ethers. Mechanistic studies disclosed that the reaction proceeds through a radical pathway. While using α-amino ketones a α-alkylation product was formed rather than formylation. By replacing dioxane with Tetramethylethylenediamine (TMEDA) under standard conditions also gave the N-formamide derivatives in moderate yields. (Figure presented.).
- Mutra, Mohana Reddy,Dhandabani, Ganesh Kumar,Wang, Jeh-Jeng
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supporting information
p. 3960 - 3968
(2018/09/10)
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- Imidazolium chloride: An efficient catalyst for transamidation of primary amines
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A highly efficient and convenient protocol of imidazolium chloride (30 mol %) catalyzed amidation of amines with moderate to excellent yields was reported. The protocol shows broad substrate scope for aromatic, aliphatic, and heterocyclic primary amines.
- Tian, Qingqiang,Gan, Zongjie,Wang, Xuetong,Li, Dan,Luo, Wen,Wang, Huajun,Dai, Zeshu,Yuan, Jianyong
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supporting information
(2018/09/10)
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- Copper-(II) Catalyzed N-Formylation and N-Acylation of Aromatic, Aliphatic, and Heterocyclic Amines and a Preventive Study in the C-N Cross Coupling of Amines with Aryl Halides
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A Cu-(II) catalyzed N-formylation and N-acylation of amines with moderate to excellent yields, using N, N-dimethyl formamide (DMF) and N, N-dimethyl acetamide (DMA) as a formyl and acylating sources in the presence of 1,2,4-triazole is reported. This novel, highly efficient and simple protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines. In addition, the conditions to prevent N-formylation and N-acylation impurities in the C?N cross coupling of amines and aryl halides are described typically when DMF and DMA are used as solvents, with various catalysts, ligands, and bases.
- Sonawane, Rahul B.,Rasal, Nishant K.,Bhange, Dattatraya S.,Jagtap, Sangeeta V.
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p. 3907 - 3913
(2018/09/12)
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- Consecutive Lossen rearrangement/transamidation reaction of hydroxamic acids under catalyst- and additive-free conditions
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The Lossen rearrangement is a classic process for transforming activated hydroxamic acids into isocyanate under basic or thermal conditions. In the current report we disclosed a consecutive Lossen rearrangement/transamidation reaction in which unactivated hydroxamic acids were converted into N-substituted formamides in a one-pot manner under catalyst- and additive-free conditions. One feature of this novel transformation is that the formamide plays triple roles in the reaction by acting as a readily available solvent, a promoter for additive-free Lossen rearrangement, and a source of the formyl group in the final products. Acyl groups other than formyl could also be introduced into the product when changing the solvent to other low molecular weight aliphatic amide derivatives. The solvent-promoted Lossen rearrangement was better understood by DFT calculations, and the intermediacy of isocyanate and amine was supported well by experiments, in which the desired products were obtained in excellent yields under similar conditions. Not only monosubstituted formamides were synthesized from hydroxamic acids, but also N,N-disubstituted formamides were obtained when secondary amines were used as precursors.
- Jia, Mengmeng,Zhang, Heng,Lin, Yongjia,Chen, Dimei,Chen, Yanmei,Xia, Yuanzhi
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p. 3615 - 3624
(2018/05/26)
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- Electrochemical N -Formylation of Amines via Decarboxylation of Glyoxylic Acid
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A new method for the synthesis of formamides has been developed through electrochemical decarboxylative N-formylation of amines with glyoxylic acid. This protocol provides an efficient approach to formamides with a broad range of functional group tolerance under ambient conditions.
- Lin, Dian-Zhao,Huang, Jing-Mei
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supporting information
p. 2112 - 2115
(2018/04/14)
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- Supported Palladium Nanoparticles Catalyzed Reductive Carbonylation of Nitroarenes to N-Arylformamides
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A facile reductive carbonylation reaction of nitroarenes to N-arylformamide synthesis was investigated under polymer supported palladium (Pd@PS) nanoparticles catalyzed conditions. Dual role of oxalic acid dihydrate ((CO2H)2 ? 2H2O) as H2 source for hydrogenation and CO source for carbonylation reaction for desired products synthesis was critically investigated under favorable DMF solvent conditions. Several cross experiments were performed to establish the best possible hypothesis for the proposed mechanism and understanding about the involvement of CO in the reaction pathway. Further, ortho-substituted nitroarenes were found to be highly specific for facile para-hydroxylation to give corresponding para-hydroxy N-aryl formamides. (Figure presented.).
