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One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis
A convergent paired electrolysis catalyzed by a B12 complex for the one-pot synthesis of a tertiary amide from organic trichlorides (R-CCl3) has been developed. Various readily available organic trichlorides, such as benzotrichloride and its derivatives, chloroform, dichlorodiphenyltrichloroethane (DDT), trichloro-2,2,2-trifluoroethane (CFC-113a), and trichloroacetonitrile (CNCCl3), were converted to amides in the presence of tertiary amines through oxygen incorporation from air at room temperature. The amide formation mechanism in the paired electrolysis, which was mediated by a cobalt complex, was proposed.
Luo, Zhongli,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio,Shimakoshi, Hisashi
p. 5983 - 5990
(2021/05/04)

Mechanistic Insights into Fe Catalyzed α-C?H Oxidations of Tertiary Amines
We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C?H oxidation of a wide variety of amines. In contrast to other catalysts that effect α-C?H oxidations of tertiary amines, the system under investigation exclusively employs peroxy esters as oxidants. More common oxidants (e. g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C?H oxidation products in combination with the described catalyst system. The investigations described herein employ initial rate kinetics, kinetic profiling, DFT calculations as well as Eyring, kinetic isotope effect, Hammett, ligand coordination, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C?H abstraction at a coordinated substrate molecule. This rate-determining step occurs either through an Fe(IV) oxo pathway or a 2-electron pathway at an Fe(II) intermediate with bound oxidant. DFT calculations indicate that the Fe(IV) oxo mechanism will be the preferred route of these two possibilities. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3tBu to tBuOOH. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, inducing selectivity for α-C?H functionalization.
Legacy, Christopher J.,Hope, Taylor O.,Gagné, Yohann,Greenaway, Frederick T.,Frenette, Mathieu,Emmert, Marion H.
p. 235 - 246
(2020/10/19)

Production method of N,N-diethyl acetamide
The invention discloses a preparation method of N,N-dimethylformamide. The production method comprises the following steps: n a self-reflux reactor filled with a heterogeneous catalyst, firstly addingethyl acetate and ethylamine, carrying out heating to 30 DEG C within 10-20 minutes, then gradually adding ethanol within 20-30 minutes, then carrying out heating to 50-60 DEG C at a speed of 30-50 DEG C/h, performing reacting for 20-30 minutes, ending the reaction, and finally carrying out purifying to obtain N,N-diethyl acetamide. The obtained N,N-diethyl acetamide is high in yield, selectivityand purity, and the method is mild in reaction condition and easy to operate.
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Paragraph 0018; 0025; 0035; 0045; 0055; 0065; 0075

(2020/06/30)

Manganese-mediated acetylation of alcohols, phenols, thiols, and amines utilizing acetic anhydride
Manganese(II) chloride-catalyzed acetylation of alcohols, phenols thiols and amines with acetic anhydride is reported. This method is environment-friendly and economically viable as it involves inexpensive, relatively benign catalyst, mild reaction condition, and simple workup. Acetylation is performed under the solvent-free condition at ambient temperature and acetylated products obtained in good to excellent yields. Primary, secondary heterocyclic amines, and phenols with various functional groups are smoothly acetylated in good yields. This method exhibits exquisite chemoselectivity, the amino group is preferentially acetylated in the presence of a hydroxyl/thiol group.
Jain, Isha,Sharma, Ramandeep,Malik, Payal
supporting information
p. 2952 - 2960
(2019/09/13)

Amide Bond Formation Catalyzed by Recyclable Copper Nanoparticles Supported on Zeolite Y under Mild Conditions
A series of catalysts based on supported copper nanoparticles have been prepared and tested in the amide bond formation from tertiary amines and acid anhydrides, in the presence of tert-butyl hydroperoxide as an oxidant. Copper nanoparticles on zeolite Y (CuNPs/ZY) was found to be the most efficient catalyst for the synthesis of amides, working in acetonitrile as solvent, under ligand- and base-free conditions in air. The products were obtained in good to excellent yields and in short reaction times. The CuNPs/ZY system also exhibited higher catalytic activity than some commercially available copper and iron sources and it was reused in ten reaction cycles without any further pre-treatment. This methodology has been successfully scaled-up to a gram scale with no detriment to the yield.
Moglie, Yanina,Buxaderas, Eduardo,Mancini, Agustina,Alonso, Francisco,Radivoy, Gabriel
p. 1487 - 1494
(2019/02/16)

Pivotal role of intramolecular catalysis in the selective acetylation of alkyl amines
Preparation of amides by the use of esters as the "acyl donor" is less explored because they are less reactive and usually more steric demanding than conventional acid halides and anhydrides. Here, we report that 3-acetoxy-2-naphthoic acid, an aspirin analogue, can be used as a mild amine acetylating agent in ethanol at 25°C. The reaction is sensitive to steric and polar effects of the attacking amine, and the rate constants can be appropriately fitted by the Pavelich-Taft correlation. Density functional theory calculations used to study all reaction steps indicate that the o-carboxy group plays a pivotal role, guiding the attacking amine and accelerating the reaction. The reaction can be conveniently used for the acylation of a variety of primary and secondary amines.
Nishida, Elvis N.,Vitto, Ramon,Peixoto, R?mulo C.R.,Nome, Faruk,Souza, Bruno S.
(2018/04/14)

