870-23-5Relevant academic research and scientific papers
Synthesis of 3a,4-dihydro-8-substituted-3H-isoxazolo [c- 4,3] thiapyrano [5,6-3,2] quinolines
Prabhuswamy,Ambekar, Sarvottam Y.
, p. 3477 - 3485 (1999)
Condensation of 2-chloro-3-formylquinoline 1a-c with allylthiol 2 afforded 2-allysulfanyl-3-formylquinolines 3a-c. Oximation followed by oxidation of 3a-c with NaOCl or chloramine-T, in cold or mercuric acetate resulted in the formation of respective nitrile oxides, which underwent insitu intramolecular 1,3-dipolar cycloaddition reaction and afforded the title compounds 5a-c in high yield.
Preparation method of thiocarboxylate silane coupling agent
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Paragraph 0023-0025; 0030-0032; 0037-0039; 0044-0046, (2018/03/24)
The invention provides a preparation method of a thiocarboxylate silane coupling agent. The preparation method comprises steps as follows: allyl mercaptan is prepared from allyl haloalkane and hydrosulfide under the condition of a phase transfer catalyst and subjected to a reaction with acyl chloride in the presence or absence of a solvent, allyl thiocarboxylate is obtained, and low-boiling-point substances are removed through evaporation for purification of a product; purified allyl thiocarboxylate and trialkoxysilane are subjected to an addition reaction in presence of a transition metal catalyst, and after decoloration and distillation, a thiocarboxylate silane product is obtained. The preparation method has the advantages as follows: use of mercapto silane with pungent smell is avoided, and harm to the environment is reduced; the reaction of acyl chloride and sulfide or hydrosulfide under the aqueous phase condition is avoided, so that side reactions are reduced, and impurities are reduced; hydrolysis rate of the product is lower, yield is increased, and product purity is high.
OLEFIN METATHESIS REACTIONS OF AMINO ACIDS, PEPTIDES AND PROTEINS CONTAINING ALLYL SULFIDE GROUPS
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Page/Page column 9, (2012/07/27)
A method for the modification of an amino acid, protein or peptide is disclosed. The method comprises reacting a carbon-carbon double bond-containing compound with an amino acid, a protein or a peptide containing an allyl sulfide group in the presence of a catalyst which promotes olefin metathesis, to form a modified amino acid, protein or peptide. Preferred carbon-carbon double bond-containing compounds include carbohydrates.
METHOD FOR PRODUCING ALKENYL MERCAPTAN
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Page/Page column 3-4, (2011/10/02)
The present invention relates to a process for producing an alkenyl mercaptan (2), comprising reacting an alkenyl halide (1) with an alkali hydrosulfide, wherein the reaction is carried out in the presence of a disulfide (3) in an amount of 0.5 part by weight or more based on 100 parts by weight of the total amount of the alkenyl halide (1) and the alkenyl mercaptan (2).
CHLOROTHIOFORMATE MANUFACTURING METHOD
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Page/Page column 3, (2011/10/19)
The present invention relates to a process for producing chlorothioformate comprising reacting an alkenyl mercaptan with phosgene in a reactor in the presence of a carboxylic acid amide in an organic solvent, characterized in that the carboxylic acid amide is preliminary charged to the reactor in an amount of 10 to 50% by weight based on the whole amount of the carboxylic acid amide, and subsequently, the compound of the formula (I), phosgene and the remaining carboxylic acid amide are charged to the reactor.
Reaction mechanisms of allicin and allyl-mixed disulfides with proteins and small thiol molecules
Miron, Talia,Listowsky, Irving,Wilchek, Meir
body text, p. 1912 - 1918 (2010/07/04)
Allylsulfides from garlic are chemopreventive agents. Entering cells they are expected to initially interact with glutathione. Accordingly, reaction mechanisms of the product, S-allylthio-glutathione, with model proteins and thiols were analyzed in cell f
Allyl sulfides are privileged substrates in aqueous cross-metathesis: Application to site-selective protein modification
Lin, Yuya A.,Chalker, Justin M.,Floyd, Nicola,Bernardes, Goncalo J. L.,Davis, Benjamin G.
