- Nickel-Catalyzed Reductive Cross-Coupling of N-Acyl and N-Sulfonyl Benzotriazoles with Diverse Nitro Compounds: Rapid Access to Amides and Sulfonamides
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Herein we report a Ni-catalyzed reductive transamidation of conveniently available N-acyl benzotriazoles with alkyl, alkenyl, and aryl nitro compounds, which afforded various amides with good yields and a broad substrate scope. The same catalytic reaction conditions were also applicable for N-sulfonyl benzotriazoles, which could undergo smooth reductive coupling with nitroarenes and nitroalkanes to afford the corresponding sulfonamides.
- Qu, Erdong,Li, Shangzhang,Bai, Jin,Zheng, Yan,Li, Wanfang
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- Metal-free transamidation of benzoylpyrrolidin-2-one and amines under aqueous conditions
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N-Acyl lactam amides, such as benzoylpyrrolidin-2-one, benzoylpiperidin-2-one, and benzoylazepan-2-one reacted with amines in the presence of DTBP and TBAI to afford the transamidated products in good yields. The reactions were conducted under aqueous conditions and good functional group tolerance was achieved. Both aliphatic and aromatic primary amines displayed good activity under metal-free conditions. A radical reaction pathway is proposed.
- Joseph, Devaneyan,Lee, Sunwoo,Park, Myeong Seong
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supporting information
p. 6227 - 6232
(2021/07/28)
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- Chromium-catalyzed ligand-free amidation of esters with anilines
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Amides are important structural motifs in pharmaceutical and agrochemical chemistry because of the intriguing biological active properties. We report here the amidation of commercially available esters with anilines that was promoted by low-cost and air-stable chromium(III) pre-catalyst combined with magnesium, providing access to amides. This reaction occurs without the use of external ligands in a simple operation. Mechanistic studies indicate that a reactive aminated Cr species responsible for the amidation can be considered, which may be formed by reaction of low-valent Cr with aniline followed by reduction with hydrogen evolution.
- Chen, Changpeng,Ling, Liang,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 762 - 766
(2021/04/14)
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- Selective hydrogenation dehalogenation method of ortho-halogenated acylaniline
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The invention discloses a selective hydrogenation dehalogenation method of copper-catalyzed ortho-halogenated acylaniline. The method comprises the following steps: by using ortho-halogenated acylaniline as a starting raw material and copper acetylacetonate/vasicine as a catalyst, adding an organic alkali, reacting in an alcoholic solution at 80-100 DEG C for 12 hours, and regioselectively catalytically hydrogenating ortho-bromine and iodine atoms. The preparation method has the characteristics of simplicity and convenience in operation, wide substrate application range, low cost, high regioselectivity and the like, and has practicability.
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Paragraph 0099-0103
(2021/01/20)
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- Exploration of Cu-catalyzed regioselective hydrodehalogenation of o-haloanilides using EtOH as hydrogen source
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In present work, we have explored a Cu(acac)2/vasicine-catalyzed regioselective hydrodehalogenation methodology of o-haloanilides using EtOH as hydrogen source and solvent. The catalytic system could selectively dehalogenate 2-Br and 2-I, and features regioselective, efficient and functional group tolerance.
