1974-86-3

Upstream product

• 768-90-1 1-Adamantyl bromide 
• 591-17-3 meta-bromotoluene 
• 28987-79-3 m-tolylmagnesium bromide 
• 2094-72-6 1-Adamantanecarbonyl chloride 
• 108-88-3 toluene 
• 935-56-8 1-chloroadamantane 
• 281-23-2 adamantane 
• 19214-04-1 2-(3-methylphenyl)adamantane 
• 768-95-6 1-adamanthanol 
• 2283-34-3 4-(1-adamantyl)-2-methylaniline hydrochloride 

Downstream Products

• 19214-04-1 2-(3-methylphenyl)adamantane 

Relevant academic research and scientific papers

Acidity and Catalytic Activity of a Nafion-H/Silica Nanocomposite Catalyst Compared with a Silica-Supported Nafion Sample

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.

Modes of Micromolar Host-Guest Binding of β-Cyclodextrin Complexes Revealed by NMR Spectroscopy in Salt Water

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

Flow Friedel–Crafts alkylation of 1-adamantanol with arenes using HO-SAS as an immobilized acid catalyst

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.

Indium-catalyzed Friedel-crafts Alkylation of monosubstituted benzenes by 1-bromoadamantane

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

Tetraflic acid (1,1,2,2-Tetrafluoroethanesulfonic acid, HC 2F4SO3H) and gallium tetraflate as effective catalysts in organic synthesis

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

Triflic acid-catalyzed adamantylation of aromatics in [BMIM][OTf] ionic liquid; synthetic scope and mechanistic insight

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.

The role of enthalpic and entropic factors in the isomerization equilibrium of aryladamantanes

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.

Hafnium(IV)Trifluoromethanesulfonate, An Efficient Catalyst for the Friedel-Crafts Acylation and Alkylation Reactions

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.

Boron Tris(triflate) Catalyzed Adamantylation of Benzene and Toluene with 1- and 2-Haloadamantanes and Adamantanoyl Chlorides. Isomerization of Phenyl- and Tolyladamantanes

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.

Cross-Coupling Reaction of tert-Alkyl halides with Grignard Reagents in Dichloromethane as a Non-Lewis Basic Medium

In dichloromethane as a non-Lewis basic solvent, 1-haloadamantane 1 underwent a cross-coupling reaction with Grignard reagents to give bridgehead-substituted products 3-16 in moderate yields.In this case the same kind of halogen in both 1 and a Grignard reagent was favored; if not, functional exchange (i.e., 1a to 1c) occurred first.The reaction using 5-hexenylmagnesium bromide as a radical probe afforded uncyclized/cyclized coupling products in a 6/4 ratio.These fact suggested the significant participation of the single-electron-transfer process in these reactions.The present method could be extended to tert-butylation with some Grignard reagents.Interestingly, 1,3-dichloro-3-methylbutane coupled with butylmagnesium chloride selectively at the tertiary position. for the above displacement reaction of 1, an organozinc was also found to be effective.