- Thakur, Vandna,Kumar, Ajay,Sharma, Nishtha,Shil, Arun K.,Das, Pralay
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supporting information
p. 432 - 437
(2017/12/26)
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- A green, efficient, and rapid procedure for the hydrogenation of nitroarenes to formanilides in water
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Abstract: A green, efficient, and rapid procedure for the hydrogenation of nitroarenes to formanilides in Pd(TFA)2/HCOOH system in water is described. Under optimized conditions, the reaction of most substrates is complete within 30?min with yields of 30–93%. Furthermore, this procedure is applied successfully for the modification of natural products, such as arctigenin, vindoline, and estrone. Graphical abstract: [Figure not available: see fulltext.].
- Wang, Yingying,Zhan, Zhajun,Zhou, Yang,Lei, Min,Hu, Lihong
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p. 527 - 533
(2018/01/27)
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- One-pot selective N-formylation of nitroarenes to formamides catalyzed by core-shell structured cobalt nanoparticles
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One-pot direct N-formylation of readily available nitroarenes with ammonium formate catalyzed by core-shell structured cobalt nanoparticles has been developed. A broad set of nitroarenes was successfully converted to their corresponding formamides in good to high yields with various functional group tolerance. This heterogeneous catalyst can be easily removed from the reaction medium and can be reused several times without a significant loss of reaction efficiency.
- Dong, Xiaosu,Wang, Zhaozhan,Duan, Yanan,Yang, Yong
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supporting information
p. 8913 - 8916
(2018/08/17)
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- Biocatalytic α-Oxidation of Cyclic Amines and N-Methylanilines for the Synthesis of Lactams and Formamides
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An environmentally friendly method for the synthesis of lactams and formamides through the biocatalytic α-oxidation of amines was developed by employing Pseudomonas plecoglossicida ZMU-T04 as a biocatalyst. In this biocatalytic process, the α-oxidation of cyclic amines and N-methylanilines proceeded smoothly to give the corresponding amides in low to high yields. Furthermore, it was demonstrated that synthetic 3,4-dihydroquinolin-2(1H)-one could be used as a key precursor of antidepressant bioactive molecules. The mechanism of this biocatalytic α-oxidation process was investigated by isotope- labeling experiments.
- Zheng, Daijun,Zhou, Xiaojian,Cui, Baodong,Han, Wenyong,Wan, Nanwei,Chen, Yongzheng
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p. 937 - 940
(2017/03/27)
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- Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles
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A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a13C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.
- Hu, Zhongyan,Dong, Jinhuan,Men, Yang,Lin, Zhichen,Cai, Jinxiong,Xu, Xianxiu
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supporting information
p. 1805 - 1809
(2017/02/05)
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- New catalytic performance of immobilized sulfuric acid on activated charcoal for n-formylation of amines with ethyl formate
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Summary: Simple and highly efficient procedure for N-formylation of various amines was carried out in the presence of the immobilized sufuric acid on activated charcoal as an efficient promoter system. All reactions were taken place in refluxing ethyl formate (54 °C) under mild reaction conditions. The product formamides were obtained in high to excellent yields (83-95%) within 4-80 min.
- Abdollahi, Mohammad,Zeynizadeh, Behzad,Sadighnia, Leila
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p. 619 - 627
(2017/11/06)
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- Acidic ionic liquid immobilized on nanoporous Na+-montmorillonite as an efficient and reusable catalyst for the formylation of amines and alcohols
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In this work, nanoporous sodium montmorillonite clay (Na+-MMT) was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The Na+-MMT chemical modification ([Na+-MMT-[pmim]HSO4) was confirmed by a variety of techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy and potentiometric titration. The catalytic performance of this immobilized acidic ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent-free conditions. This reagent is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also, this catalyst can be reused ten times without loss of its catalytic activity.
