21490-63-1Relevant articles and documents
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Hoesch,L.,Dreiding,A.S.
, p. 1995 - 2009 (1975)
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Sato,Cvetanovic
, p. 1668,1671 (1958)
PROCESS FOR SYNTHESIS OF PICOLINAMIDES
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Paragraph 0236, (2021/04/23)
The present technology relates to processes, mixtures and intermediates useful for making picolinamide fungicides. The picolinamide compounds are prepared by processes that include coupling together a 4-methoxy-3-acyloxypicolinic acid with key 2-amino-L-alaninate esters derived from substituted 2-phenylethanols.
Oxidation of lower alkenes by Α-oxygen (FeIII–O??)Α on the FeZSM-5 surface: The epoxidation or the allylic oxidation?
Starokon, Eugeny V.,Malykhin, Sergei E.,Parfenov, Mikhail V.,Zhidomirov, Georgy M.,Kharitonov, Alexander S.
, p. 43 - 51 (2017/11/15)
Reactions of anion-radical α-oxygen (FeIII–O??)α with propylene and 1-butene on sodium-modified FeZSM-5 zeolites were studied in the temperature range from ?60 to 25 °C. Products were extracted from the zeolite surface and identified. It was found that main reaction pathway was the epoxides formation. Selectivity for epoxides at ?60 °C was 59–64%. Other products were formed as a result of secondary transformations of epoxides on the zeolite surface. According to IR spectroscopy, the oxidation of propylene over the entire temperature range and 1-butene at ?60 °C were not accompanied by the formation of (FeIII–OH)α groups, in distinction to methane oxidation. This testifies that hydrogen abstraction does not occur. In case of 1-butene reaction with α-oxygen at 25 °C, hydrogen abstraction occurred but was insignificant, ca 7%. According to DFT calculation ferraoxetane intermediate formation is preferable over hydrogen abstraction. Following decomposition of this intermediate leads to the propylene oxide (PO) formation. The results may be relevant to the low selectivity problem of the silver catalyst in propylene epoxidation and raise doubts about the presently accepted mechanism explaining an adverse effect of allylic hydrogen.
Gas-phase dehydration of vicinal diols to epoxides: Dehydrative epoxidation over a Cs/SiO2 catalyst
Kim, Tae Yong,Baek, Jayeon,Song, Chyan Kyung,Yun, Yang Sik,Park, Dae Sung,Kim, Wooyoung,Han, Jeong Woo,Yi, Jongheop
, p. 85 - 99 (2015/09/28)
A novel type of dehydration reaction that produces epoxides from vicinal diols (dehydrative epoxidation) using a basic catalyst is reported. Epoxyethane, 1,2-epoxypropane, and 2,3-epoxybutane were produced from the dehydrative epoxidation of ethylene glycol, 1,2-propanediol, and 2,3-butanediol, respectively. Among a number of tested basic catalysts, the Cs/SiO2 catalyst showed outstanding performance for the dehydrative epoxidation of 2,3-butanediol and is considered to be the most promising catalyst for this type of reaction. In order to identify the superiority of the Cs/SiO2 catalyst and a mechanism of the reaction, structure-activity relationships were studied along with density functional theory (DFT) calculations. The following features are found to be responsible for the excellent activity of the Cs/SiO2 catalyst: i) strong basic sites formed by Cs+, ii) low penetration of Cs+ into SiO2 which permits basic sites to be accessible to the reactant, iii) stable basic sites due to the strong interactions between Cs+ and SiO2 surface, and iv) mildly acidic surface of SiO2 which is advantageous for the elimination to H2O. In addition, the dehydrative epoxidation involves an inversion of chirality (e.g. meso-2,3-butanediol (R,S) to trans-2,3-epoxybutane (R,R or S,S)), which is in agreement with DFT results that the reaction follows a stereospecific SN2-like mechanism.