- Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
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To expand the toolbox of dynamic covalent and systems chemistry, we investigated the acid-catalyzed exchange reaction of trithioorthoesters with thiols. We found that trithioorthoester exchange occurs readily in various solvents in the presence of stoichiometric amounts of strong Bronsted acids or catalytic amounts of certain Lewis acids. The scope of the exchange reaction was explored with various substrates, and conditions were identified that permit clean metathesis reactions between two different trithioorthoesters. One distinct advantage of S, S, S-orthoester exchange over O, O, O-orthoester exchange is that the exchange reaction can kinetically outcompete hydrolysis, thereby making the process less sensitive to residual moisture. We expect that the relatively high stability of the products might be beneficial in future supramolecular receptors or porous materials.
- Bothe, Michael,Furlan, Ricardo L. E.,Orrillo, A. Gastón,Von Delius, Max
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supporting information
p. 1988 - 1994
(2019/10/22)
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- A facile, safe and inexpensive preparation of S -methyl arylcarbamothioates by methylthiocarbonylation of primary arylamines with O, S -dimethyl carbonodithioate
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O,S-Dimethyl carbonodithioate is proposed as a suitable and safely handled reagent that can be used in the methylthiocarbonylation of primary arylamines to give S-methyl arylcarbamothioates. Optimal conditions involved a one-step procedure that was carried out at 45C in a solvent-free system, in the presence of triethyl(methyl)ammonium S-methyl carbonodithioate as a reaction promoter. The title products were obtained pure in yields that, with one exception, varied between 72 and 91% (average yield of the 12 considered examples was 83%). The by-product S,S-dimethyl carbonodithioate is also a valuable reagent. Georg Thieme Verlag Stuttgart · New York.
- Degani, Iacopo,Fochi, Rita,Magistris, Claudio
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experimental part
p. 1113 - 1122
(2010/05/19)
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- Identification and biosynthesis of tropone derivatives and sulfur volatiles produced by bacteria of the marine Roseobacter clade
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Bacteria of the Roseobacter clade are abundant marine bacteria and are important contributors to the global sulfur cycle. The volatiles produced by two of its members, Phaeobacter gallaeciensis and Oceanibulbus indolifex, were analyzed to investigate whether the released compounds are derived from sulfur metabolism, and which biosynthetic pathways are involved in their formation. Both bacteria emitted different sulfides and thioesters, including new natural compounds such as 5-methyl phenylethanethioate (16) and butyl methanesulfonate (21). The S-methyl alkanoates were identified by comparison with standards that were synthesized from the respective methyl alkanoates by a new method using an easily prepared aluminium/sulfur reagent. Phaeobacter gallaeciensis is also able to produce tropone (37) in large amounts. Its biosynthesis was investigated by various feeding experiments, showing that 37 is formed via a deviation of the phenylacetate catabolism. The unstable tropone hydrate 42 was identified as an intermediate of the tropone biosynthesis that was also released together with tropolone (38). The Royal Society of Chemistry 2010.
- Thiel, Verena,Brinkhoff, Thorsten,Dickschat, Jeroen S.,Wickel, Susanne,Grunenberg, Joerg,Wagner-Doebler, Irene,Simon, Meinhard,Schulz, Stefan
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experimental part
p. 234 - 246
(2010/04/29)
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- O,S-Dimethyl carbonodithioate as a phosgene substitute for the preparation of S-methyl alkylcarbamothioates and dialkylcarbamothioates
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O,S-Dimethyl carbonodithioate is proposed as a suitable and safely handled reagent that can be used as a replacement for phosgene in the synthesis of S-methyl alkyl- and dialkylcarbamothioates. The former were obtained by a two-step procedure, which can also be carried out in a one-pot fashion without isolating the intermediates O-methyl alkylcarbamothioates; the overall yields of the pure S-methyl alkylcarbamothioates were 94-98%. Optimal conditions for the synthesis of S-methyl dialkylcarbamothioates involved a one-step procedure in a solvent-free system in the presence of triethyl(methyl)ammonium methyl carbonate as a catalyst; yields of the pure products were 85-98%. A mechanism is proposed for the carbamothioate-formation reaction. Georg Thieme Verlag Stuttgart.
- Degani, Iacopo,Fochi, Rita,Magistris, Claudio
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experimental part
p. 3807 - 3818
(2010/03/30)
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- PYRAZOLE DERIVATIVES AS INHIBITORS OF RECEPTOR TYROSYNE KINASES
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Compounds of formula (I): and their use in the inhibition of Trk activity are described.
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Page/Page column 116
(2008/06/13)
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- Catalytic thione-thiol rearrangement of xanthates by 4- dialkylaminopyridine
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Pyridines bearing electron-donating substituents are useful catalysts for the rearrangement of O,S-dialkyl xanthates (1) to S,S-dialkyl dithiocarbonates (2). The rearrangement was analyzed by semiempirical and ab initio molecular orbital methods. The transition-structure analyses indicate that the pyridine-ring nitrogen of dialkylaminopyridine rather than the dialkylamino nitrogen attacks the O-alkyl carbon of xanthates. The reaction proceeds through an S(N)2 mechanism to give the dithiolcarbonate anion (RSCOS-) which acts as an actual catalyst.
