- Byproducts formed During Thiol-Acrylate Reactions Promoted by Nucleophilic Aprotic Amines: Persistent or Reactive?
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The nucleophile-initiated mechanism of thiol-Michael reactions naturally leads to the formation of undesired nucleophile byproducts. Three aza-Michael compounds representing nucleophile byproducts of thiol-acrylate reactions initiated by 4-dimethylaminopyridine (DMAP), 1-methylimidazole (MIM), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) have been synthesized and their reactivity in the presence of thiolate has been investigated. Spectroscopic analysis shows that each nucleophile byproduct reacts with thiolate to produce a desired thiol-acrylate product along with liberated aprotic amines DMAP, MIM, or DBU, thus demonstrating that these byproducts are reactive rather than persistent. Density functional theoretical computations support experimental observations and predict that a β-elimination mechanism is favored for converting each nucleophile byproduct into a desired thiol-acrylate product, though an SN2 process can be competitive (i. e. within 2.5 kcal/mol) in less polar solvents.
- Drogkaris, Vasileios,Northrop, Brian H.
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p. 2466 - 2474
(2020/12/03)
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- 2-Azaadamantane N-oxyl (AZADO)/Cu Catalysis Enables Chemoselective Aerobic Oxidation of Alcohols Containing Electron-Rich Divalent Sulfur Functionalities
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The chemoselective oxidation of alcohols containing electron-rich sulfur functionalities (e.g., 1,3-dithianes and sulfides) into their corresponding carbonyl compounds with the sulfur groups can sometimes be a demanding task in modern organic chemistry. A reliable method for this transformation, which features azaadamantane-type nitroxyl radical/copper catalysis using ambient air as the terminal oxidant is reported. The superiority of the developed method was demonstrated by comparing it with various conventional alcohol oxidation methods.
- Sasano, Yusuke,Kogure, Naoki,Nagasawa, Shota,Kasabata, Koki,Iwabuchi, Yoshiharu
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supporting information
p. 6104 - 6107
(2018/09/27)
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- Preparation of 3,3 the dimethyl generation of two propionic acid[...] -sulfur the new process
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The invention belongs to the technical field of organic synthesis, and particularly relates to a new process for preparing 3,3'-dimethyl thiodipropionate. In the invention, methyl acrylate and an inorganic salt sodium hydrosulfide, taken as raw materials, are reacted in a proton solvent, so that the quantitative problem of reactants is solved, reaction raw materials are fully reacted, and the product yield is relatively increased; and a solution subjected to reaction can be applied for multiple times, and no three wastes are produced in the whole reaction process, so that the process is environmental-friendly, low in production cost and more conducive to industrial production.
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Paragraph 0026; 0027
(2017/02/24)
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- Carboxamide and amine compounds as well as preparation method and applications thereof
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The invention discloses carboxamide and amine compounds as well as a preparation method and applications thereof as stable and efficient antioxidation sterilizers, belonging to the technical field of invention and preparation of novel antioxidation sterilizer compounds. All the compounds disclosed by the invention are stable antioxidation sterilizers which have different stable structures formed by connecting carboxamide and amine bonds, and meanwhile, products having different lengths of aliphatic chains are produced by adjusting an n value, such that the products can be completely matched with a specific high polymer material in performance, the problems that a micromolecular stabilizer is volatilized fast, easily drawn from high polymer materials and the like are solved, the service life of the material is greatly prolonged, and the carboxamide and amine compounds have relatively strong and durable high polymer material protection performance. Compared with the prior art, the stable high polymer antioxidants disclosed by the invention have relatively high capabilities of resisting hydrolysis, acidolysis, alkaline hydrolysis, degradation in a chemical pollution environment, and these performances provides a new better antioxidant selection range for the development of modern new materials. Furthermore, this kind of carboxamide and amine compounds also have the characteristics of difficulty in volatilization, good matching performance with high polymer materials, good high polymer protection capability, good environmental performance, attractive appearance and durability, low cost and the like.
