700-58-3Relevant articles and documents
Temperature deactivation of excited Tb3+ in the presence of 1,2-dioxetane in acetonitrile
Ableeva, N. Sh.,Voloshin, A. I.,Ostakhov, S. S.,Kukovinets, A. G.,Korobeinikova, V. N.,et al.
, p. 1667 - 1671 (1994)
Quenching the fluorescence (FL) of terbium perchlorate by 2,2'-adamantane-2,2'-dioxide (1) was shown to have a chemical character and was caused by the formation of the 3+> complex.The dependence of the lifetime (τ) of FL of Tb.3+ in acetonitrile on the temperature and concentration of 1 has been studied.The temperature dependence of τ is caused by rearrangement of the inner sphere of the aquasolvate complexes of Tb3+, which leads to the replacement of H2O with MeCN and 1.The energy of replacing the H2O molecule in the inner sphere of complexes with a solvent molecule has been calculated. - Key words: chemiluminiscence, fluorescence, Tb(ClO4)3*6H2O, 2,2'-adamantane-2,2'-dioxide, lifetime, quenching.
Solvent-cage effect (viscosity dependence) as a diagnostic probe for the mechanism of the intramolecular chemically initiated electron-exchange luminescence (CIEEL) triggered from a spiroadamantyl-substituted dioxetane
Adam, Waldemar,Bronstein, Irena,Trofimov, Alexei V.,Vasil'ev, Rostislav F.
, p. 958 - 961 (1999)
The excitation step of the intramolecular CIEEL generation in the triggered cleavage of spiroadamantyl-substituted dioxetane has been studied. The electron back-transfer (BET) process versus the direct chemiexcitation of the phenolate-anion emitter have been considered as mechanistic alternatives. The observed solvent-cage effect on the CIEEL generation, manifested by the increase of the singlet chemiexcitation yield at increased viscosity, provides evidence that the BET process operates in the intramolecular CIEEL mechanism.
NEW STABLE 1,2-DIOXETANE AND STERIC FACTORS IN THE OXIDATION OF SINGLET OXYGEN
Tolstikov, G.A.,Kazakov, V.P.,Sharipov, G.L.,Voloshin, A.I.,Ostakhov, S.S.,et al.
, p. 2209 (1984)
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Highly selective production of 2-adamantanone by photocatalytic oxidation of adamantane
Song, Sun-Jung,Kim, Kyoung Seok,Kim, Kyung Hwan,Kim, Jong Beom,Kim, Jong-Ho,Kim, Keun-Sik,Shin, Honghyun,Cho, Dong Lyun
, p. 1052 - 1053 (2008)
2-Adamantanone was selectively produced by photocatalytic oxidation of adamantane in acetic acid using TiO2 powders. The reactions were carried out at ambient and acetic acid reflux temperatures with and without an oxidant. Adding oxidant in refluxing acetic acid under irradiation remarkably increased conversion and selectivity. Rutile TiO2 powders showed better conversion and selectivity in the presence of H2O2. The total conversion was 67% and the highest selectivity of 2-adamanta-none was 89%. Copyright
STEREOISOMERIC DIOXETANES: THE EFFECT OF STRUCTURE ON THERMAL STABILITY AND EXCITATION YIELDS
Tolstikov, G. A.,Kazakov, V. P.,Sharipov, G. L.,Voloshin, A. I.,Lerman, B. M.,et al.
, p. 1775 (1987)
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Selective and mild oxyfunctionalization of model polyolefins
Boaen, Nicole K.,Hillmyer, Marc A.
