- Boron Tris(triflate) Catalyzed Adamantylation of Benzene and Toluene with 1- and 2-Haloadamantanes and Adamantanoyl Chlorides. Isomerization of Phenyl- and Tolyladamantanes
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Boron tris(triflate) catalyzed adamantylation of benzene and toluene was studied with isomeric 1- and 2-haloadamantanes.The alkylations give 1- and 2-phenyl- and isomeric tolyladamantanes in varying ratios.Interconversion of isomeric 2-phenyl(tolyl)adamantanes into the corresponding 1-phenyl(tolyl)adamantanes was observed through intermolecular isomerization involving adamantyl cations and adamantane, which is formed in significant amount in all the reactions.Decarbonylative alkylation of aromatics with adamantanoyl chlorides was also investigated.Adamantanoylated aromatics were formed only in very low amounts, the major product being adamantylated aromatics in accord with extensive decarbonylation of the adamantanoyl cations.The mechanism of the studies adamantylations was further substantiated by studying the boron tris(triflate) catalyzed isomerization of 1- and 2-aryladamantanes under comparable conditions.
- Olah, George A.,Farooq, Omar,Farnia, S. Morteza F.,Wu, An-hsiang
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- Synthesis of 1,4-Disubstituted 1 H -1,2,3-Triazoles from 4-(1-Adamantyl)benzyl Azide through a 1,3-Dipolar Cycloaddition Reaction
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A series of new 1,4-disubstituted 1 H -1,2,3-triazole derivatives were synthesized by an efficient copper-catalyzed 1,3-dipolar cycloaddition reaction of 4-(1-adamantyl)benzyl azide with several terminal alkynes. The copper catalyst was used to provide 1,
- Hocine, Oussama Bencheikh Le,Tebbani, Dahmane,Silva, Artur M. S.
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- Sonogashira cross-coupling reaction catalyzed by N-heterocyclic carbene-Pd(II)-PPh3 complexes under copper free and aerobic conditions
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NHC-Pd-PPh3 complexes with the bulky benzyladamantyl substited N-heterocyclic carbene (NHC) were synthesized and characterised by NMR, HRMS and micro analyse. These complexes were proceeded to Sonogashira-Hagihara coupling reaction between aryl
- Dehimat, Zineb Imene,Ya?ar, Sedat,Tebbani, Dahmane,?zdemir, ?smail
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- Synthesis of sterically hindered N-benzyladamantyl substituted benzimidazol-2-ylidene palladium complexes and investigation of their catalytic activity in aqueous medium
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NHC-Pd-PEPPSI complexes with bulky benzyladamantyl substituted N-heterocyclic carbenes (NHC) were synthesized and characterized by NMR, HRMS, and micro analysis. These complexes were then used for Suzuki-Miyaura coupling reactions between aryl bromides an
- Dehimat, Zineb Imene,Pa?ahan, Aziz,Tebbani, Dahmane,Ya?ar, Sedat,?zdemir, ?smail
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- Modes of Micromolar Host-Guest Binding of β-Cyclodextrin Complexes Revealed by NMR Spectroscopy in Salt Water
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Multitopic supramolecular guests with finely tuned affinities toward widely explored cucurbit[n]urils (CBs) and cyclodextrins (CDs) have been recently designed and tested as functional components of advanced supramolecular systems. We employed various spa
- Tomecek, Josef,Cablova, Andrea,Hromadkova, Aneta,Novotny, Jan,Marek, Radek,Durnik, Ivo,Kulhanek, Petr,Pruckova, Zdenka,Rouchal, Michal,Dastychova, Lenka,Vicha, Robert
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p. 4483 - 4496
(2021/04/02)
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- Preparation and application of thiosemicarbazone compound
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The invention discloses a thiosemicarbazone compound, and biological activity analysis is carried out on the thiosemicarbazone compound. The invention also discloses application of the thiosemicarbazone compound in preparation of antibacterial drugs. According to the invention, important intermediates 6a-6h are synthesized from hydrazine hydrate and react with adamantane benzaldehyde respectivelyto synthesize eight adamantane aromatic aldehyde thiosemicarbazone compounds, the structures of the compounds can be confirmed by infrared, nuclear magnetic hydrogen spectrum, carbon spectrum and massspectrum methods, and the antibacterial activity of the compounds is tested in vitro. The result shows that the compound has a good antibacterial effect on escherichia coli and bacillus subtilis.