- Nakagawa, Hidetoshi,Eto, Masashi,Harano, Kazunobu
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- Thione-thiol rearrangement of xanthates catalyzed by pyridine N-oxides. Remarkably enhanced reactivity of 4-dialkylaminopyridine N-oxides
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Pyridine N-oxides bearing electron-donating substituents (III) are efficient catalysts for rearrangement of O-alkyl S-methyl dithiocarbonates (xanthates) (I) to the corresponding S-alkyl S-methyl dithiocarbonates (dithiolcarbonates) (II). Of the catalysts tested, 4-piperidinopyridine N-oxide (IIIh) is the best from the viewpoints of catalytic activity and solubility in I. Heating of I in the presence of catalytic amounts (0.02-0.05 molar eq) of IIIh gave II together with the symmetric S,S-dialkyl and S,S-dimethyl dithiocarbonates in good yields. The catalytic behavior of donor-substituted pyridine N-oxides is discussed on the basis of kinetic and molecular orbital calculation data. The complete calculation of the perturbation equation on the initial stage of the reaction was consistent with the experimentally observed activity of the catalysts.
- Harano,Nakagawa,Kamei,Kiyonaga,Hisano
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p. 1675 - 1682
(2007/10/02)
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- The invention of radical reactions. Part XXVII. Modified Julia synthesis of olefins using radical deoxygenation
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Xanthate derivatives of β-hydroxy sulfones react with methyl radicals generated from the photolysis of N-acetyloxy-2-thiopyridone to give the corresponding olefin. Under identical conditions a secondary alcohol is transformed into its thiopyridyl derivative.
- Barton, Derek H. R.,Tachdjian, Catherine
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p. 7109 - 7120
(2007/10/02)
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- Catalytic Rearrangement of O,S-Dialkyl Dithiocarbonates to S,S-Dialkyl Dithiocarbonates by Pyridine N-Oxides. The Reaction Mechanism
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The reaction of O-alkyl S-methyl dithiocarbonates (xanthates) (I) with pyridine N-oxides (II) gave the corresponding S-alkyl S-methyl dithiocarbonates (dithiolcarbonate) (III) together with the symmetric S,S-dialkyl and S,S-dimethyl dithiocarbonates in good yields.Pyridine N-oxides bearing electron-donating substituents are efficient catalysts for rearrangement of I to III.The reaction is pseudo-first-order and the apparent first-order rate constant is proportional to the concentration of II.The role of pyridine N-oxides and the reaction behavior of O,S-dialkyldithiocarbonates are discussed on the basis of kinetic and molecular orbital calculation data.The rearrangement may proceed by nucleophilic attack of -SCOSR derived from a complex of I and II on the O-alkyl group of xanthates.The reaction provides a useful preparation method for alkanethiols by aminolysis of the products with ethanolamine.Keywords O,S-dialkyl dithiocarbonate; S,S-dialkyl dithiocarbonate; pyridine N-oxide; thiol; charge transfer; catalytic rearrangement; kinetics; ethanolamine; frontier molecular orbital
- Harano, Kazunobu,Shinohara, Ikuo,Sugimoto, Shin-ichiro,Matsuoka, Toshikazu,Hisano, Takuzo
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p. 576 - 581
(2007/10/02)
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- 4-DIMETHYLAMINOPYRIDINE N-OXIDE AS AN EXCELLENT CATALYST FOR THIONE TO THIOL REARRANGEMENT OF XANTHATES
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4-Dimethylaminopyridine N-oxide effectively catalyzes the thione to hiol rearrangement of O,S-dialkyl dithiocarbonates (xanthates) to provide S,S-dialkyl dithiocarbonates.
- Harano, Kazunobu,Kiyonaga, Hideo,Sugimoto, Shin-ichiro,Matsuoka, Toshikazu,Hisano, Takuzo
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p. 2327 - 2330
(2007/10/02)
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- Synthetic Application of Tris(methylthio)methyl Salts. An Efficient Route to Trithioorthocarboxylic Esters from Strongly Activated Aromatic and Heteroaromatic Systems
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Nine trithioorthocarboxylic esters were synthesized by reaction of tris(methylthio)methyl methyl sulfate or tetrafluoroborate with electron-rich aromatic and heteroaromatic compounds, i.e.N,N-dialkylarylamines, pyrroles, and indoles.The new procedure is simple and offers the following advantages: easy preparation of reagents; mild reaction condition; possibility to introduce two tris(methylthio)methyl groups into the same ring, good to excellent yields.
