- Enhanced two-photon absorption of novel four-branched chromophore via vibronic coupling
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A novel four-branched chromophore TOZ-4 with starburst linker was synthesized and showed two-photon absorption cross-section (δ) as large as 5254 GM, which was principally resulted from vibronic coupling enhancement.
- Wang, Deqiang,Wang, Xiaomei,He, Qingguo,Zhou, Maoyi,Rui, Wenwen,Tao, Xutang,Bai, Fenglian,Jiang, Minhua
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Read Online
- Single-pot tandem oxidative/C-H modification amidation process using ultrasmall PdNP-encapsulated porous organosilica nanotubes
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Herein, we studied a single-pot method with a dual catalysis process towards the conversion of primary aromatic alcohols to amides using ultrasmall PdNPs of controlled uniform size (1.8 nm) inside hybrid mesoporous organosilica nanotubes (MO-NTs). The cat
- Gholipour, Behnam,Liu, Xiao,Rostamnia, Sadegh,Zonouzi, Afsaneh
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p. 4276 - 4287
(2022/02/16)
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- PCl3-mediated transesterification and aminolysis of tert-butyl esters via acid chloride formation
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A PCl3-mediated conversion of tert-butyl esters into esters and amides in one-pot under air is developed. This novel protocol is highlighted by the synthesis of skeletons of bioactive molecules and gram-scale reactions. Mechanistic studies revealed that this transformation involves the formation of an acid chloride in situ, which is followed by reactions with alcohols or amines to afford the desired products.
- Wu, Xiaofang,Zhou, Lei,Li, Fangshao,Xiao, Jing
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p. 491 - 497
(2021/01/20)
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- Regioselective Synthesis of 2° Amides Using Visible-Light-Induced Photoredox-Catalyzed Nonaqueous Oxidative C-N Cleavage of N, N-Dibenzylanilines
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A visible-light-driven photoredox-catalyzed nonaqueous oxidative C-N cleavage of N,N-dibenzylanilines to 2° amides is reported. Further, we have applied this protocol on 2-(dibenzylamino)benzamide to afford quinazolinones with (NH4)2S2O8 as an additive. Mechanistic studies imply that the reaction might undergo in situ generation of α-amino radical to imine by C-N bond cleavage followed by the addition of superoxide ion to form amides.
- Neerathilingam, Nalladhambi,Bhargava Reddy, Mandapati,Anandhan, Ramasamy
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supporting information
p. 15117 - 15127
(2021/10/25)
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- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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- Manganese Catalyzed Direct Amidation of Esters with Amines
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The transition metal catalyzed amide bond forming reaction of esters with amines has been developed as an advanced approach for overcoming the shortcomings of traditional methods. The broad scope of substrates in transition metal catalyzed amidations remains a challenge. Here, a manganese(I)-catalyzed method for the direct synthesis of amides from a various number of esters and amines is reported with unprecedented substrate scope using a low catalyst loading. A wide range of aromatic, aliphatic, and heterocyclic esters, even in fatty acid esters, reacted with a diverse range of primary aryl amines, primary alkyl amines, and secondary alkyl amines to form amides. It is noteworthy that this approach provides the first example of the transition metal catalyzed amide bond forming reaction from fatty acid esters and amines. The acid-base mechanism for the manganese(I)-catalyzed direct amidation of esters with amines was elucidated by DFT calculations.
- Fu, Zhengqiang,Wang, Xinghua,Tao, Sheng,Bu, Qingqing,Wei, Donghui,Liu, Ning
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p. 2339 - 2358
(2021/02/03)
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- Homoleptic Bis(trimethylsilyl)amides of Yttrium Complexes Catalyzed Hydroboration Reduction of Amides to Amines
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Homoleptic lanthanide complex Y[N(TMS)2]3 is an efficient homogeneous catalyst for the hydroboration reduction of secondary amides and tertiary amides to corresponding amines. A series of amides containing different functional groups such as cyano, nitro, and vinyl groups were found to be well-tolerated. This transformation has also been nicely applied to the synthesis of indoles and piribedil. Detailed isotopic labeling experiments, control experiments, and kinetic studies provided cumulative evidence to elucidate the reaction mechanism.
