2094-74-8Relevant academic research and scientific papers
Why does pivalaldehyde (trimethylacetaldehyde) unexpectedly seem more basic than 1-adamantanecarbaldehyde in the gas phase? FT-ICR and high-level ab initio studies
Quintanilla, Esther,Davalos, Juan Z.,Abboud, Jose-Luis M.,Alcami, Manuel,Cabildo, M. Pilar,Claramunt, Rosa M.,Elguero, Jose,Mo, Otilia,Yanez, Manuel
, p. 1826 - 1832 (2005)
Fourier transform ion cyclotron resonance spectroscopy (FT ICR) techniques, including collision-induced dissociation (CID) methodology, were applied to the study of the gas-phase protonation of pivalaldehyde (1) and 1-adamantanecarbaldehyde (2). A new synthetic method for 2 was developed. The experiments, together with a thorough computational study involving ab initio and density functional theory (DFT) calculations of high level, conclusively show that upon monoprotonation in the gas phase, compound 1 yields monoprotonated methyl isopropyl ketone 3. The mechanism of this gas-phase acid-catalyzed isomerization is different from that reported by Olah and Suryah Prakash for the reaction in solution. In the latter case, isomerization takes place through the diprotonation of 1.
Synthesis and structural studies of symmetric and unsymmetric adamantylmethyleneazines
Sanz, Dionisia,Ponce, Maria Alejandra,Claramunt, Rosa Maria,Fernandez-Castano, Cristina,Foces-Foces, Concepcion,Elguero, Jose
, p. 455 - 469 (1999)
The synthesis and spectroscopic properties (1H, 13C and 15N NMR, in solution and in the solid state) of six new 1-adamantylmethlene azines are reported. The crystal and molecular structures of 1-adamantylcarbaldehyde azine and 1-adamantyl methyl ketone azine, which exist in the solid state in the E,E-configuration, were determined by x-ray analysis. The geometric characteristics of the azine central bridge and the preferred configuration with regard to it (E,E, E,Z, or Z,Z) were investigated by means of the crystallographic data retrieved from the Cambridge Structural Database and ab initio quantum chemical calculations. Copyright
Synthesis of Bilin-1,19-diones and Biladiene-ac-1,19-diones with C(10) Adamantyl and tert-Butyl Groups
Kar, Ari K.,Lightner, David A.
, p. 795 - 803 (1998)
Bilirubin and biliverdin analogs bearing bulky adamantyl and tert-butyl groups at the central C(10) position were synthesized and their structures were analyzed by nmr and ultraviolet-visible spectroscopy and by molecular mechanics calculations, all of which collectively indicated a preference for helical conformations.
Efficient synthesis of 1-adamantanecarboxaldehyde by the GaCl 3-mediated carbonylation of adamantane under mild reaction conditions
Oshita, Masayuki,Chatani, Naoto
, p. 4323 - 4325 (2004)
(Chemical Equation Presented) The reaction of adamantane (1) with CO (1 atm) in 1,2-dichloroethane at room temperature in the presence of GaCl 3 results in formylation to give 1-adamantanecarboxaldehyde (2) in up to 84% yield.
Superacid-Catalyzed Electrophilic Formylation of Adamantane with Carbon Monoxide Competing with Koch-Haaf Carboxylation
Farooq, Omar,Marcelli, Mike,Prakash, G. K. Surya,Olah, George A.
, p. 864 - 867 (1988)
The superacid-catalyzed reaction of adamantane with carbon monoxide was investigated. 1-Adamantanecarboxaldehyde together with 1-adamantaneecarboxylic acid and 1-adamantanol (the products of the reaction of intermediate 1-adamantyl cation) was obtained.The mechanism of the formation of 1-adamantanecarboxaldehyde by electrophilic formylation involving ?-insertion of the formyl cation is indicated.This is contrasted by the competing protolytic ionization of adamantane to 1-adamantyl cation which gives with CO 1-adamantanoyl cation and subsequently 1-adamantanecarboxylic acid (Koch-Haaf reaction) or by hydrolysis 1-adamantanol.
