- Copper(II)-Catalysed Aerobic Oxidative Coupling of Arylamines with Hexafluoroisopropanol: An Alternative Methodology for Constructing Fluorinated Compounds
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The selective functionalisation of arylamine derivatives with hexafluoroisopropanol through copper(II)-catalysed aerobic oxidative coupling was developed to generate various fluoroalkylated arylamines under mild conditions. This method has a wide substrat
- Guo, Jiabao,Li, Zhanchong,Song, Yang,Wu, Liangying,Yao, Xiaoquan
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supporting information
p. 268 - 274
(2020/12/04)
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- Synthesis, Structure, and Properties of Amino-Substituted Benzhydrylium Ions – A Link between Ordinary Carbocations and Neutral Electrophiles
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Optimized synthetic procedures for the straightforward access to eleven amino-substituted diarylmethylium tetrafluoroborates are described. These benzhydrylium ions cover a range of seven orders of magnitude in electrophilicity and provide a link between ordinary carbocations and neutral electrophiles. Five of these highly stabilized benzhydrylium tetrafluoroborates were characterized by single-crystal X-ray crystallography. While the experimentally determined bond lengths and angles in the solid state perfectly agree with those calculated by DFT methods for the gas phase and aqueous solution, crystal packing accounts for large differences in the twist angles of the aryl groups found in the solid state as compared to calculated structures.
- Mayer, Robert J.,Hampel, Nathalie,Mayer, Peter,Ofial, Armin R.,Mayr, Herbert
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supporting information
p. 412 - 421
(2018/09/14)
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- SILICA-BASED ZINC CATALYSTS. THEIR PREPARATION AND USE IN THE ALKOXYCARBONYLATION OF AMINES
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The present invention relates to silica-based heterogeneous zinc compounds which are suitable as catalysts in the reaction of amines with dialkyl carbonates to produce carbamates. The catalysts have the formula [SiO2]-CH2-CHR-X-COOZn[Y], wherein [SiO2] represents a silica carrier selected from the group consisting of ordered mesoporous silica and irregular amorphous narrow pore silica, R represents a moiety selected from the group consisting of hydrogen, -CH3, and -CH2CH3, preferably hydrogen, X is an aliphatic chain of 2 to 11 carbon atoms that optionally comprises ether moieties and [Y] represents a mono anion. The invention is also directed towards a method for the preparation of the aforementioned compounds and towards method for the alkoxycarbonylation of amines.
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Page/Page column 22-28
(2018/12/13)
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- Full N,N-Methylation of 4,4′-Methylenedianiline with Dimethyl Carbonate: A Feasible Access to 4,4′-Methylene bis(N,N-Dimethylaniline)
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The full N,N-methylation of 4,4′-methylenedianiline (MDA) with dimethyl carbonate (DMC) was investigated. The yield of the major product 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) reached as high as 97% over NaY catalyst at 190°C for 6 h. The catalyst could be used for two more times with acceptable MBDMA yields higher than 90%. The main by-products were identified as three N-methylated derivatives. Surprisingly, the formation of the N-methoxycarbonylation product was extremely restrained, which could be produced in high yields of 98% on zinc acetate catalyst. Furthermore, the reaction pathway to the major product MBDMA was proposed. Finally, a feasible synthetic route of 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) was established, featuring a high yield, mild reaction conditions, and simple operations.
- Qiu, Zegang,Wang, Kunjie,Li, Zhiqin,Li, Tao,Bai, Jinhao,Yin, Chanjuan,Ye, Xiushen,Liu, Haining
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- Highly regioselective para-methylthiolation/bridging methylenation of arylamines promoted by NH4I
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Aryl methyl thioethers and methylene-bridged arylamines were synthesized via highly regioselective para-methylthiolation/bridging methylenation of arylamines using DMSO as the methylthio or methylene source in the presence of NH4I under metal-free conditions. For the substrates with both electron-donating and electron-withdrawing substituents, the reaction proceeded smoothly and gave moderate to good yields.
