- Kinetics and Mechanism of Amitraz Hydrolysis
-
As a precursor to the development of effective vat management and waste disposal strategies, the kinetics and basic mechanisms of amitraz, N′-(2,4-dimethylphenyl)-N-[[(2,4-dimethylphenyl)imino]- methyl]-N-methylmethanimidamide, hydrolysis were examined as was the effect of cosolvents and metal ions. Amitraz was readily hydrolyzed at low pH values, forming acid-stable 2,4-dimethylphenylformamide, which can be further hydrolyzed to 2,4-dimethylaniline. The hydrolysis of 2,4- dimethylphenylformamide was faster under basic conditions. Thus, the addition of lime, a management technique used to stabilize the amitraz, will enhance the hydrolysis of its degradation products to aniline.
- Pierpoint, Anthony C.,Hapeman, Cathleen J.,Torrents, Alba
-
-
Read Online
- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
-
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
-
p. 5627 - 5639
(2021/11/11)
-
- HCl-mediated transamidation of unactivated formamides using aromatic amines in aqueous media
-
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
-
p. 3729 - 3739
(2021/10/14)
-
- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
-
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)
-
- Direct: N -formylation of nitroarenes with CO2
-
Herein we describe a straightforward N-formylation of nitroarenes with CO2 to access N-aryl formamides exclusively in the presence of iron and hydrosilane as additives. This protocol showcases a good tolerance of a wide range of nitroarenes and nitroheteroarenes.
- Shen, Ni,Zhai, Shi-Jing,Cheung, Chi Wai,Ma, Jun-An
-
supporting information
p. 9620 - 9623
(2020/09/03)
-
- Mild Access to N-Formylation of Primary Amines using Ethers as C1 Synthons under Metal-Free Conditions
-
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
-
supporting information
p. 3960 - 3968
(2018/09/10)
-
- Copper-(II) Catalyzed N-Formylation and N-Acylation of Aromatic, Aliphatic, and Heterocyclic Amines and a Preventive Study in the C-N Cross Coupling of Amines with Aryl Halides
-
A Cu-(II) catalyzed N-formylation and N-acylation of amines with moderate to excellent yields, using N, N-dimethyl formamide (DMF) and N, N-dimethyl acetamide (DMA) as a formyl and acylating sources in the presence of 1,2,4-triazole is reported. This novel, highly efficient and simple protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines. In addition, the conditions to prevent N-formylation and N-acylation impurities in the C?N cross coupling of amines and aryl halides are described typically when DMF and DMA are used as solvents, with various catalysts, ligands, and bases.
- Sonawane, Rahul B.,Rasal, Nishant K.,Bhange, Dattatraya S.,Jagtap, Sangeeta V.
-
p. 3907 - 3913
(2018/09/12)
-
- Nickel-(II)-Catalyzed N-Formylation and N-Acylation of Amines
-
A highly efficient protocol of Ni(II) metal complex, [Ni(quin)2], catalyzing N-formylation and N-acylation of amines with moderate to excellent yields, using N,N-dimethylformamide and N,N-dimethylacetamide in the presence of imidazole, is described here. The protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines.
- Sonawane, Rahul B.,Rasal, Nishant K.,Jagtap, Sangeeta V.
-
supporting information
p. 2078 - 2081
(2017/04/28)
-
- NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 as a new and reusable heterogeneous hybrid catalyst for efficient solvent-free formylation of amines
-
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
-
p. 1767 - 1772
(2017/07/27)
-
- Co3O4 nanoparticles prepared by oxidative precipitation method: an efficient and reusable heterogeneous catalyst for N-formylation of amines
-
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
-
p. 413 - 422
(2017/01/14)
-
- Regiochemistry of nucleophilic substitution of pentachloropyridine with N and O bidentate nucleophiles
-
Site reactivity of some enol-imines derived from N-aryl formamides with pentachloropyridine under basic conditions in dry CH3CN was investigated. The aromatic nucleophilic substitution of pentachloropyridine with enol-imines occurs at the 4-position of pyridine ring by both oxygen and nitrogen site of enol-imines. Nucleophilic attack by the oxygen of enol-imine gave corresponding oximino compounds as a mixture of E- and Z-isomers. In contrast, nucleophilic attack by the nitrogen of enol-imine gave the unexpected N,N-di-substituted aryl compounds. The structures of all the compounds were confirmed by IR, 1H NMR, 13C NMR and 19F NMR spectroscopy as well as elemental analysis and X-ray crystallography.
