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Cas Database

100-01-6

100-01-6

Identification

  • Product Name:4-Nitroaniline

  • CAS Number: 100-01-6

  • EINECS:202-810-1

  • Molecular Weight:138.126

  • Molecular Formula: C6H6N2O2

  • HS Code:2921.42 Oral rat LD50: 750 mg/kg

  • Mol File:100-01-6.mol

Synonyms:Aniline,p-nitro- (8CI);1-Amino-4-nitrobenzene;4-Amino-1-nitrobenzene;4-Aminonitrobenzene;4-Nitro-1-aminobenzene;

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Safety information and MSDS view more

  • Pictogram(s):ToxicT,FlammableF

  • Hazard Codes: T:Toxic;

  • Signal Word:Danger

  • Hazard Statement:H301 Toxic if swallowedH311 Toxic in contact with skin H331 Toxic if inhaled H412 Harmful to aquatic life with long lasting effects

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Artificial respiration may be needed. Refer for medical attention. In case of skin contact Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer for medical attention . In case of eye contact First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention. If swallowed Induce vomiting (ONLY IN CONSCIOUS PERSONS!). Refer for medical attention . Inhalation or ingestion causes headache, drowsiness, shortness of breath, nausea, methemoglobinemia, and unconsciousness; fingernails, lips, and ears become bluish; prolonged and excessive exposures may also cause liver damage. Contact with eyes causes irritation and possible corneal damage. Contact with skin causes irritation; continued exposure may cause same symptoms as inhalation or ingestion. (USCG, 1999) INHALATION: Fresh air, rest. Artificial respiration if indicated. Refer for medical attention. SKIN: Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer for medical attention. EYES: First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then take to a doctor.

  • Fire-fighting measures: Suitable extinguishing media This chemical is a combustible solid. Use dry chemical, carbon dioxide, water spray, or alcohol foam extinguishers. Poisonous gases including sulfur dioxide and nitrogen oxides are produced in fire. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. If employees are expected to fight fires, they must be trained and equipped in OSHA 1910.156. Special Hazards of Combustion Products: Toxic oxides of nitrogen may form in fire. Behavior in Fire: Melts and burns (USCG, 1999) Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Personal protection: particulate filter respirator adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment. Sweep spilled substance into covered containers. If appropriate, moisten first to prevent dusting. Wash away remainder with plenty of water. 1. Ventilate area of spill. 2. For small quantities, sweep onto paper or other suitable material, place in an appropriate container & burn in a safe place (such as a fume hood). Large quantities may be reclaimed; however, if this is not practical, dissolve in a flammable solvent (such as alcohol) & atomize in a suitable combustion chamber equipped with an appropriate effluent gas cleaning device.

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Separated from strong acids, strong oxidants, combustible substances, reducing agents and food and feedstuffs. Dry.Store in a cool, dry, well-ventilated location. Separate from acids, oxidizing materials, & reducing agents.

  • Exposure controls/personal protection:Occupational Exposure limit valuesRecommended Exposure Limit: 10 Hr Time-Weighted Avg: 3 mg/cu m (skin).Biological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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  • Manufacture/Brand:TRC
  • Product Description:4-Nitroaniline
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  • Product Description:4-Nitroaniline >98.0%(GC)
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  • Product Description:4-Nitroaniline ≥99%
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  • Product Description:4-Nitroaniline ≥99%
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  • Product Description:4-Nitroaniline ≥99%
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  • Product Description:4-Nitroaniline analytical standard
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:4-Nitroaniline for synthesis. CAS 100-01-6, chemical formula H NC H NO ., for synthesis
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:4-Nitroaniline for synthesis
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  • Manufacture/Brand:Sigma-Aldrich
  • Product Description:4-Nitroaniline for synthesis. CAS 100-01-6, chemical formula H NC H NO ., for synthesis
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Relevant articles and documentsAll total 673 Articles be found

Development of chemoselective photoreduction of nitro compounds under solar light and blue LED irradiation

Zand, Zahra,Kazemi, Foad,Hosseini, Saber

, p. 338 - 341 (2014)

Solar light and blue light irradiation of the commercially available heterogeneous nano photocatalyst TiO2-P25 leads to reduction of nitro compounds to give the corresponding amines. The methodology provides a green and mild approach to this useful class of organic compounds. Aromatic nitro compounds containing a wide range of functional groups tolerated the conditions to give, chemoselectively the corresponding amines in excellent yields.

Gold catalysts supported on TiO2-nanotubes for the selective hydrogenation of p-substituted nitrobenzenes

Torres, Cecilia C.,Jiménez, Verónica A.,Campos, Cristian H.,Alderete, Joel B.,Dinamarca, Robinson,Bustamente, Tatiana M.,Pawelec, Barbara

, p. 21 - 27 (2018)

Gold nanoparticles supported on titania nanotubes (TiO2NT) were synthesized and employed as an efficient catalysts for the selective hydrogenation of nitrobenzenes. Materials characterization by N2 adsorption-desorption isotherms, XR

A new palladium complex supported on magnetic nanoparticles and applied as an catalyst in amination of aryl halides, Heck and Suzuki reactions

Ghorbani-Choghamarani, Arash,Tahmasbi, Bahman,Noori, Nourolah,Ghafouri-nejad, Raziyeh

, p. 681 - 693 (2017)

A simple, efficient and less expensive protocol for the phosphine-free C–C coupling reactions and synthesis of anilines in the presence of 2-aminobenzamide complex of palladium supported on Fe3O4 magnetic nanoparticles (Pd(0)-ABA-Fe3O4) has been reported. The Suzuki reaction was carried out in water or PEG using phenylboronic acid (PhB(OH)2) or sodium tetraphenyl borate (NaBPh4). Pd(0)-ABA-Fe3O4 has been found promising for Heck reaction of butyl acrylate, styrene or acrylonitrile with aryl halides (including Cl, Br and I). Also, Pd(0)-ABA-Fe3O4 has been found as efficient catalyst for the amination of aryl halides using aqueous ammonia. The products have been obtained in short reaction times and high yields. The catalyst was easily separated using an external magnet from the reaction mixture and reused for several runs without significant loss of its catalytic efficiency or palladium leaching. The leaching of catalyst has been examined by hot filtration and ICP-OES technique. The nanomagnetical catalyst was characterized by FTIR, TGA, XRD, VSM, TEM, SEM, EDS, DLS and ICP-OES techniques.