- Shirini, Farhad,Mazloumi, Masoumeh,Seddighi, Mohadeseh
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p. 1759 - 1776
(2016/03/16)
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- Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
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A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.
- Ke, Zhengang,Zhang, Yan,Cui, Xinjiang,Shi, Feng
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p. 808 - 816
(2016/02/12)
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- An efficient method for the synthesis of formamidine and formamide derivatives promoted by sulfonated rice husk ash (RHA-SO3H)
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A mild, simple and efficient method has been developed for the promotion of the preparation of N,N′-diphenylformamidines from various aromatic amines and ethyl orthoformate using sulfonated rice husk ash (RHA-SO3H) solid acid catalyst. This reagent has also been used for the N-formylation of a variety of amines using formic acid under solvent-free conditions. The procedures gave the products in very short reaction times and good-to-high yields. Also this catalyst can be reused for five times without loss of its catalytic activity.
- Seddighi, Mohadeseh,Shirini, Farhad,Mamaghani, Manouchehr
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p. 433 - 439
(2015/02/05)
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- The ortho effect on the acidic and alkaline hydrolysis of substituted formanilides
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The kinetics of formanilides hydrolysis were determined under first-order conditions in hydrochloric acid (0.01-8 M, 20-60°C) and in hydroxide solutions (0.01-3 M, 25 and 40°C). Under acidic conditions, second-order specific acid catalytic constants were used to construct Hammett plots. The ortho effect was analyzed using the Fujita-Nishioka method. In alkaline solutions, hydrolysis displayed both first- and second-order dependence in the hydroxide concentration. The specific base catalytic constants were used to construct Hammett plots. Ortho effects were evaluated for the first-order dependence on the hydroxide concentration. Formanilide hydrolyzes in acidic solutions by specific acid catalysis, and the kinetic study results were consistent with the AAC2 mechanism. Ortho substitution led to a decrease in the rates of reaction due to steric inhibition of resonance, retardation due to steric bulk, and through space interactions. The primary hydrolytic pathway in alkaline solutions was consistent with a modified BAC2 mechanism. The Hammett plots for hydrolysis of meta- and para-substituted formanilides in 0.10 M sodium hydroxide solutions did not show substituent effects; however, ortho substitution led to a decrease in rate constants proportional to the steric bulk of the substituent.
- Desai, Salil Dileep,Kirsch, Lee E.
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p. 471 - 488
(2015/06/30)
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- An attractive route to transamidation catalysis: Facile synthesis of new o-aryloxide-N-heterocyclic carbene ruthenium(II) complexes containing trans triphenylphosphine donors
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Well-defined robust ruthenium(II) complexes 3a-d bearing o-aryloxide-N-heterocyclic carbene ligands with different wingtip substituents (3a (R = Me), 3b (R = Ph), 3c (R = iPr) and 3d (R = Mes)) in the imidazole ring were synthesized in good yields by the reaction of imidazolium proligands with metal precursor [RuHCl(CO)(PPh3)3] by transmetallation from the corresponding silver carbene complexes. All the Ru(II)-NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. The molecular structure of the complex 3a was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted octahedral geometry. In order to explore the catalytic potential of the synthesized complexes, all the four [Ru-NHC] complexes [3a-d] were tested as catalysts for transamidation of carboxamides with amines. Notably, the complex 3a was found to be very efficient and versatile catalyst toward transamidation of a wide range of amides with amines.
- Nirmala, Muthukumaran,Prakash, Govindan,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz
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- A metal-free approach for transamidation of amides with amines in aqueous media
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An efficient, environmentally benign and a mild protocol for transamidation of amides with a variety of amines in the presence of K2S2O8 using stoichiometric quantity in aqueous conditions has been established. This method works under conventional thermal conditions and in microwave irradiation as well. A series of amides have been prepared using this reaction and this is a greener protocol for transamidation, which offers a diverse kind of substrate scope with exclusive product formation (yields 90-98%).
