- Ethylene-Bridged Tetradentate Bis(amidines): Supramolecular Assemblies through Hydrogen Bonding and Photoluminescence upon Deprotonation
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Sterically crowded tetradentate bis(amidines) encapsulate their N–H functionalities or unveil them to undergo inter- and intramolecular hydrogen bonding both in solid state and solution, depending on a subtle interplay between the amidine backbone substituents. X-ray crystallography reveals for four distinct ZZ(syn/syn) and EE(syn/syn) bis(amidines) that bulky terminal N-Mes groups in combination with N2C-tBu or N2C-Ph substituents result in steric protection of the N–H moieties, whereas less crowded terminal p-tBu(C6H4) groups either show encapsulation (N2C-tBu) or hydrogen bonding (N2C-Ph), the latter resulting in a bis(amidine) dimer formed by inter- and intramolecular hydrogen bonds. Moreover, a supramolecular solvent adduct consisting of one bis(amidine) and four ethanol molecules is presented. DFT calculations show that both the dimerization and formation of the solvent adduct is associated with a significant energy gain (dimerization: ΔE = –27.7 kcal/mol; formation of ethanol adduct: ΔE = –64.3 kcal/mol). The corresponding four Li bis(amidinates) are weakly blue to green-emissive in THF solution. Overall, a new series of highly flexible bis(amidines) has been examined.
- Calderón-Díaz, Alvaro,Arras, Janet,Miller, Ethan T.,Bhuvanesh, Nattamai,McMillen, Colin D.,Stollenz, Michael
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- Synthesis, characterization, in vitro biological and molecular docking evaluation of N,N'-(ethane-1,2-diyl)bis(benzamides)
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The present research describes the synthesis, characterization, in vitro biological and docking evaluation of N,N'-(ethane-1,2-diyl)bis(benzamides) (3a-3j). Consequently, in in vitro hRBCs hemolysis assay, only the bis-amide (3d) induced 52.4% hemolysis at higher concentration (1000?μg/mL) that decreased drastically with concentration (250?μg/mL) to 27.9% (CC50 = 400.41). Similarly, the tested bis-amide (3j) was found to be the least toxic with 7.8% hemolysis at higher concentration (1000?μg/mL) that gradually decreases to 6.1% (CC50 = 19,347.83) at lower concentration (250?μg/mL). Accordingly, the tested bis-amides were found to be highly biocompatible against hRBCs at higher concentrations with much higher CC50 values (> 1000?μg/mL). The biocompatible bis-amides (3a-3j) were subjected to in vitro DNA ladder assay to analyze their apoptotic potential. The results obtained suggest the tested bis-amides (3a-3j) are highly degradative toward DNA causing the appearance of more than one bands or complete degradation of DNA except (3a), (3c), (3i) and (3?g). Moreover, the synthesized bis-amides (3a-3j) were tested in in vitro antileishmanial assay to unveil their leishmaniacidal potential. The results obtained clearly indicated that some of the tested bis-amides displayed good dose dependent response. The tested bis-amides were highly active at higher concentration (1000?μg/mL) against the leishmanial promastigotes and their % inhibitory potential decreased drastically with concentration (250?μg/mL). Consequently, at higher concentration (1000?μg/mL), the bis-amide (3f) caused 85% inhibition and was ranked as the most effective leishmaniacidal bis-amides followed by the bis-amide (3?g) with 73.54% inhibition of leishmanial promastigotes. However, in terms of their IC50 values, the best leishmaniacidal potential was displayed by the bis-amide (3f) followed by (3b), (3j) and (3?g) with IC50 values increasing in the order of 633.16, 680.22, 680.22 and 712.93?μg/mL, respectively. Molecular docking studies revealed that bis-amides having electron-donating groups showed good binding potential against antileishmanial target. Graphic abstract: [Figure not available: see fulltext.].
- Aziz, Hamid,Saeed, Aamer,Jabeen, Farukh,Ullah, Nazif,Rehman, Ashfaq Ur
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p. 2425 - 2436
(2021/03/03)
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- One-Pot Anodic Conversion of Symmetrical Bisamides of Ethylene Diamine to Unsymmetrical gem-Bisamides of Methylene Diamine
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Symmetrical bisamides of ethylene diamine of type ArCONHCH2CH2NHCOAr undergo anodic C-C bond cleavage in acetonitrile-LiClO4 under controlled-potential electrolysis. The electrogenerated carbocation intermediates react with the solvent acetonitrile to afford unsymmetrical gem-bisamides of type ArCONHCH2NHCOMe in a one-pot reaction. The yields of the latter products are moderate (up to 60%). Other minor products involve two symmetrical gem-bisamides of type ArCONHCH2NHCOAr and MeCONHCH2NHCOMe and fragmentation products (e.g., ArCONHCHO, ArCONH2, and ArCN).
- Golub, Tatiana,Dou, Gui-Yuan,Zeng, Cheng-Chu,Becker, James Y.
