- Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd&at;MCP) for chemoselective N-formylation and N-acylation of amines
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Novel palladium nanoparticles stabilized by clinoptilolite as a natural inexpensive zeolite prepared and used for N-formylation and N-acylation of amines at room temperature at environmentally benign reaction conditions in good to excellent yields. Pd (II) was immobilized on the surface of clinoptilolite via facile multi-step amine functionalization to obtain a sustainable, recoverable, and highly active nano-catalyst. The structural and morphological characterizations of the catalyst carried out using XRD, FT-IR, BET and TEM techniques. Moreover, the catalyst is easily recovered using simple filtration and reused for 7 consecutive runs without any loss in activity.
- Amirsoleimani, Mina,Khalilzadeh, Mohammad A.,Zareyee, Daryoush
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- N-formylation of amines using phenylsilane and CO2 over ZnO catalyst under mild condition
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Several research studies have been conducted on N-formylation of amines using phenylsilane and CO2. However, most of these studies involved tedious processes of catalyst preparation or complex procedures. In the present study, we describe the use of a simple and commercially available ZnO catalyst for selective N-formylation of amines under mild condition. High-yielding N-formylation products with good recyclability and wide substrate scope were obtained, which can promote fine chemical synthesis and CO2 capture.
- Cheng, Yujie,Gan, Tao,He, Qian,He, Xiaohui,Ji, Hongbing,Sun, Qingdi,Wang, Pengbo,Zhang, Hao
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- Selective N-formylation of amines catalysed by Ag NPs festooned over amine functionalized SBA-15 utilizing CO2 as C1 source
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N-formylation of amines using CO2 as C1 source has been an uphill transformation in the catalysis research as it involves the utilization of abundant thermodyanamically stable and kinetically inert CO2 to form the N-formylated products, which are potential intermediates for the synthesis of valuable chemicals. Previously various noble as well as non-noble metal nanoparticles have been employed for N-formylation of amines. However, herein for the first time we explored N-formylation reaction under lenient conditions utilizing silver nanoparticles, which are decorated over amine functionalized periodically ordered 2D-hexagonal SBA-15 material, serving as a robust heterogeneous catalyst. The AgNPs@SBA-15-NH2 has been intensively characterized by powder XRD, Brunauer-Emmett-Teller (BET), FEG-TEM, SEM, XPS, TGA, CO2-TPD, FTIR and UV–vis spectroscopic analyses. This supported AgNPs material showed remarkable catalytic activity for N-formylation over a wide range of amines under 0.5 MPa CO2 pressure and at mild temperature (35 °C) conditions. In addition, this AgNPs@SBA-15-NH2 material exhibited high chemical stability and reusability, suggesting its promising future in the CO2 fixation reactions.
- Azad, Shiyana,Bal, Rajaram,Bhattacharjee, Sudip,Bhaumik, Asim,Chongdar, Sayantan
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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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- Direct Synthesis of N,N-Disubstituted Formamides by Oxidation of Imines Using an HFIP/UHP System
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The straightforward synthesis of N,N-disubstituted formamides using a combination of 1,1,1,3,3,3-hexafluoroispropanol (HFIP) and H2O2 is described. The unique features of HFIP allowed the utilization of a green oxidant such as H2O2, and the products, arising from an oxidation-rearrangement sequence, were obtained in good to high yields under smooth reaction conditions.
- Llopis, Natalia,Gisbert, Patricia,Baeza, Alejandro
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p. 11072 - 11079
(2020/10/12)
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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
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supporting information
p. 5317 - 5324
(2020/09/17)
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- Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source
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We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.
- Zou, Qizhuang,Long, Guangcai,Zhao, Tianxiang,Hu, Xingbang
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supporting information
p. 1134 - 1138
(2020/03/11)
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- Graphene oxide: A convenient metal-free carbocatalyst for facilitating amidation of esters with amines
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Herein, we report a graphene oxide (GO) catalyzed condensation of non-activated esters and amines, that can enable diverse amides to be synthesized from abundant ethyl esters forming only volatile alcohol as a by-product. GO accelerates ester to amide conversion in the absence of any additives, unlike other catalysts. A wide range of ester and amine substrates are screened to yield the respective amides in good to excellent yields. The improved catalytic activity can be ascribed to the oxygenated functionalities present on the graphene oxide surface which forms H-bonding with the reactants accelerating the reaction. Improved yields and a wide range of functional group tolerance are some of the important features of the developed protocol.