- Barbero, Margherita,Cadamuro, Silvano,Degani, Iacopo,Fochi, Rita,Gatti, Antonella,Regondi, Valeria
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- DECARBONYLATION DES DITHIOCARBONATES: UNE VOIE D'ACCES GENERALE AUX COMPLEXES BINUCLEAIRES BIS-μ-(S-ALKYL)-HEXACARBONYLEDIFER
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Dithiocarbonates R1SC(O)SR2 (IV) react with to afford the bis-μ-(S-alkyl)-hexacarbonyldiiron coordination compounds: I (R1=R2), II (R1R2=bridging hydrocarbon chain) and III (R1*R2) after a double fragmentation pattern accompanied by loss of carbonyl groups.This unexpected reactivity of ligands IV offers a general route to binuclear iron compounds such as I and II.Some reaction intermediates (V) which led to I, have been identified.However the redistribution of S-alkyl groupings which occurs during the complexation of IV (R1*R2) shows that the decarbonylation reaction can follow several pathways.
- Lagadec, Armelle,Dabard, Rene,Misterkiewicz, Boguslaw,Le Rouzic, Arnette,Patin, Henri
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p. 381 - 388
(2007/10/02)
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- Production of isoxanthate salts and dithiocarbonate diesters
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This invention provides a process for preparing a novel class of isoxanthate salts, such as sodium S-benzylisoxanthate: STR1 The process involves a reaction between carbonyl sulfide and a metal mercaptide under aprotic conditions. This invention further provides a process for converting a metal mercaptide via an isoxanthate salt intermediate to a dithiocarbonate diester such as dimethyl dithiocarbonate: STR2 These compounds have found application as rust inhibitors, plasticizers, insecticides, herbicides and the like.
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- Synthesis and Characterisation of Bispolysulphanes
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Bispolysulphanes with a linear chain of 1-6 sulphurs have been prepared and characterised; in particular X-ray crystallographic analyses proved the structures of the tri- and tetra-sulphanes.The tri-to hexa-sulphanes were formed by reactions of O,S-dimethyl dithiocarbonate with the appropriate dichlorosulphane containing two less sulphurs.The disulphane was prepared by chlorination of O-t-butyl S-methyl dithiocarbonate or by controlled desulphurisation of the trisulphane using triphenylphosphine; further desulphurisation provided the monosulphide. (Methyl thio)carbonylsulphenyl chloride is proposed as an intermediate in the above chlorination; it was synthesised by an indirect route and shown to rearrange to its isomer, (methylthio)carbonyl chloride.
- Mott, Andrew W.,Barany, George
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p. 2615 - 2621
(2007/10/02)
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- SYNTHESIS OF MONO- AND 1,4-DICARBONYL COMPOUNDS BASED ON THE OXYGENATION OF PHOSPHONATE CARBANIONS. SYNTHESIS OF DIHYDROJASMONE, ALLETHRONE AND METHYLENOMYCIN B
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Oxidation of the α-alkylthio-substituted phosphonate carbanions was found to give the corresponding carbonyl compounds.A new synthesis of 1,4-dicarbonyl systems involving the oxygenation of phosphonate carbanions as a key step is described.Total synthesis of dihydrojasmone and allethrone and formal synthesis of methylenomycin B is reported.
- Mikolajczyk, Marian,Midura, Wanda,Grzejszczak, Slawomir
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p. 2489 - 2492
(2007/10/02)
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- A General Strategy for Elaboration of the Dithiocarbonyl Functionality, -(C=O)SS-: Application to the Synthesis of Bis(chlorocarbonyl)disulfane and Related Derivatives of Thiocarbonic Acids
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A variety of sulfenyl chlorides have been reacted with a variety of alkoxythiocarbonyl compounds to give adducts which then lose (spontaneously, or upon thermolysis, or in the presence of Lewis acid catalyst) the alkyl chloride to provide an assortment of dithiocarbonyl compounds in good to excellent yields.The preparations of bis(chlorocarbonyl)disulfane (1), ((trichloromethyl)dithio)carbonyl chloride (2), ((alkoxycarbonyl)dithio)carbonyl chlorides (3 and 4), and (((alkylthio)carbonyl)dithio)carbonyl chlorides (5 and 6) by this methodology were optimized; some of the (alkoxydichloromethyl)disulfanyl adducts, e.g., ROCCl2SS(C=O)Cl (10) and ROCCl2SS(C=O)OR'(54), were reasonable stable and could be isolated.All new compounds were characterized by analytical data, 1H and 13C NMR, IR, UV, and mass spectrometry, and high-yield derivatizations with alcohols or N-methylaniline.The reaction with N-methylaniline was also adapted to a rapid, convenient, and precise analytical-scale assay of mixtures of compounds containing acid chloride and/or sulfenyl chloride functionalities.The kinetics, mechanism, and stereochemistry of the dithiocarbonyl synthesis are discussed.
- Barany, George,Schroll, Alayne L.,Mott, Andrew W.,Halsrud, David A.
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p. 4750 - 4761
(2007/10/02)
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- A NEW ROUTE TO THE 4H-1,2-OXAZETE RING SYSTEM BY THE STEREOSPECIFIC OXIDATION OF (Z)-3,3-DIMETHYL-1,1-BIS(METHYLTHIO)-2-BUTANONE OXIME
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A new synthesis of a funktionalized 4H-1,2-oxazete by oxidation of α,α-bis-(alkylthio) oxime is described.
- Corkins, H. Glenn,Storace, Lou,Osgood, Edmond R.
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p. 2025 - 2028
(2007/10/02)
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