- One-step synthesis of dicarboxamides through Pd-catalysed aminocarbonylation with diamines as N-nucleophiles
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An efficient one-step synthetic strategy was used to prepare a set of dicarboxamides through palladium-catalysed aminocarbonylation of iodoalkenyl and iodoaryl compounds, with use of various alkyl- and aryldiamines as N-nucleophiles. The isolated yields of the dicarboxamides depended significantly on the iodo substrate and diamine structures, as well as on the reaction conditions, the best one (ca. 70%) being achieved with 1-iodocyclohexene as substrate and 1,4-diaminobutane as nucleophile, at 100°C and 30 bar of CO. When iodobenzene was used as model aryl halide, the highest yield of the target dibenzamides (ca. 65%) was obtained with 1,4-diaminobenzene as coupling amine, at 100°C and 10 bar of CO. Preliminary studies on their in vitro cytotoxicity against human lung carcinoma A549 cells showed N,N′(butane-1,4-diyl)dibenzamide and androst-16-ene-based dicarboxamides to be the most efficient cytotoxic agents, with IC50 values of approximately 40 μM.
- Carrilho, Rui M.B.,Almeida, Ana R.,Kiss, Mercédesz,Kollár, László,Skoda-F?ldes, Rita,D?browski, Janusz M.,Moreno, Maria José S.M.,Pereira, Mariette M.
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- Microwave-assisted catalytic method for a green synthesis of amides directly from amines and carboxylic acids
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Amide bonds are among the most interesting and abundant molecules of life and products of the chemical pharmaceutical industry. In this work, we describe a method of the direct synthesis of amides from carboxylic acids and amines under solvent-free conditions using minute quantities of ceric ammonium nitrate (CAN) as a catalyst. The reactions are carried out in an open microwave reactor and allow the corresponding amides to be obtained in a fast and effective manner when compared to other procedures of the direct synthesis of amides from acids and amines reported so far in the literature. The amide product isolation procedure is simple, environmentally friendly, and is performed with no need for chromatographic purification of secondary amides due to high yields. In this report, primary amines were used in most examples. However, the developed procedure seems to be applicable for secondary amines as well. The methodology produces a limited amount of wastes, and a catalyst can be easily separated. This highly efficient, robust, rapid, solvent-free, and additional reagent-free method provides a major advancement in the development of an ideal green protocol for amide bond formation.
- Kolanowski, Jacek L.,Markiewicz, Wojciech T.,Zarecki, Adam P.
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supporting information
(2020/04/23)
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- Anodic oxidation of bisamides from diaminoalkanes by constant current electrolysis
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In general, bisamides derived from diamines and involving 3 and 4 methylene groups as spacers between the two amide functionalities behave similar to monoamides upon anodic oxidation in methanol/LiClO4 because both types undergo majorly mono- and dimethoxylations at the α-position to the N atom. However, in cases where the spacer contains two methylene groups only the anodic process leads mostly to CH2-CH2 bond cleavage to afford products of type RCONHCH2OCH3. Moreover, upon replacing LiClO4 with Et4NBF4 an additional fragmentation type of product was generated from the latter amides, namely RCONHCHO. Also, the anodic process was found to be more efficient with C felt as the anode, and in a mixture of 1:1 methanol/acetonitrile co-solvents.
- Golub, Tatiana,Becker, James Y.
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p. 861 - 868
(2018/04/30)
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- N-Acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides: Highly selective and efficient reagents for acylation of amines in water
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A variety of N-acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides (1a-e) were synthesized in one pot from 4-chloroaniline under solvent-free conditions and have been developed as chemoselective N-acylation reagents. Selective protection of primary amines in the presence of secondary amines, acylation of aliphatic amines in the presence of aryl amines, and monofunctionalization of primary-secondary diamines as well as selective N-acylation of amino alcohols using these reagents are described. All of the acylation reactions were carried out in water as a green solvent. High stability and easy preparation of these acylating reagents are other advantages of this method.
- Ebrahimi, Sara,Saiadi, Safoura,Dakhilpour, Simin,Mirsattari, Seyed Nezamoddin,Massah, Ahmad Reza
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- CDI-mediated monoacylation of symmetrical diamines and selective acylation of primary amines of unsymmetrical diamines
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A highly efficient and green protocol for monoacylation of symmetrical diamines and chemoselective acylation of primary amines of unsymmetrical diamines has been developed.