- Patel, Khushbu P.,Gayakwad, Eknath M.,Shankarling, Ganapati S.
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p. 2661 - 2668
(2020/02/20)
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- Biomass-derived N-doped porous carbon: An efficient metal-free catalyst for methylation of amines with CO2
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Developing green, efficient, and low-cost catalysts for methylation of N-H by using CO2 as the C1 resource is highly desired yet remains a significant challenge. Herein, N-doped porous carbons (NPCs) were designed, synthesized, and proved to be an excellent metal-free catalyst for CO2-participated methylation conversion. NPCs were prepared via the pyrolysis of a mixture of tannic acid and urea. Both theoretical calculation and experiment demonstrate that the N species especially pyridinic N and pyrrolic N within NPCs can work as Lewis basic sites for attacking CO2 to weaken the CO bonds and lower the molecule conversion barrier, facilitating the subsequent methylation of N-H to produce, for example, N,N-dimethylaniline. Besides, the unique porous structure can enrich CO2 and accelerate mass transfer, synergistically promoting the conversion of CO2. The optimized NPC(1/5) catalyst, integrating the porous structure and strong Lewis basicity, exhibits excellent catalytic activity for CO2-based methylation reaction under mild conditions (1 bar CO2, 75 °C). Our work, for the first time, demonstrates the feasibility of using NPCs to catalyze the methylation of amino compounds to produce N,N-dimethylamine by exploiting CO2 as the C1 resource.
- Tang, Feiying,Wang, Liqiang,Liu, You-Nian
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supporting information
p. 6252 - 6257
(2019/12/03)
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- Graphene Oxide: A Metal-Free Carbocatalyst for the Synthesis of Diverse Amides under Solvent-Free Conditions
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An environmentally friendly, inexpensive, carbocatalyst, graphene oxide (GO) promoted efficient, metal-free transamidation of various carboxamides with aliphatic, cyclic, and aromatic amines is demonstrated. The protocol is equally applicable to phthalimide, urea, and thioamide determining its adaptability. The oxygenated functionalities such as carbonyl (?C=O), epoxy (?O?), carboxyl (?COOH) and hydroxyl (?OH), present on graphene oxide surface impart acidic properties to the catalyst. The graphene oxide being heterogeneous in nature, work efficiently under solvent-free reaction conditions providing desired products in good to excellent yields. The one-pot synthesis of 2,3-Dihydro-5H-benzo[b]-1,4-thiazepin-4-one moiety by GO catalyzed Aza Michael addition followed by intramolecular transamidation is also described. A plausible reaction mechanistic pathway involving H-bonding is discussed. The graphene oxide can be recycled and reused up to five cycles without much loss in catalytic activity. (Figure presented.).
- Patel, Khushbu P.,Gayakwad, Eknath M.,Patil, Vilas V.,Shankarling, Ganapati S.
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supporting information
p. 2107 - 2116
(2019/03/26)
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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
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supporting information
p. 387 - 392
(2019/01/11)
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- Synthesis of a Zeolitic Imidazolate-Zinc Metal-Organic Framework and the Combination of its Catalytic Properties with 2,2,2-Trifluoroethanol for N-Formylation
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A novel protocol is reported for the N-formylation of amines with formic acid by using the nanoporous zeolitic imidazolate framework ZIF-8 as a heterogeneous catalyst in 2,2,2-trifluoroethanol.
- Alamgholiloo, Hassan,Rostamnia, Sadegh,Hassankhani, Asadollah,Banaei, Reza
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supporting information
p. 1593 - 1596
(2018/06/08)
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- N-aryl formamide prepared by using ethyl bromodifluoroacetate as formylating reagent
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The invention discloses a compound of N-aryl formamide prepared by using ethyl bromodifluoroacetate as a formylating reagent. The compound is prepared by using N-alkyl arylamine as a raw material, ethyl bromodifluoroacetate as a formylating reagent and copper as a catalyst, adding different ligands, bases, etc., performing reaction under stirring in a reaction solvent at 100-120 DEG C for 10-14 hours; then filtering the reaction solution to obtain filtrate after reaction ending; concentrating the filtrate, removing the solvent by using a rotary evaporator to obtain a residue, treating the residue by silica gel column chromatography, eluting with an eluent, collecting the effluent according to the actual gradient; combining the effluent containing the product, concentrating the combined effluent to remove the solvent, and performing vacuum drying to obtain the target product. The compound has the advantages of simple and easily obtained raw materials, simple preparation process, less pollution, low energy consumption and high yield.