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Paragraph 0104; 0105; 0106; 0107
(2016/10/08)
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- METHOD OF PREPARING METHYL 3-MERCAPTOPROPIONATE AND DIMETHYL 3,3’-THIOPROPIONATE
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The present invention relates to a manufacturing method of methyl 3-mercaptopropionate comprises a step of reacting hydrogen sulfide with a mixture containing an organic solvent and methyl acrylate, in the presence of a catalyst containing a quaternary ammonium salt compound, wherein the organic solvent has heat of dissolution below 9.2 kcal/mol (room temperature, 1 atm) with respect to the methyl acrylate. In addition, the present invention relates to a manufacturing method of dimethyl 3,3andprime;-thiopropionate comprises a step of reacting methyl 3-mercaptopropionate with a mixture containing an organic solvent and methyl acrylate, in the presence of a catalyst containing a quaternary ammonium salt compound, wherein the organic solvent has heat of dissolution below 9.2 kcal/mol (room temperature, 1 atm) with respect to the methyl acrylate.COPYRIGHT KIPO 2016
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Paragraph 0071; 0080; 0081
(2016/10/09)
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- SEMICONDUCTING THIN [60]FULLERENE FILMS AND THEIR USE
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?The present invention relates to the use of soluble pentakis(alkylthio)derivatives of [60] fullerene as precursors for semiconducting thin [60] fullerene films by thermal decomposition and organic electronic devices using these films.
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Page/Page column 12; 13
(2013/07/25)
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- A SUCCESSIVE PREPARATION METHOD OF 3-ISOTHIAZOLONE DERIVATES AND THEIR INTERMEDIATES
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The present application provides a process for continuously producing 3-isothiazolinone derivatives and intermediate products thereof, comprising continuously carrying out four steps, i.e., sulfuration, purification, amination and chlorination. Compared with the batch process of the prior art, the process of the present application may reduce the amount of manufacturing devices, lower energy consumption, simplify operations, and is therefore particularly suitable for mass production.
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Page/Page column 13
(2010/08/18)
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- An efficient and straightforward access to sulfur substituted [2.2]paracyclophanes: Application to stereoselective sulfenate salt alkylation
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A straightforward and high-yielding access to various [2.2]paracyclophanes possessing a sulfur-based functional group is reported, the key step being a SEAr reaction mediated by a sulfonium salt. The versatility of the methodology was exemplified by an original application in sulfenate salt chemistry, from which a remarkable chirality transfer was observed.
- Lohier, Jean-Francois,Foucoin, Florian,Jaffres, Paul-Alain,Garcia, Jose I.,Santos, Jana Sopkova-De Oliveira,Perrio, Stephane,Metznert, Patrick
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supporting information; body text
p. 1271 - 1274
(2009/10/01)
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- Synthesis of 5 H-Imidazo[1,2-a]thiopyrano-[4',3':4,5]thieno[2,3-d]pyrimidin-5-one
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The enamino-ester, ethyl, 2-amino-4,7-dihydro-5H-thieno[2,3-c]thiopyrano-3-carboxylate (5) was prepared from tetrahydrothiopyran-4-one (4). Annelating reagent, 5-methyl-2-methylthioimidazoline (8) was prepared starting from 1, 2-diaminopropane (6) via 5-methyl-2-imidazolidinethione (7). The reaction of enamino-ester (5) with the annelating reagent (8) in HMPTA leaded to new 1,2,3,6,7,9-hexahydro-5H-imidazo[1,2-a]thiopyrano[4',3':4,5]thieno[2,3-d]pyrimidin-5-one (9) in good yield.
- Chowdhury, A. Z. M. Shaifullah,Khadker, M.M. Rahman,Bhuiyan, M. M. H.,Hossain, M. K.
