- Olefin functionalized IPr.HCl monomer as well as preparation method and application thereof
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The invention relates to an olefin functionalized IPr.HCl monomer, a preparation method thereof, a method for preparing an N-heterocyclic carbene functionalized organic polymer (PS-IPr-x) by using the olefin functionalized IPr.HCl monomer, and application of the N-heterocyclic carbene functionalized organic polymer as a heterogeneous catalyst for catalyzing reduction N-formylation of carbon dioxide and amine. A heterogeneous catalyst is prepared by using cheap and easily available DVB as a polymerization cross-linking agent through an AIBN-initiated olefin polymerization method, and has the advantages of low preparation cost and simple preparation method. Meanwhile, the catalytic activity of the catalyst is obviously higher than that of reported catalysts, and the catalyst has a wide practical application prospect.
- -
-
Paragraph 0069-0073; 0074; 0078
(2021/06/21)
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- Copper-Catalyzed Cascade N-Dealkylation/N-Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants
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A novel tandem N-dealkylation and N-methyl aerobic oxidation of tertiary aromatic amines to N-arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N-methylarylamines to N-arylformamides.
- Li, Dianjun,Wang, Shihaozhi,Yang, Jiale,Yang, Jinhui
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supporting information
p. 6768 - 6772
(2021/12/31)
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- Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines
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The shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C2 and C3 biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single CuII sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and .NHPh radicals, in which the selective formation of .OOH radicals might play a key role.
- Brückner, Angelika,Dai, Xingchao,Kreyenschulte, Carsten,Rabeah, Jabor,Shi, Feng,Wang, Xinzhi
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p. 16889 - 16895
(2021/09/25)
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- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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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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- A Practical Approach for the Transamidation of N, N-Dimethyl Amides with Primary Amines Promoted by Sodium tert-Butoxide under Solvent-Free Conditions
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A practical sodium tert-butoxide (NaO t Bu)-mediated protocol is disclosed for the transamidation of various N, N-dimethyl amides with primary amines to afford the corresponding amides in moderate to good yields at room temperature under solvent-free conditions. This protocol features a facile work-up procedure and good functional group compatibility, especially for N, N-dimethyl amides with long-chain alkyl groups and heteroatom-containing amines. Notably, a few representative gram-scale reactions proceed smoothly to furnish the desired amides in high yields, which demonstrates the potential of this process for further practical applications. Several control experiments are carried out and a plausible mechanism is provided.
- Zhang, Rui,Zhang, Jun-Chao,Zhang, Wei-Yi,He, Yu-Qing,Cheng, Hua,Chen, Cheng,Gu, Yu-Cheng
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p. 3286 - 3294
(2020/09/23)
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- Effective and selective direct aminoformylation of nitroarenes utilizing palladium nanoparticles assisted by fibrous-structured silica nanospheres
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Abstract: Palladium nanoparticles (~ 1–3?nm, 0.4?wtpercent Pd) were uniformly distributed over the surface of fibrous silica nanospheres (KCC-1) modified via aminopropyltriethoxysilane using a fast and cost-effective palladium (II) chloride reduction process. The Pd nanoparticles (Pd NPs) distribution over the ensuing catalyst Pd/KCC-1-NH2 showed much more uniform distribution, and smaller size compared with the tedious hydrothermal reduction method. The morphological, chemical, and size analyses of Pd/KCC-1-NH2 by BET, UV–Vis spectra, XRD, HR-TEM, EDS and XPS analysis revealed that the succeeding material consist of a distinct fibrous silica nanospheres support adorn with Pd NPs. The resultant nanocatalyst was tested for the one-step reductive aminoformylation of aromatic nitro compounds using formic acid. A wide range of substituted nitroarenes including electron withdrawing, releasing, sterically hindered and multifunctional groups have been converted to corresponding aryl formamide in quantitative yields (yields up to 98percent) at moderate temperature (70?°C). Optimization study has proved that the 6 equivalent of formic acid is required and toluene was found to be the better solvent. The established practice is beneficial due to the use of formic acid as H2 source and formylating agent, easiness in handling of the catalyst and simple workup procedure with efficient catalyst reusability. Graphic abstract: [Figure not available: see fulltext.].