Purification of an aminopeptidase preferentially releasing N-terminal alanine from cucumber leaves and its identification as a plant aminopeptidase N

Yamauchi, Yasuo,Ejiri, Yukinori,Tanaka, Kiyoshi

, p. 2802 - 2805 (2001)

In this study, a highly active foliar aminopeptidase preferentially releasing N-terminal alanine from artificial substrates was purified and characterized from cucumber (Cucumis sativus L. suyo). The enzyme had a molecular mass of 200 kDa consisting of two subunits of 95 kDa. It was a metalloprotease the pH optimum of which was 8 to 9. It cleaved Ala-, Gly-, Met-, Ser-, Leu-, Lys-, and Arg artificial substrates. An internal amino acid sequence was similar to those of aminopeptidase N (clan MA, family M1) of microorganisms, and was very similar to that of a putative aminopeptidase N of Arabidopsis thaliana. From these results, the highly active aminopeptidase in cucumber leaves was identified to be a plant aminopepitdase N.

1,1,1-trimethylhydrazinium iodide: A novel, highly reactive reagent for aromatic amination via vicarious nucleophilic substitution of hydrogen

Pagoria, Philip F.,Mitchell, Alexander R.,Schmidt, Robert D.

, p. 2934 - 2935 (1996)

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Self-protonation upon the electroreduction of 2- and 4-nitrophenylhydroxylamines in aprotic media

Syroeshkin, Mikhail A.,Mendkovich, Andrei S.,Mikhalchenko, Ludmila V.,Rusakov, Alexander I.,Gul'tyai, Vadim P.

, p. 258 - 259 (2009)

Cyclic voltammetry and controlled potential electrolysis were used to show that radical anions of 2- and 4-nitrophenylhydroxylamines electrochemically generated in a 0.1 M Bu4NClO4 solution in DMF undergo protonation with the startin

Structural characterization and function determination of a nonspecific carboxylate esterase from the amidohydrolase superfamily with a promiscuous ability to hydrolyze methylphosphonate esters

Xiang, Dao Feng,Kumaran, Desigan,Swaminathan, Subramanyam,Raushel, Frank M.

, p. 3476 - 3485 (2014)

The uncharacterized protein Rsp3690 from Rhodobacter sphaeroides is a member of the amidohydrolase superfamily of enzymes. In this investigation the gene for Rsp3690 was expressed in Escherichia coli and purified to homogeneity, and the three-dimensional structure was determined to a resolution of 1.8 ? The protein folds as a distorted (β/α)8-barrel, and the subunits associate as a homotetramer. The active site is localized to the C-terminal end of the β-barrel and is highlighted by the formation of a binuclear metal center with two manganese ions that are bridged by Glu-175 and hydroxide. The remaining ligands to the metal center include His-32, His-34, His-207, His-236, and Asp-302. Rsp3690 was shown to catalyze the hydrolysis of a wide variety of carboxylate esters, in addition to organophosphate and organophosphonate esters. The best carboxylate ester substrates identified for Rsp3690 included 2-naphthyl acetate (kcat/Km = 1.0 × 105 M-1 s-1), 2-naphthyl propionate (k cat/Km = 1.5 × 105 M-1 s -1), 1-naphthyl acetate (kcat/Km = 7.5 × 103 M-1 s-1), 4-methylumbelliferyl acetate (kcat/Km = 2.7 × 103 M-1 s-1), 4-nitrophenyl acetate (kcat/Km = 2.3 × 105 M-1 s-1), and 4-nitrophenyl butyrate (kcat/Km = 8.8 × 105 M -1 s-1). The best organophosphonate ester substrates included ethyl 4-nitrophenyl methylphosphonate (kcat/Km = 3.8 × 105 M-1 s-1) and isobutyl 4-nitrophenyl methylphosphonate (kcat/Km = 1.1 × 104 M-1 s-1). The (SP)-enantiomer of isobutyl 4-nitrophenyl methylphosphonate was hydrolyzed 10 times faster than the less toxic (RP)-enantiomer. The high inherent catalytic activity of Rsp3690 for the hydrolysis of the toxic enantiomer of methylphosphonate esters make this enzyme an attractive target for directed evolution investigations.

Selective reduction of aromatic azides in solution/solid-phase and resin cleavage by employing BF3·OEt2/EtSH. Preparation of DC-81

Kamal, Ahmed,Shankaraiah,Reddy, K. Laxma,Devaiah

, p. 4253 - 4257 (2006)

An efficient method for the reduction of aromatic azides in both solution and solid-phase has been developed by employing BF3·OEt2/EtSH. This report also describes resin cleavage employing this reagent system. Further, this protocol has been utilized for the solution as well as the solid-phase synthesis of pyrrolo[2,1-c][1,4]benzodiazepines, including the naturally occurring antibiotic DC-81 and fused [2,1-b]quinazolinones.

Nickel catalysis for hydrogenation of p-dinitrobenzene to p-phenylenediamine

Shuvalova,Kirichenko,Kustov

, p. 34 - 38 (2017)

The activity of supported nickel catalysts (5–20% Ni) in the hydrogenation of p-dinitrobenzene to p-phenylenediamine was investigated. The catalysts were obtained by ureainduced precipitation. Activated carbon, alumina, titania, and silica gel were evaluated as supports. The most active catalysts, 5%Ni/TiO2 and 20%Ni/SiO2, provided 50–54% yields of p-phenylenediamine at complete dinitrobenzene conversion.

β-Sultams - A novel class of serine protease inhibitors

Beardsell,Hinchliffe,Wood,Wilmouth,Schofield,Page

, p. 497 - 498 (2001)

N-Benzoyl β-sultam is an irreversible inactivator of elastase by sulfonation of the active site serine.

Photochemistry of p-Nitrophenyl Azide: Single-Electron-Transfer Reaction of the Triplet Nitrene

Liang, Tsuei-Yun,Schuster, Gary B.

, p. 546 - 548 (1986)

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Purification and characterization of an N-terminal acidic amino acid-specific aminopeptidase from soybean cotyledons (glycine max)

Asano, Minao,Nakamura, Nami,Kawai, Misako,Miwa, Tetsuya,Nio, Noriki

, p. 113 - 118 (2010)

A novel enzyme that catalyzes the efficient hydrolysis of Glu-Glu was isolated from soybean cotyledons by ammonium sulfate fractionation and successive column chromatographies of Q-sepharose, Phenyl sepharose, and Superdex 200. The apparent molecular mass of this enzyme was found to be 56kDa and 510 kDa by SDS-polyacrylamide gel electrophoresis and Superdex 200 HR 10/30 column chromatography respectively. The enzyme had high activity against Glu-/7-nitroanilide (/NA) and Asp-pNA, whereas Leu-pNA, Phe-pNA, Ala-/;NA, and Pro-pNA were not hydrolyzed. The synthetic dipeptides Glu-Xxx and Asp-Xxx were hydrolyzed, but Xxx-Glu was not. The digestion of a Glu-rich oligopep-tide, chromogranin A (Glu-Glu-Glu-Glu-Glu-Met-Ala-Val-Val-Pro-Gln-Gly- Leu-Phe-Arg-Gly-NH2) using this purified enzyme was also investigated. Glutamic acid residues were cleaved one by one from the N-terminus. These observations indicate that the enzyme removes glutamyl or aspartyl residues from N-terminal acidic amino acid-containing peptides. It is thought that it was an N-terminal acidic amino acid-specific aminopeptidase from a plant.

