497-38-1Relevant articles and documents
Acid-catalyzed hydrolysis of bridged bi- and tricyclic compounds. XXXVII. Kinetics and mechanisms of 1- and 3-acetoxynortricyclanes
Lajunen, Martti,Yli-Mannila, Rita,Salminen, Outi
, p. 133 - 138 (2000)
The disappearance of 3- and 1-acetoxynortricyclanes (1 and 2) in aqueous perchloric acid was followed by capillary gas chromatography at different temperatures and acid concentrations. According to the activation parameters, solvent deuterium isotope effe
Role of Dioxygen as an Activator in Olefin Metathesis
Ivin, Kenneth J.,Reddy, Boreddy S. R.,Rooney, John J.
, p. 1062 - 1064 (1981)
Evidence is presented that the beneficial or essential influences often noted when small amounts of dioxygen are added to catalytic systems for olefin metathesis and ring-opening polymerization are due to the formation of epoxides and the corresponding me
Acid-catalyzed hydrolysis of bridged bi- and tricyclic compounds. XXXVIII - Kinetics and mechanisms of 1- and 3-nortricyclanols
Lajunen, Martti,Lahti, Veli
, p. 854 - 858 (2001)
The disappearance of 1- and 3-nortricyclanols (1-OH and 2-OH) in aqueous perchloric acid was followed by capillary GC at different temperatures and acid concentrations. 1-OH is ca 1000 times more reactive than 2-OH. The activation parameters, solvent deut
OXIDATION OF NON-ACTIVATED C-H BONDS IN HYDROCARBONS AND STEROIDS
Linz, T.,Schaefer, H. J.
, p. 6581 - 6582 (1987)
CrO3 in CH2Cl2/CH3COOH/(CH3CO)2O oxidizes hydrocarbons to alcohols and ketones, 5α-androstane and 3β-acetoxy-5α-androstane are converted to 5α-androst-14-en-16-ones.
Supported rhenium nanoparticle catalysts for acceptorless dehydrogenation of alcohols: Structure-activity relationship and mechanistic studies
Kon, Kenichi,Onodera, Wataru,Toyao, Takashi,Shimizu, Ken-Ichi
, p. 5864 - 5870 (2016)
Al2O3-supported Re with different oxidation states and Re0 metal nanoparticles on various supports are prepared, characterized and tested for the dehydrogenation of 2-octanol. The activity of Re/Al2O3 increases with the fraction of metallic Re. The activity of metallic Re depends on the support oxides, and the support with moderate electronegativity (Al2O3) gives the highest turnover frequency (TOF) per surface Re0 site. Re/Al2O3 is effective for acceptorless dehydrogenation of various aliphatic secondary alcohols to ketones. The kinetic isotope effects on the dehydrogenation of 2-propanol show that dissociation of the α-C-H bond of 2-propanol is the rate-limiting step. The IR study of the reaction of gas phase 2-propanol over the Re/Al2O3 surface shows that the acid-base pair site of Al2O3 is responsible for the O-H dissociation of 2-propanol. The structural requirements are discussed on the basis of the mechanistic results.
Improved synthesis of 2-norbornanone
Zhang, Heng,Fu, Shuixiang,Tao, Ming,Liao, Zutai,Qian, Chao,Chen, Xinzhi
, p. 3325 - 3332 (2016)
Herein a two-step process for the synthesis of 2-norbornanone with 91 % overall yield has been developed. The addition of sublimation inhibitors suppressed the sublimation of norbornene in the process of sulfuric acid-promoted hydration and increased the yield of 2-norbornanol significantly under mild conditions. Additionally, reuse of sulfuric acid has been achieved. A 4-hydroxy-TEMPO/CuCl/TBN triple-component catalyst system for the highly selective aerobic oxidation of 2-norbornanol was developed and displayed high atom efficiency and yield.
Aerobic oxidation and oxidative esterification of alcohols through cooperative catalysis under metal-free conditions
Karimi, Babak,Ghahremani, Mina,Vali, Hojatollah,Ciriminna, Rosaria,Pagliaro, Mario
supporting information, p. 8897 - 8900 (2021/09/10)
The ABNO@PMO-IL-Br material obtained by anchoring 9-azabicyclo[3.3.1]nonane-3-oneN-oxyl (keto-ABNO) within the mesopores of periodic mesoporous organosilica with bridged imidazolium groups is a robust bifunctional catalyst for the metal-free aerobic oxidation of numerous primary and secondary alcohols under oxygen balloon reaction conditions. The catalyst, furthermore, can be successfully employed in the first metal-free self-esterification of primary aliphatic alcohols affording valued esters.