- Jaseer, E. A.,Qureshi, Ziyauddin S.
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- A NHC-silyliumylidene cation for catalytic N?formylation of amines using carbon dioxide
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This study describes the use of a silicon(II) complex, namely, the NHC-silyliumylidene cation complex [(IMe)2SiH]I (1, IMe =:C{N(Me)C(Me)}2), to catalyze the chemoselective N-formylation of primary and secondary amines using CO2 and PhSiH3 under mild conditions to afford the corresponding formamides as a sole product (average reaction time: 4.5 h; primary amines, average yield: 95%, average TOF: 8 h?1; secondary amines, average yield: 98%, average TOF: 17 h?1). The activity of 1 and product yields outperform the currently available non-transition-metal catalysts used for this catalysis. Mechanistic studies show that the silicon(II) center in complex 1 catalyzes the C?N bond formation via a different pathway in comparison with non-transition-metal catalysts. It sequentially activates CO2, PhSiH3, and amines, which proceeds via a dihydrogen elimination mechanism, to form formamides, siloxanes, and dihydrogen gas.
- Leong, Bi-Xiang,Teo, Yeow-Chuan,Condamines, Cloe,Yang, Ming-Chung,Su, Ming-Der,So, Cheuk-Wai
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p. 14824 - 14833
(2020/12/21)
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- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
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We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
-
supporting information
p. 5317 - 5324
(2020/09/17)
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- Potassium tert-Butoxide Prompted Highly Efficient Transamidation and Its Coordination Radical Mechanism
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A simple and highly efficient protocol was developed for the transamidation of N,N-disubstituted amides with primary amines in the presence of tBuOK, affording desired products in good to excellent yields. This reaction proceeded under nitrogen atmosphere and featured extensive substrate tolerance. Experimental investigation suggested that a coordination radical process enhanced this transformation.
- Tan, Zhiyong,Li, Zhenhua,Ma, Yao,Qin, Jinjing,Yu, Chuanming
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p. 4538 - 4545
(2019/07/18)
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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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- 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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- 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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- MXene (Ti3C2) Vacancy-Confined Single-Atom Catalyst for Efficient Functionalization of CO2
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A central topic in single-atom catalysis is building strong interactions between single atoms and the support for stabilization. Herein we report the preparation of stabilized single-atom catalysts via a simultaneous self-reduction stabilization process at room temperature using ultrathin two-dimensional Ti3-xC2TyMXene nanosheets characterized by abundant Ti-deficit vacancy defects and a high reducing capability. The single atoms therein form strong metal-carbon bonds with the Ti3-xC2Ty support and are therefore stabilized onto the sites previously occupied by Ti. Pt-based single-atom catalyst (SAC) Pt1/Ti3-xC2Ty offers a green route to utilizing greenhouse gas CO2, via the formylation of amines, as a C1 source in organic synthesis. DFT calculations reveal that, compared to Pt nanoparticles, the single Pt atoms on Ti3-xC2Ty support feature partial positive charges and atomic dispersion, which helps to significantly decrease the adsorption energy and activation energy of silane, CO2, and aniline, thereby boosting catalytic performance. We believe that these results would open up new opportunities for the fabrication of SACs and the applications of MXenes in organic synthesis.
- Zhao, Di,Chen, Zheng,Yang, Wenjuan,Liu, Shoujie,Zhang, Xun,Yu, Yi,Cheong, Weng-Chon,Zheng, Lirong,Ren, Fuqiang,Ying, Guobing,Cao, Xing,Wang, Dingsheng,Peng, Qing,Wang, Guoxiu,Chen, Chen
-
supporting information
p. 4086 - 4093
(2019/02/26)
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- Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2
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Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.