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- Syntheses of 4H-thiopyran-4-one 1,1-dioxides as precursors to sulfone-containing analogues of tetracyanoquinodimethane
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Synthetic routes to the unsubstituted 4H-thiopynan-4-one 1,1-dioxide (5a), 2,6-dialkyl-substituted, 2-aryl- or 2-heteroaryl-6-alkyl-substituted, 2,6-diaryl- or diheteroaryl-substituted, and 2-heteroaryl-6-aryl-substituted 4H-thiopyran-4-one 1,1-dioxides 5b-s are described. Sodium hydrosulfide hydrate in buffered aqueous alcohol can be used as a substitute for hydrogen sulfide gas for the introduction of sulfur to methyl acrylate, to 1,5-disubstituted-1,4-pentadien-3-ones 13, or to 1,5-disubstituted-1,4-pentadiyn-3-ones 17. The double dehydrogenation of 2,3,5,6-tetrahydrothiopyran-4-one 1,1-dioxides 13 with iodine-DMSO-sulfuric acid gives thiopyran-4-one 1,1-dioxides 5 in good yield and small amounts of 1,4-pentadien-3-ones 13. 2,3,5,6-Tetrahydrothiopyran-4-one 1,1-dioxide (9) and 5,6-dihydrothiopyran-4-one 1,1-dioxide (12), which lack aryl or heteroaryl substituents, give poor yields of 4H-thiopyran-4-one 1,1-dioxide (5a) with iodine-DMSO-sulfuric acid.
- Rule,Detty,Kaeding,Sinicropi
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p. 1665 - 1673
(2007/10/02)
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- Pulse Radiolysis Investigations on Electron-transfer Reactions in Aqueous Solutions of Substituted Alkyl Sulfides
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The transient optical absorption band (λmax = 345 nm, t1/2 = 4.0 μs, ε = 2.6 * 103 dm3 mol-1 cm-1) formed on pulse radiolysis of N2O-saturated dilute neutral aqueous solutions of dimethyl 3,3'-thiodipropionate (DTDP) is assigned to an .OH-adduct.The rate constant for the reaction of .OH radicals has been determined to be 1.4 * 1010 dm3 mol-1 s-1.At higher solute concentrations the .OH-adduct is converted to sulfur centered dimer radical cations (λmax = 510 nm, ε = 4.9 * 103 dm3 mol-1 cm-1, t1/2 = 14.0 μs).In acidic solutions, only dimer radical cations are formed.In neutral aqueous solutions of 3,3'-thiodipropanol (TDP) .OH radicals are able to bring about one-electron oxidation, forming intramolecular radical cations with p-orbital overlap between the oxidized sulfur and oxygen (λmax = 420 nm, t1/2 = 17 μs, ε = 2.6 * 103 dm3 mol-1 cm-1).In acidic solutions, sulfur centred dimer radical cations are formed (λmax = 510 nm, t1/2 = 12 μs, ε = 6.3 * 103 dm3 mol-1 cm-1).In the presence of halide ions, the oxidized sulfur in DTDP and TDP stabilizes by formation of an SX type species.
- Mohan, Hari,Mittal, Jai P.
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p. 207 - 212
(2007/10/02)
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- SULFUR-CONTAINING CARBOXYLIC ACIDS. 5. SYNTHESIS AND STRUCTURE OF DIALKYL SULFIDES AND DIALKYL SULFOXIDES WITH VICINAL CARBOXYL OR ACYLAMINO GROUPS
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Bifunctional sulfides and sulfoxides containing carboxy, carbamoyl, or acylamino groups in the β-position are synthesized, and their IR spectra were studied.An unusual decrease in the frequencies of the carbonyl vibrations (by 20-34 cm-1) was found for thiodipropionic acid, its amides, and bis(β-acylaminoethyl) sulfides by comparison with the corresponding sulfoxides.The low-frequency shift of the CO bond in these carbonylsulfides was not, as expected, associated with the intramolecular S...O coordination, since the x-ray structural investigation of thiodipropionic acid and bis(2-trifluoroacetylaminoethyl) sulfide did not show short intra- and intermolecular contacts involving the sulfur atom.Both structures contain intermolecular hydrogen bonds (C=O...HO or C=O...HN).Keywords: derivatives of thiodipropionic acid, 2-(acylaminoethyl) sulfides, derivatives of β,β'-sulfinyldipropionic acid, 2-(acylaminoethyl) sulfoxides, x-ray structural analysis, bis(2-trifluoroacetylaminoethyl) sulfide, molecular structure.