- Ye, Pengqing,Shao, Yinlin,Ye, Xuanzeng,Zhang, Fangjun,Li, Renhao,Sun, Jiani,Xu, Beihang,Chen, Jiuxi
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supporting information
p. 1306 - 1310
(2020/02/22)
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- Ultrafast amidation of esters using lithium amides under aerobic ambient temperature conditions in sustainable solvents
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Lithium amides constitute one of the most commonly used classes of reagents in synthetic chemistry. However, despite having many applications, their use is handicapped by the requirement of low temperatures, in order to control their reactivity, as well as the need for dry organic solvents and protective inert atmosphere protocols to prevent their fast decomposition. Advancing the development of air- and moisture-compatible polar organometallic chemistry, the chemoselective and ultrafast amidation of esters mediated by lithium amides is reported. Establishing a novel sustainable access to carboxamides, this has been accomplished via direct C-O bond cleavage of a range of esters using glycerol or 2-MeTHF as a solvent, in air. High yields and good selectivity are observed while operating at ambient temperature, without the need for transition-metal mediation, and the protocol extends to transamidation processes. Pre-coordination of the organic substrate to the reactive lithium amide as a key step in the amidation processes has been assessed, enabling the structural elucidation of the coordination adduct [{Li(NPh2)(OCPh(NMe2))}2] (8) when toluene is employed as a solvent. No evidence for formation of a complex of this type has been found when using donor THF as a solvent. Structural and spectroscopic insights into the constitution of selected lithium amides in 2-MeTHF are provided that support the involvement of small kinetically activated aggregates that can react rapidly with the organic substrates, favouring the C-O bond cleavage/C-N bond formation processes over competing hydrolysis/degradation of the lithium amides by moisture or air.
- Bole, Leonie J.,Fairley, Michael,García-Alvarez, Joaquín,Hevia, Eva,Kennedy, Alan R.,Main, Laura,Mulks, Florian F.,O'Hara, Charles T.
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p. 6500 - 6509
(2020/07/15)
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- Facile amidation of esters with aromatic amines promoted by lanthanide tris (amide) complexes
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The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe3)2]3(μ-Cl)Li (THF)3 as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine.
- Li, Zhao,Guo, Chenjun,Chen, Jue,Yao, Yingming,Luo, Yunjie
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- Frustrated Lewis Pair Catalyzed Hydrogenation of Amides: Halides as Active Lewis Base in the Metal-Free Hydrogen Activation
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A method for the metal-free reduction of carboxylic amides using oxalyl chloride as an activating agent and hydrogen as the final reductant is introduced. The reaction proceeds via the hydrogen splitting by B(2,6-F2-C6H3)3 in combination with chloride as the Lewis base. Density functional theory calculations support the unprecedented role of halides as active Lewis base components in the frustrated Lewis pair mediated hydrogen activation. The reaction displays broad substrate scope for tertiary benzoic acid amides and α-branched carboxamides.
- Sitte, Nikolai A.,Bursch, Markus,Grimme, Stefan,Paradies, Jan
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supporting information
p. 159 - 162
(2019/01/04)
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- Method for preparing N,N-diarylamide derivatives
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The invention provides a method for preparing N,N-diarylamide derivatives and belongs to the technical field of chemical synthesis. The method comprises the following steps: taking N-arylamide and phenylboronic acid as raw materials, stirring in an organic solvent under blue light irradiation for 30-44 hours so as to obtain crude N,N-diarylamide, extracting and washing the crude product, and performing column chromatography isolation, thereby obtaining the high-purity N,N-diarylamide derivative. The method disclosed by the invention is simple and readily available in raw materials, mild in reaction condition and simple in operation, and the N,N-diarylamide derivatives with structural diversity can be easily obtained by changing the structures of the raw materials and have excellent application and market value.