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Paragraph 0010-0012
(2021/02/20)
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- Synthesis and antibacterial activity of novel Schiff bases of thiosemicarbazone derivatives with adamantane moiety
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Increased bacterial resistance to antibiotics is a major threat to human health, and it is particularly important to develop novel antibiotic drugs. Here, we designed a series of Schiff base thiosemicarbazone derivatives containing an adamantane moiety, and carried out the structural characterization of the compounds and in vitro antibacterial activity tests. Compound 7e was as effective as the commonly used antibiotic ampicillin against the Gram-negative bacterium Escherichia coli, and compound 7g had a good inhibitory effect against Gram-positive Bacillus subtilis. These findings provide data for the development of better thiosemicarbazone antibacterial agents.
- Zhu, Jiahui,Teng, Guosheng,Li, Dongfeng,Hou, Ruibin,Xia, Yan
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p. 1534 - 1540
(2021/06/16)
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- Flow Friedel–Crafts alkylation of 1-adamantanol with arenes using HO-SAS as an immobilized acid catalyst
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In this communication flow Friedel–Crafts alkylation was studied using hydroxy-substituted sulfonic acid-functionalized silica as a catalyst and 1-adamantanol as a model substrate. The reaction of 1-adamantanol (1a) with toluene (2a) proceeded well with 5 min of residence time at 120°C to give good yield of 1-tolyladamantane (3a) as a 1:9 mixture of meta and para isomers. When the flow synthesis was carried out over 2.5 hr of running time, the collected five fractions contain the product 3a in 97–92% yields, suggesting the durability of the catalyst.
- Kasakado, Takayoshi,Hyodo, Mamoru,Furuta, Akihiro,Kamardine, Aina,Ryu, Ilhyong,Fukuyama, Takahide
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p. 2253 - 2257
(2020/12/15)
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- Adamantane styrene derivatives, and preparation method and application thereof
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The invention discloses adamantane styrene derivatives and analysis of the biological activity of the adamantane styrene derivatives. According to the invention, a synthesized compound retains an adamantane structure, an adamantane ring structure is conne
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Paragraph 0016
(2018/02/04)
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- 4-(1-Adamantyl)phenylalkylamines with potential antiproliferative activity
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Background: In our previous publications we have described the synthesis of aminosubstituded diaryl adamantanes and their pharmacological evaluation in vitro and in vivo against many cancer cell lines. More recently, we have reported the synthesis of mono
- Koperniku, Ana,Foscolos, Angeliki-Sofia,Papanastasiou, Ioannis,Foscolos, George B.,Tsotinis, Andrew,Schols, Dominique
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p. 171 - 176
(2016/03/01)
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- Alkylation of aromatic compounds with 1-bromoadamantane in the presence of metal complex catalysts
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Synthesis of aryladamantanes was performed by reaction of 1-bromoadamantane with aromatic compounds in the presence of metal complex catalysts containing Mo, Cr, W, Cu, and Co.
- Khusnutdinov,Shchadneva,Khisamova
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p. 1545 - 1550
(2015/12/30)
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- Indium-catalyzed Friedel-crafts Alkylation of monosubstituted benzenes by 1-bromoadamantane
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Indium salts such as InCl3 and InBr3 (ca. 1-5 mol%) efficiently catalyzed the Friedel-Crafts reaction of 1-bromoadamantane with benzene and monosubstituted benzenes to give 1-adamantyl benzenes. Indium bromide enabled faster reaction
- Mosset, Paul,Grée, René
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p. 1142 - 1146
(2013/06/27)
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- Adamantylation of β-dicarbonyl compounds
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Reactions of adamantan-1-ol with β-dicarbonyl compounds in 1,2-dichloroethane in the presence of In(OTf)3, Ga(OTf)3, Sc(OTf)3, or Cu(OTf)2 give the corresponding adamantylated derivatives in 45-93% yields.