- Huang, Zijun,Jiang, Xiaolin,Zhou, Shaofang,Yang, Peiju,Du, Chen-Xia,Li, Yuehui
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p. 3054 - 3059
(2019/04/10)
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- Mild and facile synthesis of formamide: Reduction and functionalization of CO2 using NaBH(OAc)3 under atmospheric pressure
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An approach for N-formylation of amines was developed using NaBH(OAc)3 as a reductant under an atmospheric pressure of CO2 at 50 °C. The corresponding formylated products of various amines, including aliphatic and aromatic amines, amines with reductive-sensitive nitro groups and alkynyl groups and benzamides were obtained in good to excellent yields, and the possible reaction mechanism was also proposed.
- Liu, Huan,Nie, Zhuang,Shao, Jiaan,Chen, Wenteng,Yu, Yongping
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supporting information
p. 3552 - 3555
(2019/07/09)
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- Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines
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A simple catalyst- and promoter-free protocol has been developed for the transamidation of weakly nucleophilic aromatic amines with formamide derivatives and low-reactivity tertiary amides with aliphatic amines. This strategy is advantageous because no catalyst or promoters are needed, no additives are required, separation and purification is easy, and the reaction is scalable. Significantly, this strategy was further applied to synthesize several pharmaceutical molecules on a gram scale, and excellent yields were achieved.
- Yin, Jiawen,Zhang, Jingyu,Cai, Changqun,Deng, Guo-Jun,Gong, Hang
-
supporting information
p. 387 - 392
(2019/01/11)
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- A non-catalyst non-promoter under the conditions of amide derivatives of aromatic amine with transfers the amine reaction
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The present invention discloses a non-catalyst under the condition of non-accelerator [...] amide derivatives of aromatic amine with transfers the amine reaction, yield of synthetic N - aryl amide derivatives. The method has a wide range of the substrate, its raw materials and cheap and easy to obtain acylation reagent, the reaction yield is high, one-step reaction, low cost, high reaction selectivity, simple operation and the like. Adopting this method can be gram scale can realize the high yield of the synthesis of drug molecules. Therefore, the method in the N - aryl amide derivatives of synthesis application field has very good application prospect. The method overcomes the existing technologies such as the reaction reagent toxicity is large, the need to use different type catalyst, synthesis method and the cost is high, more reaction steps, more byproducts and the like.
- -
-
Paragraph 0033; 0034
(2019/03/28)
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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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- Method for preparing N-formylated amine compounds
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The invention discloses a method for preparation N-formylated amine compounds. In the method, the amine compounds and 1,3-dihydroxy acetone are taken as reaction raw materials reacting in a reactor for 2-48 hours at the reaction temperature of 0-100DEG C in a reaction medium in the presence of composite catalysts and oxidants, and the N-formylated amine compounds are obtained. The method is simpleand moderate in reaction conditions, cost can be reduced, target products can be obtained with high yield, and the catalysts used have high catalytic activity and are easy to be separated from a reaction system and reuses; the method is environment friendly during the whole process, the reaction raw materials are easy to be converted from biodiesel by-product propylene glycol, and use of glycerolis facilitated.
- -
-
Paragraph 0040; 0048; 0049
(2018/11/03)
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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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- 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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- 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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- Co3O4 nanoparticles prepared by oxidative precipitation method: an efficient and reusable heterogeneous catalyst for N-formylation of amines
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Abstract: N-formylation of different amines was carried out with formic acid in the presence of the Co3O4 nanoparticles as an efficient, stable heterogeneous catalyst to give the corresponding formamides under solvent-free conditions. This method has advantages over the reported methods such as high yields, mild conditions, easy work-up and short reaction times. The catalyst was characterized by different techniques such as XRD, SEM and FT-IR spectroscopy. Graphical Abstract: [Figure not available: see fulltext.]
