1724-39-6Relevant academic research and scientific papers
Comparative study of the reactions of n-BuMgBr and n-BuLi with cyclododecanone
Zakharkin, L. I.,Churilova, I. M.,Petrovskii, P. V.
, p. 863 - 865 (1993)
The composition of the products obtained in the reaction of n-BuMgBr and n-BuLi with cyclododecanone (1) has revealed that 1 exhibits the properties of a sterically hindered ketone.The highest yield of 1-butylcyclododecanol (2) was achieved with the use of n-BuMgBr, but in this case cyclododecanol was also formed, whereas the use of n-BuLi led to the tertiary alcohol more distinctly.Dehydration of alcohol 2 resulted in a mixture of three olefins containing up to 90percent of E- and Z- isomers of 1-butylcyclododecene.
The effect of vanadium sources on the synthesis and catalytic activity of VMCM-41
Selvam,Dapurkar
, p. 64 - 71 (2005)
Mesoporous VMCM-41 was synthesized hydrothermally using various vanadium sources, viz, tetravalent vanadium such as vanadyl sulfate and vanadyl acetylacetonate, as well as pentavalent vanadium like sodium vanadate and ammonium vanadate. The influence of different vanadium sources on the framework substitution of vanadium, as well as their catalytic activity for the oxidation of cyclohexane, was investigated. Among the different vanadium stocks, the tetravalent vanadium sources showed maximum vanadium incorporation in the silicate framework of MCM-41. As a consequence, these catalysts gave much higher substrate conversion and excellent product selectivity. On the other hand, the catalysts prepared from pentavalent vanadium sources showed lower activity owing to the smaller amounts of vanadium in the matrix. Although the activity of the catalyst slightly decreased after first recycle as due to leaching of small amounts of active vanadium species, it however remained nearly the same even after several recycles. This was further confirmed by washing experiments wherein non-framework vanadium ions were removed upon ammonium acetate treatment; the washed catalysts showed a similar activity to those of the recycled catalysts. Thus, recycled/washed VMCM-41 behaves truly as heterogeneous catalyst. Furthermore, the influence of pore size of the catalyst was tested for the oxidation of bulkier substrate, viz, cyclododecane.
SELECTIVE OXIDATION OF SATURATED HYDROCARBONS USING AN ELECTROCHEMICAL MODIFICATION OF THE GIF SYSTEM.
Balavoine, Gilbert,Barton, Derek H. R.,Boivin, Jean,Gref, Aurore,Ozbalik, Nubar,Riviere, Henriette
, p. 2849 - 2852 (1986)
The Gif system for selective hydrocarbon oxidation can be carried out replacing the zinc by a cathodic electrochemical reduction; the yields obtained and the selectivities observed are very similar.
An original one-pot approach to boronic esters using the titanium-catalyzed reaction of cyclic olefins with alkyldichloroboranes
Khusainova, Liliya I.,Khafizova, Leila O.,Tyumkina, Tatyana V.,Ryazanov, Kirill S.,Popodko, Natalya R.,Dzhemilev, Usein M.
, p. 8 - 11 (2018)
Boronic esters (dicycloheptylalkylboronates, dicyclooctylalkylboronates, dicyclododecylalkylboronates, dibicyclo[2.2.1]hept-2-ylalkylboronates) are produced with yields ranging from moderate to excellent (52–96%) by the reaction between cyclic olefins (cycloheptene, cis-cyclooctene, cis/trans-cyclododecene, norbornene) and alkyldichloroboranes (alkyl = Et, n-Pent) in the presence of metallic magnesium and the Cp2TiCl2 catalyst with subsequent addition of water.
Synergistic oxidation of cyclohexane and hydrogen sulfide under Gif conditions
Barton, Derek H. R.,Li, Tingsheng,MacKinnon, John
, p. 557 - 558 (1997)
Saturated hydrocarbons and hydrogen sulfide can be synergistically oxidised by oxygen (or air) to give efficiently ketones (and the corresponding alcohols) and sulfur in the presence of a Gif catalyst based on FeII, picolinic acid and 4-tert-butylpyridine with acetonitrile as solvent at room temperature and nearly neutral pH.