- Srinivas, Mahesuni,Hudwekar, Abhinandan D.,Venkateswarlu, Vunnam,Reddy, G. Lakshma,Kumar, K. A. Aravinda,Vishwakarma, Ram A.,Sawant, Sanghapal D.
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supporting information
p. 4775 - 4779
(2015/07/20)
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- Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile
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Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. Renewable formic acid as a flexible feedstock: A versatile heterogeneous gold-based catalytic system has been developed for the controlled, flexible, and target-specific reductive transformation of nitro compounds using stoichiometric equivalents of formic acid as a key starting material under mild and convenient conditions. The overall operational simplicity, high chemoselectivity, functional-group tolerance, and reusability of the catalyst make this approach an attractive and reliable tool for organic and process chemists.
- Yu, Lei,Zhang, Qi,Li, Shu-Shuang,Huang, Jun,Liu, Yong-Mei,He, He-Yong,Cao, Yong
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p. 3029 - 3035
(2015/09/28)
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- Heteropolyanion-based sulfated ionic liquid catalyzed formamides synthesis by grindstone chemistry
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A novel heteropolyanion-based sulfated ionic liquid (HIL-[Ch-OSO 3H]3W12PO40) was prepared by pairing sulfate functionalized cholinium cation [N,N,N-trimethyl-2-(sulfooxy) ethanaminium] with catalytically active phosphotungstic acid anion (W 12PO403-). It was characterized by 1H NMR, FT-IR, EDX, XRD, TGA and elemental analysis. Catalytic activity of thus prepared HIL was studied in N-formylation of amines under solvent-free grinding condition. The methodology provided cleaner conversion over shorter reaction time with high turnover frequency (TOF) and chemoselectivity.
- Satasia, Shailesh P.,Kalaria, Piyush N.,Raval, Dipak K.
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- Br?nsted acidic ionic liquid supported on rice husk ash (RHA-[pmim]HSO4): A highly efficient and reusable catalyst for the formylation of amines and alcohols
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In this work, rice husk ash (RHA), as a natural source of amorphous silica, was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The immobilized acidic ionic liquid was characterized with a variety of techniques including infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and pH analysis. The catalytic performance of this heterogeneous ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent free conditions. It is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also this catalyst can be reused ten times without loss of its catalytic activity.
- Shirini, Farhad,Seddighi, Mohadeseh,Mamaghani, Manouchehr
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p. 50631 - 50638
(2014/12/10)
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- A green protocol for the N-formylation of amines using molybdate sulfuric acid as a reusable solid catalyst
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A novel and efficient method for the N-formylation of amines via the reaction of orthoformates and amines is developed. The reactions are mediated by a catalytic amount of molybdate sulfuric acid as a heterogeneous solid acid.
- Karami, Bahador,Farahi, Mahnaz,Pam, Fariba
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p. 6292 - 6296
(2015/02/19)
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- Chitosan: An efficient recyclable catalyst for transamidation of carboxamides with amines under neat conditions
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A novel chitosan-catalyzed transamidation of carboxamides with amines under solvent-free conditions is described. A series of amide derivatives as well as more challenging aryl and alkyl amines with long-chain alkyl substituents could be selectively converted into the corresponding transamidation products, which are frequently found in biologically active compounds and pharmaceuticals. Under similar reaction conditions benzo[d]heterocycles were also obtained via a one-pot synthesis through transamidation and subsequent dehydration. Recyclability of chitosan was demonstrated, with quantitative yields of products obtained without any loss of catalytic activity. the Partner Organisations 2014.
- Nageswara Rao, Sadu,Chandra Mohan, Darapaneni,Adimurthy, Subbarayappa
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supporting information
p. 4122 - 4126
(2014/10/15)
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- Highly efficient rhodium-catalyzed transfer hydrogenation of nitroarenes into amines and formanilides
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An efficient and selective rhodium-catalyzed transfer hydrogenation of nitroarenes with formic acid as the hydrogen source to give amines or formanilides has been developed. The addition of iodide ion accelerates the reaction, which can take place at room temperature. Georg Thieme Verlag Stuttgart New York.