- Marjani, Ahmad Poursattar,Hosseini, Seyed Ali,Shokri, Zahra,Maleki, Nasim
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p. 413 - 422
(2017/01/14)
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- An efficient reduction of N-substituted carbonylimidazolides into formamides by NaBH4
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A novel, simple and versatile protocol was investigated for highly efficient synthesis of formamides through reducing N-substituted carbonylimidazolides by NaBH4 under mild reaction conditions. By this method, not only carboxylic acids or isocyanates, but also amines can readily access formamides with high yields.
- Chen, Zhiyong,Cao, Yiming,Tian, Zeyu,Zhou, Xuan,Xu, Wenjin,Yang, Jia,Teng, Hanbing
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p. 2166 - 2170
(2017/05/10)
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- Method for synthesizing formamide compound
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The invention discloses a method for synthesizing a formamide compound. The synthetic method comprises the following steps: taking carbamyl imidazole compound as a raw material, preparing the formamide compound in a mixed solution of tetrahydrofuran and water by taking hydroboron as a reducing agent. The catalyst hydroboron used in the method disclosed by the invention has the advantages of environment friendliness, stable performance, high conversion rate and the like. Moreover, the initial raw material and used reagents are simple and readily available, the cost is low, and the operation is simple and feasible. Therefore, the route is a route which is low in cost, simple in operation and suitable for industrial production.
- -
-
Paragraph 0032-0034
(2017/09/01)
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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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- Synthesis of selenazolopyridine derivatives with capability to induce apoptosis in human breast carcinoma MCF-7 cells through scavenge of intracellular ROS
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A series of selenazolopyridine derivatives have been synthesized and characterized by X-ray diffraction, high resolution NMR and Mass spectrum. The in vitro anticancer activities of the synthetic compounds were screened against a panel of human cancer cell lines, human breast carcinoma MCF-7 cells, human liver carcinoma HepG2 cells and L02 normal cell line by MTT assay. By analyzing the structure-activity relationship among the synthetic compounds, it was found that 2-(phenylamino) selenazolo [5,4-b] pyridine, (PSeD, 7) had higher growth inhibitory effect on MCF-7 cells. The intracellular mechanism of cell death was evaluated by flow cytometric analysis and ROS assay, which revealed that PSeD could induce MCF-7 cells apoptosis by scavenging intracellular ROS. Taken together, we regard PSeD as an antioxidant which could inhibit cancer cell growth through induction of apoptosis.
- Zhou, Meiyun,Ji, Shengbin,Wu, Zhaojun,Li, Yiqun,Zheng, Wenjie,Zhou, Hua,Chen, Tianfeng
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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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- 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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- A Highly Water-Dispersible/Magnetically Separable Palladium Catalyst: Selective Transfer Hydrogenation or Direct Reductive N-Formylation of Nitroarenes in Water
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Simple ion exchange of the chloride anion of an ionic-liquid-functionalized magnetic nanoparticle with [PdCl4]2- provided a highly water-dispersible and magnetically separable palladium catalyst that exhibited excellent activity toward transfer hydrogenation reactions in water as a solvent. The catalyst demonstrated outstanding performance in aqueous-phase transfer hydrogenation of various nitroarenes in a highly chemo- and regioselective manner by using HCOONH4 as a low-cost, green, and easily available hydrogen donor. Also, by using only 0.25 mol % of the catalyst and formic acid as both a hydrogen donor and formylating agent, the catalyst showed excellent activity in the one-pot, direct synthesis of N-arylformamides from nitroarenes in water as a solvent. Notably, owing to the presence of a hydrophilic ionic liquid on the surface of silica-coated iron oxide nanoparticles, the catalyst showed highly stable dispersion in water, as evidenced by the zeta potential and extremely low affinity to the organic phase. These features make this catalyst system suitable for an efficient double-separation strategy (successive extraction/final magnetic separation). The recovered aqueous phase containing the catalyst can be simply and efficiently reused in eight runs without a decrease in activity and can be easily separated from the aqueous phase at the end of the process by applying an external magnetic field.