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Paragraph 0044-0046
(2019/02/04)
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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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- Cross-Dehydrogenating Coupling of Aldehydes with Amines/R-OTBS Ethers by Visible-Light Photoredox Catalysis: Synthesis of Amides, Esters, and Ureas
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A straightforward synthesis of amides, ureas, and esters is reported by visible-light cross-dehydrogenating coupling (CDC) of aldehydes (or amine carbaldehydes) and amines/R-OTBS ethers by photoredox catalysis. The reaction is found to be general and high yielding. A plausible mechanistic pathway has been proposed for these transformations and is supported by appropriate controlled experiments.
- Pandey, Ganesh,Koley, Suvajit,Talukdar, Ranadeep,Sahani, Pramod Kumar
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supporting information
p. 5861 - 5865
(2018/09/21)
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- An efficient procedure for chemoselective amidation from carboxylic acid and amine (ammonium salt) under mild conditions
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Presented here is an efficient one-pot and catalyst-free procedure for the synthesis of amides starting from carboxylic acids and amine/ammonium salts using 2,2-dichloro-1,3-diisopropylimidazolidine-4,5-dione as the coupling agent. Reactions can proceed smoothly even with those bearing thermosensitive group(s) at ambient temperature, and the corresponding products of primary, secondary and tertiary amides can be afforded in moderate to excellent yields of up to 96%.
- Li, Jianhui,He, Shaopo,Fu, Haiqing,Chen, Xin,Tang, Min,Zhang, Dela,Wang, Bo
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p. 2289 - 2303
(2017/12/26)
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- Copper nanoparticles on charcoal: An effective nanocatalyst for the synthesis of enol carbamates and amides via an oxidative coupling route
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The catalytic activity of copper nanoparticles on charcoal (Cu/C) was investigated as an environmentally friendly heterogeneous catalyst for the synthesis of enol carbamates and amides via the oxidative coupling of N,N-dialkyl formamides with 1,3-dicarbonyl compounds and aromatic aldehydes with amine hydrochloride salts, respectively. Various enol carbamates and amides were synthesized in moderate to good yields using this method. Moreover, the catalyst could be recovered and subsequently reused in further reactions.
- Saberi, Dariush,Mansoori, Sakineh,Ghaderi, Esmali,Niknam, Khodabakhsh
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supporting information
p. 95 - 99
(2015/12/23)
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- Acidylation method of amine
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The invention discloses an acidylation method of amine.The method includes the following steps that amine derivatives, hydrazide derivatives, organic peroxide and a catalyst are dissolved in a solvent and react at the temperature of 40-80 DEG C, and amide derivatives are obtained.The amide derivatives and hydrazide derivatives serve as initiators, the raw materials are easy to obtain and the number of varieties is large.Products obtained through the method are diverse in type, can be directly used and can also be used for other further reactions.The method is mild in reaction condition, simple in reaction operation and post-processing process, high in product yield and suitable for scale production.
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Paragraph 0038
(2016/10/10)
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- Efficient tandem aqueous room temperature oxidative amidations catalysed by supported Pd nanoparticles on graphene oxide
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Pd nanoparticles deposited onto graphene oxide nanosheets (SE-GO/PdNPs) were found to successfully promote two oxidative processes for the synthesis of amides, providing alternative possibilities to these important compounds. SE-GO/PdNPs exhibited excellent activities with an optimum efficiency in tandem one-pot conversion of alcohols to amides in the presence of various amines.
- Rostamnia, Sadegh,Doustkhah, Esmail,Golchin-Hosseini, Habib,Zeynizadeh, Behzad,Xin, Hongchuan,Luque, Rafael
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p. 4124 - 4133
(2016/07/06)
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- Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
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The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms.
- Rovira, Mireia,Soler, Marta,Güell, Imma,Wang, Ming-Zheng,Gómez, Laura,Ribas, Xavi
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p. 7315 - 7325
(2016/09/09)
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- Efficient synthesis of tertiary acyclic amides by the Chapman rearrangement of aryl benzimidates in ionic liquids
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The Chapman rearrangement of aryl N-arylbenzimidates to tertiary acyclic amides is accelerated in ionic liquids and proceeds at lower temperatures as 120-190°C.
