73861-71-9

Upstream product

• 768-90-1 1-Adamantyl bromide 
• 108-38-3 m-xylene 
• 172975-69-8 3,5-dimethylphenyl boronic acid 
• 34696-73-6 3,5-dimethyphenylmagnesium bromide 
• 768-95-6 1-adamanthanol 
• 935-56-8 1-chloroadamantane 
• 281-23-2 adamantane 

Downstream Products

• 106888-17-9 1-(3,5-dimethylphenyl)-3-hydroxyadamantane 

Relevant academic research and scientific papers

Importance of monodentate mono-ligand designs in developing N-stabilized Pd catalysts for efficient ambient temperature C[sbnd]C coupling: Donor strengths and steric features

Unfriendly temperature profiles and costs of carbon coupling catalysis, which pose challenge to both synthetic organic chemists as well as industrial applicability, motivated our design of new monodentate N-donors as support ligands for the purpose of constructing ambient temperature precatalysts that are molecularly close to the hypothetical active forms. Therefore, a series of sterically varied monodentate N-donor imidazoles (1–7) and oxazoles (8–9) have been synthesized and their N-donor strengths, which were estimated as pKas, are systematically varied from 0.9 to 8.5 by substituent variations. Eleven target mono-ligand complexes (1-PdCl2MeCN – 9-PdCl2MeCN, 6-PdCl2PhCN and 7-PdCl2PhCN) and six trans-bis-ligand complexes (12-PdCl2, 22-PdCl2, 32-PdCl2, 62-PdCl2, 12-Pd(OAc)2 and 22-Pd(OAc)2) were isolated and catalytically studied along with PdI2(PPh3)2. Results of coupling reactions, which were conducted both via in situ ‘Pd(II) salt + ligand’ approach and by use of the precatalysts, show that the mono-ligand precatalyst designs (1-PdCl2MeCN – 9-PdCl2MeCN, 6-PdCl2PhCN and 7-PdCl2PhCN) represent a true catalyst improvement initiative among the phosphine-free catalyst community; i.e. yields approaching 100% (TOF ≈ 2000) at 0.2 mol % catalyst loading, 45 °C and within 15 min. On the other hand, the complexes with trans-bis-ligand coordination were inactive at ambient temperatures. Therefore, it was concluded that coordinative saturation, which results from implementing two or more ligand equivalents or use of polydentate ligands on palladium, should be strongly discouraged. Such saturation necessitates the undesirable and avoidable high temperature necessities, long reflux durations and needlessly high catalyst loadings. Correlation between catalyst activity and donor strengths or steric properties were analysed leading to important conclusions. The catalyst design also supported coupling of activated aryl chlorides from 60 °C while Heck coupling activities were observed only at the early minutes of reactions.

Organic metal compounds and organic light emitting diodes comprising the same

PURPOSE: An organic metal compound is provided to have excellent thermal properties and light emitting efficiency, thereby being useful for a display and lighting device. CONSTITUTION: An organic metal compound is represented by chemical formula 1. In chemical formula 1, each of R and Z is hydrogen, deuterium, cyano, halogen hydroxy, nitro, C1-40 alkyl, C1-40 alkoxy, C1-40 alkylamino, C6-40 arylamino, C3-40 heteroarylamino, C1-40 alkoxy group, C1-40 alkylamino, C6-40 aryl group, C3-40 aryloxy group, germanium, phosphorous, and boron; each of A, B, C, D, and E is a substituted or unsubstituted aromatic cycle, or substituted or unsubstituted hydrocycle, X is carbon or nitrogen, G is chemical bond or C1-4 alkylene which can be substituted by (R-Zi)n.

Alkylation of aromatic compounds with 1-bromoadamantane in the presence of metal complex catalysts

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.

Adamantylation of polysubstituted arenes in trifluoroacetic acid

A reaction of 2,3-xylenol, 2,3-dichlorophenol, and 1,3-disubstituted benzenes with 1-adamantanol in trifluoroacetic acid leads to the corresponding monoand diadamantylated products.

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.

Synthesis of Adamantyl-substituted benzenedicarboxylic acids and their derivatives

A new procedure was developed for the synthesis of adamantyl benzene derivatives by alkylation of o-and m-xylenes with l-adamantyl bromide. Adamantyl-substituted benzenedicarboxylic acids were synthesized by catalytic liquid-phase oxidation of the corresp

Direct Clay-Catalyzed Friedel-Crafts Arylation and Chlorination of the Hydrocarbon Adamantane

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.