NITROGEN-CONTAINING BIOPOLYMER-BASED CATALYSTS, THEIR PREPARATION AND USES IN HYDROGENATION PROCESSES, REDUCTIVE DEHALOGENATION AND OXIDATION
The present invention relates to a process for the preparation of a nitrogen containing biopolymer-based catalyst by pyrolysis of a metal complex with a nitrogen-containing biopolymer and to the nitrogen containing biopolymer-based catalysts obtainable by this process. In particular, the invention relates to a nitrogen containing biopolymer-based catalyst comprising metal particles and at least one nitrogen containing carbon layer. The invention also relates to the use of a nitrogen containing biopolymer-based catalyst in a hydrogenation process, preferably in a process for hydrogenation of nitroarenes, nitriles or imines; in a reductive dehalogenation process of C-X bonds, wherein X is CI, Br or I, preferably in a process for dehalogenation of organohalides or in a process for deuterium labelling of arenes via dehalogenation of organohalides; or in an oxidation process. Further, the invention relates to a metal complex with the nitrogen containing biopolymer, wherein the metal is a transition metal selected from the group consisting of manganese, ruthenium, cobalt, rhodium, nickel, palladium and platinum, preferably cobalt or nickel, and wherein the nitrogen containing biopolymer is selected from chitosan, chitin and a polyamino acid, preferably chitosan or chitin.
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(2018/07/29)

Cu(II)-Mediated keto C(sp3)-H bond α-acyloxylation of N, N-dialkylamides with aromatic carboxylic acids
The selective oxidative coupling of aromatic carboxylic acids with the C(sp3)-H bond adjacent to the keto group of alkylamides has been developed by employing a low cost copper source. This provides an efficient approach for synthesis of O-benzoylglycolamides. The protocol displayed good functional group tolerance. A broad range of benzoic acids directly coupled with alkylamides to afford a variety of O-benzoylglycolamides in moderate to good yields. In addition, a reasonable radical mechanism was proposed based on EPR experiments.
Li, Wenjing,Yin, Changzhen,Yang, Xiao,Liu, Hailong,Zheng, Xueli,Yuan, Maolin,Li, Ruixiang,Fu, Haiyan,Chen, Hua
supporting information
p. 7594 - 7599
(2017/09/27)

Method for preparing methallyl alcohol and amide simultaneously
A method for preparing methallyl alcohol and amide simultaneously is characterized in that methylallyl carboxylate taken as a raw material and an amine compound taken as an ammonolysis agent react under the action of a catalyst to produce methallyl alcohol and an amide compound. The methylallyl carboxylate and the amine compound taken as the ammonolysis agent are firstly adopted, and the methallyl alcohol and the amide compound are obtained under the action of the catalyst. The reaction process is a bulk reaction, no solvents are added, almost no wastewater or salt are produced, and byproduct methyl allyl ether is not produced; the defect that a large number of wastewater is produced through hydrolysis is overcome due to adoption of ammonolysis, the methallyl alcohol and the amide compound are coproduced directly by use of ammonoysis, coupling production is realized, and the cost is reduced.
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Paragraph 0042-0043

(2017/11/29)

Sunlight assisted direct amide formation: Via a charge-transfer complex
We report on the use of charge-transfer complexes between amines and carbon tetrachloride, as a novel way to activate the amine for photochemical reactions. This principle is demonstrated in a mild, transition metal free, visible light assisted, dealkylative amide formation from feedstock carboxylic acids and amines. The low absorption coefficient of the complex allows deep light penetration and thus scale up to a gram scale.
Cohen, Irit,Mishra, Abhaya K.,Parvari, Galit,Edrei, Rachel,Dantus, Mauricio,Eichen, Yoav,Szpilman, Alex M.
supporting information
p. 10128 - 10131
(2017/09/23)

A Biomass-Derived Non-Noble Cobalt Catalyst for Selective Hydrodehalogenation of Alkyl and (Hetero)Aryl Halides
Hydrodehalogenation is a straightforward approach for detoxifications of harmful anthropogenic organohalide-based pollutants, as well as removal of halide protecting groups used in multistep syntheses. A novel sustainable catalytic material was prepared from biowaste (chitosan) in combination with an earth-abundant cobalt salt. The heterogeneous catalyst was fully characterized by transmission electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy measurements, and successfully applied to hydrodehalogenation of alkyl and (hetero)aryl halides with broad scope (>40 examples) and excellent chemoselectivity using molecular hydrogen as a reductant. The general usefulness of this method is demonstrated by successful detoxification of non-degradable pesticides and fire retardants. Moreover, the potential of the catalyst as a deprotection tool is demonstrated in a multistep synthesis of (±)-peronatin B (alkaloid).
Sahoo, Basudev,Surkus, Annette-Enrica,Pohl, Marga-Martina,Radnik, J?rg,Schneider, Matthias,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
supporting information
p. 11242 - 11247
(2017/09/02)

Doping of copper (I) oxide onto a solid support as a recyclable catalyst for acetylation of amines/alcohols/phenols and synthesis of trisubstituted imidazole
A study of copper-mediated C-heteroatom especially C-N and C-O bond formations using simpler methodologies has been carried out. In the present work, acetylation of various substrates such as amines, phenols and alcohols; synthesis of 2,4,5-trisubstituted imidazole is done using simple and easily available starting materials. Copper (I) oxide was synthesized in situ by the reduction of Fehling's solution with glucose followed by its anchoring onto different supports like silica, HAP, basic alumina and cellulose. Comparison and contrasts between the reactivity of copper (I) oxide supported onto different supports for these reactions are made. The reactivity of copper (I) oxide seems to be largely dependent on the nature of support and the most active catalyst for a particular reaction was further characterized by different spectroscopic techniques such as FTIR, XRD, TGA, XPS, SEM, TEM and AAS. The catalysts were found to be stable, easily recyclable without any significant loss in activity. Graphical abstract: Applications of solid supported copper (I) oxides (where solid support is silica, HAP, cellulose and basic alumina) are studied for various organic transformations with special emphasis on C-N and C-O bond formation reactions.[Figure not available: see fulltext.]
Gupta, Manjulla,Gupta, Monika
p. 231 - 241
(2016/01/09)