- Li, Min-Xin,Li, Mei-Ling,Tang, Yan-Ling,Sun, Yun,Qu, Lu,Huang, Feng,Mao, Ze-Wei
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supporting information
(2021/05/03)
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- Discovery of Potent Inhibitors of Streptococcus mutans Biofilm with Antivirulence Activity
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Dental caries is a bacterial infectious disease characterized by demineralization of the tooth enamel. Treatment of this disease with conventional antibiotics is largely ineffective as the cariogenic bacteria form tenacious biofilms that are resistant to such treatments. The main etiological agent for dental caries is the bacterium Streptococcus mutans. S. mutans readily forms biofilms on the tooth surface and rapidly produces lactic acid from dietary sucrose. Glucosyl transferases (Gtfs) secreted by S. mutans are mainly responsible for the production of exopolysaccharides that are crucial for the biofilm architecture. Thus, inhibiting S. mutans' Gtfs is an effective approach to develop selective biofilm inhibitors that do not affect the growth of oral commensals. Herein, we report a library of 90 analogs of the previously identified lead compound, G43, and exploration of its structure activity relationships (SAR). All compounds were evaluated for the inhibition of S. mutans biofilms and bacterial growth. Selected compounds from this library were further evaluated for enzyme inhibition against Gtfs using a zymogram assay and for growth inhibition against oral commensal bacterial species such as Streptococcus gordonii and Streptococcus sanguinis. This study has led to the discovery of several new biofilm inhibitors with enhanced potency and selectivity. One of the leads, IIIF1, showed marked reduction in buccal, sulcal, and proximal caries scores in a rat model of dental caries.
- Nijampatnam, Bhavitavya,Ahirwar, Parmanand,Pukkanasut, Piyasuda,Womack, Holly,Casals, Luke,Zhang, Hua,Cai, Xia,Michalek, Suzanne M.,Wu, Hui,Velu, Sadanandan E.
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supporting information
p. 48 - 55
(2020/12/21)
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- Efficient Pd-Catalyzed Hydrodehalogenation of o -Haloanilides in Water
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In the present work, we have developed a practical methodology for the hydrodehalogenation of o -haloanilides using PdCl 2at 100 °C under mild conditions in water. The catalytic system could selectively dehalogenate both aryl chloride and aryl bromide and exhibit a broad functional group tolerance.
- Gao, Hui,Li, Minxin,Mao, Zewei,Rao, Gaoxiong,Tang, Yanling
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supporting information
p. 1121 - 1125
(2020/07/03)
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- Nickel/briphos-catalyzed transamidation of unactivated tertiary amides
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The transamidation of tertiary amides was achieved via nickel catalysis in combination with briphos ligands. N-Methyl-N-phenylbenzamide derivatives reacted with primary amines in the presence of NiCl2/briphos L4 to provide the transamidated products in moderate to good yields. Primary aromatic amines delivered higher product yields than aliphatic amines.
- Kim, Hyunwoo,Lee, Sunwoo,Shin, Taeil,Yang, Dahyeon
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supporting information
p. 6053 - 6057
(2020/10/27)
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- Nickel-catalyzed reductive amidation of aryl-triazine ethers
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The reaction of activated phenolic compounds, 2,4,6-triaryloxy-1,3,5-triazine (aryl-triazine ethers), with various isocyanates or carbodiimides in the presence of a nickel pre-catalyst resulted in the synthesis of aryl amides in good to excellent yields.
- Heravi, Majid M.,Panahi, Farhad,Iranpoor, Nasser
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supporting information
p. 1992 - 1995
(2020/02/22)
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- Chromium-Catalyzed Activation of Acyl C-O Bonds with Magnesium for Amidation of Esters with Nitroarenes
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Here, we report a chromium-catalyzed activation of acyl C-O bonds with magnesium for amidation of esters with nitroarenes. Low-cost chromium(III) chloride shows high reactivity in promoting amidation by using magnesium as reductant and chlorotrimethylsilane as additive. It provides a step-economic strategy to the synthesis of centrally important amide motifs using inexpensive and air-stable nitroarenes as amino sources.
- Ling, Liang,Chen, Changpeng,Luo, Meiming,Zeng, Xiaoming
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supporting information
(2019/03/19)
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- Synthesis of Amides by Mild Palladium-Catalyzed Aminocarbonylation of Arylsilanes with Amines Enabled by Copper(II) Fluoride
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A general Pd-catalyzed synthesis of amides by oxidative aminocarbonylation of arylsilanes under mild conditions was accomplished for the first time. The reaction is promoted by a commercially available copper(II) fluoride, which acts as a dual silane activator and mild oxidant, enabling highly efficient aminocarbonylation of versatile arylsilanes at atmospheric CO pressure. The reaction is tolerant of a wide range of arylsilanes and various sensitive halide functional groups as well as a broad scope of amines are compatible with this oxidative process using cheap CO. A significant aspect involves the increased efficiency by the catalyst system. The reaction represents a segue into the powerful Pd-catalyzed oxidative transformations of organosilanes.