- -
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Paragraph 0039
(2018/12/02)
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- Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
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Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.
- Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
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p. 12815 - 12821
(2018/10/20)
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- Ru@PsIL-Catalyzed Synthesis of N-Formamides and Benzimidazole by using Carbon Dioxide and Dimethylamine Borane
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This work reports the synthesis and characterization of ruthenium nanoparticles (Ru NPs) supported on polymeric ionic liquids (PILs). This catalyst shows high catalytic activity towards the N-formylation of amines and synthesis of benzimidazoles from 1,2-diamines and carbon dioxide (CO2) by reductive dehydrogenation of dimethylamine borane. This methodology shows excellent functional group tolerance with broad substrate scope towards the synthesis of N-formamides and benzimidazoles. Interestingly, this protocol also provides the tandem reduction of 2-nitroamines and CO2 to synthesize benzimidazoles. It was proposed that the ionic liquid phase of the polymer plays pivotal roles such as assisting the stabilization of nanoparticles electrostatically, providing an ionic environment, and controlling the easy access of the substrates/reagents to the active sites. The developed methodology utilizes CO2 as a C1 source and water/ethanol as a green solvent system. Additionally, the catalyst was found to be recyclable in nature and shows five consecutive recycling runs without significant loss in its activity.
- Saptal, Vitthal B.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
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p. 2593 - 2600
(2018/04/30)
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- Tungstate catalysis: Pressure-switched 2- and 6-electron reductive functionalization of CO2 with amines and phenylsilane
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An efficient and environmentally benign tungstate catalyst for reductive functionalization of CO2 with amines and phenylsilane was developed. By simply varying the pressure, 2-electron or 6-electron reduction of CO2 was successfully achieved with simultaneous C-N bond formation, thus leading to the formation of formamides and methylamines, respectively. That is, secondary and primary amines furnished the corresponding methylamines or dimethylamines in excellent yields under atmospheric pressure of CO2, while various formamides were formed in yields ranging from 52% to 98% when increasing the CO2 pressure to 2 MPa. 1H NMR studies and control experiments demonstrate that N-formylation proceeds through the formation of silyl formate, while N-methylation proceeds through an aminal intermediate generated by 4-electron reduction of CO2.
- Wang, Mei-Yan,Wang, Ning,Liu, Xiao-Fang,Qiao, Chang,He, Liang-Nian
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supporting information
p. 1564 - 1570
(2018/04/12)
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- Visible-light-induced oxidative formylation of N-alkyl-N-(prop-2-yn-1-yl)anilines with molecular oxygen in the absence of an external photosensitizer
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Visible-light-induced oxidative formylation of N-alkyl-N-(prop-2-yn-1-yl)anilines with molecular oxygen in the absence of an external photosensitizer was developed and afforded the corresponding formamides in good yields under mild conditions. The investigation of the mechanism disclosed that both the starting material and the product act as photosensitizers, and 1O2 and O2- are generated through energy transfer and a single electron transfer pathway and play an important role in the reaction.
- Ji, Wangqin,Li, Pinhua,Yang, Shuai,Wang, Lei
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supporting information
p. 8482 - 8485
(2017/08/03)
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- NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 as a new and reusable heterogeneous hybrid catalyst for efficient solvent-free formylation of amines
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NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 [NaY/SA/Cu(II)] was synthesized and used as a new, efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst was characterized by several techniques such as FT-IR, XRD, SEM, EDX and TG analysis. Chemoselectivity, easy procedure, excellent yields, very short reaction times, solvent-free and mild reaction conditions are some benefits of this new protocol.