One-pot aromatic amination based on carbon-nitrogen coupling reaction between aryl halides and azido compounds

Maejima, Toshihide,Shimoda, Yutaka,Nozaki, Kei,Mori, Shigeki,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao

, p. 1712 - 1722 (2012)

An efficient copper-mediated C-N coupling reaction between various aryl halides and azido compounds to produce the corresponding aromatic primary amines was established. The present amination is apparently involved in both the reduction of an azido functionality to the corresponding primary amino group and its cross-coupling reaction with aryl halides in a one-pot manner. The present amination could be applied to the synthesis of procaine, a local anesthetic drug. A mechanistic study indicated that 2-aminoethanol could work as a major hydrogen donor and the reaction would proceed without the formation of the intermediary aryl azide.

Reduction of organic azides to amines using reusable Fe3O 4 nanoparticles in aqueous medium

Pagoti, Sreenivasarao,Surana, Subham,Chauhan, Ajay,Parasar, Bibudha,Dash, Jyotirmayee

, p. 584 - 588 (2013)

Aromatic, heteroaromatic and sulfonyl azides were conveniently reduced to the corresponding amines in excellent yields using hydrazine hydrate in the presence of iron oxide nanoparticles. The Fe3O4-MNPs could be easily separated by an external magnet, and recycled ten times without significant loss of the catalytic efficiency. The Royal Society of Chemistry 2013.

Selective nitrolytic deprotection of N-BOC-amines and N-BOC-amino acids derivatives

Strazzolini, Paolo,Melloni, Tiziana,Giumanini, Angelo G

, p. 9033 - 9043 (2001)

The extension of the deprotection procedure using HNO3 in CH2Cl2 to a number of appropriately selected N-BOC-masked amines and derivatives of natural amino acids was investigated. The method was found to work effectively with almost all tested substrates, with the exception of activated aromatic amines and heterocycles which underwent unavoidable faster oxidation. Alanine, phenylalanine, serine and lysine derivatives were efficiently deprotected, as well as dipeptide Ala-Phe, preserving the configuration of the substrates and without affecting copresent Z and ester functions, with a remarkable selectivity towards acid sensitive t-butyl esters. The obtained amino acids esters, isolated and characterized in the form of nitrates salts, proved to be suitable intermediates to be used in peptide synthesis.

Mo(CO)6 Mediated Selective Reduction of Azides and Nitro Compounds to Amines under Neutral Conditions

Iyer, Suresh,Kulkarni, Girish M.

, p. 721 - 725 (2004)

Mo(CO)6 selectively reduces various azides and nitro compounds to the corresponding amines in refluxing ethanol.

Selective Reduction of Nitroarenes to Arylamines by the Cooperative Action of Methylhydrazine and a Tris(N-heterocyclic thioamidate) Cobalt(III) Complex

Ioannou, Dimitris I.,Gioftsidou, Dimitra K.,Tsina, Vasiliki E.,Kallitsakis, Michael G.,Hatzidimitriou, Antonios G.,Terzidis, Michael A.,Angaridis, Panagiotis A.,Lykakis, Ioannis N.

, p. 2895 - 2906 (2021)

We report an efficient catalytic protocol that chemoselectively reduces nitroarenes to arylamines, by using methylhydrazine as a reducing agent in combination with the easily synthesized and robust catalyst tris(N-heterocyclic thioamidate) Co(III) complex [Co(κS,N-tfmp2S)3], tfmp2S = 4-(trifluoromethyl)-pyrimidine-2-thiolate. A series of arylamines and heterocyclic amines were formed in excellent yields and chemoselectivity. High conversion yields of nitroarenes into the corresponding amines were observed by using polar protic solvents, such as MeOH and iPrOH. Among several hydrogen donors that were examined, methylhydrazine demonstrated the best performance. Preliminary mechanistic investigations, supported by UV-vis and NMR spectroscopy, cyclic voltammetry, and high-resolution mass spectrometry, suggest a cooperative action of methylhydrazine and [Co(κS,N-tfmp2S)3] via a coordination activation pathway that leads to the formation of a reduced cobalt species, responsible for the catalytic transformation. In general, the corresponding N-arylhydroxylamines were identified as the sole intermediates. Nevertheless, the corresponding nitrosoarenes can also be formed as intermediates, which, however, are rapidly transformed into the desired arylamines in the presence of methylhydrazine through a noncatalytic path. On the basis of the observed high chemoselectivity and yields, and the fast and clean reaction processes, the present catalytic system [Co(κS,N-tfmp2S)3]/MeNHNH2 shows promise for the efficient synthesis of aromatic amines that could find various industrial applications.

Chemoselective N-deacetylation under mild conditions

Sultane, Prakash R.,Mete, Trimbak B.,Bhat, Ramakrishna G.

, p. 261 - 264 (2014)

A mild and efficient chemoselective N-deacetylation using the Schwartz reagent at room temperature in rapid time is described. The mild and neutral conditions enable orthogonal N-deacetylation in the presence of some of the common protecting groups (viz. Boc, Fmoc, Cbz, Ts). The deprotection conditions did not induce any epimerization at the chiral amino centre.

Electrochemical control of the catalytic activity of immobilized enzymes

Kadambar, Vasantha Krishna,Bellare, Madhura,Bollella, Paolo,Katz, Evgeny,Melman, Artem

, p. 13800 - 13803 (2020)

Regulation of the catalytic activity of enzymes immobilized on carbon nanotube electrodes was achieved by changing their local pH environment using electrochemical reactions. Reduction of oxygen increased the interfacial pH while oxidation of ascorbate decreased it, thus allowing changing rates of enzymatic reactions of electrode-immobilized amyloglucosidase and trypsin enzymes over a wide activity range.