, p. 7027 - 7034 (2003)
The direct oxyfunctionalization of a model polyolefin, polyethylene-alt-propylene (PEP), was achieved utilizing a straightforward, mild process. In the presence of a manganese complex, manganese meso-tetra-2,6-dichlorophenylporphyrin acetate (Mn(TDCPP)OAc), imidazole, a phase transfer agent, and potassium peroxymonosulfate (Oxone), PEP was functionalized under ambient conditions without chain degradation. The primary oxidation products contained tertiary alcohols and ketones based on IR, 1H NMR, 13C NMR, and DEPT 13C NMR spectroscopy of the oxyfunctionalized products. The oxyfunctionalization of squalane, a small molecule, structural analogue of PEP, was also demonstrated. Spectroscopic analyses of the main products from the squalane oxidation were nearly identical with the functional groups identified in the PEP oxidation products. The degree of functionalization was modulated by changing the relative concentration of the oxidant, Oxone. The degree of functionalization and the thermal properties are reported for these new polymeric materials.
Geluk,Schlatmann
, p. 5361,5367 (1968)
MECHANISM OF SENSITIZATION OF CHEMILUMINESCENCE IN THE THERMOLYSIS OF DIADAMANTYLIDENEDIOXETHANE
Tolstikov, G. A.,Sharipov, G. L.,Voloshin, A. I.,Ostakhov, S. S.,Kazakov, V. P.
, p. 715 - 721 (1986)
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Synthetic Methods and Reactions; 110. Fluorination of 1-Haloadamantanes and -diadamantane with Nitronium Tetrafluoroborate/Pyridine Polyhydrogen Fluoride or Sodium Nitrate/Pyridine Polyhydrogen Fluoride
Olah, George A.,Shih, Joseph G.,Singh, Brij P.,Gupta, B. G. B.
, p. 713 - 715 (1983)
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Zirconia-supported 11-molybdovanadophosphoric acid catalysts: effect of the preparation method on their catalytic activity and selectivity
Bakkali, Bouchra El,Trautwein, Guido,Alca?±iz-Monge, Juan,Reinoso, Santiago
, p. 1334 - 1347 (2018)
The oxidation of adamantane with hydrogen peroxide catalyzed by zirconia-supported 11-molybdovanadophosphoric acid is shown to be a suitable green route for the synthesis of adamantanol and adamantanone. This work evaluates how the catalyst activity and selectivity are affected by some of its preparative parameters, such as the method for supporting the catalytically active heteropoly acid over the zirconia matrix or the pretreatments applied to the resulting materials before being used as heterogeneous catalysts. Our results indicate that the most effective catalysts able to maintain their activity after several reaction runs are those prepared by following the sol-gel route, whereas the most selective catalysts are those obtained by impregnation methods. Moreover, the calcination temperature has also been identified as a relevant parameter influencing the performance of catalysts based on supported heteropoly acids. The increasing catalytic activity observed over several consecutive reaction runs has been attributed to the formation of peroxo derivatives of polyoxometalate clusters at the surface of the catalyst and their accumulation after each reaction cycle.
Chemiluminescence and catalysis of the decomposition of dispiro(diadamantane-l,2-dioxetane) in solutions of lanthanide perchlorates 1: Catalysis of the 1,2-dioxetane decomposition
Kazakov,Voloshin,Ostakhov,Khusainova
, p. 2350 - 2354 (1996)
Decomposition of dispiro(diadamantane-l,2-dioxetane) u1, Cd1, Tb1, Pr1, and Ce1 perchlorates was studied by the chemiluminescencc method. The rate constants of decomposition of 1 in complexes of composition 1 Ln"1 and stability constants of these complexes, as well as activation parameters of the decomposition of 1 and thermodynamic parameters of the complexation were determined. A correlation between the thermodynamic parameters of complexation and ionic radii of Ln"1 was found.
Mechanism of RuO4-mediated oxidations of saturated hydrocarbons, isotope effects, solvent effects and substituent effects
Bakke, Jan M.,Frohaug, Astrid E.