- Zhang, Jin,Hou, Yanyan,Ma, Yangmin,Szostak, Michal
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p. 338 - 345
(2019/01/10)
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- Secondary/tertiary amide compound and synthesis method thereof
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The invention discloses a secondary/tertiary amide compound and a synthesis method thereof. The method comprises the following steps: adding arylsilane and an amine compound, a catalyst and an additive to a solvent, introducing CO under a certain pressure, carrying out a carbonylation reaction, and carrying out separation and purification to obtain the secondary/tertiary amide. The method for preparing the secondary/tertiary amide by the carbonylation reaction has the advantages of concision, high efficiency, directness in the reaction, high atom economy, and wide sources and good stability ofa substrate. The reaction system of the invention does not require inert gas protection, and has mild conditions, and the target product is easy to separate and the yield reaches up to 92% under optimized reaction conditions.
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Paragraph 0146; 0147; 0148; 0149
(2019/01/21)
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- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
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The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
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p. 4087 - 4101
(2019/04/30)
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- N-Ethynylation of Anilides Decreases the Double-Bond Character of Amide Bond while Retaining trans-Conformation and Planarity
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Activated amide bonds have been attracting intense attention; however, most of the studied moieties have twisted amide character. To add a new strategy to activate amide bonds while maintaining its planarity, we envisioned the introduction of an alkynyl group on the amide nitrogen to disrupt amide resonance by nN→Csp conjugation. In this context, the conformations and properties of N-ethynyl-substituted aromatic amides were investigated by DFT calculations, crystallography, and NMR spectroscopic analysis. In contrast to the cis conformational preference of N-ethyl- and vinyl-substituted acetanilides, N-ethynyl-substituted acetanilide favors the trans conformation in the crystal and in solution. It also has a decreased double bond character of the C(O)?N bond, without twisting of the amide. N-Ethynyl-substituted acetanilides undergo selective C(O)?N bond or N?C(sp) bond cleavage reactions and have potential applications as activated amides for coupling reactions or easily cleavable tethers.
- Yamasaki, Ryu,Morita, Kento,Iizumi, Hiromi,Ito, Ai,Fukuda, Kazuo,Okamoto, Iwao
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supporting information
p. 10118 - 10122
(2019/07/05)
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- Synthesis of Secondary Amides through the Palladium(II)-Catalyzed Aminocarbonylation of Arylboronic Acids with Amines or Hydrazines and Carbon Dioxide
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A new Pd-catalyzed aminocarbonylation of arylboronic acids with amines or phenylhydrazines has been developed. Various secondary amides were produced from readily available substrates and cheap common metal catalysts in a CO atmosphere (balloon). Remarkably, we presents the first example of aminocarbonylations between arylboronic acids and phenylhydrazines.
- Zhang, Jin,Ma, Yuqiang,Ma, Yangmin
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supporting information
p. 1720 - 1725
(2018/04/24)
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- Quantitative investigation of C-H?π and other intermolecular interactions in a series of crystalline: N -(substituted phenyl)-2-naphthamide derivatives
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In this study, we have investigated the nature and characteristics of different intermolecular interactions present in a series of seven N-(substituted phenyl)-2-naphthamides. The seven structures comprise 2-naphthyl ring systems linked by amide bridges to N-bound phenyl 1, or substituted benzene rings 3-7, or in the case of 2, a cyclohexane ring. A common feature of the crystal packing for all but the o-nitro derivative 7 is the presence of a strong intermolecular N-H?O interaction. In the case of 7, the possibility of such an interaction is obviated by the formation of an intramolecular N-H?O hydrogen bond. An additional feature of the crystal packing for 1-6 is the significant roles that C-H?π contacts play in generating three-dimensional networks. In contrast for 7, the intramolecular N-H?O hydrogen bond precludes the formation of molecular chains but the planar nature of this molecule allows significant π?π stacking interactions to stabilize the packing.