Copper-catalyzed coupling of aryl halides and nitrite salts: A mild Ullmann-type synthesis of aromatic nitro compounds

Saito, Shinichi,Koizumi, Yuichiro

, p. 4715 - 4717 (2005)

Nitration of aromatic halides proceeded smoothly in the presence of catalytic amounts of Cu bronze and N,N′-dimethylethylenediamine. Sodium nitrite-18-crown-6, or tetra-n-butylammonium nitrite (n-Bu4NNO 2) turned out to be efficient nitrating agents. The aromatic nitro compounds were synthesized under essentially neutral conditions.

Hydrogen-bond-regulated distinct functional-group display at the inner and outer wall of vesicles

Sikder, Amrita,Das, Anindita,Ghosh, Suhrit

, p. 6755 - 6760 (2015)

A unique supramolecular strategy enables the unidirectional assembly of two bola-shaped unsymmetric π-amphiphiles, NDI-1 and NDI-2, which feature a naphthalene-diimide chromophore connected to nonionic and anionic head groups on opposite arms. The amphiphiles differ only in the location of a hydrazide group, which is placed either on the nonionic or on the anionic arm of NDI-1 and NDI-2, respectively. The formation of hydrogen bonds between the hydrazides, which compensates for electrostatic and steric factors, promotes unidirectional alignment and the formation of monolayer vesicles. The zeta potentials and cation-assisted quantitative precipitation reveal negatively charged and nonionic outer surfaces for NDI-1 and NDI-2, respectively, indicating that hydrogen bonding also dictates the directionality of the monolayer curvature, ensuring that in both cases, the hydrazides remain at the inner wall to benefit from stronger hydrogen bonding where they are in closer proximity. This is reflected in their different abilities to inhibit α-chymotrypsin, which possesses a positively charged surface: NDI-1 induced an inhibition of 80% whereas hardly any inhibition was observed with NDI-2.

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

Dang-Bao, Trung,Pradel, Christian,Favier, Isabelle,Gómez, Montserrat

, p. 2832 - 2846 (2017)

Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly prepared from Cu(I) and Cu(II) precursors in glycerol and in the presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vapor pressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solid state, exhibiting relevantly homogeneous colloidal dispersions, also even after catalysis. CuNPs coming from the well-defined coordination complex di-μ-hydroxobis[(N,N,N′,N′-tetramethylethylenediamine)copper(II)] chloride {[Cu(κ2-N,N-TMEDA)(μ-OH)]2Cl2} have been highly efficient in C–C and C–heteroatom bond formation processes. This new catalytic system has proved its performance in C–N couplings and in the synthesis of differently substituted propargylic amines through cross-dehydrogenative couplings, multi-component reactions such as A3 (aldehyde-alkyne-amine) and KA2 (ketone-alkyne-amine) couplings, as well as in the formation of heterocycles such as benzofurans, indolizines, and quinolines under smooth conditions. No significant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES) analyses, proving a highly efficient immobilization of copper nanoparticles in glycerol. From a mechanistic point of view, spectroscopic data (infrared and ultraviolet-visible spectra) agree with a surface-like catalytic reactivity. (Figure presented.).

Development and Application of Efficient Ag-based Hydrogenation Catalysts Prepared from Rice Husk Waste

Unglaube, Felix,Kreyenschulte, Carsten Robert,Mejía, Esteban

, p. 2583 - 2591 (2021)

The development of strategies for the sustainable management and valorization of agricultural waste is of outmost importance. With this in mind, we report the use of rice husk (RH) as feedstock for the preparation of heterogeneous catalysts for hydrogenation reactions. The catalysts were prepared by impregnating the milled RH with a silver nitrate solution followed by carbothermal reduction. The composition and morphology of the prepared catalysts were fully assessed by IR, AAS, ICP-MS, XPS, XRD and STEM techniques. This novel bio-genic silver-based catalysts showed excellent activity and remarkable selectivity in the hydrogenation of nitro groups in both aromatic and aliphatic substrates, even in the presence of reactive functionalities like halogens, carbonyls, borate esters or nitriles. Recycling experiments showed that the catalysts can be easily recovered and reused multiple times without significant drop in performance and without requiring re-activation.

Chemoselective reduction of azides with sodium sulfide hydrate under solvent free conditions

Kazemi, Foad,Kiasat, Ali Reza,Sayyahi, Sohyl

, p. 1813 - 1817 (2004)

Sodium sulfide hydrate has been employed for an efficient reduction of a variety of azides to the primary amines in good-to-excellent yields under solvent-free system and without perturbing many active functionalities such as ether, carbonyl, sulfonyl, and nitro.

Highly efficient nitrobenzene and alkyl/aryl azide reduction in stainless steel jars without catalyst addition

Martina, Katia,Baricco, Francesca,Tagliapietra, Silvia,Moran, Maria Jesus,Cravotto, Giancarlo,Cintas, Pedro

, p. 18881 - 18888 (2018)

The mechanochemical and selective reduction of aryl nitro and aryl/alkyl azide derivatives, with either formate salts or hydrazine, to the corresponding, synthetically useful amines occurs in excellent yields in a planetary ball mill without the addition of a catalyst. This newly developed and solvent-free protocol is efficient, fast and does not require the addition of a metal hydrogenation catalyst as the stainless steel jar itself fulfils that role. The method has been applied to a broad range of compounds and excellent yields have been obtained. The formylation of alkyl amines has been successfully performed, by means of mechanochemical activation, in the presence of ammonium formate alone.

A mild procedure for the clay catalyzed selective removal of the tert- butoxycarbonyl protecting group from aromatic amines

Shaikh, Nadim S.,Gajare, Anil S.,Deshpande, Vishnu H.,Bedekar, Ashutosh V.

, p. 385 - 387 (2000)

The application of solid acidic catalysts for the selective removal of N-Boc protection is presented in this report. Montmorillonite K10 was found to be an effective catalyst in removing aromatic N-Boc groups while leaving aliphatic N-Boc amines untouched.

100% selective yield of m-nitroaniline by rutile TiO2 and m-phenylenediamine by P25-TiO2 during m-dinitrobenzene photoreduction

Kaur, Jaspreet,Pal, Bonamali

, p. 25 - 28 (2014)

Photoreduction of m-dinitrobenzene (25 μmol) in the deaerated aqueous iso-propanol exhibits 100% selective yield of m-nitroaniline (25 μmol) by rutile TiO2 (50 mg) or m-phenylenediamine (25 μmol) by P25-TiO2 separately under 8 and 4 h of UV light irradiation (125 W Hg arc, 10.4 mW/cm2), respectively. It revealed that insertion of a second -NO2 in nitrobenzene ring has an important role in expediting -NO2 reduction to -NH2 as compared to a negligible reduction of nitrobenzene under similar conditions, indicating that electron withdrawing groups lower the electron density on -NO2 present on meta position and favor quick reduction of the -NO2 group.