- Kazemi, Samira,Mobinikhaledi, Akbar,Zendehdel, Mojgan
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p. 1767 - 1772
(2017/07/27)
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- A capable cobalt nano-catalyst for the N-formylation of various amines and its biological activity studies
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The Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) were modified with 1,10-phenanthroline-5,6-diol and the relevant Co complex (Fe3O4@Phendiol@Co) synthesized as a nano-magnetic heterogeneous catalyst to be used for the N-formylation of various amines at room temperature under solvent-free conditions. Also, in order to find the better concept of the catalyst role, the N-formylation reaction was carried out by the use of ultrasound irradiation in the absence of the Co nano-catalyst and the results were compared. The catalyst characterized by different methods such as the elemental analysis (CHN), ICP, FT-IR, XRD, EDX, SEM, TEM, TG-DTA, VSM and XPS. In addition, the antioxidant and the antibacterial activities of the Fe3O4@Phendiol@Co nano-catalyst and its Phendiol ligand were in vitro screened by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging and disc diffusion methods. Results showed that they possess strong antioxidant activity (IC50; 0.182?±?0.006?mg/ml) and good antibacterial potential in comparison to standards.
- Habibi, Davood,Heydari, Somayyeh,Afsharfarnia, Mina
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- Sulfated polyborate-catalyzed N-formylation of amines: a rapid, green and efficient protocol
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Abstract: A rapid, green and efficient method for N-formylation reaction of various amines with formic acid in the presence of sulfated polyborate catalyst under solvent-free conditions has been described. The catalyst has the advantage of mild Bronsted as well as Lewis acid character. The catalyst is recyclable with no significant loss in catalytic activity. The present protocol is advantageous due to its solvent-free condition, short reaction time, high yields, easy workup and ability to tolerate a variety of functional groups.
- Khatri, Chetan K.,Chaturbhuj, Ganesh U.
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p. 2513 - 2519
(2017/11/06)
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- Photoinduced Oxidative Formylation of N,N-Dimethylanilines with Molecular Oxygen without External Photocatalyst
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A photoinduced oxidative formylation of N,N-dimethylanilines with molecular oxygen in the absence of an external photocatalyst was developed and provided the corresponding formamides in good yields under mild reaction conditions. Investigations indicated that both the starting material and product act as photosensitizers and that 1O2 coexists with O2?- during the reaction through energy transfer and single electron transfer process.
- Yang, Shuai,Li, Pinhua,Wang, Zhihui,Wang, Lei
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supporting information
p. 3386 - 3389
(2017/07/15)
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- Iron-Catalyzed Amide Formation from the Dehydrogenative Coupling of Alcohols and Secondary Amines
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The five-coordinate iron(II) hydride complex (iPrPNP)Fe(H)(CO) (iPrPNP = N[CH2CH2(PiPr2)]2) selectively catalyzes the dehydrogenative intermolecular coupling of alcohols and secondary amines to form tertiary amides. This is the most productive base-metal catalyst for dehydrogenative amidation reported to date, in some cases achieving up to 600 turnovers. The catalyst works well for sterically undemanding amines and alcohols or cyclic substrates and is particularly effective in the synthesis of formamides from methanol. However, the catalyst performance declines rapidly with the incorporation of large substituents on the amine or alcohol substrate. Variable-temperature NMR spectroscopic studies suggest that the catalyst resting state is an off-cycle iron(II) methoxide species, (iPrPN(H)P)Fe(H)(OCH3)(CO), resulting from addition of methanol across the Fe-N bond of (iPrPNP)Fe(H)(CO). This reversibly formed iron(II) methoxide complex is favored at mild temperatures but eliminates methanol upon heating.
- Lane, Elizabeth M.,Uttley, Katherine B.,Hazari, Nilay,Bernskoetter, Wesley
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p. 2020 - 2025
(2017/06/13)
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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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- Solvent- and catalyst-free N-formylations of amines at ambient condition: Exploring the usability of aromatic formates as N-formylating agents
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A solvent- and catalyst-free N-formylation protocol has been developed for amines (1s–21s) where aromatic formates (1r–6r) were used as the N-formylating agents. The amine substrates include both primary and secondary aromatic amines (1s–19s) as well as aliphatic amine (20s) and a primary amide (21s). Structures of both the aromatic formate and amine components strongly influenced the rate of the reaction and yield of the N-formamide products. The reaction condition is mild and easy to operate. This protocol can be done smoothly under ambient conditions and gives high yield of formamide products. Furthermore, the present method cannot be applied for the formylation of thiol group (22s). This signifies its possible use for the chemoselective N-formylation of amine in the presence of thiol functionality.
