6 November 2012 in Petroleum Chemistry
The catalytic activity of the Pd(PPh3)4-TsOH and Pd(PPh3)4-PPh3-TsOH systems in the reaction of isobutylene hydromenthoxycarbonylation with carbon monoxide and l-menthol has been examined. It has been found that the reaction proceeds regioselectively yielding the linear product l-menthyl isovalerate. Optimal conditions have been found for running the process. The spatial structure of l-menthyl isovalerate synthesized via the isobutylene hydromenthoxycarbonylation reaction has been established by 1H and 13C NMR techniques.
15 May 2012 in Petroleum Chemistry
The reaction of isobutylene hydroalkoxycarbonylation at low carbon monoxide pressures (≤2.0 MPa) with ethylene glycol and glycerol in the presence of catalytic systems based on Pd and mono- and bidentate organic phosphines has been studied. The effect of different conditions of the reaction in the presence of the Pd(Acac)2-PPh3-TsOH catalyst system on the ratio of the products, mono- and diglycolides (mono-, di-and triglycerides) of isovaleric acid has been investigated. The relative catalytic activity of a number of binary and ternary systems based on synthesized Pd(Acac)2, Pd(PPh3)4, and PdCl2(PPH3)2 complexes has been determined.
1 May 2008 in Petroleum Chemistry
The reaction of isobutylene hydroxycarbonylation with carbon monoxide and an alcohol (ethanol, 1-menthol) in the presence of the palladium acetylacetonate-triphenylphosphine-p-toluenesulfonic acid catalytic system was investigated. It was shown that the reaction proceeds regioselectively with the formation of linear products (ethyl isovalerate, 1-menthyl isovalerate). The optimum conditions for running the process were found, at which the yield of the main products is 67–79%.
31 July 2016 in Petroleum Chemistry
Carboxylation of -cresol, -cresol, and -cresol with sodium ethyl carbonate (SEC) proceeds regioselectively with the formation of cresotic acids: 2-hydroxy-3-methylbenzoic acid, 2-hydroxy-4-methylbenzoic acid, and 2-hydroxy-5-methylbenzoic acid, respectively. Optimal conditions for conducting the process have been found to be as follows: the reactants ratio of [cresol]: [sodium ethyl carbonate] = (1.5–2): 1, = 180–185°C, = 10 atm, and = 6–7 h. Simple and convenient methods for the synthesis of cresotic acids, which can be used for their industrial manufacturing, have been developed.
1 April 2016 in Russian Journal of Organic Chemistry
10 November 2014 in Eurasian Chemico-Technological Journal
Hydroalkoxycarbonylation of olefins with carbon monoxide and alcohols under condition of homogeneous – catalysis with transition metal complexes allows facile one-step synthesis of practically useful carbon acid esters. Many of them have biological activity and are constituents of drugs or valuable intermediate products in drug synthesis. Hydroalkoxycarbonylation of isobutylene with carbon monoxide and alcohols in the presence of catalytic system Pd(PPh3)4-PPh3-TsOH was applied for preparing of biological active isovaleric acid esters: 1-menthylisovalerate (main active component of the spasmolytic medicine “Validolum”), ethylisovalerate (intermediate product for obtaining sedative and spasmolytic medicines “Ethyl ester of α-bromisovaleric acid” and “Corvalolum”), cyclohexylisovalerate (bactericide activity) and benzylisovalerate (bactericide and antifungus activity). Hydroalkoxycarbonylation reaction of isobutylene with carbon monoxide and alcohols (ethanol, cyclohexanol, l-menthol, benzyl alcohol) in the presence Pd(PPh3)4-PPh3-TsOH system carried out at conditions: temperature 100 ºC; CO pressure 2.0 MPa; reaction time 4 h; reactants and catalyst components ratio [alcohol]:[isobutylene]:[Pd(PPh3)4]:[PPh3]:[TsOH] = 435:550:1:3:12. The yields of the products were 71-95% (on converted alcohols). The selectivity in linear reaction products was 100%. Such a high regioselectivity is apparently provided both by the structure of the starting alkene (isobutylene) and by the reaction mechanism. The most probable is a hydride mechanism. Due to the more advanced technology of production the Medicines will have better qualitative characteristics. The cost of production of the Medicines with the use of new technologies is 2-3 times lower as compared to the medicines produced by existing at the present traditional technologies.