- Karimi, Babak,Mansouri, Fariborz,Vali, Hojatollah
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p. 1750 - 1759
(2016/01/25)
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- Effective Formylation of Amines with Carbon Dioxide and Diphenylsilane Catalyzed by Chelating bis(tzNHC) Rhodium Complexes
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The reductive formylation of amines using CO2 and hydrosilanes is an attractive method for incorporating CO2 into valuable organic compounds. However, previous systems required either high catalyst loadings or high temperatures to achieve high efficiency, and the substrate scope was mostly limited to simple amines. To address these problems, a series of alkyl bridged chelating bis(NHC) rhodium complexes (NHC=N-heterocyclic carbene) have been synthesized and applied to the reductive formylation of amines using CO2 and Ph2SiH2. A rhodium-based bis(tzNHC) complex (tz=1,2,3-triazol-5-ylidene) was identified to be highly effective at a low catalyst loading and ambient temperature, and a wide substrate scope, including amines with reducible functional groups, were compatible. Beyond the norm: Rhodium complexes bearing a strong electron-donating bis(1,2,3-triazol-5-ylidene) ligand were found to be excellent catalysts for the reductive formylation of amines with CO2 and Ph2SiH2 at ambient temperature. The catalyst system possesses a broad substrate scope which tolerates a variety of reducible functional groups and is suitable for the synthesis of bioactive compounds. Tf=trifuoromethanesulfonyl.
- Nguyen, Thanh V. Q.,Yoo, Woo-Jin,Kobayashi
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supporting information
p. 9209 - 9212
(2015/08/06)
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- An eco-friendly n-formylation of amines using nano cerium oxide as a recyclable catalyst under solvent-free and ultrasound irradiation conditions at room temperature
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A new method for the synthesis of formamides has been developed by the N-formylation of amines with formic acid in the presence of nano cerium oxide as an efficient and recyclable catalyst under ultrasound irradiation. The reaction system is remarkably simple and environmentally benign.
- Sajadi, S. Mohammad,Maham, Mehdi,Rezaei, Akbar
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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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- Synthesis, structural characterization, and catalytic activity of flower like zno nanostructures
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Tageteserecta flower like zinc oxide nanostructures composed of hexagonal nanorods were synthesized via sonochemical method at room temperature. The synthesized nanomaterials exhibited wurtzite hexagonal phase structure with the single crystalline nature. The diameter of the individual nanorods that constitute the flower shaped zinc oxide structures is in the range of 120-160 nm. The sonication time effectively determined the morphological properties of the prepared materials. The catalytic activity of prepared zinc oxide nanostructures towards N-formylation reactions were evaluated without any surface modification and the nanostructures exhibited good reaction yield with the prompt recyclability behavior.
- Ramachandran,Gnana Kumar,Kim, Ae Rhan,Yoo, Dong Jin
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p. 1091 - 1097
(2014/05/06)
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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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- A binuclear Mn(ii) complex as an efficient catalyst for transamidation of carboxamides with amines
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A binuclear Mn(ii) complex has been synthesized and characterized by different structural methods. The complex contains two unique oxo-bridged metal centres and has been explored as an excellent catalyst for transamidation of carboxamides with amines under solvent-free conditions.
- Singh, Divya Pratap,Allam, Bharat Kumar,Singh, Krishna Nand,Singh, Vinod Prasad
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p. 1155 - 1158
(2014/01/06)
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- Nano CoFe2O4 as a magnetically separable catalyst for the solvent-free synthesis of formamides under ultrasound irradiation at room temperature
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Formamides were efficiently synthesized from N-formylation of amines using CoFe2O4 nanoparticles as a magnetically recoverable and reusable catalyst under ultrasound irradiation. The main advantages allocated to this method are chemoselectivity, reduced reaction times, high yields, magnetically recyclable catalyst, non-solvent green conditions and simple work-up procedure.