- Batuta, Shaikh,Begum, Naznin Ara
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supporting information
p. 137 - 147
(2017/01/11)
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- Catalyst-free: N -formylation of amines using BH3NH3 and CO2 under mild conditions
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The catalyst-free N-formylation of amines using CO2 as the C1 source and BH3NH3 as the reductant has been developed for the first time. The corresponding formylated products of both primary and secondary amines are obtained in good to excellent yields (up to 96% of isolated yield) under mild conditions.
- Zhao, Tian-Xiang,Zhai, Gao-Wen,Liang, Jian,Li, Ping,Hu, Xing-Bang,Wu, You-Ting
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supporting information
p. 8046 - 8049
(2017/07/22)
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- A tertiary amine oxidation cracking method of preparing carboxamide
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The invention provides a method for preparing formamide through tertiary amine oxicracking. According to the method, tertiary amine serves as a substrate, air or oxygen serves as an oxygen source, and oxicracking occurs on the tertiary amine under the action of a catalyst to generate the formamide. The method is high in oxidation efficiency and product yield and economical and environmentally friendly by taking the air or oxygen as the oxygen source and has a very good application prospect.
- -
-
Paragraph 0014; 0023; 0024
(2017/08/26)
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- Novel method for synthesizing N-substitute amide derivative
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The invention discloses a novel method for synthesizing an N-substitute amide derivative. The novel method is characterized by comprising the steps that at the air atmosphere, no catalyst or alkali or other any additives are added, an organic amine compound shown in a formula (I) is adopted as a reaction substrate, a solvent shown in a formula (II) is adopted as an acylation reagent, an acylation reaction is performed under the reaction temperature of 120-150 DEG C to generate the N-substitute amide derivative shown in a formula (III), and the equation is shown in the description. The novel method has the advantages that environmental protection is achieved, and post-treatment and product separation are easy; the range of the substrate is wide, and the substrate can be primary amine and can also be secondary amine; the solvent can be amide and can also be carboxylic acid, and the solvent can be adopted as the acylation reagent to participate in the reaction; the reaction efficiency is high, and the majority of reactions can reach the quantified yield; water and air have no effect on the reaction, inert gas shielding is not needed, and operation is easy.
- -
-
Paragraph 0035; 0036; 0037; 0038; 0039; 0040-0041; 0122-0124
(2017/09/02)
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- Copper-catalyzed N-formylation of amines with CO2 under ambient conditions
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We carried out work on N-formylation of amines with CO2 and PhSiH3 to produce formamides catalyzed by a copper complex. It was found that the Cu(OAc)2-bis(diphenylphosphino)ethane (dppe) catalytic system was very efficient for these kind of reactions at room temperature and 1 atm CO2 with only 0.1 mol% catalyst loading.
- Zhang, Suqi,Mei, Qingqing,Liu, Hangyu,Liu, Huizhen,Zhang, Zepeng,Han, Buxing
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p. 32370 - 32373
(2016/04/26)
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- Amine modified mesoporous Al2O3@MCM-41: An efficient, synergetic and recyclable catalyst for the formylation of amines using carbon dioxide and DMAB under mild reaction conditions
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This work reports an amine modified meso Al2O3@MCM-41, particularly the ordered mesoporous silica, as a catalyst for the formylation of amines with carbon dioxide (CO2) and with dimethylamine-borane (DMAB) as a green reducing source. This newly developed catalytic system represents a heterogeneous and environmentally benign protocol. Besides this, the catalyst could be reused for five consecutive cycles without any significant loss in its catalytic activity towards the synthesis of formamides. The amine modified meso Al2O3@MCM-41 catalysts were well characterized by high and low angle XRD, temperature programmed desorption (TPD), BET-surface area, TGA/DTA and FT-IR analysis techniques. The effect of various reaction parameters such as temperature, CO2 pressure, time and the ratio of substrates to DMAB for the synthesis of formamides has been investigated. The developed protocol can be applicable for the synthesis of most important key intermediates like formoterol, orlistat, leucovarin and iguratimod in biologically active compounds.