- Epishina, Margarita A.,Kulikov, Alexander S.,Ignat'Ev, Nikolai V.,Schulte, Michael,Makhova, Nina N.
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p. 126 - 128
(2015/04/14)
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- An attractive route to transamidation catalysis: Facile synthesis of new o-aryloxide-N-heterocyclic carbene ruthenium(II) complexes containing trans triphenylphosphine donors
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Well-defined robust ruthenium(II) complexes 3a-d bearing o-aryloxide-N-heterocyclic carbene ligands with different wingtip substituents (3a (R = Me), 3b (R = Ph), 3c (R = iPr) and 3d (R = Mes)) in the imidazole ring were synthesized in good yields by the reaction of imidazolium proligands with metal precursor [RuHCl(CO)(PPh3)3] by transmetallation from the corresponding silver carbene complexes. All the Ru(II)-NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. The molecular structure of the complex 3a was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted octahedral geometry. In order to explore the catalytic potential of the synthesized complexes, all the four [Ru-NHC] complexes [3a-d] were tested as catalysts for transamidation of carboxamides with amines. Notably, the complex 3a was found to be very efficient and versatile catalyst toward transamidation of a wide range of amides with amines.
- Nirmala, Muthukumaran,Prakash, Govindan,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz
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- CATALYSTS AND PROCESSES FOR THE HYDROGENATION OF AMIDES
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There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.
- -
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Paragraph 0185
(2014/06/24)
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- Molybdenum-mediated desulfurization of dhiols and disulfides
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We have successfully achieved the molybdenum hexacarbonyl [Mo(CO) 6] mediated desulfurization of thiols and disulfides. In this reaction, the sulfhydryl (SH) mercapto groups of aryl, benzyl, primary and secondary alkyl thiols, and S-S single bonds of disulfides can be removed. This reaction has high functional group tolerance and is not affected by steric hindrance. The results of the reactions in acetone-d 6 suggest that the sources of hydrogen in the thiol and disulfide desulfurizations are the hydrogen atom(s) of a sulfhydryl group and acetone (solvent), respectively, and that the desulfurization proceeds via the formation of an organomolybdenum species. Georg Thieme Verlag Stuttgart. New York.
- Wang, Zhen,Kuninobu, Yoichiro,Kanai, Motomu
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supporting information
p. 1869 - 1872
(2014/08/18)
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- Ligand-free Ullmann-type C-heteroatom couplings under practical conditions
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A new practical ligand-free protocol for copper-catalyzed C-heteroatom cross-coupling reactions (Ullmann-type) is described. The use of dimethyl sulfoxide (DMSO) as the solvent overcomes the need to use organic auxiliary ligands; thus, DMSO is revealed as a nontoxic and superior solvent for Ullmann-type coupling reactions. This method allows the arylation of a wide range of amides, alcohols, and amines under practical conditions with bromobenzene and iodobenzene derivatives and will likely find direct application in current organic synthesis. The competitive reactivity among different functional groups is reported and rationalized, and the possibility to achieve selective arylation reactions is demonstrated. Copyright
- Gueell, Imma,Ribas, Xavi
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p. 3188 - 3195
(2014/06/09)
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- Homogeneous catalytic hydrogenation of amides to amines
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Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4-pentanedione), triphos [1,1,1-tris- (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from prepared from [Ru(acac) 3], triphos and MSA, or from reactions of [RuX-(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crys-tallographically characterised complexes include: [Ru(OAc-κ1O) 2(H2O)-(triphos)], [Ru(OAc-κ2O,O') (CH3SO3-κ1O)(triphos)], [Ru(CH 3SO3-κ1O)2-(H 2O)(triphos)] and [Ru2(μ-CH3SO 3)3-(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc-κ1O)(OAc- κ2O,O')(triphos)],[Ru(CH3SO3- κ1O)(CH3SO3-κ2O,O')- (triphos)], H[Ru(CH3SO3-κ1O) 3-(triphos)], [RuH(CH3SO3-κ1O) (CO)-(triphos)] and [RuH(CH3SO3-k2O,O')- (triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.