Palladium-catalyzed cleavage of O/N-propargyl protecting groups in aqueous media under a copper-free condition

Pal, Manojit,Parasuraman, Karuppasamy,Yeleswarapu, Koteswar Rao

, p. 349 - 352 (2003)

(Figure presented) A copper-free palladium-mediated cleavage of O/N-propargyl bonds in aqueous media has been investigated, affording a mild and convenient method for the deprotection of phenols and anilines. The methodology could be utilized for the selective removal of propargyl groups from aryl ethers and amines without affecting a variety of unprotected functional groups present in the substrates. The mechanism and scope of the reaction is discussed.

A Highly Water-Dispersible/Magnetically Separable Palladium Catalyst: Selective Transfer Hydrogenation or Direct Reductive N-Formylation of Nitroarenes in Water

Karimi, Babak,Mansouri, Fariborz,Vali, Hojatollah

, p. 1750 - 1759 (2015)

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.

Cobalt Entrapped in N,S-Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid

Guo, Haotian,Gao, Ruixiao,Sun, Mingming,Guo, Hao,Wang, Bowei,Chen, Ligong

, p. 487 - 494 (2019)

Catalysts with Co nanoparticles (NPs) entrapped in N,S-codoped carbon shells were successfully fabricated by pyrolysis of porous organic polymers (POPs) with cobalt salts. The encapsulated structure consisting of Co NPs and N,S-codoped carbon layers was verified by TEM, XRD, and X-ray photoelectron spectroscopy. The catalysts displayed excellent activity and stability for the catalytic transfer hydrogenation (CTH) of nitrobenzene with formic acid under base-free conditions. Furthermore, the resultant catalysts allowed for highly efficient and selective transfer hydrogenation of various functionalized nitroarenes to the corresponding anilines. Through control experiments, the covered Co NPs were identified as active sites for CTH. The incorporation of S into the N-doped carbon lattice promoted the electron transfer from metallic cobalt NPs to their shells, which played a significant role in the acceleration of CTH. Moreover, the Co-NSPC-850 catalyst pyrolyzed at 850 °C showed excellent stability in the recycling experiments.

Revisiting ring-degenerate rearrangements of 1-substituted-4-imino-1,2,3-triazoles

Fletcher, James T.,Hanson, Matthew D.,Christensen, Joseph A.,Villa, Eric M.

, p. 2098 - 2105 (2018)

The 1-substituted-4-imino-1,2,3-triazole motif is an established component of coordination compounds and bioactive molecules, but depending on the substituent identity, it can be inherently unstable due to Dimroth rearrangements. This study examined parameters governing the ring-degenerate rearrangement reactions of 1-substituted-4-imino-1,2,3-triazoles, expanding on trends first observed by L’abbé et al. The efficiency of condensation between 4-formyltriazole and amine reactants as well as the propensity of imine products towards rearrangement was each strongly influenced by the substituent identity. It was observed that unsymmetrical condensation reactions conducted at 70 °C produced up to four imine products via a dynamic equilibrium of condensation, rearrangement and hydrolysis steps. Kinetic studies utilizing 1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbaldehyde with varying amines showed rearrangement rates sensitive to both steric and electronic factors. Such measurements were facilitated by a high throughput colorimetric assay to directly monitor the generation of a 4-nitroaniline byproduct.

-

Tingle,Rolker

, p. 1890 (1908)

-

Secretory leukocyte protease inhibitor: Inhibition of human immunodeficiency virus-1 infection of monocytic THP-1 cells by a newly cloned protein

Shine,Wang,Konopka,Burks,Duzgunes,Whitman

, p. 249 - 263 (2002)

The ability of the salivary protein, secretory leukocyte protease inhibitor (SLPI), to inhibit human immunodeficiency virus-1 (HIV-1) infection in vitro has been reported previously and has led to the suggestion that SLPI may be partially responsible for

Development of molecular sieves-supported palladium catalyst and chemoselective hydrogenation of unsaturated bonds in the presence of nitro groups

Maegawa, Tomohiro,Takahashi, Tohru,Yoshimura, Masatoshi,Suzuka, Hiroyasu,Monguchi, Yasunari,Sajiki, Hironao

, p. 2091 - 2095 (2009)

The chemoselective hydrogenation of unsaturated bonds and azide functionalities is achieved in the presence of nitro groups by a heterogeneous palladium catalyst supported on molecular sieves (MS3A). The present method shows a widerange of applicability with regard to substrates and the catalyst can be easily prepared and reused at least three times without any loss of activity.

A novel trypsin Kazal-type inhibitor from Aedes aegypti with thrombin coagulant inhibitory activity

Watanabe, Renata M.O.,Soares, Tatiane S.,Morais-Zani, Karen,Tanaka-Azevedo, Anita M.,Maciel, Ceres,Capurro, Margareth L.,Torquato, Ricardo J.S.,Tanaka, Aparecida S.

, p. 933 - 939 (2010)

Kazal-type inhibitors play several important roles in invertebrates, such as anticoagulant, vasodilator and antimicrobial activities. Putative Kazal-type inhibitors were described in several insect transcriptomes. In this paper we characterized for the fi

N3 as an efficient reagent for the Schmidt reactions of ketones, arylaldehydes and aromatic carboxylic acids

Valizadeh, Hassan,Gholipour, Hamid,Ahmadi, Mina,Vaghefi, Sevil

, p. 1287 - 1294 (2014)

Schmidt reaction of arylaldehydes, ketones and aromatic carboxylic acids using task-specific ionic liquid, [bmim]N3 in the presence of AcOH/H2SO4 proceeds at 50-60 °C within 2-4 h to give the corresponding products. Benzaldehydes containing electron releasing groups afforded to the related benzamide derivatives. Benzonitrile derivatives were formed from the reaction of benzaldehydes containing electron withdrawing groups under these conditions. High yields of the related amides and anilines were obtained from the reaction of a variety of ketones and aromatic carboxylic acids, respectively, utilizing this procedure.

Unprecedented iron-catalyzed selective hydrogenation of activated amides to amines and alcohols

Garg, Jai Anand,Chakraborty, Subrata,Ben-David, Yehoshoa,Milstein, David

, p. 5285 - 5288 (2016)

The first example of hydrogenation of amides homogeneously catalyzed by an earth-abundant metal complex is reported. The reaction is catalyzed by iron PNP pincer complexes. A wide range of secondary and tertiary N-substituted 2,2,2-trifluoroacetamides were hydrogenated to form amines and trifluoroethanol.