- Turmasova,Spesivaya,Konshina, Dzh. N.,Konshin
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p. 1733 - 1735
(2013/11/19)
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- Tetraflic acid (1,1,2,2-Tetrafluoroethanesulfonic acid, HC 2F4SO3H) and gallium tetraflate as effective catalysts in organic synthesis
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Tetraflic acid offers ample acidity for various organic reactions that require high acidity. Its gallium(III) salt is an efficient catalyst under mild condtions for synthetic transformations such as the ketonic Strecker reaction for the synthesis of fluorinated α-amino nitriles and condensation- cyclzation reactions using suitable fluoro ketones and 1,2-disubstituted benzenes for the direct preparation of 5-membered or 6-membered fluorinated heterocycles. Copyright
- Prakash, G. K. Surya,Mathew, Thomas,Panja, Chiradeep,Kulkarni, Aditya,Olah, George A.,Harmer, Mark A.
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p. 2163 - 2171
(2012/11/07)
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- Nickel-catalyzed cross-coupling of aryl bromides with tertiary grignard reagents utilizing donor-functionalized N-heterocyclic carbenes (NHCs)
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Metal-catalyzed cross-coupling reactions are among the most important transformations in organic synthesis, allowing the efficient construction of complex structures from simpler, readily available building blocks.Many applications in large and small-scale synthesis can be found in different areas such as agrochemicals, pharmaceuticals and supramolecular chemistry. Whereas the coupling of sp2-hybridized carbon atoms in either reaction partner is well established, the use of CACHTUNGTRENUNG(sp3)-hybridized substrates presents some challenges. Catalytic cross-coupling of sterically hindered tertiary alkyl substrates is especially difficult, generally resulting in low yields, and thus, only few reports exist.[27] A big challenge in this field is not only to get the required level of reactivity, but also to overcome competing pathways like β-hydride elimination, hydrodehalogenation or isomerization
- Lohre, Claudia,Droege, Thomas,Wang, Congyang,Glorius, Frank
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supporting information; experimental part
p. 6052 - 6055
(2011/06/25)
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- Triflic acid-catalyzed adamantylation of aromatics in [BMIM][OTf] ionic liquid; synthetic scope and mechanistic insight
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A mild and efficient process has been developed for the one-pot adamantylation of aromatic substrates employing 1-AdaOH, 1-AdaCl, 1-AdaBr, and 1-Br-3,5,7-trimethyladamantane as adamantylating agents, with triflic acid (TfOH) as promoter and n-butylmethylimidazolium triflate [BMIM][OTf] room temperature ionic liquid (IL) as solvent. The influence of reaction temperature, reaction time and the amount of TfOH was gauged in model reactions employing 1-AdaOH, 1-AdaCl and 1-AdaBr with toluene as the substrate. Under optimal conditions, the reactions exhibit high para selectivity with little or no adamantane side-product being formed. The synthetic scope of this transformation was tested for representative alkylbenzenes and haloalkylbenzenes. Comparative reactions carried out in 1,2-dichloroethane (DCE) produce increased amounts of the meta isomer and substantial amounts of adamantane. Substrate selectivities (KT/KB) were measured in competitive experiments in [BMIM][OTf] and in DCE as solvents. Isomerization tests were performed to shed light on the origin of the meta isomer. A DFT study was also conducted to compare relative stabilities of the isomeric products, to gauge the relative stabilities of the intermediate isomeric benzenium ions of adamantylation and their charge distribution modes, and to explore the intramolecular process for isomerization in the benzenium ion. The Royal Society of Chemistry 2005.