Synthesis and characterization of Mn/Co/Ti LDH and its utilization as a photocatalyst in visible light assisted degradation of aqueous Rhodamine B
Luminescent Mn/Co/Ti LDH, synthesized by a single step hydrothermal route, has been found to be optically responsive for utilization as a highly efficient photocatalyst in destruction of the cationic dye Rhodamine B, in aqueous solution under visible light irradiation. The material has been found to be better than the commercial catalysts like MnO, CoO, TiO2 and Degussa P25. Multiple techniques like XRD, XPS, FT-IR, EIS, TG, UV-visible DRS, PL, TRES, N2-sorption-desorption, dynamic light scattering, TEM-EDS and AFM analyses were used to characterize the LDH. The results indicated Mn/Co/Ti LDH to have a multilayered crystalline structure with hexagonal morphology that carries metal ions in mixed valences, oxygen vacancies, defect states, thermal stability, narrow band gap, high surface area, and electrostatic surface charge variation with pH. The photocatalytic activity of the LDH could be co-related with the structural aspects such as oxidation states, narrow band gap, high surface area and existence of defects. The active species responsible for photocatalysis have been evaluated with EPR, terephthalic acid fluorescence probe and indirect radical-hole trapping experiments. The photodegradation mechanism involves electron and hole hopping across the material and also photosensitization of the dye. Ex situ1H-NMR and GC-MS analyses of the colorless end products of Rhodamine B destruction provide further insight into the reaction mechanism. The complete mineralization of the decolorized end product of degradation was evaluated with TOC analysis. The results indicate the potential for using multi metal incorporated LDH in destroying dyes and their degradation products in industrial wastewater.
Chowdhury, Priyadarshi Roy,Bhattacharyya, Krishna G.
p. 112016 - 112034
(2016/12/07)

Magnetically separable γ-Fe2O3 nanoparticles: An efficient catalyst for acylation of alcohols, phenols, and amines using sonication energy under solvent free condition
This paper reports a facile synthesis of magnetically separable iron oxide (γ-Fe2O3) nanoparticles using thermolysis method. The structural and morphological study of the synthesized γ-Fe2O3 nanoparticles was carried out using X-ray diffraction (XRD), field emission gun-scanning electron microscopy (FEG-SEM), energy dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) techniques. The electron microscopy reveals that the γ-Fe2O3 nanoparticles have spherical morphology with a particle size in the range of 40-100 nm. The XPS study confirmed the Fe is in +3 oxidation state. The synthesized γ-Fe2O3 nanoparticles have been used as an efficient heterogeneous catalyst for the organic transformation between phenols, alcohols, and amines with acetic anhydride under sonication using mild reaction conditions. Various electrons withdrawing and electrons donating substrates show an excellent yield of desired products with the advantage of magnetic separation and reusability of γ-Fe2O3 nanocatalyst.
Bhosale, Manohar A.,Ummineni, Divya,Sasaki, Takehiko,Nishio-Hamane, Daisuke,Bhanage, Bhalchandra M.
p. 8 - 17
(2015/04/27)

Direct Preparation of Amides from Amine Hydrochloride Salts and Orthoesters: A Synthetic and Mechanistic Perspective
The conversion of a wide range of primary and secondary aliphatic and a few arylamine hydrochloride salts to their corresponding acetamides with trimethyl orthoacetate is described. Mechanistic studies using NMR and gas chromatography-mass spectrometry techniques indicate these reactions proceed via an O-methylimidate intermediate that undergoes in situ demethylation by chloride, affording the corresponding acetamides. Synthetically, this reaction represents a practical, high-yielding protocol with a simple workup for the rapid conversion of amine hydrochloride salts to acetamides.
Di Grandi, Martin J.,Bennett, Caitlin,Cagino, Kristen,Muccini, Arnold,Suraci, Corey,Saba, Shahrokh
supporting information
p. 2601 - 2607
(2015/11/28)

Iron-catalyzed Cα-H oxidation of tertiary, aliphatic amines to amides under mild conditions
De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe-catalyzed Cα-H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα-H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. Let′s iron it out! The title reaction enables the oxidative synthesis of amides directly from tertiary, noncyclic alkyl amines under synthetically useful, mild conditions through a biologically inspired approach employing oxidative iron catalysis. Mechanistic studies suggest that hemiaminals are likely intermediates in this reaction and that the catalytic system can be employed for other Cα-H oxidations of amines.
Legacy, Christopher J.,Wang, Anqi,O'Day, Brian J.,Emmert, Marion H.
supporting information
p. 14907 - 14910
(2016/02/05)

The oxidation of the alpha-carbon of amines in hydrothermal condition: An alternative synthetic route of compounds containing amide bond
Here we report experimental evidence for the simple synthesis of N,N-diethylhydroxylamine and an amide bond formation reaction from oxidation of the alpha-carbon of tertiary amines by the reaction of triethylamine and hydrogen peroxide in hydrothermal conditions. It is proved that 120 C is a turning point: when the temperature is lower than that, the main product is N,N-diethylhydroxylamine as a result of a cope rearrangement reaction mechanism; on the contrary, the product is more complex and the main products are amides via a radical chain mechanism involving three steps: initiation, propagation, and oxidation, followed by decarbonylation and electrocyclization because the radical is easier to form under high temperature.
Bai, Xueyin,Liu, Ziwei,Ye, Kaiqi,Wang, Yu,Zhang, Xianlong,Yue, Huijuan,Tian, Ge,Feng, Shouhua
p. 319 - 321
(2014/01/06)