- Coetzee, Jacorien,Dodds, Deborah L.,Klankermayer, Jürgen,Brosinski, Sandra,Leitner, Walter,Slawin, Alexandra M. Z.,Cole-Hamilton, David J.
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p. 11039 - 11050
(2013/09/02)
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- Cobalt carbonyl-based catalyst for hydrosilylation of carboxamides
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The cobalt carbonyl [Co2(CO)8] complex is employed as a useful catalyst for the reduction of tertiary amides to the corresponding tertiary amines using 1,1,3,3-tetramethyldisiloxane (TMDS) and poly(methylhydrosiloxane) (PMHS) as silane reagents under thermal (100 °C) or photo-assisted conditions (UV, 350 nm at room temperature). Of particular interest, a low catalytic amount (0.5 mol%) of [Co2(CO)8] is used to perform the reaction with 2.2 equiv. of PMHS at 100 °C for 3 h. This reaction is the first example of a cobalt-catalyzed hydrosilylation of amides. Copyright
- Dombray, Thomas,Helleu, Camille,Darcel, Christophe,Sortais, Jean-Baptiste
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supporting information
p. 3358 - 3362
(2013/12/04)
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- A palladium-catalyzed carbonylation approach to acid chloride synthesis
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We describe a new approach to acid chloride synthesis via the palladium-catalyzed carbonylation of aryl iodides. The combination of sterically encumbered phosphines (PtBu3) and CO coordination has been found to facilitate the rapid carbonylation of aryl iodides into acid chlorides via reductive elimination from (tBu3P)(CO) Pd(COAr)Cl. The formation of acid chlorides can also be exploited to perform traditional aminocarbonylation reactions under exceptionally mild conditions (ambient temperature and pressure), and with a range of weakly nucleophilic substrates.
- Quesnel, Jeffrey S.,Arndtsen, Bruce A.
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supporting information
p. 16841 - 16844
(2013/12/04)
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- Synthesis of novel triarylamine-based dendrimers with N4,N 6-dibutyl-1,3,5-triazine-4,6-diamine probe for electron/energy transfers in H-bonded donor-acceptor-donor triads and as efficient Cu 2+ sensors
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Two novel highly soluble triarylamine dendrimers TPAD1 and TPAD2 with N4,N6-dibutyl-1,3,5-triazine-4,6-diamine probe were synthesized via normal synthetic routes. Both dendrimers (TPAD1 and TPAD2) form H-bonded donor-acceptor-donor (D-A-D) supramolecular triads TPAD1-PBI-TPAD1 and TPAD2-PBI-TPAD2 with 3,4,9,10-perylene tetra carboxylic diimide derivative (PBI). The presence of multiple H-bonds in the solution state was elucidated by 1H NMR titrations and IR spectral studies. J-aggregations and electron/energy transfers provided by both dendrimers were verified by UV-Vis and photoluminescence (PL) titrations with PBI and the particle sizes of supramolecular triads were calculated by X-ray diffraction (XRD) analysis. Similarly, both dendrimers also showed sensitivities towards Cu2+ in comparison with 19 interfering metal ions, which were evidenced via UV-Vis and PL titraions in both single and dual metal systems. The maximum detection limit of Cu2+ ions was determined to be 20 ppm from PL titrations for both dendrimers, and the 1:2 stoichiometry of the complexes formed by both dendrimers (TPAD1-Cu2+ and TPAD2-Cu2+) were calculated by Job plots based on UV-Vis absorption titrations. More importantly, the binding mechanism of the 1,3,5-triazine-4,6-diamine probe of both dendrimers was well characterized by 1H and 13C NMR titrations ([D 8]THF:D2O = 2:1 in vol.) and supported by the fluorescence reversibility by adding metal ions and PMDTA sequentially.