- Shukla, Rahul,Saeed, Aamer,Simpson, Jim,Chopra, Deepak
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p. 5473 - 5491
(2017/09/26)
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- Development of Method for Amide Bond Formation via Metal-Free Aerobic Oxidative Amination of Aldehydes
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The present invention relates to a method for preparing an amide compound by using an aerobic oxidative amination reaction using an oxygen resource as an oxidizer in an organic solvent without metal by using a cyanide as a catalyst. An expensive metal catalyst is not needed to prepare the amide compound of the present invention. Therefore, the amide compound does not have a problem of toxicity caused by remaining metal and has excellent economic efficiency of atoms. Moreover, the amide compound can be used for industries in an easy manner because complicated processes such as a strong acid, low temperatures, and anhydrous conditions are not needed to prepare the amide compound.COPYRIGHT KIPO 2015
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Paragraph 0094; 0120; 0121
(2016/11/17)
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- Formation of Amides from Imines via Cyanide-Mediated Metal-Free Aerobic Oxidation
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A new protocol for the direct formation of amides from imines derived from aromatic aldehydes via metal-free aerobic oxidation in the presence of cyanide is described. This protocol was applicable to various aldimines, and the desired amides were obtained in moderate to good yields. Mechanistic studies suggested that this aerobic oxidative amidation might proceed via the addition of cyanide to imines followed by proton transfer from carbon to nitrogen in the original imines, leading to carbanions of α-amino nitriles, which undergo subsequent oxidation with molecular oxygen in air to provide the desired amide compounds.
- Seo, Hong-Ahn,Cho, Yeon-Ho,Lee, Ye-Sol,Cheon, Cheol-Hong
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p. 11993 - 11998
(2016/01/09)
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- Highly efficient dehydrogenative cross-coupling of aldehydes with amines and alcohols
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A common protocol for the synthesis of amides, esters and α-ketoesters via cross dehydrogenative coupling of aldehydes and amines/alcohols has been developed. The method is applicable to a wide variety of alcohols and amines as well as aliphatic and aromatic aldehydes. Also, the use of acetaldehyde for acetylation and ethyl glyoxalate to access 2-oxo-amino esters is presented for the first time.
- Deshidi, Ramesh,Rizvi, Masood Ahmad,Shah, Bhahwal Ali
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p. 90521 - 90524
(2015/11/11)
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- Copper-Catalyzed N-Benzoylation of Amines via Aerobic C-C Bond Cleavage
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A general copper/air catalytic system for selectively oxidative C-C bond cleavage of 1,2-diarylethan-1-one has been developed, giving aromatic aldehydes and N-benzoylation products of various amines in moderate to excellent yields. This research provides an alternative approach for the N-benzoylation of amine in mild and neutral conditions.
- Fan, Wenyou,Yang, Youqing,Lei, Jianhua,Jiang, Qijian,Zhou, Wang
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p. 8782 - 8789
(2015/09/15)
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- Synthesis of amides through an oxidative amidation of tetrazoles with aldehydes under transition-metal-free conditions
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A simple, inexpensive and efficient one-pot synthesis of amides was achieved in good yields via the direct oxidative amidation of tetrazoles with aldehydes under transition-metal-free conditions.
- Du, Juan,Luo, Kai,Zhang, Xiuli
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p. 54539 - 54546
(2015/01/09)
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- Iron pentacarbonyl in alkoxy- and aminocarbonylation of aromatic halides
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We have identified reaction conditions for a Heck-type carbonylation based on [Fe(CO)5]. Preliminary optimization of alkoxycarbonylation on 2-bromonaphthalene defined functioning composition of the reaction mixture which was then applied on a small set of (hetero)aromatic halides. Respective aminocarbonylation of these halides with different amines, including aniline and benzotriazole, was accomplished with reasonable results.