, p. 507 - 513 (1996)
Adamantane and 1,3,5,7-tetradeuterioadamantane were oxidized by RuO4 in two solvent systems, CCl4-CH3CN-H2O and acetone-water, yielding two kinetic deuterium isotope effects (KIEs), 4-8 ± 0-2 and 7.8 ± 0.l, respectively, very similar to those obtained in analogous reactions with cu-decalin and perdeuteriocis-decalin, 4-8 and 6-8. These results were interpreted as primary KIEs and small or negligible secondary KIEs. From this, sp2-hybridized intermediates were not involved in the reaction path. The kinetic effect of the solvent was investigated by performing the reaction in aqueous acetone and acetonitrile. The rates were correlated with Grunwald-Winstein Y values and with Reichardt ET(30) values. Both correlations showed the reaction to be only moderately dependent on the solvent polarity. 1-Substituted adamantanes were oxidized in CCl4-CH3CN giving a Taft ρ* value of -2.5 ± 0.1. These results were regarded as support for a reaction consisting of a pre-equilibrium with formation of a substrate-RuO4 complex followed by a rate-determining concerted reaction. Chemical Equation Presented. The results did not support a reaction mechanism with a carbocation or radical intermediate, or a scheme with two competing reactions, one with a carbocation intermediate and the other with a concerted mechanism.
QUANTUM-CHAIN PHOTOCATALYTIC DECOMPOSITION OF ADAMANTYLIDENEADAMANTANE-1,2-DIOXETANE INITIATED BY Eu*(fod)3
Kazakov, V. P.,Sharipov, G. L.,Voloshin, A. I.,Tolstikov, G. A.
, p. 1997 (1990)
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Enhancing Chemo- And Stereoselectivity in C-H Bond Oxygenation with H2O2by Nonheme High-Spin Iron Catalysts- And Role of Lewis Acid and Multimetal Centers
Das, Abhishek,Jana, Rahul Dev,Paine, Tapan Kanti
supporting information, p. 5969 - 5979 (2021/05/04)
Spin states of iron often direct the selectivity in oxidation catalysis by iron complexes using hydrogen peroxide (H2O2) on an oxidant. While low-spin iron(III) hydroperoxides display stereoselective C-H bond hydroxylation, the reactions are nonstereoselective with high-spin iron(II) catalysts. The catalytic studies with a series of high-spin iron(II) complexes of N4 ligands with H2O2 and Sc3+ reported here reveal that the Lewis acid promotes catalytic C-H bond hydroxylation with high chemo- and stereoselectivity. This reactivity pattern is observed with iron(II) complexes containing two cis-labile sites. The enhanced selectivity for C-H bond hydroxylation catalyzed by the high-spin iron(II) complexes in the presence of Sc3+ parallels that of the low-spin iron catalysts. Furthermore, the introduction of multimetal centers enhances the activity and selectivity of the iron catalyst. The study provides insights into the development of peroxide-dependent bioinspired catalysts for the selective oxygenation of C-H bonds without the restriction of using iron complexes of strong-field ligands.
Preparation method of adamantanone
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Paragraph 0033-0041; 0048-0060; 0067-0078; 0085-0096;, (2021/04/03)
The invention discloses a preparation method of adamantanone, and relates to the technical field of adamantanone synthesis. The problems that the reaction time is long and the operation process is tedious are solved. The preparation method specifically comprises the following steps: putting raw materials including adamantane, sulfuric acid and trifluoroacetic acid into a batching kettle, and stirring and mixing at 30 DEG C; raising the temperature to 50 DEG C, and introducing nitrogen into the batching kettle; pressing the mixed materials into a reaction tube, and performing standing for 1 minute; pouring the reaction solution on 500g of ice, adding a NaOH aqueous solution which is 7 times the weight of adamantane during cooling, and adjusting the pH value to 9; and extracting by using methylbenzene of which the weight is 3 times that of adamantane. The raw materials are mixed and then heated, nitrogen is introduced, then an oxidation reaction occurs, the retention time and temperatureof reaction liquid in a reaction tube are controlled in the leading-out period, the reaction liquid is extracted through methylbenzene and the NaOH aqueous solution, the extraction liquid is subjected to reduced pressure distillation concentration, cooling, separation and drying treatment, the final product is obtained, the operation process is relatively simple, the reaction is controllable, andthe time is short.