Pre-steady-state kinetic studies of rat kidney γ-glutamyl transpeptidase confirm its ping-pong mechanism

Keillor, Jeffrey W.,Ménard, Annie,Castonguay, Roselyne,Lherbet, Christian,Rivard, Caroline

, p. 529 - 536 (2004)

The enzyme γ-glutamyl transpeptidase (GGT) is implicated in cellular detoxification, the biosynthesis of leukotrienes and control of the physiological concentration of glutathione. It also plays important roles in Parkinson's disease, diabetes, apoptosis inhibition and cancer drug resistance. It catalyses the breakdown of its in vivo substrate, glutathione, by cleaving the amide bond between the γ-glutamyl and the cysteinylglycine moieties. Threonine is proposed to act as the nucleophile of GGT in the formation of the γ-glutamyl acyl enzyme intermediate during the acylation step. The γ-glutamyl moiety is then transferred to a primary amine acceptor substrate (an amino acid or dipeptide) or to a water molecule, to form a compound containing a new isopeptide bond or glutamate in the transamidation or hydrolysis reactions, respectively. In spite of the importance of the role of GGT in human physiology, there is a lack of information about the mechanisms of its catalytic reactions, and in particular the nature of the intermediate formed during the acylation step. In order to gain insight into the formation of the acyl enzyme intermediate, different D-γ-glutamylanilides substituted in the para position with electron-withdrawing and electron-, donating groups were used as donor substrates under conditions where water served as acceptor substrate. A Hammett plot with a slope of zero was obtained for the steady-state hydrolysis reaction for which deacylation is the rate-limiting step. To confirm the ping-pong mechanism, pre-steady-state kinetics of this reaction were then performed with the donor substrate D-γ-glutamyl-p-nitroanilide, which liberates the chromophore p-nitroaniline. Experiments using a stopped- flow spectrometer and a rapid mix-quench apparatus gave biphasic traces with a burst up to ~ 65 ms, the amplitude of which corresponds well with the concentration of the enzyme. These burst kinetics were also observed in the presence of L-methionine at concentrations ~ 15-fold below its KM value, where deacylation would still be rate limiting. These observations are consistent with the formation of an intermediate during the rapid acylation step and support the modified ping-pong mechanism proposed for GGT- mediated hydrolysis and aminolysis. Copyright

Synthesis and kinetics of disassembly for silyl-containing ethoxycarbonyls using fluoride ions

Camerino, Eugene,Daniels, Grant C.,Wynne, James H.,Iezzi, Erick B.

, p. 1884 - 1888 (2018)

In this study, a series of silyl-containing ethoxycarbonates and ethoxycarbamates on electron poor anilines and phenols were synthesized and their kinetics of disassembly determined in real-time upon exposure to fluoride ion sources at room temperature. The results provide a greater understanding of stability and kinetics for silyl-containing protecting groups that eliminate volatile molecules upon removal, which will allow for simplification of orthogonal protection in complex organic molecules.

-

Scott,F.L.,Fenton,D.F.

, p. 685 - 688 (1970)

-

Methyltriphenylphosphonium tetrahydroborate (MePh3PBH4). A stable, selective and versatile reducing agent

Firouzabadi, Habib,Adibi, Mina

, p. 125 - 147 (1998)

Methyltriphenylphosphonium tetrahydroborate as a stable quaternary phosphonium borohydride is introduced. This compound is able to reduce aldehydes, ketones, acyl chlorides, and azides efficiently in CH2Cl2. α,β-Unsaturated carbonyl compounds are reduced selectively via 1,2-reduction. The effect of Lewis acids upon the mode and the rate of the reaction of epoxides and acetophenone are also described. This reagent is also able to bring about reductions effectively in the absence of solvent.

An Efficient Method for the Hofmann Degradation of Amides by Use of Benzyltrimethylammonium Tribromide

Kajigaeshi, Shoji,Asano, Kohichi,Fujisaki, Shizuo,Kakinami, Takaaki,Okamoto, Tsuyoshi

, p. 463 - 464 (1989)

The reaction of amides with a calculated amount of benzyltrimethylammonium tribromide in aqueous sodium hydroxide under mild conditions gave corresponding amines in fairly good yields.

Amidines. III. A kinetic study of acid hydrolysis of unsymmetrical N1,N2-disubstituted amidines

Ono,Todoriki,Araya,Tamura

, p. 1158 - 1164 (1990)

-

Purification and properties of soluble and bound γ- glutamyltransferases from radish cotyledon

Nakano, Yoshihiro,Okawa, Satoshi,Yamauchi, Takayoshi,Koizumi, Yukio,Sekiya, Jiro

, p. 369 - 376 (2006)

Soluble and cell wall bound γ-glutamyltransferases (GGTs) were purified from radish (Raphanus sativus L.) cotyledons. Soluble GGTs (GGT I and II) had the same Mr of 63,000, and were composed of a heavy subunit (Mr, 42,000) and a light one (Mr, 21,000). The properties of GGT I and II were similar. Bound GGTs (GGT A and B) were purified to homogeneity from the pellet after the extraction of soluble GGTs. GGT A and B were monomeric proteins with an Mr of 61,000. The properties of GGT A and B were similar. Thus, bound GGTs were distinguished from soluble GGTs. The optimal pHs of soluble and bound GGTs were about 7.5. Both soluble and bound GGTs utilized glutathione, γ-L-glutamyl-p-nitroanilide, oxidized glutathione and the conjugate of glutathione with monobromobimane as substrates, and were inhibited by acivicin, but soluble GGTs were also distinguished from bound GGTs with regard to these properties.

The Kinetics and Mechansim of the Hydrolysis of p-Nitrophenyl Isothiocyanate Promoted by Soft Metal Ions

Satchell, Derek P. N.,Satchell, Rosemary S.

, p. 303 - 306 (1991)

The hydrolysis of p-nitrophenyl isothiocyanate in aqueous acid solution is powerfully promoted by the Ag+ and Hg2+ ions.The organic product is p-nitroaniline.The mercury-promoted reaction is first order in isothiocyanate and in , and has ΔH(excit.) = 56 +/- 2kJ mol-1, ΔS(excit.) = -53 +/- 4 J K-1 mol-1, and kH2O/kD2O = 1.12 +/- 0.05 at 25.0 deg C.The behaviour with silver is similar: promotion is principally first order in , but in H2O there is evidence for a small kinetic term in 2. ΔH(excit.) = 59 +/- 2kJ mol-1 and ΔS(excit.) = -88 +/- 3 J K-1 mol-1 for the first-order reaction, and ΔH(excit.) = 25 +/- 5 kJ mol-1 and ΔS(excit.) = -202 +/- 12 j K-1 mol-1 for the route second order in .Use of D2O removes the second-order term, and kH2O/kD2O = 1.07 +/- 0.06 for the route involving one Ag+ ion pre-equilibrium, followed by a rate-determining attack of water to give the soft metal derivative of the corresponding thiocarbamic acid as a rapidly decomposition intermediate.