- Poorfreidoni, Alireza,Ranjbar-Karimi, Reza,Kia, Reza
-
p. 4398 - 4406
(2015/06/16)
-
- Palladium-catalyzed C(sp2)-H arylation using formamide as a transformable directing group
-
A new process for the ortho arylation of formanilides through palladium-catalyzed C-H activation is described. Formamide is reported as a transformable directing group in the transition-metal-catalyzed C-H functionalization reaction. The resulting biarylformanilide products can be readily transformed to the corresponding biarylisocyanides or N-heterocycles.
- Wan, Congqing,Zhao, Jiaji,Xu, Mingfang,Huang, Jinbo
-
p. 4751 - 4756
(2014/06/09)
-
- Synthesis and characterization of copper nanoparticles supported on reduced graphene oxide as a highly active and recyclable catalyst for the synthesis of formamides and primary amines
-
We report here the synthesis of reduced graphene oxide supported copper nanoparticles (rGO/Cu NPs) from copper (II) sulfate pentahydrate and graphite precursors using a simple protocol. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) and energy dispersive X-ray spectroscopy (EDS). The rGO/Cu NPs is proved to be a useful heterogeneous catalyst in Cu-catalyzed formamidation and amination of arylboronic acids. The catalyst can be recovered by simple filtration from the reaction mixture and reused several times without significant loss of catalytic activity.
- Fakhri, Parisa,Jaleh, Babak,Nasrollahzadeh, Mahmoud
-
-
- Synthesis, characterization, antibacterial and catalytic activity of a nanopolymer supported copper(ii) complex as a highly active and recyclable catalyst for the formamidation of arylboronic acids under aerobic conditions
-
This paper reports on the synthesis and use of a nanopolymer supported copper(ii) complex, as a separable catalyst for the formamidation of arylboronic acids under aerobic conditions. The catalyst was characterized using powder XRD, SEM, EDS, TGA-DTG and FT-IR spectroscopy. This method has the advantages of high yields, elimination of homogeneous catalysts, simple methodology and easy work up. Catalytic efficiency remains unaltered even after several repeated cycles. The synthesized catalyst is found to be more highly toxic towards Gram-positive bacteria than Gram-negative bacteria. This journal is the Partner Organisations 2014.
- Nasrollahzadeh, Mahmoud,Zahraei, Ali,Ehsani, Ali,Khalaj, Mehdi
-
p. 20351 - 20357
(2014/06/09)
-
- α-Keto Phenylamides as P1′-Extended Proteasome Inhibitors
-
The major challenge for proteasome inhibitor design lies in achieving high selectivity for, and activity against, the target, which requires specific interactions with the active site. Novel ligands aim to overcome off-target-related side effects such as peripheral neuropathy, which is frequently observed in cancer patients treated with the FDA-approved proteasome inhibitors bortezomib (1) or carfilzomib (2). A systematic comparison of electrophilic headgroups recently identified the class of α-keto amides as promising for next generation drug development. On the basis of crystallographic knowledge, we were able to develop a structure-activity relationship (SAR)-based approach for rational ligand design using an electronic parameter (Hammett's σ) and in silico molecular modeling. This resulted in the tripeptidic α-keto phenylamide BSc4999 [(S)-3-(benzyloxycarbonyl-(S)-leucyl-(S)-leucylamino)-5-methyl-2-oxo-N-(2,4-dimethylphenyl)hexanamide, 6a], a highly potent (IC50=38 nM), cell-permeable, and slowly reversible covalent inhibitor which targets both the primed and non-primed sites of the proteasome's substrate binding channel as a special criterion for selectivity. The improved inhibition potency and selectivity of this new α-keto phenylamide makes it a promising candidate for targeting a wider range of tumor subtypes than commercially available proteasome inhibitors and presents a new candidate for future studies.