Selectivities in acylation of primary and secondary amine with diacylaminoquinazolinones and diacylanilines
The diacylaminoquinazolinones are highly selective acylating agents for primary amines in the presence of secondary amines. The chemoselective N-acetylation reagents have been investigated using 2-substituted N,Ndiacylaminoquinazolinones (DAQs) and 2-substitued-N-diacylanilines (DAAs). Determination of the selectivity ratios have been made by comparison of the crude product in each case with authentic samples of the amide products using NMR spectroscopy. The control experiments in which pairs of amines compete for acetyl chloride show some selectivity but not comparable with that of DAQs and DAAs selectivity. When the DAQs, DAAs and acetyl chloride react with mixtures of pyrrolidine and piperidine, they give amides in the corresponding ratios. The DAQs 1 and 2 react entirely with diethylamine without any competitive reaction with diphenylamine. The high level of chemoselectivity has also been observed when the 1 and 2 react exclusively with the ethanolamine without any competitive reaction with diethanolamine. Moreover, 1 and 2 react with succinimide without any competitive reaction with phthalimide.
Al-Sehemi, Abdullah G.,Al-Amri, Reem S. Abdul-Aziz,Irfan, Ahmad
p. 1115 - 1121
(2014/10/15)

Immobilization of Candida cylindracea lipase on poly lactic acid, polyvinyl alcohol and chitosan based ternary blend film: Characterization, activity, stability and its application for N-a
The ecofriendly ternary blend polymer film was prepared from the chitosan (CH), polylactic acid (PLA) and polyvinyl alcohol (PVA). Immobilization of Candida cylindracea lipase (CCL) was carried out on ternary blend polymer via entrapment methodology. The ternary blend polymer and immobilized biocatalyst were characterized by using N2 adsorption-desorption isotherm, SEM, FTIR, DSC, and (%) water content analysis through Karl Fischer technique. Biocatalyst was then subjected for the determination of practical immobilization yield, protein loading and specific activity. Immobilized biocatalyst was further applied for the determination of biocatalytic activity for N-acylation reactions. Various reaction parameters were studied such as effect of immobilization support (ratio of PLA:PVA:CH), molar ratio (dibutylamine:vinyl acetate), solvent, biocatalyst loading, time, temperature, and orbital speed rotation. The developed protocol was then applied for the N-acylation reactions to synthesize several industrially important acetamides with excellent yields. Interestingly, immobilized lipase showed fivefold higher catalytic activity and better thermal stability than the crude extract lipase CCL. Furthermore various kinetic and thermodynamic parameters were studied and the biocatalyst was efficiently recycled for four successive reuses. It is noteworthy to mention that immobilized biocatalyst was stable for period of 300 days.
Badgujar, Kirtikumar C.,Dhake, Kishor P.,Bhanage, Bhalchandra M.
p. 1335 - 1347
(2013/09/12)

Novel double-SO3h functionalized ionic liquid for acetylation
Novel double-SO3H functionalized ionic liquid (DFIL) was synthesized and its catalytic activities for acetylation studied. The result showed that the DFIL possess high acidity and was very efficient for the acetylation of alcohols, amines and phenols with good to excellent yields in short reaction times. Operational simplicity, stability to water and air, small amounts needed, low cost, high yields, high acidity, applicability to large-scale reactions and reusability are the key features of the DFIL, which indicated promising applications of DFIL in green chemical processes. Pleiades Publishing, Ltd., 2012.
Zhu, Lili,Liang, Xuezheng
p. 684 - 688
(2013/02/23)

Density and ultrasonic sound speed measurements for N,N-dimethylformamide with ionic liquids
To understand the molecular interactions between N,N-dimefhylformamide with two families of ionic liquids, the thermophysical properties such as densities and ultrasonic sound speeds have been measured over the entire composition range at 25 °C under atmospheric pressure. The materials investigated in the present study include two families of ionic liquids, viz., ammonium salts and imidazolium salts. Diethyl ammonium acetate, triethyl ammonium acetate, triethyl ammonium dihydrogen phosphate and triethyl ammonium sulphate are the ammonium salts while 1-benzyl-3-methylimidazolium chloride belongs to the imidazolium family. The intermolecular interactions and structural effects are analyzed on the basis of the measured and derived properties. A qualitative analysis of the results are discussed in terms of the ion-dipole interactions, ion-pair interactions and hydrogen bonding between the ionic liquids and N,N-dimethylformamide molecules.
Attri, Pankaj,Reddy, P. Madhusudhan,Venkatesu
experimental part
p. 736 - 742
(2011/01/05)

Synthesis and application of a microgel-supported acylating reagent by coupled ring-opening metathesis polymerization and activators Re-Generated by electron transfer for atom transfer radical polymerization
A novel microgel-supported acylating reagent (MGAR) was prepared by combining ring-opening metathesis polymerization (ROMP) and Activators Re-Generated by Electron Transfer for Atom Transfer Radical Polymerization (ARGET ATRP): (1) synthesis of an ATRP macroinitiator 3 by living ROMP of oxanorbornene-based activated ester 1, derived from Af-hydroxysuccinimide, using the Grubbs initiator RuCl2(PCy3)2(=CHPh) and (Z)-but-2-ene-l,4-diyl bis(2-bromopropanoate) (BDBP) as a terminating agent; (2) synthesis of MGAR 4 by ARGET ATRP of styrene (S) and divinylbenzene (DVB) using the prepared macroinitiator 3, a CuCI2ZMe6TREN (tris[2-(dimethylamino)ethyl]amine) catalyst system, a Sn(Oct)2 [tin(II)2ethylhexanoate] reducing agent. The synthesized microgels 4 exhibit excellent acyl (acetyl, benzoyl, phenylsulfonyl) transfer properties for primary and secondary amines (n-BuNH2, Et2NH, morpholine, etc.) under mild conditions (25 °C, 13.5-14 h) affording N-acylamines with high yield (95.6-100%) and purity (94.1-96.0%).
Li, Hong,Pang, Zi-Bo,Jiao, Zhi-Feng,Lin, Fei
experimental part
p. 255 - 259
(2010/09/03)

