Search results for "Methyl carbonate"
showing 10 items of 26 documents
Triorganotin( iv ) cation-promoted dimethyl carbonate synthesis from CO 2 and methanol: solution and solid-state characterization of an unexpected di…
2018
Two novel C,N-chelated organotin(IV) complexes bearing weakly coordinating carborane moieties were prepared by the reaction of the corresponding C,N-chelated organotin(IV) chloride (i.e. LCNR2SnCl, R = n-Bu (1) and Ph (2); LCN = 2-(N,N-dimethylaminomethyl)phenyl)) with monocarba-closo-dodecaborate silver salt (AgCB11H12; Ag·3). Both products of the metathesis, [LCN(n-Bu)2Sn]+[CB11H12]− (4) and [LCNPh2Sn]+ [CB11H12]− (5), respectively, were characterized by both multinuclear NMR spectroscopy and elemental analysis. The instability of 4 and 5 towards water is discussed. The solid-state structure of LCN(n-Bu)2SnOH·B(C6F5)3 (4a) as a model compound with a Sn–O(H)⋯B linkage is also reported. The…
A comparative study of methanol carbonation on unsupported SnO2 and ZrO2
2009
International audience; The aim of this work was to explore the catalytic properties of SnO2 in the coupling of methanol with carbon dioxide to afford dimethyl carbonate. SnO2 nanopowders were produced by hydrolysis of tin tetra-tert-butoxide dissolved in n-butanol. The samples were much more active than a commercial one due to their higher surface areas. In addition, they exhibited excellent recyclability. However, comparison with ZrO2, prepared and tested under the same experimental conditions, showed that zirconia-based catalysts were more selective and are, among the heterogeneous catalysts already reported, still the more selective. SnO2 also catalyzed the formation of dimethyl ether l…
Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions
2012
A new efficient and expeditious route to the synthesis of aliphatic polycarbonates, in solvent-free conditions and using 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) as a catalyst precursor, is described. The protocol consists of a two-step polymerization process involving the transesterification of dimethyl carbonate (DMC) with linear alkane diols and leading to high molecular weight homopolymers. The reaction went to completion quantitatively with the liberation of methanol as the only by-product. The in situ formation of N-heterocyclic carbene species resulting from BMIM-2-CO2 decarboxylation is suggested to be a key feature of the condensation process. The protocol was then …
( n ‐Bu 2 Sn) 2 O(CO 3 ): An active, robust and recyclable organotin(IV) for the direct synthesis of linear organic carbonates from carbon dioxide an…
2017
Organotin(IV) compounds are known to promote the direct synthesis of organic carbonates from carbon dioxide and alcohols. In the past, structural studies have highlighted that the carbonato moiety is a recurring ligand of tin species collected during CO2 pressurized reactions. In a mimetic approach and in order to achieve an available and recyclable precursor, the title compound (n-Bu2Sn)2O(CO3) (1) was prepared in a single step by reacting commercial di-n-butyltin dichloride with an aqueous solution of sodium carbonate. Compound 1 was characterized using infrared spectroscopy and thermogravimetric and elemental analyses. Multinuclear NMR investigations in solution were also conducted. Comp…
The role of distannoxanes in the synthesis of dimethyl carbonate from carbon dioxide
2003
Abstract The synthesis, characterization, and reactivity of 1,3-dimethoxytetrabutyldistannoxane were investigated in connection to the mechanism of the selective synthesis of dimethyl carbonate from CO2 and methanol. A new distannoxane, 1-methoxy-3-methylcarbonatotetrabutyldistannoxane, resulting from a 1:1 adduct with CO2 was isolated and characterised by volumetry, multinuclear NMR and IR spectroscopies. When this compound was submitted to 20 MPa of CO2 at 423 K in toluene no dimethyl carbonate was formed, conversely to dibutyldimethoxystannane. However, when methanol was the solvent, dimethyl carbonate was selectively produced. A promoting effect of Si(OCH3)4 was evidenced through methox…
Synthesis of dimethyl carbonate in supercritical carbon dioxide
2006
The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu3SnOCH3, n-Bu2Sn(OCH3)2 , and [n-Bu2(CH3O)Sn]2 O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO2 pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO2 pressure higher than 16 MPa. Under these conditions, CO2 acted as a reactant and a solvent.