An Efficient Electrochemical Process for the Oxidation of Saturated Hydrocarbons: the Gif-Orsay System
Balavoine, Gilbert,Barton, Derek H. R.,Boivin, Jean,Gref, Aurore,Ozbalik, Nubar,Riviere, Henriette
, p. 1727 - 1729 (1986)
The selective oxidation of saturated hydrocarbons can be carried out using triplet oxygen, pyridine, trifluoroacetic acid, and an iron catalyst in an unicellular electrochemical cell (Gif-Orsay system), cyclododecane, adamantane, and cyclo-octane being oxidised in 17-30 mmolar amounts with improved coulombic yields of up to ca. 30percent being attainable; oxidation of cyclohexane in 48 mmolar amounts gave cyclohexanone with some cyclohexanol in ca. 40percent coulombic yield, and similar yields were obtained on a 140-167 mmolar scale (saturated solution of hydrocarbon) with addition of electron transfer reagents and enough water to give two layers (good stirring) and satisfactory conductivity.
The functionalization of saturated hydrocarbons. Part XIX. Oxidation of alkanes by H2O2 in pyridine catalyzed by copper(II) complexes. A Gif-type reaction
Barton,Csuhai,Doller,Geletii
, p. 6561 - 6570 (1991)
The Cu(II)-catalyzed oxidation of saturated hydrocarbons by hydrogen peroxide proceeds in pyridine-acetic acid solutions affording mainly ketones as the reaction product. The conversion of hydrocarbon is about 20-30%. This system (called GoChAgg) shares with the Fe(III)-catalyzed system (GoAgg(II)) its unusual chemical characteristics.
Catalytic hydrogenation of aldehydes and ketones using cinchona–bipyridyl-based palladium catalyst
Chidambaram, Ramasamy R.,Sadhasivam, Velu,Mariyappan, Mathappan,Siva, Ayyanar
, p. 373 - 384 (2019)
Understanding the need for simple, robust and low effluents, in chemical processes, we have developed an elegant protocol for the catalytic reduction of aldehydes and ketones to corresponding alcohols which are used in synthetic fragrance applications using cinchona alkaloid-derived palladium catalyst. This system holds good for very low catalyst loading surfaces with the formation of fewer impurities and negligible decomposition under moderate pressure. The conversions and yields range from moderate to good (60–80%).
FUNCTIONALISATION OF SATURATED HYDROCARBONS. PART XVI. CHEMOSELECTIVE OXIDATION
Barton, Derek H. R.,Csuhai, Eva,Ozbalik, Nubar
, p. 3743 - 3752 (1990)
Cyclododecane is efficiently oxidised under GifIV and GoAggII conditions to give over 25percent of cyclododecanone with some cyclododecanol.The addition in equimolar amounts of ethanol, isopropanol, ethylene glycol, diisopropyl ether, biphenyl, anisole, diphenyl sulfide, methyl benzoate and dimethylacetamide have little effect on the oxidation.Thiophenols have a minor effect, but t-butyl thiol and dimethylaniline reduce oxidation to a major extent.In all cases, the mass balances are satisfactory.Overoxidation of cyclododecanone affords cyclododecane-1,3-, 1,4-, 1,5- and 1,6-diones.The major dione is 1,4- followed by 1,6-.
Hierarchically porous BEA stannosilicates as unique catalysts for bulky ketone conversion and continuous operation
Al-Nayili, Abbas,Yakabi, Keiko,Hammond, Ceri
, p. 1373 - 1382 (2016)
Pore size limitations typically limit the applicability of Lewis acidic zeolites, such as titano- and stanno-silicates, to catalytic processes based on small-to-mid sized substrates, and increase their rates of deactivation, prohibiting further exploitation. Herein, we demonstrate that tin-containing zeolites possessing modified hierarchical BEA matrices can be prepared. These hierarchical stannosilicates are able to mediate the catalytic conversion of bulky ketone substrates, a pertaining challenge in the field that purely microporous analogues are unable to mediate. Deactivation studies in the continuous regime also demonstrate the exceptional stability of hierarchical Sn-Beta compared to purely microporous Sn-Beta, with 20% loss of activity observed over 700 h on stream. In contrast, the purely microporous analogue lost ±70% activity in only 200 h. To the best of our knowledge, this is the first time a stannosilicate with a beneficial hierarchical BEA framework has been prepared, and the first evidence of cyclododecanone valorisation with stannosilicate catalysts.