PROCESS FOR PREPARING SECONDARY AMIDES BY CARBONYLATION OF A CORRESPONDING TERTIARY AMINE
The present invention relates to a process for preparing secondary amides with good selectivity by carbonylating a corresponding tertiary amine with carbon monoxide in a reaction mixture in the presence of a metal catalyst and in the presence of a halogen containing promoter. The metal catalyst comprises palladium. A same or even a much better catalytic activity can be obtained with palladium than with the much more expensive rhodium, especially when the palladium is used in a low concentration. Moreover, also a good selectivity can be achieved.
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(2010/06/14)

A convenient one-pot preparation of N-substituted thioamides
A convenient one-pot preparation of N-substituted thioamides from acyl halides, amines and H2O/PSCl3/Et3N in good to excellent yield has been reported through a solvent-free, microwave assisted method.
Pandey, Lokesh Kumar,Pathak, Uma,Mazumder, Avik,Mathura, Sweta
experimental part
p. 1225 - 1228
(2010/12/20)

Simple and efficient method for acetylation of alcohols, phenols, amines, and thiols using anhydrous NiCl2 under solvent-free conditions
Solvent-free acetylation of alcohols, phenols, amines, and thiols with acetic anhydride (Ac2O) in the presence of 0.1mol% (13mg) anhydrous NiCl2, an inexpensive and easily available catalyst, is described. Excellent yields, short reaction time, and mild reaction conditions are important features of this method.
Meshram, Gangadhar,Patil, Vishvanath D.
experimental part
p. 4384 - 4395
(2010/04/29)

N1,N3-Diacyl-3,4-dihydropyrimidin-2(1H)-ones: neutral acyl group transfer reagents
Readily available N1,N3-diacyl-3,4-dihydropyrimidin-2(1H)-ones efficiently acylate ammonia, primary and secondary amines to furnish primary, secondary and tertiary amides in good to excellent yields. The wide applicability of the procedure is demonstrated
Singh, Kamaljit,Singh, Kawaljit
experimental part
p. 10395 - 10399
(2010/02/28)

Mild and useful method for n-acylation of amines
Iodine is found to promote quantitative N-acylation of primary and secondary amines (aliphatic and aromatic) in a very short time with an equimolar amount of acetyl chloride and benzoyl chloride under solvent-free conditions at room temperature. This catalytic acylation of amines offers an additional useful method for the acetylation using acetyl chloride instead of acetic anhydride and other acetylating agents. This method is also useful in the N-acylation of heterocycles. Mild reaction condition, high selectivity, efficiency, and good yields are some of the major advantages of the procedure.
Phukan, Kandarpa,Ganguly, Mausumi,Devi, Nirada
experimental part
p. 2694 - 2701
(2009/12/06)

Synthesis of N,N-dialkylnitramines from secondary ammonium nitrates in liquid or supercritical carbon dioxide
An efficient explosion-proof method was developed for the preparation of N,N-dialkylnitramines by treatment of dialkylammonium nitrates with a mixture of nitric acid and acetic anhydride in the presence of ZnCl2 in liduid or supercritical carbon dioxide.
Kuchurov,Fomenkov,Zlotin
experimental part
p. 2058 - 2062
(2011/01/08)

Acyl iodides in organic synthesis: XI. Unusual N-C bond cleavage in tertiary amines
Acyl iodides reacted with excess primary and secondary amines in a way similar to acyl chlorides, yielding the corresponding carboxylic acid amide and initial amine hydroiodide. Reactions of tertiary amines with acyl iodides were accompanied by cleavage of the N-C bond with formation of the corresponding N,N-di(hydrocarbyl)carboxamide and alkyl iodide. In the presence of excess tertiary amine the latter was converted into quaternary tetra(hydrocarbyl) ammonium iodide.
Voronkov,Tsyrendorzhieva,Rakhlin
experimental part
p. 481 - 484
(2009/04/11)

Absolute rate constants for some intermolecular reactions of α-aminoalkylperoxyl radicals. Comparison with alkylperoxyls
(Graph Presented) Seven α-aminoalkylperoxyl radicals have been generated by 355 nm laser flash photolysis (LFP) of oxygen-saturated di-tert-butyl peroxide containing mono-, di-, and trialkylamines and a dialkylarylamine. All these peroxyls possess absorptions in the near-UV (strongest for the trialkylamine-derived peroxyls) which permits direct monitoring of the kinetics of their reactions with many substrates. The measured rate constants for hydrogen atom abstraction from some phenols and oxygen atom transfer to triphenylphosphine demonstrated that all seven α- aminoalkylperoxyls have similar reactivities toward each specific substrate. More importantly, a comparison with literature data for alkylperoxyls shows that α-aminoalkylperoxyls and these alkylperoxyls have essentially the same reactivities. The combination of LFP and alkylamines provides a quick, reliable method for determining absolute rate constants for alkylperoxyl radical reactions, an otherwise laborious task.
Lalevee, Jacques,Allonas, Xavier,Fouassier, Jean-Pierre,Ingold
p. 6489 - 6496
(2008/12/22)