- Laali, Kenneth K.,Sarca, Viorel D.,Okazaki, Takao,Brock, Aaron,Der, Paul
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p. 1034 - 1042
(2007/10/03)
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- 1-adamantyl chalcones for the treatment of proliferative disorders
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The present invention relates to the compounds of the general formula (I), a composition for and a method of treating breast cancer or other proliferative disorders in a subject using a compound of general formula [I], wherein the substituents are as defi
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Page/Page column 19
(2008/06/13)
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- The role of enthalpic and entropic factors in the isomerization equilibrium of aryladamantanes
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The chemical equilibrium of five positional isomerization reactions of aryladamantanes with different structures was studied in the liquid phase in the presence of AlCl3 in the range 303-423 K. Contributions to the equilibrium constants were analyzed using experimental and calculated data. The contributions were from symmetry, intermolecular interactions, differences in heat capacities of isomers, overall rotation of molecules, free or hindered rotation of groups in molecules, contribution of vibrations, differences in conformational composition, and intramolecular effects of interaction of substituents in molecules involved in the reaction. The significance of these contributions to the equilibrium constants of the transformations in question was shown. The enthalpies and changes in entropy for the reactions in the liquid and gaseous states were determined and discussed. A comparative analysis of the thermodynamic characteristics of positional isomerization of aryladamantanes, methyladamantanes, methyldiamantanes, and phenylcyclohexanes is given.
- Pimerzin,Sarkisova
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- Acidity and Catalytic Activity of a Nafion-H/Silica Nanocomposite Catalyst Compared with a Silica-Supported Nafion Sample
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The characterization of acid sites in the recently developed Nafion-H/silica nanocomposite catalyst was carried out through pyridine adsorption using the surface FT-IR technique. For comparison, an impregnated Nafion-H/SiO2 catalyst was also studied. A large number of free surface SO3H groups was detected on the surface of the Nafion-H/silica nanocomposite, in contrast to the impregnated catalyst. Pyridine adsorption demonstrates that Broensted as well as Lewis acid sites are present on the surface of the samples. There was a large number of available Broensted sites on the surface of the Nafion-H/silica nanocomposite catalyst. As well as pyridine adsorption, the surface reaction of cyclopropane also revealed that the nanocomposite catalyst has a high number of acid sites. The impregnated sample exhibits much lower activity. The effect of different types of acidity and of acid strength were studied by means of the Friedel-Crafts alkylation (adamantylation of toluene) and various rearrangements. In agreement with the results of surface studies, the nanocomposite specimen exhibits activity which is several orders of magnitude higher than that observed for the other Nafion samples studied. This outstanding activity is attributed to the large surface area and to the increased accessibility of surface-active sites to reactants in catalytic transformations.
- Toeroek, Bela,Kiricsi, Imre,Molnar, Arpad,Olah, George A.
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p. 132 - 138
(2007/10/03)
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- Palladium-Catalyzed Coupling Reactions of 1-Bromoadamantane with Styrenes and Arenes
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The palladium-catalyzed reaction of 1-bromoadamantane (1-Br) with styrene and donor-substituted styrenes gave the corresponding Heck-type coupling products 3a and b, and 5a and b in moderate yields (15-41percent), while the reaction of 1-Br with various arenes 6a-p under palladium catalysis gave the corresponding adamantyl-substituted arenes 7a-p in good to excellent yields (35-98percent). - Keywords: cross-coupling reactions; metal-catalyzed/adamantylation of styrene and alkenes/arylation of 1-bromoadamantane/Heck reaction; palladium catalysis
- Braese, Stefan,Waegell, Bernard,Meijere, Armin de
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p. 148 - 152
(2007/10/03)
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- Hafnium(IV)Trifluoromethanesulfonate, An Efficient Catalyst for the Friedel-Crafts Acylation and Alkylation Reactions
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Hafnium(IV) trifluoromethanesulfonate (hafnium(IV) triflate, Hf(OTf)4) was synthesized from hafnium tetrachloride and trifluoromethanesulfonic acid.The triflate thus prepared was found to be effective in the catalytic Friedel-Crafts acylation reactions of various substituted benzenes with acid anhydrides in lithium perchlorate-nitromethane (LiClO4-MeNO2).Lithium perchlorate-nitromethane is an excellent solvent system, and the catalytic activity of the Lewis acid was much improved in this medium.The product was obtained in up to 250000percent molar amounts baaed on the catalyst.Hafnium(IV) triflate was also found to be quite effective in the catalytic Friedel-Crafts alkylation reactions of aromatic compounds with alkyl chlorides.The reactions proceeded smoothly in the presence of 5percent molar amount of Hf(OTf)4 and 50percent molar amount of LiClO4 by using a slow addition procedure.