supporting information; experimental part, p. 9642 - 9643 (2009/02/04)
Allyl sulfides undergo efficient cross-metathesis in aqueous media with Hoveyda-Grubbs second generation catalyst 1. The high reactivity of allyl sulfides in cross-metathesis was exploited in the first examples of cross-metathesis on a protein surface. S-Allylcysteine was incorporated chemically into the protein, providing the requisite allyl sulfide handle. Preliminary efforts to genetically incorporate S-allylcysteine into proteins are also reported. Copyright
Synthesis of conformationally restricted nicotine analogues by intramolecular [3+2] cycloaddition
Yang, Xiaobao,Luo, Shengjun,Fang, Fang,Liu, Peng,Lu, Yong,He, Mingyuan,Zhai, Hongbin
, p. 2240 - 2246 (2007/10/03)
We describe the synthesis of a series of conformationally constrained nicotine analogues 2-5 from appropriate pyridine-containing enals, featuring an intramolecular azomethine ylide-alkene [3+2] cycloaddition. The objective of the current project is to develop new selective nAChRs-targeting ligands. Of the nicotine analogues that we have studied, the conformation-restricting ring B unit can be either a five-membered carbocycle, or a six-membered carbocycle or heterocycle. The present work constitutes a general method for rapid assembly of other related tricyclic nicotine analogues.
Kinetics and mechanism of the nucleophilic substitution of tellurium(II) dialkanethiolates, Te(SR1)2 with thiols, HSR2
Fleischer, Holger
, p. 815 - 825 (2007/10/03)
The equilibrium reaction between tellurium(II) dithiolates and thiols, Te(SR1)2 + 2 HSR2 ? Te(SR 2)2 + 2 HSR1 was studied by means of 1H- and 125Te NMR spectroscopy and ab initio quantum chemical methods. It was found that the reaction is catalyzed by Bronsted acids and bases, the catalytic activity corresponding to the strength of the respective acid or base. Investigation of the initial step of the reaction, Te(SR1)2 + HSR2 ? Te(SR 1)(SR2) + HSR1, showed it to proceed according to first order kinetics for Te(SR1)2, HSR2 and for the catalyst. Ab initio geometry optimizations and frequency calculations suggest [Te(SR1)(HSR1)(HSR2)]+ and [Te(SR1)2(SR2)]- to be stable intermediates and not transition states in the acid and base catalyzed reactions, respectively. The reaction hence proceeds via an additional elimination rather than an SN2 mechanism. The catalytic activity displayed by acids and bases can be applied to reduce the temperature in synthesis of thermally labile tellurium(II) dithiolates. Copyright Taylor & Francis Inc.
Absolute Rate Constants for Reactions of Tributylstannyl Radicals with Bromoalkanes, Episulfides, and α-Halomethyl-Episulfides, -Cyclopropanes, and -Oxiranes: New Rate Expressions for Sulfur and Bromine Atom Abstraction
Franz, James A.,Shaw, Wendy J.,Lamb, Claude N.,Autrey, Tom,Kolwaite, Douglas S.,Camaioni, Donald M.,Alnajjar, Mikhail S.
, p. 1020 - 1027 (2007/10/03)
Arrhenius rate expressions were determined for the abstraction of bromine atom from 2-phenethyl bromide by tri-n-butylstannyl radical (Bu 3Sn.) in benzene using transient absorption spectroscopy, (log(kabs,Br/M-1 s-1) = (9.21 ± 0.20) - (2.23 ± 0.28)/θ, θ = 2.3RT kcal/mol, errors are 2σ) and for the abstraction of sulfur atom from propylene sulfide to form propylene, (log(ks/M-1 s-1) = (8.75 ± 0.91) - (2.35 ±1.33)/θ). Rate constants for reactions of organic bromides, RBr, with Bu3Sn. were found to vary as R = benzyl (15.6) > thiiranylmethyl (6.2) > oxiranylmethyl (3.1) > cyclopropylmethyl (1.3) > 2-phenethyl (1.0), with kabs,Br = 6.8 × 10 7 M-1 s-1 at 353 K for 2-phenethyl bromide. Bromine abstraction from α-bromomethylthiirane is about 7-fold faster than sulfur atom abstraction and is comparable to the reactivity of a secondary alkyl bromide. The potential surface for the vinylthiomethyl → allylthiyl radical rearrangement at UB3LYP/6-31G(d) and UB3LYP/6-311+G-(2d,2p) levels of theory suggests that the thiiranylmethyl radical is produced about 9 kcal/mol above the allylthiyl radical on the rearrangement surface, consistent with the observed enhancement of the Br atom abstraction from the thiirane and with synchronous C-S bond scission of the thiirane ring. The selectivities reported in this work for S vs Cl and Br abstraction provide applications for radical-based synthesis and new competition basis rate expressions for trialkylstannyl radicals.