- Shellaiah, Muthaiah,Rajan, Yesudoss Christu,Lin, Hong-Cheu
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supporting information
p. 8976 - 8987
(2013/01/13)
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- Optimization and antifungal activity of chalcone analogues
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Using chalcone as a leading compound, a series of its analogues (compounds 1-16) were designed and synthesized. Their activity of antipathogenic fungi of plants has been evaluated in the laboratory. The results showed that these compounds had certain antifungal activity against Sclerotinia sclerotiorum and Botrytis cinerea. Among them, the inhibition of growth for 2-chloro-N- phenylbenzamide (compound 2) reached 92.6 and 90.1 % at a concentration of 100 mg L-1, respectively.
- Tang, Xiaorong,Chen, Shaoling,Wang, Ling
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experimental part
p. 2516 - 2518
(2012/09/08)
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- Development and mechanistic investigation of a highly efficient iridium(V) silyl complex for the reduction of tertiary amides to amines
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The cationic Ir(III) acetone complex (POCOP)Ir(H)2(acetone) + (POCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) was shown to catalyze the reduction of a variety of tertiary amides to amines using diethylsilane as reductant. Mechanistic studies established that a minor species generated in the reaction, the neutral silyl trihydride Ir(V) complex (POCOP)IrH3(SiEt2H), was the catalytically active species. High concentrations of this species could be conveniently generated by treatment of readily available (POCOP)IrHCl with tert-butoxide in the presence of Et2SiH2 under H2. Thus, using this mixture in the presence of a trialkylammonium salt, a wide array of tertiary amides, including extremely bulky substrates, are rapidly and quantitatively reduced to tertiary amines under mild conditions with low catalyst loading. A detailed mechanistic study has been carried out and intermediates identified. In brief, (POCOP)IrH3(SiEt2H) reduces the amide to the hemiaminal silyl ether that, in the presence of a trialkylammonium salt, is ionized to the iminium ion, which is then reduced to the tertiary amine by Et 2SiH2. Good functional group compatibility is demonstrated, and a high catalyst stability has provided turnover numbers as high as 10 000.
- Park, Sehoon,Brookhart, Maurice
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experimental part
p. 640 - 653
(2012/03/13)
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- Aminocarbonylation of aryl iodides with primary and secondary amines in aqueous medium using polymer supported palladium-N-heterocyclic carbene complex as an efficient and heterogeneous recyclable catalyst
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Aminocarbonylation of aryl iodides with primary and secondary aromatic/aliphatic amines to corresponding amides using polymer supported palladium-N-heterocyclic carbene complex (PS-Pd-NHC) as an efficient heterogeneous, recyclable catalyst is described. The catalytic system was optimized with respect to various reaction parameters to give excellent yield of desired products. The catalyst can be easily separated by simple filtration process and recycled further up to four consecutive recycle without loss in any activity and selectivity. The protocol is advantageous due to the ease in handling of the catalyst, simple workup procedure, and environmentally benign water as solvent and effective catalyst recyclability.
- Qureshi, Ziyauddin S.,Revankar, Santosh A.,Khedkar, Mayur V.,Bhanage, Bhalchandra M.
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p. 148 - 153
(2015/02/20)
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- A general and efficient CuBr2-catalyzed N-arylation of secondary acyclic amides
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A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene. A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene. Copyright
- Wang, Mangang,Yu, Hua,You, Xinwen,Wu, Jun,Shang, Zhicai
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p. 2356 - 2362,7
(2020/09/16)
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- A highly active catalyst for the hydrogenation of amides to alcohols and amines
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Amide-zing: The reaction between 2 equivalents of Ph2P(CH 2)2NH2 and cis-[Ru(CH3CN) 2(η3-C3H5)(cod)]BF4 (cod=1,5-cyclooctadiene) forms a highly active catalyst precursor for the selective hydrogenation of amides. The reaction proceeds with excellent atom economy, yield, and turnover numbers (TONs) under moderate reaction conditions. The technology offers a greener, practical approach to the use of metal hydride reagents commonly employed in both academia and industry. Copyright
- John, Jeremy M.,Bergens, Steven H.