- Hachiya, Iwao,Moriwaki, Mitsuhiro,Kobayashi, Shu
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p. 2053 - 2060
(2007/10/02)
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- TRIFLUOROACETIC ANHYDRIDE AS A MEDIUM FOR ORGANIC REACTIONS. FUNCTIONAL SUBSTITUTION OF ADAMANTANE AND ITS DERIVATIVES
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The role of trifluoroacetic anhydride during the oxidation of adamantane and its derivatives with sulfuric acid was studied. 1-Adamantanol, 1-(4-methyl-3-nitrophenyl)-3-adamantanol.The latter was used without isolation from the reaction mixture for the production of 1-adamantanecarboxylic acid, N-(1-adamantyl)acetamide, 1-(1-adamantyl)butan-1-ol, 1-(4-methylphenyl)adamantane, 4-(1-adamantyl)phenoxyacetic acid, 4-(1-adamantyl)acetanilide, and 4-(1-adamantyl)bromobenzene.
- Kovalev, V. V.,Fedorova, O. A.,Shokova, E. A.
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p. 1672 - 1675
(2007/10/02)
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- 1-(TRIFLUOROACETOXY)ADAMANTANE AND SYNTHESES BASED ON IT
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The trifluoroacetolysis of 1-bromoadamantane was realized.It was shown that the obtained 1-(trifluoroacetoxy)adamantane can be used for the synthesis of 1-(1-adamantyl)-1-alkanols, (1-adamantyl)arenes, and 1-(acetylamino)adamantane.
- Kovalev, V. V.,Shokova, E. A.
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p. 1908 - 1912
(2007/10/02)
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- Direct Clay-Catalyzed Friedel-Crafts Arylation and Chlorination of the Hydrocarbon Adamantane
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Multiple chlorinations and arylations at the tertiary positions of adamantane are promoted by FeCl3-doped K10 montmorillonite in CCl4 or in aromatic solvents.The process, remarkably easy implement, can be tailored to selective formation of monosubstituted 1-adamantyl derivatives or 1,3-disubstituted adamantanes.The process achieves alkylation at the meta- and para-positions of toluene leading to a purely statistical distribution and displays no substrate specificity in competition experiments between toluene and benzene.
- Chalais, Stephane,Cornelis, Andre,Gerstmans, Andre,Kolodziejski, Waclaw,Laszlo, Pierre,et al.
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p. 1196 - 1203
(2007/10/02)
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- REACTIONS OF ADAMANTYL NITRATES WITH AROMATIC COMPOUNDS.
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It has been shown to be possible to use adamantyl nitrates in the synthesis of mono- and diaryladamantanes.The effects of substituents and the acidity of the medium on the yields of reaction products have been studied.
- Moiseev, I. K.,Doroshenko, R. I.
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p. 1067 - 1069
(2007/10/02)
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- Synthesis of Adamantane Derivatives. 49. Substitution Reaction of 1-Adamantyl Chloride with Some Trimethylsilylated Unsaturated Compounds
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Catalytic substitution reactions at the adamantane bridgehead were studied by using α,β- and β,γ-unsaturated trimethylsilanes.Treatment of 1-adamantyl (Ad) chloride (1) with allyltrimethylsilane and its heteroanalogues, X=Y-Z-SiMe3, in the presence of Lewis acid as a catalyst gave the products Ad-X-Y=Z, X=Y+(Ad)-Z-, and X=Y-Z-Ad, depending on the attack site of the adamantyl group on each X, Y, and Z atom.Treatment of 1 with (phenylethynyl)trimethylsilane also gave a substituted adamantane in good yield.The substitution reactions of 1 with aryl- and heteroaryltrimethylsilanes under similar conditions occurred at a position distinct from that of acetylation, indicating that adamantylation was not influenced by an electronic effect of the trimethylsilyl group.
- Sasaki, Tadashi,Usuki, Arimitsu,Ohno, Masatomi
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p. 3559 - 3564
(2007/10/02)
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