- Nale, Deepak B.,Rath, Dharitri,Parida,Gajengi, Aravind,Bhanage, Bhalchandra M.
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p. 4872 - 4881
(2016/07/07)
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- Biomass-derived γ-valerolactone as an efficient solvent and catalyst for the transformation of CO2 to formamides
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Efficient conversion of carbon dioxide (CO2) into valuable chemicals is a very attractive topic. Herein, we conducted the first work on the utilization of biomass-derived γ-valerolactone (GVL) as the solvent and catalyst for transformation of CO2 with various primary and secondary amines in the presence of phenylsilane (PhSiH3), and the corresponding desired formamides were produced with high yields without any additional catalyst. Systematic studies indicated that the lactone structure of GVL played a key role in the formation of the active silyl formates and the activation of N-H bonds in amines, thus leading to the excellent performance of GVL for the catalytic reactions.
- Song, Jinliang,Zhou, Baowen,Liu, Huizhen,Xie, Chao,Meng, Qinglei,Zhang, Zhanrong,Han, Buxing
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supporting information
p. 3956 - 3961
(2016/07/21)
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- Covalently bonded zwitterionic sulfamic acid onto the SBA-15 (SBA-15/PrEn-NHSO3H) reveals good Bronsted acidity behavior and catalytic activity in N-formylation of amines
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Ethylenediamine-functionalization of SBA-15 with N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine (PrEn) was then underwent covalent sulfonation over secondary and primary amine groups (SBA-15/PrEn-NHSO3H) on the surface of the mesoporous SBA-15 pore walls. Scanning electron microscope (SEM), transmission electron microscope (TEM), SEM-energy dispersive X-ray (SEM-EDX), BET surface are analysis, thermal gravimetric (TG), FT-IR spectrums and CHNS were recorded for the characterization of SBA-15/PrEn-NHSO3H. This material was studied as a novel catalyst for N-formylation of amines. Based on the results, SBA-15/PrEn-NHSO3H acted as zwitterionic IL-type heterogeneous catalyst with simple separation feature from the reaction mixture. Moreover, it exhibited excellent recyclability at least for 12 times, and a higher catalytic activity toward N-formylation.
- Rostamnia, Sadegh,Doustkhah, Esmail
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p. 317 - 324
(2015/11/28)
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- Metal-free n -arylation of secondary amides at room temperature
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The arylation of secondary acyclic amides has been achieved with diaryliodonium salts under mild and metal-free conditions. The methodology has a wide scope, allows synthesis of tertiary amides with highly congested aryl moieties, and avoids the regioselectivity problems observed in reactions with (diacetoxyiodo)benzene.
- Tinnis, Fredrik,Stridfeldt, Elin,Lundberg, Helena,Adolfsson, Hans,Olofsson, Berit
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p. 2688 - 2691
(2015/06/16)
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- CO2 Adducts of Phosphorus Ylides: Highly Active Organocatalysts for Carbon Dioxide Transformation
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A series of phosphorus ylide (P-ylide) CO2 adducts were synthesized and first used as organocatalysts for CO2 transformation. Detailed studies on the cycloaddition reaction of CO2 with terminal epoxides show that P-ylide CO2 adducts are efficient metal-free and halogen-free organocatalysts to mediate this reaction under ambient conditions (25 °C, 1 atm of CO2). More importantly, the reactions proceeded with a broad scope, high efficiency, and good functional group tolerance and the corresponding cyclic carbonate products were obtained in good to excellent yields (46-99%). Meanwhile, the kinetic study by in situ FTIR methods suggested an intermolecular cooperation effect for effectively accelerating the ring opening of terminal epoxides. Furthermore, from an investigation of the catalytic diversity of P-ylide CO2 adducts, CO2 also could be converted to functionalized cyclic α-alkylidene carbonates, oxazolidinone, and N-methylated and N-formylated amines by organocatalytic reactions.