- Wei, Yawen,Wu, Jianjun,Xue, Dong,Wang, Chao,Liu, Zhaotie,Zhang, Zhuozhuo,Chen, Guangfu,Xiao, Jianliang
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supporting information
p. 1295 - 1298
(2014/06/10)
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- Highly efficient N-formylation of amines with ammonium formate catalyzed by nano-Fe3O4 in PEG-400
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A simple and efficient protocol for the formylation of amines with ammonium formate with excellent yields catalyzed by Fe3O4 nanoparticles in PEG-400 is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary and secondary arylamines. Moreover, the nano-Fe3O4 catalyst and PEG-400 could be easily recovered and reused.
- Wang, Zhao-Gang,Lu, Ming
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p. 1234 - 1240
(2014/01/06)
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- A simple method for preparation of ZnO nanoparticles as a highly efficient nanocatalyst for N-formylation of primary and secondary amines under solvent-free condition
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A convenient reaction between alky, aryl, and heteroalkyl amines and formic acid as a formylating agent in the presence of catalytic amount of mechanochemically synthesized zinc oxide nanoparticles under solvent-free condition for the synthesis of corresponding N-formyl derivatives is described. Copyright Taylor and Francis Group, LLC.
- Alinezhad, Heshmatollah,Salehian, Fatemeh
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p. 532 - 538
(2013/07/19)
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- Nanoceria-catalyzed highly efficient procedure for N-formylation of amines at room temperature under solvent-free conditions
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Nanoceria-catalyzed simple and efficient protocol for the N-formylation of amines using formic acid at room temperature under solvent-free conditions shows high yield of desired product chemoselectivity and improvement in reaction time.
- Patil, Umakant B.,Singh, Abhilash S.,Nagarkar, Jayashree M.
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supporting information
p. 524 - 526
(2013/06/05)
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- Deep eutectic solvent promoted highly efficient synthesis of N, N'-diarylamidines and formamides
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A deep eutectic solvent was used as a dual catalyst and reaction medium for the efficient N-formylation of aromatic amines without hazardous organic solvent and catalyst. Treatment of aromatic amines with trimethyl orthoformate and formic acid in deep eutectic solvent at 70 °C gives the corresponding N-formyl derivatives in good to excellent yields. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and SnCl2, with 100% atom economy and making it applicable to industry and laboratory. Furthermore, heating the trimethyl orthoformate and aromatic primary amines in the deep eutectic solvent results in formation of the corresponding N,N'-diarylamidines in high yields.
- Azizi, Najmadin,Gholibeglo, Elham,Babapour, Mahbobe,Ghafuri, Hossein,Bolourtchian, Seyed Mohammad
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p. 768 - 773
(2012/10/30)
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- Synthesis of N-formylated β-lactams using nano-sulfated TiO 2 as catalyst under solvent-free conditions
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An easily accessible catalyst, nano-sulfated titania, efficiently catalyzes the N-formylation of β-lactams and all types of amines (primary, secondary, aromatic, and aliphatic) in solvent-free conditions at room temperature.
- Hosseini-Sarvari, Mona,Safary, Ensieh,Jarrahpour, Aliasghar,Heiran, Roghaye
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p. 980 - 987
(2013/02/22)
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- Highly chemo-and regioselective transfer reduction of aromatic nitro compounds using ammonium formate catalyzed by supported gold nanoparticles
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A highly chemo-and regioselective reduction of a wide diversity of aromatic nitro compounds to the corresponding amines has been achieved by a combination of gold nanoparticles supported on titania and ammonium formate (HCOONH 4) in ethanol at room temperature. Furthermore, a direct and mild route to formanilides from aromatic nitro compounds bearing different functional groups by reductive N-formylation using the gold-mediated transfer reduction protocol is also established.