- Voss, Constantin,Scholz, Christoph,Knorr, Sabine,Beck, Philipp,Stein, Martin L.,Zall, Andrea,Kuckelkorn, Ulrike,Kloetzel, Peter-Michael,Groll, Michael,Hamacher, Kay,Schmidt, Boris
-
supporting information
p. 2557 - 2564
(2015/08/24)
-
- A very simple, highly efficient and catalyst-free procedure for the N-formylation of amines using triethyl orthoformate in water under ultrasound-irradiation
-
N-Formylation of amines has efficiently been carried out in excellent yields by treatment of amines with triethyl orthoformate in water under ultrasound irradiation. The process is remarkably simple and environmentally benign.
- Habibi, Davood,Sahebekhtiari, Hesam,Nasrollahzadeh, Mahmoud,Taghipour, Ahmad
-
p. 209 - 212
(2013/07/26)
-
- An ultrasound-promoted green approach for the N-formylation of amines under solvent- and catalyst-free conditions at room temperature
-
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
-
p. 1008 - 1016
(2013/11/06)
-
- Green synthesis of formamides using the Natrolite zeolite as a natural, efficient and recyclable catalyst
-
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
-
p. 148 - 155
(2013/08/23)
-
- Palladium-catalyzed cascade process consisting of isocyanide insertion and benzylic C(sp3)-H activation: Concise synthesis of indole derivatives
-
Synthesis of the indole skeleton was achieved using a Pd-catalyzed cascade process consisting of isocyanide insertion and benzylic C(sp3)-H activation. It was found that slow addition of isocyanide is effective for reducing the amount of catalyst needed and Ad2PnBu is a good ligand for C(sp3)-H activation. The construction of the tetracyclic carbazole skeleton was also achieved by a Pd-catalyzed domino reaction incorporating alkyne insertion.
- Nanjo, Takeshi,Tsukano, Chihiro,Takemoto, Yoshiji
-
supporting information; experimental part
p. 4270 - 4273
(2012/10/08)
-
- Palladium-catalyzed intramolecular C(sp2)-H amidination by isonitrile insertion provides direct access to 4-aminoquinazolines from N-arylamidines
-
An efficient method for the synthesis of 4-amino-2-aryl(alkyl)quinazolines from readily available N-arylamidines and isonitriles via palladium-catalyzed intramolecular aryl C-H amidination by isonitrile insertion has been developed.
- Wang, Yong,Wang, Honggen,Peng, Jiangling,Zhu, Qiang
-
supporting information; experimental part
p. 4604 - 4607
(2011/10/12)
-
- Synthesis and antiproliferative activity of pyridinylcarbonylpyrimidines against melanoma cell line
-
The synthesis of the series of pyrimidinylamines 1a-d and pyrimidinylureas 1e-u bearing a novel pyridinylcarbonylpyrimidine scaffold and their antiproliferative activities against A375 human melanoma cell line were described. Among them, three compounds 1
- Ahn, Hyemi,Lee, Jun A.,Kim, Hwan,Oh, Chang-Hyun,Lee, So Ha,Sim, Taebo,Hah, Jung-Mi,Kim, Dong Jin,Yoo, Kyung Ho
-
experimental part
p. 1209 - 1214
(2011/11/06)
-
- REACTIONS OF α-CHLORO- AND α,α-DICHLORO-β-CARBONYL-SUBSTITUTED ALDEHYDES WITH AMINES
-
Depending on the nature of the substrate (the chlorodicarbonyl compound) and the nature of the nucleophilic reagent (the amine), the reaction of α-chloro- and α,α-dichloro-β-carbonyl-substituted aldehydes with amines takes place mainly in three directions i.e., with the formation of enamines or imines or with cleavage of the C-CHO bond of the aldehydes.
- Guseinov, F. I.,Klimentova, G. Yu.,Moskva, V. V.
-
p. 530 - 533
(2007/10/02)
-