NOVEL 8-HYDROXYQUINOLINE ACETAMIDE COMPOUND, 8-HYDROXY QUINOLINE THIOAMIDE COMPOUND AND USE THEREOF
Disclosed are a novel 8-hydroxyquinoline acetamide compound, an 8-hydroxyquinoline thioamide and use thereof. More specifically, disclosed are a novel 8-hydroxyquinoline thioamide compound suitable for use as a selective chemodosimeter that shows considerably high detection sensitivity to mercury ions, an 8-hydroxyquinoline acetamide compound as an intermediate thereof, preparation thereof, and a chemodosimeter for mercury ion-selective detection, the chemodosimeter comprising the 8-hydroxyquinoline thioamide compound. The compounds as disclosed herein exhibit considerably effective fluorescence specificity of an off-on type, detect a micromole of mercury ions from chemical and biological aqueous systems, and allow 100% desulfurization within 5 minutes, thus being considerably useful in the chemical industry.
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(2008/06/13)

Synthesis and reactions of heterodinuclear organopalladium complex having an unsymmetrical PN ligand
Novel heterodinuclear organopalladium complexes having an unsymmetrical PN ligand (Et2NC2H4PPh2-κ2N,P)RPd-MLn (MLn = Co(CO)4; R = Me (2a), Ph (2b), MLn = MoCp(CO)3; R = Ph (3b)) are synthesized by metathetical reactions of PdRX(Et2NC2H4PPh2-κ2N,P) (X = I, NO3) with Na+[MLn]-. Reversible dissociation of the Pd-N bond in 3b is revealed by variable temperature NMR studies. Reactions of 2a and 2b with CO yield corresponding acyl complexes (Et2NC2H4PPh2-κ2N,P)(RCO)Pd-Co(CO)4 (R = Me (5a), Ph (5b)). Rate of CO insertion for 2a and 2b is significantly faster than those for mononuclear methylpalladium complex, PdMeI(Et2NC2H4PPh2-κ2N,P) (1a), and methylpalladium-cobalt complex with a 1,2-bis(diphenylphosphino)ethane (dppe) ligand, (dppe-κ2P,P′)MePd-Co(CO)4 (6a). 5a smoothly reacts with nucleophiles such as diethylamine, methanol and benzenethiol to give corresponding amide, ester and thioester, respectively. These reactions of 5a are also significantly faster than those of corresponding mononuclear analogues and the similar heterodinuclear complexes with symmetrical bidentate ligands such as 1,2-bis(diphenylphosphino)ethane or N,N,N′,N′-tetramethylethylenediamine ligand.
Komine, Nobuyuki,Tsutsuminai, Susumu,Hirano, Masafumi,Komiya, Sanshiro
p. 4486 - 4494
(2008/02/13)

Efficient chemoselective liquid phase acylation of amines, alcohols and bifunctional compounds over ZSM-35
ZSM-35, is a medium pore zeolite, has been synthesized using ethylene diamine as organic template. The catalyst is used in the acylation of different amines, alcohols and bifunctional compounds. This material is found to be active and selective acid catalyst, exhibits not only very good activity but also very high chemo-selectivity towards monoacylation of bifunctional compounds. This material is more reactive for smaller organic compounds because of its pore dimension. In case of bifunctional compounds like amino alcohols, amines are selectively acylated at lower temperature.
Srivastava,Venkatathri
p. 888 - 891
(2007/10/03)

Preparation of tertiary amides from carbamoyl chlorides and organocuprates
(Chemical Equation Presented) Reaction of carbamoyl chlorides with cyano-Gilman cuprates affords tertiary amides in good to excellent yields. The reaction is general due to the possibility of using reagents made either from organolithium or from Grignard compounds. The characterization of the main side products allowed for the suggestion of a possible mechanism.
Lemoucheux, Laurent,Seitz, Thomas,Rouden, Jacques,Lasne, Marie-Claire
p. 3703 - 3706
(2007/10/03)

(Pyridine)(tetrahydroborato)zinc complex mediated acetylation of amines with ethyl acetate
(Pyridine)(tetrahydroborato)zinc complex, (Py)Zn(BH4)Z, can efficiently perform acetylation of a variety of aliphatic and aromatic amines with ethyl acetate under refluxing THF.
Zeynizadeh, Behzad,Zahmatkesh, Karam
p. 801 - 805
(2007/10/03)

Transacylation of α-Aryl-β-keto Esters
The acyl group of an α-aryl-β-keto ester was readily transferred to N-, O-, and S-nucleophiles. The transacylation from arylated diethyl 3-oxoglutarate to amines led to unsymmetrical malonic acid amide esters in high yields. The present reaction proceeded under mild conditions without formation of detectable byproducts. Only simple experimental manipulations were required. This reaction was also found to be sensitive to steric factors, which enabled the chemoselective monoacylation of diamines and amino alcohols without any modifications such as protection.
Nishiwaki, Nagatoshi,Nishida, Daisei,Ohnishi, Tetsuya,Hidaka, Fumie,Shimizu, Satoru,Tamura, Mina,Hori, Kazushige,Tohda, Yasuo,Ariga, Masahiro
p. 8650 - 8656
(2007/10/03)

Formal synthesis of angiogenesis inhibitor NM-3
We report the formal synthesis of angiogenesis inhibitor NM-3 (1) in six steps from either of the 2,4-dimethoxyhalobenzenes 13a,b or 3,5-dimethoxychlorobenzene (13c). The first key reaction is the regiospecific alkylation/rearrangement between the aryne derived from 13a-c with sodium diethylmalonate in THF to produce diester 11, which after hydrolysis and cyclization affords homophthalic anhydride 3. The second is the reaction of anhydride 3 with either ethyl 2-methylmalonate (28a), in the presence of 1,1′-carbonyldiimidazole, or ethyl-2-methylmalonyl chloride (28b) under basic conditions to afford key isocoumarin 27. The conversion of 27 constitutes a formal synthesis of NM-3.
Bauta, William E.,Lovett, Dennis P.,Cantrell Jr., William R.,Burke, Brian D.
p. 5967 - 5973
(2007/10/03)