- Verma, Sanjeev K.,Ghorpade, Ramarao,Pratap, Ajay,Kaushik
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experimental part
p. 326 - 329
(2012/04/10)
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- Efficient and continuous monoacylation with superior selectivity of symmetrical diamines in microreactors
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Efficient and continuous monoacylation of symmetrical diamines performed in microreactors yielded superior selectivity to that predicted by statistical considerations. It is highly valuable that the kinetically controlled product in high yields was achieved without any special catalyst at ambient temperature.
- Maurya, Ram Awatar,Hoang, Phan Huy,Kim, Dong-Pyo
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scheme or table
p. 65 - 68
(2012/03/26)
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- Inclusion compound of β-cyclodextrin with binuclear guests containing residues of some pharmocologically important aromatic monocarboxylic acids
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Stable monomeric and dimeric inclusion compounds of β-cyclodextrin with binuclear guests containing the residues of some pharmacologically important aromatic monocarboxylic acids were obtained. Pleiades Publishing, Ltd., 2011.
- Grachev,Charaev,Kurochkina,Batalova,Soboleva,Vasyanina,Nifant'ev
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experimental part
p. 2129 - 2135
(2012/03/12)
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- Imidazole-catalyzed monoacylation of symmetrical diamines
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Figure Presented. An imidazole-catalyzed protocol for monoacylation of symmetrical diamines has been developed. The protocol gave selective monoacylation of aliphatic (cyclic and acyclic) primary and secondary diamines. In the reaction, imidazole acts as both catalyst and a leaving group. Different monoacylated piperazines and other diamines were synthesized at room temperature in an ethanol/water solvent system.
- Verma, Sanjeev K.,Acharya,Kaushik
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supporting information; experimental part
p. 4232 - 4235
(2010/11/04)
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- Selective Monoacylation of Symmetrical Diamines via Prior Complexation with Boron
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(Equation presented) Pretreatment of a symmetrical primary or secondary diamine with 9-BBN prior to the addition of an acyl chloride significantly suppressed undesired diacylation, and the product of monoacylation predominated. The reactive preference is interpreted as the result of a selective deactivation of one nitrogen atom of the diamine by 9-BBN.
- Zhang, Zhongxing,Yin, Zhiwei,Meanwell, Nicholas A.,Kadow, John F.,Wang, Tao
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p. 3399 - 3402
(2007/10/03)
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- Aziridines. 76: Neglected aspects of anthracenide (anthracenidyl) chemistry - Reactions with two N-benzoylaziridines
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Reaction of anthracenide A.- with N-benzoylaziridines 1a,b forms charged radicals 3a,b by single electron transfer and homolytic ring opening. Reactions follow that are known or expected as e.g. coupling with position 9 of A.- forming dihydroanthracene anions 9a,b that yield amidoethylated dihydroanthracenes 10a,b, or react with 1a,b giving finally 9,10-bis-amidoethylated dihydroanthracenes 11a,b. Results depend on experimental conditions and on the counter ions Na+ or Li+. Coupling is not regiospecific: contributions by positions 2 and 1 reach 29% or 4%, respectively, of total coupling with the primary radical 3a; much higher contributions are possible with Li. Product 21s (probably 3,3′-disubstituted tetrahydrobianthryl) may arise by hydrogen detachment from the first intermediate (29) of coupling with position 2 and dimerization of the formed 2-substituted A.- (30). Coupling products may be fully aromatized or may be hydroxylated in one of the benzylic positions. With counter ion Li+ a non-SET reaction of 1a with the dimer of A.- is indicated by the isolation of 9-benzoyl-dihydroanthracene 15 and by 19% yield of 16a (aromatized 10a). Reaction of 3b with anthracene is indicated by 10,10′-disubstituted tetrahydrobianthryl 37. Wiley-VCH Verlag GmbH, 2000.