- Xu, Yinfeng,Cong, Tiantian,Liu, Ping,Sun, Peipei
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supporting information
p. 9742 - 9745
(2015/10/05)
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- Synthesis of GN8 derivatives and evaluation of their antiprion activity in TSE-infected cells
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A series of GN8 derivatives were synthesized from various diamines, carboxylic acid derivatives, and nitrogen nucleophiles, and their antiprion activity was tested in TSE-infected mouse neuronal cells. We found that two ethylenediamine units, hydrophobic substituents on the nitrogen atoms, and the diphenylmethane scaffold were essential structural features responsible for the activity. Seven derivatives bearing substituents at the benzylic position exhibited an improved antiprion activity with the IC50 values of 0.51-0.83 μM. Conformational analysis of model compounds suggested that the introduction of the substituent at the benzylic position restricted the conformational variability of the diphenylmethane unit.
- Kimura, Tsutomu,Hosokawa-Muto, Junji,Kamatari, Yuji O.,Kuwata, Kazuo
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supporting information; experimental part
p. 1502 - 1507
(2011/04/23)
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- Metal organic frameworks as heterogeneous catalysts for the selective N-methylation of aromatic primary amines with dimethyl carbonate
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Metal organic frameworks (MOFs) with aluminium, copper and iron as central metal atoms with 1,4-benzenedicarboxylic acid (aluminium) and 1,3,5-benzenetricarboxylic acid (copper and iron) as ligands are selective and active catalysts in promoting the polymethylation of aromatic amines with dimethyl carbonate (DMC). N-methylation prevails over carbamoylation even though they are competing parallel processes. The present N-methylation protocol using DMC enjoys advantages such as convenient reaction conditions, benign, reusable, cost-effective catalyst, avoids the use of additional solvent and uses a safe, green methylating agent that only produces CO2 and methanol as by-products.
- Dhakshinamoorthy, Amarajothi,Alvaro, Mercedes,Garcia, Hermenegildo
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experimental part
p. 19 - 25
(2010/08/20)
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- Application of a regioselective Mannich reaction on naringenin and its use in fluorescent labeling
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A novel strategy for site-specific fluorescent labeling on naringenin (1) was established by a new direct Mannich reaction in combination with a Huisgen [3+2]-cycloaddition reaction. High regioselectivity was observed for direct Mannich reactions on narin
- Chen, Lei,Hu, Tai-Shan,Zhu, Jing,Wu, Houming,Yao, Zhu-Jun
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p. 1225 - 1229
(2007/10/03)
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- A general procedure to selectively prepare N-alkylanilines by an unexpected reaction of (Z)-(tert-butylsulfanyl)(aryl)diazenes with alkyllithium reagents
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A general procedure has been set up to prepare, selectively, the N-monoalkylanilines 7, reacting (Z)-(tert-butylsulfanyl)(aryl)diazenes 3 with alkyllithium 6 (MeLi, BuLi, s-BuLi, n-C6H13Li). The reactions were carried out in anhydrous diethyl ether at 0°C or - 78°C, depending on the reagent 6, and then at room temperature. In optimal conditions the yields of the pure products 7 (uncontaminated by dialkylation products) were from good to excellent: for 38 considered examples, 34 were positive with yields varying between 61percent and 91percent (average yield 78percent). Collateral proofs were carried out to support a hypothesized reaction mechanism.
- Barbero, Margherita,Degani, Iacopo,Dughera, Stefano,Fochi, Rita
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p. 742 - 750
(2007/10/03)
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- Synthesis of new macrocyclic aminomethylphosphines based on 4,4'-diaminodiphenylmethane and its derivatives
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The reaction of bis(hydroxymethyl)phenylphosphine with 4,4'-diaminodiphenylmethane in DMF afforded 1,1',5,5'-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis
- Kuutetsov, R. M.,Balueva, A. S.,Litvinov, I. A.,GubaiduUin, A. T.,Nikonov, G. N.,Karasik, A. A.,Sinyashin, O. G.