DIBAL-H-H2NR and DIBAL-H-HNR1R2·HCl complexes for efficient conversion of lactones and esters to amides
The reaction of a lactone or an ester with organoaluminum species generated from DIBAL-H-H2NR or DIBAL-H-HNR1R2·HCl complexes provided efficient methods for preparation of amides. Conditions were defined for the preparation of both secondary and tertiary amides, including Weinreb amides in excellent yields.
Huang, Pei-Qiang,Zheng, Xiao,Deng, Xian-Ming
p. 9039 - 9041
(2007/10/03)

Raney Nickel: An effective reagent for reductive dehalogenation of organic halides
Raney Nickel is an effective reagent to achieve the chemoselective reductive dehalogenation of organic halides. Fluorides and vinyl halides are unreactive under the used experimental conditions.
Barrero,Alvarez-Manzaneda,Chahboun,Meneses,Romera
p. 485 - 488
(2007/10/03)

A simple route to N,N-dialkyl derivatives of 2-amino-5-thiophenecarboxylates
Starting from acetamides 4 and using three different routes - via thioacetamides 5, 3-amino-thioacrylamides 7, or 3-chloropropeniminium salts 6 - a series of new N,N-dialkyl derivatives of 2-amino-5-thiophenecarboxylates 10 has been prepared and analytically and spectroscopically characterized.
Heyde, Cornelia,Zug, Ines,Hartmann, Horst
p. 3273 - 3278
(2007/10/03)

(N,N-Dialkylaminomethyl) acetates as aminomethylating reagents
(N,N-Diethylaminomethyl) acetate is a thermally labile compound which decomposes into N,N-diethylacetamide and formaldehyde at attempted distillation. When dissolved in aprotic polar solvent (acetic anhydride) it apparently exists as a solvent-separated ion pair of the corresponding imonium-carbenium cation and acetate anion. In anhydrous acetic acid diethylaminomethyl acetate dissociates to form free (solvated) immonium-carbenium ion which is highly active in Mannich reaction.
Kachurin,Zaraiskii,Velichko,Zaraiskaya,Matvienko
p. 1117 - 1120
(2007/10/03)

Chlorothioketene, the ultimate reactive intermediate formed by cysteine,conjugate β-lyase-mediated cleavage of the trichloroethene metabolite S-(1,2-dichlorovinyl)-L-cysteine, forms cytosine adducts in organic solvents, but not in aqueous solution
Chlorothioketene has been suggested as a reactive intermediate formed by the cysteine conjugate β-lyase-mediated cleavage of S-(1,2-dichlorovinyl)- L-cysteine, a minor metabolite of trichloroethene. Halothioketenes are highly reactive, and their intermediate formation may be confirmed by reactions such as cycloadditions and thioacylations of nucleophiles. A precursor of chlorothioketene, S-(1,2-dichlorovinyl)thioacetate, is readily accessible by the reaction of dichloroethyne with thioacetic acid. In presence of base, S- (1,2-dichlorovinyl)thioacetate is cleaved to chlorothioketene. Chlorothioketene is not stable at room temperature and was characterized after transformation to stable products by reaction with compounds such as cyclopentadiene, N,N-diethylamine, and ethanol. In organic solvents, the cleavage of S-(1,2-dichlorovinyl)thioacetate in the presence of cytosine results in N4-acetylcytosine, N4-(chlorothioacetyl)cytosine; and small amounts of 3-(N4-thioacetyl)cytosine. No reaction products were seen with guanosine, adenosine, and thymidine under identical conditions. When cytosine was reacted with S-(1,2-dichlorovinyl)thioacetate in aqueous solutions, only N4-acetylcytosine was formed. N4-(Chlorothioacetyl)cytosine and 3-(N4- thioacetyl)cytosine were not detected even when using a very sensitive method, derivatization with pentafluorobenzyl bromide and electron capture mass spectrometry with a detection limit of 50 fmol/μL of injection volume. Aqueous solutions of DNA cleave S-(1,2-dichlorovinyl)thioacetate to give N4- acetyldeoxycytidine in DNA, but chlorothioketene adducts of deoxynucleosides were also not detected in these experiments. These results confirm the electrophilic reactivity of chlorothioketene toward nucleophilic groups of DNA constituents in inert solvents but also demonstrate that the formation of DNA adducts under physiological conditions likely is not efficient. Therefore, DNA adducts may not represent useful biomarkers of exposure and biochemical effects for trichloroethene.
Voelkel, Wolfgang,Dekant, Wolfgang
p. 1082 - 1088
(2007/10/03)