Carbon dioxide conversion to dimethyl carbonate: The effect of silica as support for SnO2 and ZrO2 catalysts
2011
International audience; Abundant in nature, CO2 poses few health hazards and consequently is a promising alternative to phosgene feedstock according with the principles of Green Chemistry and Engineering. The synthesis organic carbonates from CO2 instead of phosgene is highly challenging as CO2 is much less reactive. As part of our ongoing research on the investigation of catalysts for dimethyl carbonate (DMC) synthesis from methanol and CO2, we herein report results aimed at comparing the catalytic behavior of new SnO2-based catalysts with that of ZrO2. Silica-supported SnO2 and ZrO2 exhibit turnover numbers which are an order of magnitude higher than those of the unsupported oxides. Tin-b…
Di-n-butyltin(IV)-catalyzed dimethyl carbonate synthesis from carbon dioxide and methanol: An in situ high pressure 119Sn{1H} NMR spectroscopic study
2011
The reactivity of five di-n-butyltin(IV) complexes, n-Bu2Sn(OR)(2) (1), n-Bu2SnO (3), [n-Bu2Sn(OR)](2)O (4), (n-Bu2SnO)(2)(CO2) (6) and (n-Bu2SnO)(6)[(n-Bu2SnOR)(2)(CO3)](2) (7) (R = CH3), with CO2, suggested as possible catalyst precursors and key-intermediates for the direct synthesis of dimethyl carbonate from carbon dioxide and methanol, has been investigated using high-pressure Sn-119{H-1} NMR (HP-NMR) spectroscopy. Four of the five precursors studied, i.e. 3, 4, 6 and 7 give rise to an identical Sn-119{H-1} NMR pattern which can be explicitly attributed to the fingerprint of the dimeric form of the 1-methoxy-3-methylcarbonatotetrabutyldistannoxane {5}(2). However, with 1, a new pair o…
C,N-chelated organotin(IV) trifluoromethanesulfonates: Synthesis, characterization and preliminary studies of its catalytic activity in the direct sy…
2012
Abstract C,N-chelated tri- and diorganotin(IV) halides react with 1 or 2 mol equiv of silver trifluoromethanesulfonate (triflate, AgOTf, OTf = OSO2CF3−) to give corresponding C,N-chelated organotin(IV) triflates. The triorganotin(IV) triflates of general formula LCNR2SnOTf (R = n-Bu (1), Ph (2)) are presumably more stable towards hydrolysis than the diorganotin(IV) triflates LCNRSn(OTf)2 (R = n-Bu (3), Ph (4)). All prepared organotin(IV) triflates bearing the LCN ligand (where LCN is 2-(N,N-dimethylaminomethyl)phenyl-) were characterized by multinuclear NMR spectroscopy and elemental analysis. In addition, the structure of 3 was determined by the X-ray diffraction analysis. The catalytic ac…
CO2: from waste to resource for methanol-based processes
2009
This paper reports on research aiming at developing sustainable processes for the production of methanol (CH3OH) and dimethyl carbonate (DMC, (CH3)2CO3) using carbon dioxide (CO2) as a raw material. Using carbon dioxide as a raw material has several advantages; it is non-toxic, in abundant supply, and promises innovative routes to the production of commodity chemicals. Methanol and dimethyl carbonate are important products and feedstocks of the chemical industry. Methanol is produced commercially from synthesis gas, but it is also possible to use carbon dioxide as a feedstock. Conventional production of dimethyl carbonate involves the use of toxic phosgene or carbon monoxide, while the met…