Liquid-phase oxidation of olefins with rare hydronium ion salt of dinuclear dioxido-vanadium(V) complexes and comparative catalytic studies with analogous copper complexes
Maurya, Abhishek,Haldar, Chanchal
, (2021/02/26)
Homogeneous liquid-phase oxidation of a number of aromatic and aliphatic olefins was examined using dinuclear anionic vanadium dioxido complexes [(VO2)2(salLH)]? (1) and [(VO2)2(NsalLH)]? (2) and dinuclear copper complexes [(CuCl)2(salLH)]? (3) and [(CuCl)2(NsalLH)]? (4) (reaction of carbohydrazide with salicylaldehyde and 4-diethylamino salicylaldehyde afforded Schiff-base ligands [salLH4] and [NsalLH4], respectively). Anionic vanadium and copper complexes 1, 2, 3, and 4 were isolated in the form of their hydronium ion salt, which is rare. The molecular structure of the hydronium ion salt of anionic dinuclear vanadium dioxido complex [(VO2)2(salLH)]? (1) was established through single-crystal X-ray analysis. The chemical and structural properties were studied using Fourier transform infrared (FT-IR), ultraviolet–visible (UV–Vis), 1H and 13C nuclear magnetic resonance (NMR), electrospray ionization mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR) spectroscopy, and thermogravimetric analysis (TGA). In the presence of hydrogen peroxide, both dinuclear vanadium dioxido complexes were applied for the oxidation of a series of aromatic and aliphatic alkenes. High catalytic activity and efficiency were achieved using catalysts 1 and 2 in the oxidation of olefins. Alkenes with electron-donating groups make the oxidation processes easy. Thus, in general, aromatic olefins show better substrate conversion in comparison to the aliphatic olefins. Under optimized reaction conditions, both copper catalysts 3 and 4 fail to compete with the activity shown by their vanadium counterparts. Irrespective of olefins, metal (vanadium or copper) complexes of the ligand [salLH4] (I) show better substrate conversion(%) compared with the metal complexes of the ligand [NsalLH4] (II).
Catalytic alcohol oxidation using cationic Schiff base manganeseIII complexes with flexible diamino bridge
Kakavand, Meysam,Mastrorilli, Piero,Mesto, Ernesto,Neshat, Abdollah,Osanlou, Farzane,Schingaro, Emanuela,Todisco, Stefano
, (2020/11/04)
Four Schiff base manganese(III) complexes with derivatives of [(R,R)-N,N’-bis(salicy1idene)-1,2-cyclohexanediaminato)] including substituents on salicylaldehyde such as 3-methoxy, 3,5-di-tert-butyl and 3,5-chloro were synthesized and characterized using a combination of IR, UV–Vis, and HR ESI-MS techniques. The catalytic activity of these complexes was tested in the oxidation of 1-phenylethanol to acetophenone, revealing very good performances for all of the four manganese complexes. The catalytic reactions were carried out in the presence of tert-butyl hydroperoxide (TBHP) as oxidant and imidazole as co-catalyst. Complex Mn-4, bearing electron withdrawing [(R,R)-N,N’-bis(3,5-di-chloro-salicylidene)-1,2-cyclohexanediaminato)] ligand was found to be the most stable of the tested Mn(III) complexes and was selected for the oxidation of several primary and secondary alcohols.
New Cu(II), Co(II) and Ni(II) azo-Schiff base complexes: Synthesis, characterization, catalytic oxidation of alkenes and DFT study
Lashanizadegan, Maryam,Asna Ashari, Hadiseh,Sarkheil, Marzieh,Anafcheh, Maryam,Jahangiry, Samira
, (2021/03/22)
Three new complexes with general formula of ML (M = Cu (1), Co (2), Ni (3)) containing an azo-Schiff base ligand (H2L) derived from 2,3-butanediamine and 4-(benzeneazo) salicylaldehyde were synthesized by template method. Characterization of the ligand and complexes were accomplished with FT-IR, UV–Vis, and 1H NMR. The catalytic activity of the complexes (1–3) were tested for the oxidation of various alkenes (cyclooctene, cyclohexene, styrene, α-methyl styrene, and norbornene) applying tert-butyl hydroperoxide (TBHP) as an oxidizing agent, and it was found that they were acceptable catalysts. Under the optimized reaction conditions, CuL complex displayed 94% conversion for the oxidation of cyclooctene, and CoL and NiL complexes exhibited 90 and 85% conversions for oxidizing α-methyl styrene, respectively. Based on our density functional computations, diffuse functions are compulsory in the basis set for geometry optimization of these systems. Therefore, the most stable structures and the vibrational frequencies were calculated at the M06-2X/6–311++G(d,p) level. By establishing the correlation between observed and calculated frequencies, the assignment of the vibrational modes was performed. Based on natural charge analysis (NAO), the back electron transfer from ML to the TBHP breaks the O–O bond and facilitates the formation of tert-butoxyl radicals.