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supporting information
p. 7961 - 7964
(2019/10/11)
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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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- ANTIMICROBIAL COMPOUNDS
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The invention provides compounds for use in treating microbial infection in an animal. Example compounds include Pyridin-3-ylmethyl (4-((2-aminophenyl)- carbamoyl)benzyl)carbamate ("Entinostat"). The compounds can act via induction of the innate antimicrobial peptide defense system, and stimulation of autophagy.
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Page/Page column 41; 42
(2015/05/19)
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- Structure-property relationships of aromatic polyamides and polythioamides: comparative consideration with those of analogous polyesters, polythioesters and polydithioesters
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Conformational characteristics and configurational properties of aromatic polyamides and polythioamides, analogues of common aromatic polyesters such as poly(ethylene terephthalate) and poly(trimethylene terephthalate), have been investigated via NMR experiments and molecular orbital calculations on model compounds, and the refined rotational isomeric state calculations for the polymers. The polyamides and polythioamides were actually synthesized and characterized in terms of solubility, molecular weight, crystallinity, thermal transition, and thermal stability. Herein, the experimental results are discussed mainly from the viewpoint of the conformational characteristics and compared with those obtained from analogous aromatic polyesters, polythioesters, and polydithioesters to reveal the effects of the heteroatoms O, S, and NH included in the backbone on the polymer structures and properties.
- Nagasawa, Masayuki,Ishii, Tatsuya,Abe, Daisuke,Sasanuma, Yuji
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p. 96611 - 96622
(2015/11/24)
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- 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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supporting information
p. 1840 - 1847
(2015/05/27)
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- An efficient, green and scale-up synthesis of amides from esters and amines catalyzed by Ru-MACHO catalyst under mild conditions
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An efficient, green and scale-up synthesis of amides from esters and amines has been developed using Ru-MACHO as a readily available catalyst. A diverse range of amides were obtained in moderate to excellent yields (55-98%). Furthermore, when the scale of the amidation reaction was increased to 240.0 mmol, the desired amide still could be obtained in high yield (48.2 g of N-benzylbenzamide, 95%).
- Han, Qian,Xiong, Xingquan,Li, Sizhong
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- Bisamides as ligands in Suzuki coupling reactions catalyzed by palladium
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This protocol uses palladium chloride and bisamides as ligands for Suzuki cross-coupling reactions, in mild (25 for 2 h) aerobic conditions. This study was efficient for arylboronic acids and/or aryl bromides with activating or deactivating substituents in the ring with high yields (81-95%).
- Da Costa, Daniel P.,Nobre, Sabrina M.
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p. 4582 - 4584
(2013/08/23)
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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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- Preparation of (Z)-1-fluoro-1-alkenyl carboxylates, carbonates and carbamates through chromium mediated transformation of dibromofluoromethylcarbinyl esters and the reactivity as double acyl group donors
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CrCl2/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters including carboxylates, carbonates and carbamates provided 1-fluoro-1-alkenyl esters via [2,3]-sigmatropic rearrangement of ester group. Reaction proceeded by using CrCl2/Mn system under mild conditions (in THF at room temperature) to give 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.
- Saito, Akio,Tojo, Manabu,Yanai, Hikaru,Wada, Fukiko,Nakagawa, Muga,Okada, Midori,Sato, Azusa,Okatani, Rieko,Taguchi, Takeo
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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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- 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
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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
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experimental part
p. 255 - 259
(2010/09/03)
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- Mild and useful method for n-acylation of amines
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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
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experimental part
p. 2694 - 2701
(2009/12/06)
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- Competitive amide hydrolysis in mono- and diformylated ethylenediamines
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Alkaline hydrolysis of formylated ethylenediamines of the general structure R1-N(X)-CH2CH2-N(CHO)-R2 (R 1, R2 = H, benzyl, benzoyl; X = H, CHO) was studied in mild conditions. Breaking of the N-C amide bonds took place easily for HN-CHO or (benzoyl)N-CHO, hardly for (benzyl)N-CHO, and did not occur at all for N-COPh. Generally speaking, the various amide bonds underwent hydrolysis according to the following qualitative order of increasing reactivity: PhCO-N(H or alkyl)(alkyl or CHO) ?HCO-N(alkyl)2 1H- and 13C-NMR features of all compounds of interest are presented and discussed. Hindered rotation about the C-N amide bond(s) caused E/Z isomerism in mono- and diformylated derivatives.
- Petride, Horia,Costan, Oana,Florea, Cristina,Udrea, Silvia
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p. 245 - 253
(2007/10/03)
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- The application of N,N′dibromo-N,N′-1,2-ethanediyl bis(P-toluenesulfonamide) as a powerful reagent for conversion of carboxylic acids into esters and amides with triphenylphosphine
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In the presence of equivalent amounts of triphenylphenylphosphine and N,N′-dibromo-N,N′-1,2-ethanediylbis(p-toluenesulphonamide) ester and amide compounds can be generated in high yields from the corresponding carboxylic acid and alcohols or amines.