THE MECHANISM OF THE INTERACTION OF N-ARYL-O-PIVALOYLHYDROXYLAMINES WITH REDUCING METAL IONS

Lagerman, Robert K.,Novak. Michael

, p. 1923 - 1926 (1989)

Evidence which supports a stepwise electron transfer process for the reduction of 1 by Fe(2+) and Cu(+) is presented.

Facile and efficient amination of organic halides catalyzed by copper sulfate in PEG1000-DIL/methylcyclohexane temperature-dependent biphasic system

Hu, Yu-Lin,Wanga, Peng-Cheng,Chen, Tian,Lu, Ming

, p. 604 - 611 (2010)

A simple, efficient, and environmentally friendly procedure for the amination of organic halides catalyzed by CuSO4·5H 2O in PEG1000-DIL/methylcyclohexane temperature-dependent biphasic system is described. The product can be easily isolated by a simple decantation, and the catalytic system can be recycled and reused without loss of catalytic activity.

APPLICATION OF MICROWAVE ENERGY TO ORGANIC SYBNTHESIS: IMPROVED TECHNOLOGY

Abramovitch, R. A.,Abramovitch, D. A.,Iyanar, K.,Tamareselvy, K.

, p. 5251 - 5254 (1991)

The application of microwave energy to the sulfonation of naphthalene and anthraquinone, to the amination of p-chloronitrobenzene, and to the hydrosilylation of 2- and 4-vinylpyridine has been studied.Though faster (5-360-fold) reactions were observed problems were encountered with the available microwave technology.These were overcome by using a microwave oven equipped with stirring facility and both temperature and pressure control.

A palladium complex immobilized onto mesoporous silica: a highly efficient and reusable catalytic system for carbon–carbon bond formation and anilines synthesis

Nikoorazm, Mohsen,Noori, Nourolah,Tahmasbi, Bahman,Faryadi, Sara

, p. 469 - 481 (2017)

A palladium complex supported on functionalized mesoporous silica MCM-41 proved to be a highly efficient, recoverable catalyst for C–C coupling reactions and amination of aryl halides to afford anilines. The nanocatalyst was characterized by FT-IR spectroscopy, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, N2 adsorption–desorption isotherms and inductively coupled plasma analysis. The catalyst could be reused for several consecutive runs without significant loss of activity. The excellent yields of products, simple reaction procedures and short reaction times are the main advantages of this methodology.

Continuous-Flow Electrophilic Amination of Arenes and Schmidt Reaction of Carboxylic Acids Utilizing the Superacidic Trimethylsilyl Azide/Triflic Acid Reagent System

Chen, Yuesu,Gutmann, Bernhard,Kappe, C. Oliver

, p. 9372 - 9380 (2016)

A continuous flow protocol for the direct stoichiometric electrophilic amination of aromatic hydrocarbons and the Schmidt reaction of aromatic carboxylic acids using the superacidic trimethylsilyl azide/triflic acid system is described. Optimization of reagent stoichiometry, solvent, reaction time, and temperature led to an intensified protocol at elevated temperatures that allows the direct amination of arenes to be completed within 3 min at 90 °C. In order to improve the selectivity and scope of this direct amination protocol, aromatic carboxylic acids were additionally chosen as substrates. Selected carboxylic acids could be converted to their corresponding amine counterparts in good to excellent yields (11 examples, 55-83%) via a Schmidt reaction employing similar flow reaction conditions (5 min at 90 °C) and a similar reactor setup as for the amination. The safety issues derived from the explosive, toxic, and volatile hydrazoic acid intermediate, the corrosive nature of triflic acid, and the exothermic quenching were addressed by designing a suitable continuous flow reaction setup for both types of transformations.

Electroreductive synthesis of polyfunctionalized pyridin-2-ones from acetoacetanilides and carbon disulfide with oxygen evolution

Gao, Shulin,Hu, Xi,Li, Weili,Li, Yanni,Liang, Deqiang,Ma, Zhongxiao,Wang, Baoling,Xu, Lichun,Zhang, Xin

supporting information, p. 1013 - 1018 (2022/02/16)

A chemical reductant or a sacrificial electron donor is required in any reduction reactions, generally resulting in undesired chemical waste. Herein, we report a reductant-free reductive [3 + 2 + 1] annulation of β-keto amides with CS2 enabled by the synergy of electro/copper/base using water as an innocuous anodic sacrifice with O2 as a sustainable by-product. This electrochemical protocol is mild and provides access to polyfunctionalized pyridin-2-ones from simple starting materials in a single step.

Magnetically‐recoverable Schiff base complex of Pd(II) immobilized on Fe3O4@SiO2 nanoparticles: an efficient catalyst for the reduction of aromatic nitro compounds to aniline derivatives

Azadi, Sedigheh,Esmaeilpour, Mohsen,Sardarian, Ali Reza

, p. 809 - 821 (2021/07/20)

Fe3O4@SiO2/Schiff base/Pd(II) is reported as a magnetically recoverable heterogeneous catalyst for the chemoselective reduction of aromatic nitro compounds to the corresponding amines through catalytic transfer hydrogenation (CTH). In this regard, a small amount of the nanocatalyst (0.52?mol% Pd) and hydrazine hydrate, showing safe characteristics and perfect ability as the hydrogen donor, were added to the nitro substrates. The experiments described the successful reduction of aromatic nitro compounds with good to excellent yields and short reaction times. The catalyst, due to its magnetic property, could be simply separated from the reaction mixture by a permanent magnet and reused in seven consecutive reactions without considerable loss in its activity. Moreover, the leaching of Pd was only 3.6% after the seventh run. Thus, the most striking feature of this method is to use a small amount of the magnetic nanocatalyst along with a cheap and safe hydrogen source to produce the important amine substances selectively, which makes the method economical, cheap, environmentally friendly, and simple. Graphic abstract: [Figure not available: see fulltext.]

