- Process for preparing 2 - (methylsulfonyl) - ethylene oxide and derivatives thereof
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The invention relates to 2 - (methylsulfonyl) - ethylene oxide and a preparation method thereof, belonging to the technical field of synthesis of ethylene oxide derivatives, and the method comprises the following steps: raw materials are vinyl methyl sulfone or allyl methyl sulfone 1:2:4 or methylallyl sulfonic acid ester. @timetimepieces are added dropwise to m-chloroperoxybenzoic acid by dropwise adding time of 30 min, 25 min, 10 min, heating reflux 15 - 30h and cooling to room temperature filtration. When the starting material is a vinyl methyl sulfone, the product is 2 - (methylsulfonyl) - ethylene oxide. When the starting material is allyl methyl sulfone, the product is methyl -2 and 3 - propylene oxide sulfonate. When the starting material is methylallyl sulfonate, the product is methyl -2 and 3 - epoxypropane sulfonate. The molar ratio of the raw material and the m-chloroperbenzoic acid is 1: (1.8 - 2.4). The preparation method is simple and high in yield.
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Paragraph 0030-0032; 0043-0045
(2021/09/29)
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- Difluoro- and trifluoro diazoalkanes-complementary approaches in batch and flow and their application in cycloaddition reactions
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Herein we report on applications of fluorinated diazoalkanes in cycloaddition reactions, with the emphasis on studying subtle differences between diverse fluorinated diazo compounds. These differences led to two major synthetic protocols in batch and flow that allow the safe and scalable synthesis of fluoroalkyl-, sulfone-substituted pyrazolines.
- Hock, Katharina J.,Mertens, Lucas,Metze, Friederike K.,Schmittmann, Clemens,Koenigs, Rene M.
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supporting information
p. 905 - 909
(2017/08/14)
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- AZOLOPYRIDINE AND AZOLOPYRIMIDINE COMPOUNDS AND METHODS OF USE THEREOF
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Provided herein are azolopyridine and azolopyrimidine compounds for treatment of JAK kinase mediated diseases, including JAK2 kinase-, JAK3 kinase- or TYK2 kinase-mediated diseases. Also provided are pharmaceutical compositions comprising the compounds and methods of using the compounds and compositions.
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Page/Page column 129
(2012/03/26)
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- Episulfone substitution and ring-opening reactions via α-sulfonyl carbanion intermediates
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Three-membered cyclic sulfones undergo substitution on treatment with base-electrophile mixtures, such as LDA-Me3SiCl and Bu′-P4 phosphazene base-PhCHO, to give either substituted episulfones or the corresponding alkenes following loss of SO2. The structure of a trisilylated episulfone product, 2a, was determined by X-ray crystallography. In the absence of Me3SiCl, reaction of episulfones with lithium diisopropylamide results in ring-opening to give alkenyl sulfinate intermediates, which can be alkylated to give (E)-alkenyl sulfone products in stereoselective fashion.
- Dishington, Allan P.,Douthwaite, Richard E.,Mortlock, Andrew,Muccioli, Adriano B.,Simpkins, Nigel S.
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p. 323 - 337
(2007/10/03)
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- Novel episulfone substitution and ring-opening reactions via α-sulfonyl carbanion intermediates
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Three-membered cyclic sulfones undergo substitution on treatment with base-electrophile mixtures, such as LDA-Me3SiCl and tBu-P4-phosphazene base-PhCHO, to give either substituted episulfones or the corresponding alkenes following loss of SO2-In the absence of Me3SiCl, reaction of episulfones with LDA results in ring-opening to give alkenyl sulfinate intermediates, which can be alkylated to give (E)-alkenyl sulfone products in stereoselective fashion.
- Simpkins, Nigel S.
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p. 197 - 211
(2007/10/03)
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- Rate-Determining Steps in Michael-Type Additions and E1cb Reactions in Aqueous Solution
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Rates of equilibration of a series of 10 substituted pyridines and five Michael acceptors (CH2=CHZ, Z = CHO, COCH3, SO2CH3, CN and CONH2) with the corresponding N(ZCH2CH2) pyridinium cations have been measured in aqueous solution at ionic strength 0.1 and 25 deg C.Analysis of the dependence of the pseudo-first-order rate constants for equilibration as a function of acceptor concentration and of pH allows the evaluation of the second-order rate constants (kNu) for the nucleophilic attack of each of these pyridines upon each of these acceptors and also the second-order rate constants (kOH) for the hydroxide ion catalyzed E1cb elimination reaction which is the microscopic reverse of each of these Michael-type addition reactions.Broensted-type plots for each of these processes as a function of the basicity of the substituted pyridine are concave down for each of Z = CHO, COCH3, and CN and are consistent with a change from rate-determining nucleophilic attack for the more basic pyridines to rate-determining protonation of the carbanionic intermediate by a water molecule for less basic pyridines and the corresponding microscopic reverse processes in the elimination reactions.The "break" in these Broensted-type plots is shown to occur at a pyridine basicity that is a function of the Z-activating substituent.Broensted β1g and βnuc are evaluated for each rate-determining step (wherever accessible); these two parameters are shown to pass through minima as a function of reactivity. βeq is shown to be a simple linear function of reactivity (as log kNu) for nucleophilic addition to the acceptor species, although Keq is relatively insensitive to the nature of the Z-activating substituent.
- Heo, Christina K. M.,Bunting, John W.
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p. 3570 - 3578
(2007/10/02)
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- Reaction Mechanism of Cathodic Crossed Coupling of Acetone with Unsaturated Compounds in Acidic Solution
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It was confirmed that the cathodic crossed coupling of acetone with unsaturated compounds in aqueous sulfuric acid could proceed smoothly, when the compounds which had radical-acceptable double bonds and were adsorbed on a mercury cathode were used.From this fact, it was concluded that the coupling occurs via the addition of a radical intermediate formed by the one-electron reduction of acetone to the double bonds on the cathode surface.Possibility of the addition of an anionic intermediate derived from acetone was excluded by no occurrence of the coupling of acetone with a polar acetylenic triple bond compound adsorbed on the cathode.
- Koizumi, Toshio,Fuchigami, Toshio,Kandeel, Zaghloul El-Shahat,Sato, Norio,Nonaka, Tsutomu
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p. 757 - 762
(2007/10/02)
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