- Lou, Xia-Bing,He, Lin,Qian, Yue,Liu, Yong-Mei,Cao, Yong,Fan, Kang-Nian
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supporting information; experimental part
p. 281 - 286
(2011/04/16)
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- A convenient one-pot synthesis of formamide derivatives using thiamine hydrochloride as a novel catalyst
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Formamide derivatives have been synthesized in excellent yields from amine and formic acid in the presence of a catalytic amount of thiamine hydrochloride (VB1) at 80 °C. The advantages of this method are the use of a cheap, stable, non-toxic, and readily available catalyst, easy work-up, improved yields, and solvent-free conditions.
- Lei, Min,Ma, Lei,Hu, Lihong
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experimental part
p. 4186 - 4188
(2010/09/12)
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- Nano-MgO: An efficient catalyst for the synthesis of formamides from amines and formic acid under MWI
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Nano-MgO a basic catalyst was prepared by solution combustion technique. It was characterized by powder XRD, SEM, BET and TEM analyses. It was used as a catalyst for the study of microwave-assisted N-formylation of various aromatic and alkyl amines with formic acid under solvent-free conditions. Nano-MgO showed excellent catalytic properties and the reactions went to completion, within 1-2 min to give products in high yield (90-98%). The catalyst is recoverable quantitatively and re-cycled with almost consistent activity. This new nano catalyst has the advantages of higher yield, lower cost, reduced environmental hazards, and the procedure is highly convenient. Graphical Abstract: Nano-MgO was prepared and characterized by PXRD, SEM, BET and TEM analyses. It was used for the study of microwave-assisted N-formylation of various amines with formic acid under solvent-free condition.
- Reddy, M. B. Madhusudana,Ashoka,Chandrappa,Pasha
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experimental part
p. 82 - 87
(2010/11/03)
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- ZnO as a new catalyst for N-formylation of amines under solvent-free conditions
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The treatment of amines with formic acid in the presence of ZnO under solvent-free conditions brings about highly and efficient N-formylation to give the corresponding formamides in excellent yields. The N-formylation reaction not only involves mild conditions, simple operation, and high yields but also high chemoselectivity.
- Hosseini-Sarvari, Mona,Sharghi, Hashem
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p. 6652 - 6654
(2007/10/03)
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- Method for the synthesis of amides and related products from esters or ester-like compounds
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A versatile, eco-friendly, and efficient method for the convenient conversion of esters and ester-like compounds into amides, peptides, carbamates, ureas, oxamides, oxamates, hydrazides, oxazolidinones, pyrazolones, oxazolidinediones, barbituric acids, and other molecules containing one or more OCN moieties in the presence of a diol or polyol is disclosed.
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Page/Page column 11
(2008/06/13)
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- Cyclic amine compounds as CCR5 antagonists
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A compound of formula (I) (wherein R1is a hydrogen atom, a hydrocarbon group which may be substituted, a non-aromatic heterocyclic group which may be substituted, R2is a hydrocarbon group which may be substituted, a non-aromatic heterocyclic group which may be substituted, or R1and R2may combine to each other together with A to form a heterocyclic group which may be substituted; A is N or N+—R5.Y?(R5is a hydrocarbon group; Y?is a counter anion); R3is a cyclic hydrocarbon group which may be substituted or a heterocyclic group which may be substituted; n is 0 or 1; R4is a hydrogen atom, a hydrocarbon group which may be substituted, a heterocyclic group which may be substituted, an alkoxy group which may be substituted, an aryloxy group which may be substituted, or an amino group which may be substituted, E is a divalent aliphatic hydrocarbon group which may be substituted by group(s) other than oxo; G1is a bond, CO or SO2; G2is CO, SO2, NHCO, CONH or OCO; J is methine or a nitrogen atom; and each of Q and R is a bond or a divalent C1-3aliphatic hydrocarbon which may be substituted; provided that J is methine when G2is OCO, that one of Q and R is not a bond when the other is a bond and that each of Q and R is not substituted by oxo group(s) when G1is a bond) or a salt thereof has a potent CCR5 antagonistic activity and can be advantageously used for the treatment or prevention of infectious disease of various HIV in human (e.g. AIDS).