[1+1] Copper(II) macrocyclic Schiff base complex on rGO as a photocatalyst for reduction of nitroaromatics compounds under visible-light irradiation

Ghalebin, Saeed Nasiri,Bezaatpour, Abolfazl,Sadr, Moayad Hossaini,Sadjadi, Mirabdullah Seyed,Moghaddam, Mohammad Khodadadi,Szunerits, Sabine

, (2021/01/26)

In this work, [1 + 1] macrocyclic Copper(II) Schiff base complex ([CuL](NO3)2.H2O) was synthesized and grafted on reduced graphene oxide successfully. The novel prepared sample was characterized by physico-chemical techniques and used as a photocatalyst for the reduction of nitroaromatic compounds to their amine derivatives at room temperature under visible-light irradiation with hydrazine mono hydrate. From the prepared samples, reduced graphene oxide loaded with 30% [CuL](NO3)2.H2O catalyst (rGO/CuM30) shows the best efficiency for converting different nitroaromatic compounds to the corresponding amino compounds using visible light. As-prepared catalyst illustrated excellent activity for the reduction of 2-nitrophenol to 2-aminophenol (100% conversion) in only 90 min. Finally, the catalyst could be recovered for five times and reused without decreasing of its efficiency.

Process route upstream and downstream products

Process route

p-nitrophenyl isothiocyanate
2131-61-5

p-nitrophenyl isothiocyanate

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
With water; In dimethyl sulfoxide; at 30 ℃; Rate constant; Mechanism; different conc., without DMSO;
With oxonium; water; thallium(III) ion; at 25 ℃; Kinetics; Thermodynamic data; Rate constant; ionic strength = 0.5 mol/dm3, other temp.; ΔH(excit.), ΔS(excit.);
Multi-step reaction with 2 steps
1: triethylamine / tetrahydrofuran / 0 - 20 °C
2: dihydrogen peroxide / dimethyl sulfoxide; aq. phosphate buffer / pH 7.4
With dihydrogen peroxide; triethylamine; In tetrahydrofuran; aq. phosphate buffer; dimethyl sulfoxide;
Multi-step reaction with 2 steps
1: 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 0 - 20 °C
2: carbonic anhydrase / aq. phosphate buffer; dimethyl sulfoxide / 37 °C / pH 7.4 / Enzymatic reaction
With 1,8-diazabicyclo[5.4.0]undec-7-ene; carbonic anhydrase; In tetrahydrofuran; aq. phosphate buffer; dimethyl sulfoxide;
Multi-step reaction with 2 steps
1: 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 72 h / 20 °C
2: carbonic anhydrase / aq. phosphate buffer; dimethyl sulfoxide / 37 °C / pH 7.4 / Enzymatic reaction
With 1,8-diazabicyclo[5.4.0]undec-7-ene; carbonic anhydrase; In tetrahydrofuran; aq. phosphate buffer; dimethyl sulfoxide;
N,N'-Bis-(4-nitro-phenyl)-C-(4-nitro-phenyl)-methanediamine

N,N'-Bis-(4-nitro-phenyl)-C-(4-nitro-phenyl)-methanediamine

N-(4-nitrobenzylidene)-4-nitroaniline
10480-05-4

N-(4-nitrobenzylidene)-4-nitroaniline

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
In dimethylsulfoxide-d6; at 32 ℃; Equilibrium constant;
N-(4-Nitrophenyl)benzamide tetramethylammonium salt

N-(4-Nitrophenyl)benzamide tetramethylammonium salt

tetramethylammonium benzoate
25255-90-7

tetramethylammonium benzoate

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
With water; In nitrobenzene; at 70 ℃; for 1h; Title compound not separated from byproducts;
90 % Chromat.
4-(4-Nitro-phenylcarbamoyloxy)-butyric acid

4-(4-Nitro-phenylcarbamoyloxy)-butyric acid

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
With water; antibody 33B4F11; at 25 ℃; Rate constant; pH = 7.0, NaCl;
5-(4-Nitro-phenylcarbamoyloxy)-pentanoic acid

5-(4-Nitro-phenylcarbamoyloxy)-pentanoic acid

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
With water; antibody 33B4F11; at 25 ℃; Rate constant; pH = 7.0, NaCl;
3-(p-nitrophenylazo)-2,3'-methylenedi-indole
61844-14-2

3-(p-nitrophenylazo)-2,3'-methylenedi-indole

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
at 150 - 230 ℃; for 0.333333h;
48%
3-methyl-5-nitro-1-(p-nitrophenyl)uracil
108047-30-9

3-methyl-5-nitro-1-(p-nitrophenyl)uracil

methylamine
74-89-5

methylamine

1,3-dimethyl-5-nitrouracil
41613-26-7

1,3-dimethyl-5-nitrouracil

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
In methanol; for 0.5h; Ambient temperature;
95%
3,5-dinitro-1-(p-nitrophenyl)-4-pyridone
74197-40-3

3,5-dinitro-1-(p-nitrophenyl)-4-pyridone

methylamine
74-89-5

methylamine

3,5-dinitro-1-methyl-4-pyridone
19872-97-0

3,5-dinitro-1-methyl-4-pyridone

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

Conditions
Conditions Yield
92.5%
dimethylacetylene
503-17-3

dimethylacetylene

4'-nitrobenzenesulfenanilide
64168-52-1

4'-nitrobenzenesulfenanilide

acetonitrile
75-05-8,26809-02-9

acetonitrile

N-(4-nitrophenyl)-N'-<3-(phenylthio)but-2-en-2-yl>acetamidine
124251-48-5

N-(4-nitrophenyl)-N'-<3-(phenylthio)but-2-en-2-yl>acetamidine

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

diphenyldisulfane
882-33-7

diphenyldisulfane

Conditions
Conditions Yield
With boron trifluoride diethyl etherate; for 1h; Ambient temperature;
26%
27%
70%
1-Pentyne
627-19-0

1-Pentyne

4'-nitrobenzenesulfenanilide
64168-52-1

4'-nitrobenzenesulfenanilide

acetonitrile
75-05-8,26809-02-9

acetonitrile

N-(4-nitrophenyl)-N'-<1-(phenylthio)pent-1-en-2-yl>acetamidine
124251-46-3

N-(4-nitrophenyl)-N'-<1-(phenylthio)pent-1-en-2-yl>acetamidine

4-nitro-aniline
100-01-6,104810-17-5

4-nitro-aniline

diphenyldisulfane
882-33-7

diphenyldisulfane

Conditions
Conditions Yield
With boron trifluoride diethyl etherate; for 1h; Product distribution; Mechanism; Ambient temperature; reactions with other alkynes, reaction regioselectivity;
40%
54%
35%
With boron trifluoride diethyl etherate; for 1h; Ambient temperature;
40%
35%
54%

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