- Bahari, Siavash
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p. 532 - 537
(2013/08/23)
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- Copper-diphosphine complex catalysts for N-formylation of amines under 1 atm of carbon dioxide with polymethylhydrosiloxane
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N-formylation of a wide range of amines proceeded using copper-diphosphine complexes as homogeneous catalysts with polymethylhydrosiloxane (PMHS) under 1 atm of CO2. In the reaction of piperidine, for example, the turnover number (TON) reached 11700 in 23 h with 90% yield of the formylated product. This TON value is much higher than those of the reported catalysts for the formylation of amines under 1 atm of CO2 with hydrosilanes. The Cu complexes with phosphines having ortho-phenylene structures acted as good ligands for the formylation, as compared to a bidentate ligand connected with a propyl chain and a monodentate ligand. Among these diphosphines, ligands with alkyl functionalities, such as isopropyl and cyclohexyl groups, produced better results than the phenyl group. Not only cyclic secondary amines, but also linear secondary amines and aromatic and aliphatic primary amines were found to be reactive substrates. In the case of 2,2,6,6-tetramethylpiperidin-4-amine, the formylation proceeded regioselectively. A catalytic reaction pathway was proposed from a separate experiment using [Me2NCO2] [Me2NH2]. The Royal Society of Chemistry 2013.
- Motokura, Ken,Takahashi, Naoki,Kashiwame, Daiki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
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p. 2392 - 2396
(2013/09/02)
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- A novel and simple transamidation of carboxamides in 1,4-dioxane without a catalyst
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An easy acylation and formylation of amines has been achieved via transamidation using 1,4-dioxane. The investigation works efficiently without an added catalyst and completes within short time under microwave irradiation.
- Vanjari, Rajeshwer,Allam, Bharat Kumar,Singh, Krishna Nand
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p. 2553 - 2555
(2013/06/05)
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- An efficient method for N-formylation of amines using natural heu zeolite at room temperature under solvent-free conditions
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A rapid and practical green route for N-formylation of primary and secondary amines with formic acid at room temperature under the solvent-free conditions using HEU zeolite as a heterogeneous, reusable and highly efficient catalyst is described. The process is remarkably simple and environmentally benign. Excellent chemoselectivity was observed for the conversion of primary amines in the presence of secondary amines.
- Bahari, Siavash,Mohammadi-Aghdam, Babak,Sajadi, S. Mohammad,Zeidali, Fereshteh
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experimental part
p. 2251 - 2254
(2012/08/28)
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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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- 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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- A remarkably simple N-formylation of anilines using polyethylene glycol
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N-Formylation of anilines has efficiently been carried out at room temperature in excellent yields by treatment with formic acid in polyethylene glycol (PEG-400). No additional solvent and catalyst are required.
- Das, Biswanath,Krishnaiah, Maddeboina,Balasubramanyam,Veeranjaneyulu, Boyapati,Nandan Kumar
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p. 2225 - 2227
(2008/09/18)
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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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- Microwave enhanced reduction of nitro and azido arenes to N-arylformamides employing Zn-HCOONH4: Synthesis of 4(3H)-quinazolinones and pyrrolo[2,1-c][1,4]benzodiazepines
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Microwave mediated reduction of nitro and azido arenes to N-arylformamides using Zn-HCOONH4 is described. In the absence of microwave conditions, this methodology affords amines. This protocol has been extended to the synthesis of pyrrolo[2,1-c][1,4]benzodiazepines and 4(3H)-quinazolinones.
- Kamal, Ahmed,Srinivasa Reddy,Rajendra Prasad,Hari Babu,Ramana, A. Venkata
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p. 6517 - 6521
(2007/10/03)
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