Unidirectional Threading into a Bowl-Shaped Macrocyclic Trimer of Boron–Dipyrrin Complexes through Multipoint Recognition
Nakamura, Takashi,Yamaguchi, Gento,Nabeshima, Tatsuya
, p. 9606 - 9609 (2016)
Bowl-shaped macrocycles have the distinctive feature that their two sides are differentiated, and thus can be developed into elaborate hosts that fix a target molecule in a controlled geometry through multipoint interactions. We now report the synthesis of a bowl-shaped macrocyclic trimer of the boron–dipyrrin (BODIPY) complex and its unidirectional threading of guest molecules. Six polarized Bδ+?Fδ-bonds are directed towards the center of the macrocycle, which enables strong recognition of cationic guests. Specifically, the benzylbutylammonium ion is bound in a manner in which the benzyl group is located at the convex face of the bowl and the butyl group at its concave face. Furthermore, adrenaline was strongly captured on the convex side of the bowl by hydrogen bonding, Coulomb forces, and C?H???π interactions.
Synthesis and anti-HIV studies of 2-adamantyl-substituted thiazolidin-4-ones
Balzarini, Jan,Orzeszko, Barbara,Maurin, Jan K.,Orzeszko, Andrzej
, p. 993 - 1003 (2007)
A series of novel thiazolidin-4-ones bearing a lipophilic adamantyl substituent at position 2, and versatile substituents on the nitrogen atom of the thiazolidine ring, were synthesized whereas several compounds exhibited a modest anti-HIV-1 activity, (±)-2-adamantan-1-yl-3-(4,6-dimethyl-pyridin-2-yl)-thiazolidin-4-one 22 was endowed with a remarkable antiviral potency (EC50 = 0.35 μM). The adamantane moiety played an important role in the eventual antiviral activity of the compound. This compound behaved as a typical non-nucleoside reverse transcriptase (RT) inhibitor (NNRTI) with non-competitive inhibition against RT with respect to the substrate (Ki = 12 μM). Separation of the enantiomers via diastereoisomeric salts was performed for 22. X-ray studies enabled us to ascribe an S configuration to (-)-2-adamantan-1-yl-3-(4,6-dimethyl-pyridin-2-yl)-thiazolidin-4-one (-)-22. Furthermore, it was found that the (+)-22 isomer was predominantly responsible for the potent anti-HIV-1 activity (EC50 value of 0.178 μM), while the levo isomer was more than 60-fold less active.
Preparative synthesis of vinyl diamondoids
Fokin, Andrey A.,Butova, Ekaterina D.,Barabash, Anastasiya V.,Huu, Nhan N.,Tkachenko, Boryslav A.,Fokina, Natalie A.,Schreiner, Peter R.
, p. 1772 - 1777 (2013)
We describe a convenient four-step preparation of 1-vinyl adamantane, 1-vinyl diamantane, and 4,9-divinyl diamantane from the respective diamondoid acetic acids in 50-80% isolated yields involving esterification, reduction, and hydrobromination/dehydrobromination. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
Aluminum chloride/dichloromethane (chloroform) induced carbonylation, Ritter reaction, and cyanation of adamantane
Olah,Wang
, p. 1090 - 1092 (1992)
The aluminum chloride induced carbonylation, Ritter reaction, and cyanation of adamantane in dichloromethane (chloroform) are reported. The mechanism of the reactions is discussed involving initial hydride abstraction from adamantane by ClCH2(δ+)Cl → (δ-)AlCl3 or Cl2CH(δ+)Cl → (δ-)AlCl3 complexes (indicated by formation of chloromethane or dichloromethane) and subsequent reaction of the 1-adamantyl cation with carbon monoxide, nitriles or cyanotrimethylsilane.
Stable bromoallene oxides
Christopher Braddock,Mahtey, Areeb,Rzepa, Henry S.,White, Andrew J. P.
, p. 11219 - 11222 (2016)
The first stable bromoallene oxides were obtained by the DMDO epoxidation of 1-bromo-1,3-di-tert-alkylallenes, producing the first crystalline allene oxide of any kind. The epoxidations are regioselective for the bromine-bearing Δ1,2 alkene, and also face selective producing single diastereomer E-olefin products.