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p. 151 - 156
(2007/10/03)
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- An efficient approach to 1,3,5-tris-arylhexahydro-1,3,5-triazines
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In this paper we report a facile and efficient procedure for the synthesis of 1,3,5-tris-arylhexahydro-1,3,5-triazines (3) by reaction of anilines 1 with 1,3,6,8-tetrazatricyclo[4.4.1.13,8]-dodecane (TATD) (2). The diequatorial chair conformational preference of 3b (Ar=p-tolyl) in the solid state was established by X-ray crystallography and agrees well with molecular mechanics calculations.
- Rivera, Augusto,Torres, Olga Lucia,Leiton, Jesus D.,Morales-Rios, Martha S.,Joseph-Nathan, Pedro
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p. 1407 - 1414
(2007/10/03)
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- Studies in the synthesis and characterization of macrocycles based on N, N′-dimethyl-4,4′-methylenedianiline as the basic skeleton
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High dilution method has been employed to get the macrocycles 3 (yield 14%) and 5 (yield 47%) as monomers by reacting N,N′-dimethyl-4,4′-methylenedianiline with terephthaloyl chloride and sebacoyl chloride respectively in the presence of pyridine as the o
- Sharma, Lalit
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p. 1504 - 1506
(2007/10/03)
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- A Novel and Convenient Route to (1H-1,2,4-Triazol-1-ylmethyl)phenols, Anilines, N-Alkylanilines and N,N-Dialkylanilines
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Phenols, naphthols, anilines, N-alkylanilines and N,N-dialkylanilines are readily alkylated by 1-hydroxymethyl-1,2,4-triazole to afford the corresponding triazole derivatives in good yields.
- Katritzky, Alan R.,El-Zemity, Saad,Lang, Hengyuan
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p. 1813 - 1822
(2007/10/02)
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- Biomimetic Studies Using Artificial Systems. 3. Design, Synthesis, and Inclusion Complex Forming Ability of a Novel Water-Soluble Paracyclophane Possessing Diphenylmethane Skeletons
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A novel water-soluble paracyclophane, CP44 (1), was designed and synthesized as a host molecule possessing a hydrophobic cavity to capture organic guests in water.X-ray crystallographic study revealed the formation of 1:1 inclusion complex, and not a simp
- Odashima, Kazunori,Itai, Akiko,Iitaka, Yoichi,Koga, Kenji
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p. 4478 - 4484
(2007/10/02)
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- Effect of Substituents on the Reaction of Aromatic Amines and Formaldehyde in Acid Medium
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The kinetics and mechanism of the condensation of N- and C-substituted aromatic amines with formaldehyde in acid medium have been studied using quantitative TLC technique, and the first order rate constants and relative reactivities calculated.In all cases where para-position is free, 4-aminobenzyl alcohols are the initial products.These undergo condensation with amines to give 4-(4-aminobenzyl)anilines.The effect of substituents on the reactivity of amines has been discussed.
- Nayar, Mazhuvadyil R. Gopinathan,Francis, Joseph D.
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p. 776 - 780
(2007/10/02)
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- Alkylidene Transfer from Monochloroalkylmercury(II) Compounds to Aromatic Amines; Selective C-Alkylation
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αα-Diarylalkane derivatives have been synthesized from monochloroalkylmercury(II) compounds in a noncarbenoid alkylidene transfer reaction which takes place selectively on the aromatic ring.A mechanism is suggested for this process.Intermediate products are prepared by alternative routes to ascertain their participation in the course of the reaction.As a consequence, two different aryl groups can be successively incorporated into the alkane molecule.
- Barluenga, Jose,Campos, Pedro J.,Roy, Miguel A.,Asensio, Gregorio
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p. 1420 - 1426
(2007/10/02)
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- HYDROGENATION OF N-ARYL CARBAMATES TO N-ALICYCLIC CARBAMATES.
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An economical, high-yield process is developed for the preparation of pure N-alicyclic carbamates by the rhodium-catalyzed hydrogenation of the corresponding N-aryl carbamates. The N-aryl carbamates are obtained by the simple reaction of low-cost aromatic
- Malz Jr.,Greenfield
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p. 358 - 362
(2007/10/06)
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