- Babjak, Matej,Caletková, O?ga,?uri?ová, Diana,Gracza, Tibor
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supporting information
p. 2579 - 2584
(2015/01/09)
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- One-pot mechanosynthesis of aromatic amides and dipeptides from carboxylic acids and amines
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Environmentally friendly one-pot synthesis of amides, bis-amides and dipeptides by mechanochemical carbodiimide-mediated coupling of carboxylic acids and amines is described; high reaction yields and simple aqueous work-up allow for the clean, practical and fast preparation of a variety of compounds containing the amide bond from readily accessible reagents.
- ?trukil, Vjekoslav,Bartolec, Boris,Portada, Tomislav,Dilovi?, Ivica,Halasz, Ivan,Margeti?, Davor
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supporting information
p. 12100 - 12102
(2013/01/16)
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- Synthesis and evaluation of non-basic inhibitors of urokinase-type plasminogen activator (uPA)
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Recent drug discovery programs targeting urokinase plasminogen activator (uPA) have resulted in nonpeptidic inhibitors consisting of amidine or guanidine functional groups attached to aromatic or heteroaromatic scaffolds. There is a general problem of poor oral bioavailability of these charged inhibitors. In this paper, we report the synthesis and evaluation of a series of naphthamide and naphthalene sulfonamides as uPA inhibitors containing non-basic groups as substitute for amidine or guanidine groups.
- Venkatraj, Muthusamy,Messagie, Jonas,Joossens, Jurgen,Lambeir, Anne-Marie,Haemers, Achiel,Van Der Veken, Pieter,Augustyns, Koen
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experimental part
p. 1557 - 1568
(2012/04/17)
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- Development of fluorescent sensing of anions under excited-state intermolecular proton transfer signaling mechanism
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(Matrix presented) A substantially red-shifted fluorescence emission in 3-hydroxyl-2-naphthanilide in acetonitrile was developed and drastically enhanced upon addition of anions such as F-, AcO-, and H2PO4-, with the enhancement depending on anion basicity. Excited-state intermolecular proton transfer in the sensor-anion hydrogen-bonding complex was suggested to be the signaling mechanism.
- Zhang, Xuan,Guo, Lin,Wu, Fang-Ying,Jiang, Yun-Bao
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p. 2667 - 2670
(2007/10/03)
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- NUCLEOPHILIC ADDITION OF N-LITHIOAMIDES TO ?-ARENECHROMIUM TRICARBONYL COMPLEXES. PREPARATION OF ANILINE DERIVATIVES
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A simple procedure for the preparation of aniline derivatives by the nucleophilic addition of nitrogen anions to ?-(arene)chromium tricarbonyl complexes is described.
- Keller, L.,Times-Marshall, K.,Behar, S.,Richards, K.
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p. 3373 - 3376
(2007/10/02)
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- Kinetics of Reaction of Substituted Naphthoyl Chlorides with Aniline
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Rate constants for the reactions of aniline with 6- and 3-substituted 2-naphthoyl chlorides and 6- and 4-substituted 1-naphthoyl chlorides have been measured at several temperatures in benzene solution.The Hammett equation applies very well in all these cases.The p values for the reaction with 6-substituted 2-naphthoyl chlorides are 1.38, 1.31 and 1.26 at 30, 35 and 40 deg C respectively and those for the reaction with 6- and 4-substituted 1-naphthoyl chlorides are 1.28, 1.24 and 1.19 at 30, 35 and 40 deg C respectively.The reaction of 3-substituted 2-naphthoyl chlo-rides also adheres to the Hammett equation with ?p constants, giving a p value of 1.55 at 30 deg C.
- Ananthakrishnanadar, P.,Varghesedharumaraj, G.
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p. 506 - 507
(2007/10/02)
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