- Zhou, Hui,Wang, Guo-Xu,Zhang, Wen-Zhen,Lu, Xiao-Bing
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p. 6773 - 6779
(2015/11/18)
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- Direct amidation of carboxylic acids with amines under microwave irradiation using silica gel as a solid support
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A highly improved and green methodology for the direct amidation of carboxylic acids with amines using silica gel as a solid support and catalyst is described. The scope of this method is exemplified by the use of several aliphatic, aromatic, unsaturated and fatty acids. The reaction is also applied to different primary and secondary amines. Typically, the amines should be aliphatic, but aromatic amines can be used as well, though with lower yields. Several experiments to illustrate the selectivity of this methodology were also carried out with several more functionalized acids and amines. This approach is a substantial improvement over other previously described methods in amide synthesis.
- Ojeda-Porras, Andrea,Hernández-Santana, Alejandra,Gamba-Sánchez, Diego
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supporting information
p. 3157 - 3163
(2015/05/27)
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- Preparation and catalytically study of metal-organic frameworks of amine/MIL-53 (Al) as a powerful option in the rapid N-formylation condensation in neat conditions
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This paper reports on the preparation and application of amine/MIL-53 (Al) as highly active catalysts for the N-formylation reaction. These Al-MOFs were found to be an efficient, selective and waste-free green solid catalyst for the net condensation of amines and formic acid. The catalyst can be isolated from the reaction mixture and reused at least 6 times.
- Rostamnia, Sadegh,Karimi, Ziba
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p. 133 - 137
(2015/03/04)
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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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- 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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- Microwave-promoted direct amidation of unactivated esters catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions
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Abstract A simple and efficient procedure for the synthesis of amides directly from unactivated esters and amines catalyzed by heteropolyanion-based ionic liquids under microwave-promoted and solvent-free conditions has been reported. The practical protocol was found to be compatible with different structurally diverse substrates. Moderate to excellent yields, solvent-free media, and operational simplicity are the main highlights. Furthermore, the heteropolyanion-based ionic liquids were easily reusable for this amidation.
- Fu, Renzhong,Yang, Yang,Ma, Yunsheng,Yang, Fei,Li, Jingjing,Chai, Wen,Wang, Quan,Yuan, Rongxin
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p. 4527 - 4531
(2015/06/30)
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- Fukuyama reduction and integrated thioesterification/fukuyama reduction of thioesters and acyl chlorides using continuous flow
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Fukuyama reduction of thioesters has been achieved using a polymer-supported Pd[0] catalyst (Pd/XAD-4), and continuous flow conditions. The generality of this reaction is good with a range of aldehydes prepared in excellent yields. In addition, an integrated multistep thioesterfication/ Fukuyama reduction has been developed that allows acyl chlorides to be directly converted to the corresponding aldehydes. Integral to this process is the use of polymer-supported amine and isocyanate reagents to achieve thioesterification and scavenge unreacted thiol. In addition, catch-and-release purification has been employed to enable isolation of the aldehyde from silylthioether byproducts without the need for chromatographic purification.
- Asadi, Mousa,Bonke, Shannon,Polyzos, Anastasios,Lupton, David W.
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p. 2070 - 2074
(2014/06/24)
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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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- An eco-benign and highly efficient procedure for N-acylation catalyzed by heteropolyanion-based ionic liquids using carboxylic acid under solvent-free conditions
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An eco-benign and highly efficient route for N-acylation of amines has been developed by treating amines with corresponding carboxylic acids in the presence of 2 mol % of heteropolyanion-based ionic liquids as catalysts under solvent-free conditions. This practical reaction could tolerate a wide range of substrates. Thus, various N-acylation products including N-acyl α-amino acid derivatives were obtained in moderate to excellent yields at 70 C to 120 C. Moreover, recycling studies revealed that heteropolyanion-based ionic liquids were easily reusable for this N-acylation. This method provides a green and much improved protocol over the existing methods.
- Chen, Zhikai,Fu, Renzhong,Chai, Wen,Zheng, Hao,Sun, Lin,Lu, Qiang,Yuan, Rongxin
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p. 2237 - 2245
(2014/03/21)
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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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- Polyphosphoric acid supported on silica-coated NiFe2O 4 nanoparticles: An efficient and magnetically-recoverable catalyst for N-formylation of amines
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A rapid, green and simple method for the N-formylation of various aromatic amines with formic acid using polyphosphoric acid supported on silica-coated NiFe2O4 magnetic nanoparticles (NiFe2O 4@SiO2-PPA) under solvent-free conditions at room temperature has been developed. The magnetic catalyst can be easily removed by a simple magnet and reused at least three times without any loss of its high catalytic activity. In addition to its facility, this protocol enhances product purity and promises economic and also environmental profits.