- Khazaei, Ardeshir,Mallakpour, Shadpour,Zolfigol, Mohammad Ali,Ghorbani-Vaghei, Ramin,Kolvari, Eskandar
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p. 1715 - 1721
(2007/10/03)
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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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- Synthesis of chiral and C2-symmetric iron(II) and cobalt(II) complexes bearing a new tetradentate amine ligand system
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A synthesis for the new tetrapodal ligands -1,2-ethylene diamine (L1) (3a) and -1,2-ethylene diamine (L2) (3b) and for the related octahedral complexes (L1,2)FeCl2 (6a and 6b) and (L1,2)CoCl2 (7a and 7b) is given.The solid state structures of 3b and 6a have been determined.Three different modes are possible for a tetradentane coordination of L1,2 to FeCl2 or CoCl2.In 6a the ligand adopts a single chiral geometry around the Cl-Fe-Cl plane.Keywords: Iron; Cobalt; Tetradentane amine ligand; Solid state structures; Chirality
- Rieger, Bernhard,Abu-Surrah, Adnan S.,Fawzi, Riad,Steiman, Manfred
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- N,N'-Doacylated imidazolidines and hexahydropyrimidines
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A method for the preparation of N-monoacyl imidazolidines and hexahydropyrimidines (as hydrochlorides) by interaction of monoacylated derivatives of ethylenediamine and trimethylethylenediamine with chloromethyl methyl ether was developed.Also a method for the preparation of N,N'-diacylimidazolidines and hexahydropyrimidines either by acylation of their monoacyl derivatives or by reaction of the corresponding N,N'-diacyl alkylenediamine derivatives with dimethoxymethane, diacetoxymethane, 1,3,5-trioxane or chloromethyl methyl ether was designed. - Key words: N-mono- and N,N'-diacylated imidazolidines, N-mono- and N,N'-diacylated hexahydropyrimidines, N,N'-diacylated alkylenediamines, acylation, methylation, cyclization.
- Luk'yanov, O. A.,Pokhvisneva, G. V.,Ternikova, T. V.
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p. 1376 - 1380
(2007/10/02)
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- THE USE OF 2,2,2-TRICHLORO-1-ARYLETHANONES AS BENZOYLATING AGENTS
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The preparation of several amides and hydrazides from the reaction of the title compounds with different nitrogen nucleophiles is shown to be a general high-yield conversion of synthetic utility.
- Rebelo, Ricardo Andrade,Rezende, Marcos Caroli,Nome, Faruk,Zucco, Cesar
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p. 1741 - 1748
(2007/10/02)
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- Synthesis and Reactions of an Open-Chain bis-Reissert Salt Analog
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An open-chain bis-Reissert salt analog 5 has been synthesized and fully chacterized.The reaction of the salt analog with methyl acrylate yields the pyrrole 7 which exists in solution in the azafulvene form 7a.The reaction of the salt analog with dimethylacetylene dicarboxylate (DMAD) affords the bispyrrole 9.
- Iyer, Radhakrishnan P.,Ratnam, Rakesh K.,Kulkarni, Subodh P.,Sonaseth, Mariam S.
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p. 991 - 997
(2007/10/02)
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- NOVEL UNSYMMETRICAL N,N-BIS(METHYLENE)BIPHOSPHONIC ACIDS OF α,ω-DIAMINES. PREPARATION AND CHARACTERIZATION OF BIS(METHYLENE)>-BIPHOSPHONIC ACID AND BIS(METHYLENE)>-BIPHOSPHONIC ACID
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Reaction of ethylenediamine with phosphorous acid and formaldehyde in molar ratio 1:2:2 gives bis(methylene)>biphosphonic acid (2a) as the major product.Similarly, reaction of hexamethylenediamine with phosphorous acid and formaldehyde in molar ratio 1:2:2 yields bis(methylene)>biphosphonic acid (2b) which is isolated either as bis(methylene>biphosphonic acid (3b) or as bis(methylene)>biphosphonic acid (4b).Removal of the carbobenzoxy group with HBr 3b or the benzoyl group with HCl from 4b gives pure bis(methylene)>biphosphonic acid (2b).All compounds were characterized by 13C NMR, 31P NMR and elemental analysis.
- Redmore, Derek,Dhawan, Balram
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p. 233 - 238
(2007/10/02)
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- SYNTHESIS OF ACYLATED (2'-HYDROXYETHYL)AMINO- AND (2'-AMINOETHYL)AMINO-1,3,5-TRIAZINES
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The acylation of (2'-hydroxyethyl)amino-1,3,5-triazines with chloroacetyl chloride with subsequent reaction of the resulting (2'-chloroacetoxyethyl)aminotriazines with potassium thiocyanate is described.Acylated derivatives of substituted (2'-aminoethyl)aminotriazines were obtained by the reaction of the chlorotriazines with monoacylethylenediamines.
- Sapozhnikova, Zh. Z.,Prokof'eva, A. F.,Koroleva, T. I.,Mel'nikov, N. N.
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p. 205 - 208
(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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