Chemistry of diamino-ligated methylpalladium(II) alkoxides and aryloxides (Part II): Methoxide formation and carbonylation reactions
Reaction of N-ligated methylpalladium(II) alkoxide and aryloxide complexes [Pd(Me)(OR)(N ～ N)] (R = Ph, CH(CF3)2; N ～ N = tmeda (N,N,N′,N′-tetramethylethylenediamine) or bpy (2,2′-bipyridyl)) with carbon monoxide produces the corresponding methylesters in high yields. The insertion takes place either into the Pd-Me bond (aryloxide complexes) or into the Pd-OR bond (alkoxide complexes). Methylpalladium(II) methoxide complexes [Pd(Me)(OMe)(N ～ N)] (N ～ N = tmeda, bpy) have been generated in situ by aryloxide- or alkoxide-methanol exchange reactions for which the equilibrium constants have been determined. The bpy-ligated methylpalladium methoxide complex undergoes insertion of CO producing either a methylpalladium methoxycarbonyl complex [Pd(Me)(CO2Me)(bpy)] (at -60°C) or an acylpalladium methoxycarbonyl complex [Pd(COMe)(CO2Me)(bpy)] (at -25°C); both carbonylated species could be isolated and characterized at low temperature.
Kapteijn, Gerardus M.,Dervisi, Athanasia,Verhoef, Michel J.,Van Den Broek, M.A. Frederik H.,Grove, David M.,Van Koten, Gerard
p. 123 - 131
(2007/10/03)

Phosphorylated and silylated derivatives of alfa-mercaptocarbonyl compounds
The phosphorylation and silylation of α-mercaptocarbonyl ccmpounds have been investigated. Novel different cyclic and linear silicon(phosphorus) containing derivatives have been obtained.
Pudovik, Michael,Burilov, Alexander,Cherepashkin, Dmitry,Nikolaeva, Irina
p. 561 - 564
(2007/10/03)

Reactions of acyl nitroso compounds with amines: Production of nitroxyl (HNO) with the preparation of amides
Oxidation of hydroxamic acids in the presence of amines generates nitrous oxide (N2O) and the corresponding amide. The identification of N2O suggests the intermediacy of nitroxyl (HNO). Retro-Diels Alder dissociation of cyclopentadiene-acyl nitroso compound cycloadducts releases N2O with amide formation.
Atkinson, Robert N.,Storey, Bernadette M.,King, S. Bruce
p. 9287 - 9290
(2007/10/03)

Cyclic imidate salts in acyclic stereochemistry: Diastereoselective syn-epoxidation of 2-alkyl-4-enamides to epoxyamides
Reaction of 2-alkyl-4-enamides with I+ and aqueous sodium bicarbonate results in the diastereoselective formation of the corresponding iodohydrins with essentially no iodolactone by-product. The reaction appears to proceed through a cyclic imidate type intermediate. This methodology has been successfully employed for the synthesis of the epoxide intermediate of the orally active HIV-1 protease inhibitor MK-639 (indinavir sulfate).
Maligres,Weissman,Upadhyay,Cianciosi,Reamer,Purick,Sager,Rossen,Eng,Askin,Volante,Reider
p. 3327 - 3338
(2007/10/03)

Aluminum Chloride-Promoted Transamidation Reactions
Aluminum chloride-amine complexes promote transamidation reactions of primary, secondary, and tertiary amides.Combining this method with the known activating effect of an electron-withdrawing group on the amide nitrogen allows transamidation reactions with hindered and aromatic amines.
Bon, Eric,Bigg, Dennis C. H.,Bertrand, Guy
p. 4035 - 4036
(2007/10/02)

Nucleophilic Attack vs General Base Assisted Hydrolysis in the Reactions of Acetic Anhydride with Primary and Secondary Amines. pH-Yield Studies in the Recognition and Assessement of the Nucleophilic and General Base Reactions
The reaction of a set of primary and secondary amines with acetic anhydride in water at 25 deg C gave variable yields of the N-substituted acetamide in seven of the eight amines studied.The yield of the amide as a function of pH revealed the incursion in the most cases of a general base assisted hydrolysis of the acetic anhydride by the amine.From the pKa's of the amines and kw and kOH for acetic anhydride (the specific rates for the reaction of the anhydride with water and hydroxide, respectively), both kDN (for the formation of acetamides) and kGB (for the general base assisted hydrolysis) may be readily evaluated by fitting the pH-yield-data to pH-yield or pH-product ratio profiles.The reactions of ethyl chloroformate with aniline and benzylamine in water also showed the presence of the general base assisted reaction.It is concluded that (a) pH-yield data provide a new way of showing the existence of general base assisted hydrolysis in the presence of a direct nucleophilic displacement reaction, (b) the general base promoted reaction is sufficiently prevalent that it would be prudent to check specifically for its presence in any investigation of mechanisms of acyl transfer in water, and (c) until the extent of general base promoted hydrolysis can be predicted adequately, the possibility of such a reaction makes it difficult to predict yields of the products of the direct attack, and hence just how suitable a medium water may be for a particular preparative acyl transfer reaction.
King, James F.,Guo, Zhen Rong,Klassen, Darryl F.
p. 1095 - 1101
(2007/10/02)

Aminolysis of N-Acylpyrazoles
1-Acylpyrazoles reacted with amines having a tiny substituted to afford the corresponding amides.The aminolysis with bulky amines was controlled to be retarded by the steric factors.Due to this steric interaction, the stereoselective aminolysis was observed.This selectivity of aminolysis should increase the utility of pyrazoles as auxiliary compounds in the synthetic loop.
Kashima, Choji,Fukuchi, Iwao,Takahashi, Katsumi,Hosomi, Akira
p. 1407 - 1412
(2007/10/02)

REACTIONS OF PHOSPHORUS(III) ESTERS, THIO ESTERS, AND AMINO ESTERS WITH ACYL HALIDES
The courses of the reactions of phosphorodiamidous and phosphorothious esters with acyl halides are determined mainly by the properties of the intermediate quasi-phosphonium compound.The formation in these reactions of both Arbuzov-reaction products and replacement products can be explained by a general scheme that includes the formation of a P-acylated intermediate.
Sal'keeva, L. K.,Usmanova, L. N.,Gazizov, T. Kh.
p. 269 - 273
(2007/10/02)