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- Lifetimes of imidinium ions in aqueous solution
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Imidinium ions, ArN=CNR2+, were generated in aqueous solution from the solvolysis of fluoro and chloro formamidines at pH 9.3 and 25°C. Rate constants for the hydration of five imidinium ions were determined from a kinetic analysis of their trapping by thiolacetate anion, CH3COS-, in the presence of a pool of competing fluoride anion, and a rate constant of k(AcS)- = 5 x 109 M-1 S-1 for diffusion-controlled trapping of the carbocations with thiolacetate anion. The rate constants, k(s), for hydration of the imidinium ions, XArN=CNC4H8O+ are 3.6 x 105, 5.8 x 105, 1.5 x 106, 1.6 x 106, and 1.8 x 106 s-1 for X = H, 4-Cl, 3-CN, 4-CN, and 3-NO2, respectively. In a similar experiment a rate constant of k(s) = 3.3 x 107 s-1 was obtained for hydration of the imidinium ion 4-NO2-ArN=CNCH3(OCH3)+, by using azide anion to trap the cation and a rate constant of k(az) = 5 x 109 M-1 s-1 for diffusion-controlled trapping of the imidinium ion with azide ion. The partitioning rate constant ratio k(AcS)-/k(s) for 4-ClArN=CNC4H8O+ decreases by approximately 6-fold in 45% v/v glycerol/water in contrast to k(az)/k(s), which remains almost constant, showing that thiolacetate, but not azide anion, combines with the imidinium ion at a diffusion-limited rate. The reactivity of the imidinium ions deviate from behavior predicted by the N+ scale in a manner that may be explained by a difference in the selectivity of the cation when compared to the more stable N+ carbocations.
- Dalby, Kevin N.,Jencks, William P.
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p. 7271 - 7280
(2007/10/03)
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- 2,4-diaminopyridopyrimidine Inhibitors of Dihydrofolate Reductase from Pneumocystis carinii and Toxoplasma gondii
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Six previously unknown 2,4-diamino-6-(anilinomethyl)- and 2,4-diamino-6-pyridopyrimidines (5-10) were synthesized from 2,4-diamino-6-(bromomethyl)pyridopyrimidine hydrobromide (11*HBr) by treatment with the appropriate aniline or N-methylaniline in dimethylformamide at room temperature, with or without NaHCO3 present.Compounds 5-10 were tested as inhibitors of dihydrofolate reductase from Pneumocystis carinii, Toxoplasma gondii, and rat liver as a part of a larger effort directed toward the discovery of lipophilic nonclassical antifolates combining high enzyme selectivity and high potency.Of the six analogues tested, the most potent and selective against T. gondii DHFR was 2,4-diamino-6-pyridopyrimidine (7), which had an IC50 of 0.0047 μM against this enzyme as compared with 0.026 μM against the rat liver enzyme.The potency of 7 against T. gondii DHFR was similar to that of trimetrexate (TMQ, 1) and piritrexim (PTX, 2) but was >500-fold greater than that of trimethoprim (TMP, 3).However, while 7 was more selective than either TMQ (19*) or PTX (63*) against this enzyme, its selectivity in comparison with TMP was 8-fold lower. 2,4-Diamino-6-pyridopyrimidine (6) was 17-fold less active than 7 and was also less selective. 2,4-Diamino-6-pyridopyrimidine (10) had an IC50 of 0.022 μM against P. carinii DHFR and was comparable in potency to TMQ and PTX.The species selectivity of 10 for P. carinii versus rat liver DHFR was greater than that of either TMQ (21-fold) or PTX (31-fold).On the other hand, even though 10 was slightly more active than TMQ against the P. carinii enzyme, its selectivity was 7-fold lower than that of TMP.Thus, the goal of combining high enzyme binding activity, which is characteristic of the fused-ring compounds TMQ and PTX, with high selectivity for T. gondii and P. carinii DHFR versus rat liver DHFR, which is characteristic of the monocyclic compound TMP, remained unmet in this limited series.
- Rosowsky, Andre,Forsch, Ronald A.,Queener, Sherry F.
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p. 2615 - 2620
(2007/10/03)
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