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supporting information; experimental part
p. 10377 - 10380
(2011/12/04)
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- A simple copper-catalyzed synthesis of tertiary acyclic amides
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The N-arylation of aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, has been accomplished using a simple and cheap copper catalytic system. The corresponding tertiary acyclic amides, which can be found in numerous biologically active compounds, have been obtained in good to excellent yields.
- Racine, Emilie,Monnier, Florian,Vors, Jean-Pierre,Taillefer, Marc
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supporting information; experimental part
p. 2818 - 2821
(2011/07/09)
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- Copper-catalyzed N-arylation of amides using (S)-N-methylpyrrolidine-2- carboxylate as the ligand
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(S)-N-methylpyrrolidine-2-carboxylate, a derivative of natural L-proline, was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides with aryl halides under mild conditions. A variety of N-arylamides were synthesized in good to high yields.
- Wang, Chaoyu,Liu, Lijuan,Wang, Wei,Ma, Dong-Sheng,Zhang, Hua
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experimental part
p. 1154 - 1160
(2010/06/13)
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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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- A convenient and general iron-catalyzed reduction of amides to amines
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While the iron is hot: The first general and efficient iron-catalyzed reduction of secondary and tertiary amides into amines using polymethylhydrosiloxane (PMHS) has been developed (see scheme).
- Zhou, Shaolin,Junge, Kathrin,Addis, Daniele,Das, Shoubhik,Beller, Matthias
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supporting information; experimental part
p. 9507 - 9510
(2010/03/24)
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- Highly chemoselective metal-free reduction of tertiary amides
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This communication describes the chemoselective metal-free reduction of tertiary amides to the corresponding amines. Hantzsch ester is used as a mild reducing agent for the reduction of trifluoromethanesulfonic anhydride activated amides providing the tertiary amines with high functional group tolerance. Copyright
- Barbe, Guillaume,Charette, Andre B.
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- Microwave-assisted synthesis of amides from various amines and benzoyl chloride under solvent-free conditions: A rapid and efficient method for selective protection of diverse amines
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A number of structurally diverse amides were synthesized by reaction of the corresponding amines with benzoyl chloride under microwave irradiation. The proposed procedure ensures short reaction time, high yields, and excellent selectivity and considerably broadens the series of amines as compared to the microwave-assisted synthesis of amides directly from carboxylic acids. It can also be used for selective protection of various amines, including aromatic, aliphatic, and heterocyclic.
- Li, Yanqiu,Wang, Yulu,Wang, Jinye
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p. 358 - 361
(2008/12/22)
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- Macromolecular transformations of polyphenyl imidates into N-phenyl-substituted polyaramides and poly(N-benzoylamines)
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A possibility for the transformation of polyphenyl imidates, obtained by polycondensation of bisphenols with imidoyl chlorides of mono- and dicarboxylic acids, into N-phenyl-substituted aromatic polyamides and poly(N-benzoylamines) has been discovered. Su
- Burdukovskii,Mognonov
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experimental part
p. 1247 - 1251
(2009/08/08)
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- NUCLEAR RECEPTOR BINDING AGENTS
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The present invention relates to a novel class of selective estrogen receptor modulators (SERMs). The SERM compounds are applicable for use in the prevention and/or treatment of a variety of diseases and conditions including prevention and treatment of cancers such as prostate and breast cancer, osteoporosis, hormone-related diseases, hot flashes or vasomotor symptoms, neurological disorders, cardiovascular disease and obesity.
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Page/Page column 116; 135-137
(2008/06/13)
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- Rearrangement of polyarylene benzimidates into poly(N-arylenebenzamides)
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The transformation of polyarylene benzimidates prepared by polycondensation of bisphenols with benzimidoyl chlorides in N-methyl-2-pyrrolidone into poly(N-arylenebenzamides) was studied. Pleiades Publishing, Inc., 2006.