- Lin, Pen-Yuan,Weiss, Rainer,Werry, Juergen,Falkenstein, Reinhard,Stamm, Helmut
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p. 153 - 161
(2007/10/03)
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- Reactions of N-acylaziridines with sodium metal and sodium naphthalenide. Elimination of olefines
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Reactions of N-acylaziridines 1a-g (N-benzoyl except 1d) with sodium or naphthalenide N.- in THF provide a variety of products that usually arise via the aziridino ketyls 2. Homolytic ring opening of 2 generates the amidatoalkyl radicals 3. Only with a very short reaction time were small amounts of benzil or benzoylnaphthalenes obtained indicating a reversible trapping of 2 by dimerization or coupling with N.-. Homolysis of 2 produced always the more stable 3 apart from reactions of monomethylaziridines 1c,d where the primary radical i-3c,d is kinetically favoured. The amides R1CONHCHR4CHR2R3 (9, isopropylamides i-9c,d from 1c,d) were usually the main products. 9 arise from 3 either by H atom abstraction from THF (probably in sodium metal runs) or by reduction of 3 to carbanions 5 that abstract a proton from THF (N.- runs). Addition of 5a (R2-4 = H) to 1a gives finally the ketone 8a. Self reaction of primary radical 3a is dimerization. Self reaction of tertiary or secondary radicals is disproportionation when an allylamide arises. This isomerizes to an enamide unless it is conjugated. R2R3C=CHR4 and R1CONH2 arise (probably) always. The mechanism, possibly a cyclic process of anion 6, is not clear. Johann Ambrosius Barth 1996.
- Lin, Pen-Yuan,Bellos, Konstantinos,Werry, Juergen,Assithianakis, Petros,Weiss, Rainer,Mall, Thomas,Bentz, Gunther,Stamm, Helmut
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p. 270 - 278
(2007/10/03)
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- A Simple and Economic Synthesis of Monoacylated Alkanediamines by Thermal Transamidation
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N-(ω-Aminoalkyl)amides 2 are easily synthesized by heating mixtures of excess α,ω-alkanediamines 1 and primary amides to temperatures between 150 deg C and 200 deg C, at which thermal transamidation occurs.Under the reaction conditions ammonia is released, and 2 is in equilibrium with the alkanediamine 1 and the α,ω-bis(acylamino)alkane 3.Thus, thermal transamidation is a practicable way to overcome the problem of diacylation which appears as an often recognized problem even in the latest literature.
- Zaragoza-Doerwald, Florencio,Kiedrowski, Guenter von
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p. 917 - 918
(2007/10/02)
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- AMINOSILANES IN ORGANIC SYNTHESIS: PREPARATION OF N,N'-DISUBSTITUTED PUTRESCEINE DERIVATIVES
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Polyfunctional disubstituted putresceines are prepared from the corresponding aminosilane and electrophiles, without or in presence of Lewis acids.
- Taddei, Maurizio,Tempesti, Federica
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p. 1019 - 1024
(2007/10/02)
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- Reagents for the Stepwise Functionalization of Spermidine, Homospermidine, and Bis(3-aminopropyl)amine
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A high-yield synthesis of reagents for the selective mono-, di-, or tri-N-functionalization of the polyamines spermidine, homospermidine, and norspermidine is described.The polyamine protecting groups utilized in these reagents are each easily removable u
- Bergeron, Raymond J.,Garlich, Joseph R.,Stolowich, Neal J.
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p. 2997 - 3001
(2007/10/02)
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- ROTATION ISOMERISM OF N,N'-DIMETHYL-α,ω-BIS(BENZOYLAMINO)ALKANES
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The kow-temperature 1H n.m.r. spectra of PhCON(Me)(CH2)nN(Me)COPh show four signals for ht e methyl groups when n 3, which are atributable to the presence of three rotational isomers.Only one isomer was detectable over a wide temperature range when n
- Cirrincione, Girolamo,Hinz, Werner,Jones, R. Alan
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p. 1089 - 1092
(2007/10/02)
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- Electron Attachment to N-Benzoylaziridines followed by C-N Homolysis of the Aziridine Ring
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Reactions of N-benzoylaziridines with strong electron sources provide direct evidence for the formation of ketyls (2) and radicals (3), both of which are postulated intermediates in the single electron transfer mechanism of nucleophilic ring opening of activated aziridines.
- Stamm, Helmut,Assithianakis, Petros,Weiss, Rainer,Bentz, Gunther,Buchholz, Berthold
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p. 753 - 754
(2007/10/02)
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- Dynamic Protection of Amines using 18-Crown-6
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The regioselectivity of diamine monoacylation has been controlled by selective complexation with 18-crown-6 and a proton source.
- Barrett, Anthony G. M.,Lana, J. Carlos A.,Tograie, Shahrzad
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p. 300 - 301
(2007/10/02)
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- Process for the production of amines
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Amines and substituted ureas are produced by reaction of carboxamides with hypochlorites in the presence of bromine, iodine, polymerization inhibitors, and/or haloamides and excess alkali metal hydroxide with or without the addition of primary or secondary amines. The products are perfumes and starting materials for the production of dyes, plant protection agents and perfumes.
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