- Vasil'eva, T. P.,Mozzhukhin, A. O.,Antipin, M. Yu.,Struchkov, Yu. T.
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p. 1368 - 1376
(2007/10/02)
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- Organic compounds and their use as pharmaceuticals
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A pharmaceutical compound of the formula STR1 in which R1, R2 and R3 independently are hydrogen, hydroxy, halo, nitro, amino, C2-5 acylamino, C1-4 alkyl, --CHO, --CH2 OH, --CH2 OC1-4 alkyl, --COOH, --COC1-3 alkyl, --CH(OH)C1-3 alkyl, C1-4 alkoxy, C2-4 alkenyloxy, C1-4 alkylthio, C1-4 alkylsulphinyl, C1-4 alkylsulphonyl, N-substituted heterocyclyl, optionally substituted phenyl, optionally substituted phenylthio, optionally substituted phenylsulphinyl, optionally substituted phenylsulphonyl or optionally substituted phenylsulphonamido, or R1 and R2 together form a C3-5 alkylene bridge; provided that at least one of R2 and R3 is C1-4 alkoxy or C2-4 alkenyloxy; and X is (i) --(CH2)n N(R4)2 where each R4 independently is C1-4 alkyl, C2-4 alkenyl or optionally substituted C6 H5 CH2 --, and n is 1, 2 or 3, or (ii) a 5- to 8-membered alicyclic group containing one or two nitrogen atoms and directly attached to the amido nitrogen or attached by a C1-3 alkylene chain; and salts and esters thereof.
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- Free Radical Ring-Expansion Leading to Novel Six- and Seven-Membered Heterocycles
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Free radical promoted ring-expansion of nitrogen-, oxygen- and sulfur-containing heterocyclic β-keto esters is described.Treatment of the derived phenylselenomethyl derivatives with tri-n-butyltin hydride leads to smooth one-carbon ring expansion.
- Dowd, Paul,Choi, Soo-Chang
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p. 4847 - 4860
(2007/10/02)
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- Esters of Thiodiglycollic and Thiodipropionic Acids and 2,5-Dicarboxy-3,4-dihydroxythiophene as Potential Slow Acting Anticancer Agents
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A series of esters of thiodiglycollic and thiodipropionic acids and 2,5-dicarboxy-3,4-dihydroxythiophene have been synthesised with a view to testing their anticancer properties.The esters, as against parent acids are expected to have a prolonged effect.
- Kumar, Anil,Tilak, B. D.
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p. 880 - 882
(2007/10/02)
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- Antioxidative properties of phenyl-substituted phenols. Part I. The mechanism of synergism between 4-alkoxy-2,6-diphenylphenols and ββ′-disubstituted diethyl sulphides
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A pronounced synergism between 4-alkoxy-2,6-diphenylphenols and ββ′-disubstituted diethyl sulphides has been observed in the inhibition of autoxidation of polypropene at 180°C. The mechanism of this synergistic action (at temperatures ≥150°C) has been investigated. N.m.r. model experiments have shown that the phenolic antioxidant (AH) is regenerated continuously from the phenoxyl radical (A·) by hydrogen atom donation by the sulphenic acid, a product originating from the ββ′- disubstituted diethyl sulphide. This observation is of possible contributory importance to the understanding of the mechanism of synergistic effects.
- De Jonge, Cornelis R. H. I.,Hageman, Hendrik J.,Huysmans, Willem G. B.,Mijs, Willem J.
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p. 1276 - 1279
(2007/10/06)
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