- Khojastehnezhad, Amir,Rahimizadeh, Mohammad,Moeinpour, Farid,Eshghi, Hossein,Bakavoli, Mehdi
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p. 459 - 464
(2014/05/06)
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- Partially reduced iridium oxide clusters dispersed on titania as efficient catalysts for facile synthesis of dimethylformamide from CO2, H 2 and dimethylamine
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A novel bifunctional catalyst based on partially reduced iridium oxide supported on TiO2 was found to be exceedingly efficient for the organic-solvent-free synthesis of dimethylformamide from CO2, H 2 and dimethylamine. This journal is the Partner Organisations 2014.
- Bi, Qing-Yuan,Lin, Jian-Dong,Liu, Yong-Mei,Xie, Song-Hai,He, He-Yong,Cao, Yong
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supporting information
p. 9138 - 9140
(2014/08/05)
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- CO2 as a C1-building block for the catalytic methylation of amines
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A novel catalytic reaction has been designed to utilize, for the first time, CO2 as a C1 feedstock in the synthesis of N-methylamines. Simple zinc catalysts, based on commercially available zinc salts and ligands, prove highly efficient in promoting both a 6 electron reduction of carbon dioxide and the formation of a C-N bond, using hydrosilanes and amines.
- Jacquet, Olivier,Frogneux, Xavier,Das Neves Gomes, Christophe,Cantat, Thibault
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p. 2127 - 2131
(2013/05/21)
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- On the oxidation of different iminic bonds by excess of 3-chloroperbenzoic acid
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In the present work the behavior of different substituted iminic bonds toward the oxidative action of 3-chloroperbenzoic acid is reported. The C=N bond was or was not oxidized to oxaziridines, amides, oximes, nitroso-, nitro-, and azodioxy compounds depending on the substituents at the iminic group and on the imine/MCPBA stoichiometric ratio.
- Troisis, Lutiginon,Carrozzo, Marina M.,Citti, Cinzia,Falcicchio, Aurelia,Mansueto, Rosmara,Rosato, Francesca,Cannazza, Giuseppe
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supporting information
p. 53 - 56
(2013/02/23)
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- Preparation of esters and amides from carboxylic acids and N-formylation of amines promoted by 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-hexachloride (TAPC)
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A new method is described for the preparation of esters and amides promoted by TAPC from carboxylic acids using a solvent-free grinding technique. The solvent-free N-formylation of amines is also reported.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Targhan, Homa,Sheikh Arabi, Mehdi
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supporting information
p. 5064 - 5068
(2013/09/02)
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- An ultrasound-promoted green approach for the N-formylation of amines under solvent- and catalyst-free conditions at room temperature
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A new environmentally benign, convenient, and facile methodology for the N-formylation of amines is reported using ultrasound irradiation under solvent- and catalyst-free conditions at room temperature. Compared with conventional methods, the main advantages of the present procedure are milder, cleaner and greener conditions, shorter reaction time, higher purity and yields, simpler work-up, and lower generation of waste or pollutions.
- Habibi, Davood,Nasrollahzadeh, Mahmoud
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p. 1008 - 1016
(2013/11/06)
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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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- Green synthesis of formamides using the Natrolite zeolite as a natural, efficient and recyclable catalyst
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Chemoselective N-formylation of different amines was carried out with formic acid in the presence of the Natrolite zeolite as an efficient, stable and natural heterogeneous catalyst to give the corresponding formamides at room temperature under solvent-free conditions. This method has the advantages of high yields, mild conditions, simple methodology, easy work up and short reaction times. The catalyst was characterized by different techniques such as powder XRD, XRF, TGA-DTA, SEM and FT-IR spectroscopy. The Natrolite zeolite was recovered and reused several times without the significant loss of its catalytic performance.
- Habibi, Davood,Nasrollahzadeh, Mahmoud,Sahebekhtiari, Hesam
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p. 148 - 155
(2013/08/23)
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