- Burdukovskii,Mognonov,Botoeva,Mazurevskaya
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p. 430 - 432
(2008/02/03)
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- Synthesis of triphenylamine-cored dendritic two-photon absorbing chromophores
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(Chemical Equation Presented) A new series of dendritic two-photon absorbing chromophores containing triphenylamine moiety as a core or branching points have been synthesized through a convergent synthetic strategy. One-photon and two-photon optical prope
- Wei, Peng,Bi, Xiangdong,Wu, Zhe,Xu, Zhi
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p. 3199 - 3202
(2007/10/03)
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- Photochemical generation of nitrenium ions from protonated 1,1-diarylhydrazines
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(Chemical Equation Presented) Laser flash photolysis experiments, chemical trapping studies, and time-dependent density functional theory calculations demonstrate that photolysis of protonated 1,1-diarylhydrazines generates N,N-diarylnitrenium ions.
- Winter, Arthur H.,Thomas, Selina I.,Kung, Andrew C.,Falvey, Daniel E.
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p. 4671 - 4674
(2007/10/03)
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- The direct carbamoylation of organometallic reagents with 1,2,3- benzotriazole-1-carboxamides
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Various (hetero)aromatic amides are synthesized efficiently by the carbamoylation of organometallic reagents.
- Katritzky, Alan R.,Monteux, Daphne A.,Tymoshenko, Dmytro O.,Belyakov, Sergei A.
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p. 230 - 231
(2007/10/03)
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- 1,3,4-Oxadiazolethiol as Acyl-transfer Reagent in Acylation of Amines: A One-pot Reaction
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Amines are acylated using 5-(2,4-dichlorophenyl)-1,3,4-oxadiazolethiol in the presence of diethyl chlorothiophosphate (DCTP) in good yield.
- Goswami,Borthakur,Ghosh
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p. 268 - 269
(2007/10/03)
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- Oxidation of benzylamines to amides
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A convenient method for the conversion of tertiary benzylamines to benzamides by phase transfer oxidation is described. Yields are good. Regioselectivities are reported.
- Markgraf, J. Hodge,Sangani, Poorab K.,Finkelstein, Manuel
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p. 1285 - 1290
(2007/10/03)
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- STUDIES ON ENAMIDES. PART 4 : PHOTOCHEMICAL INVESTIGATIONS OF N-AROYLDIPHENYLAMINES
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Photolysis of N-aroyldiphenylamines affords 9-arylacridines or phenanthridinone depending on the structure of the substrates.Additionally, carbazole and photomigrated products are also obtained.
- Datta, Indira,Das, Tapas Kumar,Ghosh, Somnath
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p. 6821 - 6830
(2007/10/02)
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- The Reaction of N-Carboalkoxy Reissert Analogs with Carboxylic Acids
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The reaction of N-carboalkoxy Reissert analogs in the presence of carboxylic acids yields the corresponding ester and heterocyclic base.Use of methoxy substituted benzoic acids yields, instead of the ester, the respective anhydride.Amides can also be prepared in a similar fashion.
- Popp, Frank D.,Duarte, Frederick F.,Uff, Barrie C.
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p. 1353 - 1355
(2007/10/02)
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- Condensations of 1,4-Cyclohexanediones and Secondary Aromatic Amines. II. N-Phenylation of Diarylamines
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The condensations of 1,4-cyclohexanedione with several diphenylamines were investigated in order to determine the limit of the utility of this reaction for the N-phenylation of aromatic secondary amines. 4-Methoxy-, 4,4'-dimethyl-, and 4,4'-dibromodiphenylamines produced their N-phenylated compounds in fairly good yields, but 4-hydroxy-, 3-methoxy-, and 4,4'-bis(dimethylamino)diphenylamines produced poor yields.Nitro-substituted diphenylamines gave N-phenyl derivatives in low yields along with N-4-hydroxyphenyl derivatives.N,N'-Diphenyl-p-phenylenediamine and N,N'-diphenylbenzidine gave correspondig tetra-N-phenyl diamines in good yields.The condensation of N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, di-2-pyridylamine, phenothiazine, and carbazole with 1,4-cyclohexanedione were also examined.
- Haga, Kazuo,Iwaya, Katsumasa,Kaneko, Ryohei
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p. 803 - 808
(2007/10/02)
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