- Amide (A)–thioamide (T) interconversions using Ph3SiSH (A to T) and Ph3SnOH (T to A) reagents
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Ph3SiSH transforms amides to thioamides and Ph3SnOH performs the reverse process, with the concomitant formation of Ph3SiOH (or Ph3SiOSiPh3) and Ph3SnSSnPh3, respectively. The chemistry is a delightful illustration of the oxophilicity of silicon compared to the thiophilicity of tin and occurs under relatively mild conditions, and for amide to thioamide transformation requires no amide activation. The chemistry is in accord with available data for Si?(S)(O), Sn?(O)(S) and C?(O)(S) bond energies. Copyright
- Arias-Ugarte, Renzo N,Sharma, Hemant K,Pannell, Keith H
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p. 510 - 513
(2016/07/16)
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- Copper(I)-mediated direct trifluoromethylthiolation of allylic halides with elemental sulfur and (trifluoromethyl)trimethylsilane
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Abstract A new method has been developed for the copper-mediated trifluoromethylthiolation of allylic halides by using potassium fluoride, elemental sulfur, and (trifluoromethyl)trimethylsilane in anhydrous N,N-dimethylformamide. This protocol provides facile access to a variety of allylic trifluoromethyl thioethers in moderate to good yields under mild, ligand-free reaction conditions.
- Li, Jue,Wang, Peiqiang,Xie, Fei-Fei,Yang, Xi-Gang,Song, Xiao-Nan,Chen, Wei-Dong,Ren, Jiangmeng,Zeng, Bu-Bing
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supporting information
p. 3568 - 3571
(2015/06/08)
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- Chromatographic component of identification of the transformation products of 1,1-dimethylhydrazine in the presence of sulfur
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The gas-chromatographic retention indices of the products of 1,1-dimethylhydrazine transformations in the presence of sulfur allows one to confirm and, in ceratin cases, make more exact the results of their gas chromatography-mass spectrometry identificat
- Zenkevich,Ul'Yanov,Golub,Buryak
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p. 1106 - 1114
(2014/08/05)
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- Metal-free oxidative trifluoromethylthiolation of terminal alkynes with CF3SiMe3 and elemental sulfur
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A metal-free oxidative trifluoromethyl-thiolation of terminal alkynes using readily available CF3SiMe3 and elemental sulfur at room temperature has been developed. This reaction provides an efficient and convenient method for the preparation of alkynyl trifluoromethyl sulfides bearing a wide range of functional groups. Preliminary investigation revealed that elemental sulfur instead of air acted as the oxidant.
- Chen, Chao,Chu, Lingling,Qing, Feng-Ling
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supporting information; experimental part
p. 12454 - 12457
(2012/09/05)
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- In situ formation of thermally stable, room-temperature ionic liquids from CS2 and amidine/amine mixtures
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Amidinium dithiocarbamates salts with diverse structures are prepared in situ by adding one equivalent of CS2 to an equimolar mixture of two nonionic molecules, an amidine and an amine. Many of the salts made in this way are room temperature ionic liquids (RTILs) and the others (ILs) melt well below the decomposition temperature of the salts, ca. 80 °C. Unlike the analogous amidinium carbamate RTILs, which are made by adding CO2 to amidine/amine mixtures and decompose near 50 °C, the amidinium dithiocarbamates do not revert to their amidine/amine mixtures when they are heated. The thermal, rheological, conductance, and spectroscopic properties of representative examples from a total of 50 of these ILs and RTILs are reported, comparisons between them and their nonionic phases (as well as with their amidinium carbamates analogues) are made, and the thermolysis pathways of the ammonium dithiocarbamates are investigated.
- Yu, Tao,Yamada, Taisuke,Weiss, Richard G.
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scheme or table
p. 5492 - 5499
(2011/12/14)
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- Direct thionation and selenation of amides using elemental sulfur and selenium and hydrochlorosilanes in the presence of amines
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Reactions of amides with elemental sulfur in the presence of hydrochlorosilanes and amines give the corresponding thioamides in good to high yields. The process takes place via reduction of elemental sulfur by the hydrochlorosilane in the presence of a suitable amine. The methodology can be applied to the selenation of amides by using elemental selenium. Thlonation and selenation of an acetyl-protected sialic acid derivative are found to take place selectively at the amide group.
- Shibahara, Fumitoshi,Sugiura, Rie,Murai, Toshiaki
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supporting information; experimental part
p. 3064 - 3067
(2009/12/05)
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- Expeditious microwave-assisted thionation with the system PSCl 3/H2O/Et3N under solvent-free condition
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(Chemical Equation Presented) A novel thionation protocol for carbonyl compounds, with the system PSCl3/H2O/Et3N has been discovered. Clean, rapid, and efficient synthesis of a variety of thiocarbonyl compounds such as thioamides, thiolactams, thioketones, thioxanthones, and thioacridone can be achieved through this simple and convenient method under solventless condition with microwave irradiation.
- Pathak, Uma,Pandey, Lokesh Kumar,Tank, Rekha
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p. 2890 - 2893
(2008/09/19)
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- Dichlorothiophosphoric acid and dichlorothiophosphate anion as thionating agents in the synthesis of thioamides
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A method for the thionation of carboxylic acid amides with dichlorothiophosphoric acid and dichlorothiophosphate anion, providing thioamides in high yields, was developed. The facility of the thionation and the yields of the final products were shown to depend on the nature of the starting amide. The optimal reaction conditions are reported.
- Bezgubenko,Pipko,Sinitsa
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experimental part
p. 1341 - 1344
(2009/02/07)
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- Dichlorophosphate anion in the synthesis of thioamides
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Phosphorus thiochloride reaction with dimethylformamide and dimethylacetamide leading to corresponding thioamides is studied. The thionylating agent is dichlorothiophosphate anion generated in the reaction course. Pleiades Publishing, Inc., 2006.
- Pipko,Simurova,Shvadchak,Bezgubenko,Luk'yanenko
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p. 1019 - 1021
(2008/02/05)
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- Thionation with the reagent combination of phosphorus pentasulfide and hexamethyldisiloxane
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The combination of P4S10 and hexamethyldisiloxane efficiently converts esters, lactones, amides, lactams, and ketones to their corresponding thiono derivatives. In the presence of elemental sulfur, 3-oxoesters are converted to dithiolethiones by this reagent. Yields are comparable to or superior to those obtained with Lawesson's reagent. The method has the advantage that reagent-derived byproducts may be removed by a simple hydrolytic workup or by filtration through silica gel, rather than by chromatography, as required for Lawesson's reagent.
- Curphey, Thomas J.
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p. 6461 - 6473
(2007/10/03)
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- Orthoamides. LIV. Contributions to the chemistry of azavinylogous orthoformic acid amide derivatives
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The azavinylogous aminalester 3 reacts with primary amines to give amidines 5 and 6. In the reaction of 3 with aniline the azavinylogous amidine 7 is produced additionally to the amidine 5c. Ethylendiamine is formylated at both aminogroups, the bis-amidine 8 thus formed is transformed to the salts 9a,b. Benzoxazole and benzimidazole can be prepared from 3 and o-aminophenol and o-phenylenediamine, resp. Carboxylic acid amides, urea, thiourea, aromatic acid hydrazides 17 and the sulfonylhydrazide 19 are formylated by 3 at nitrogen to give N-acylated formamidines 14, 16, 18, 20. From 3 and aliphatic acid hydrazides 17 and alkylhydrazines, resp., can be obtained 1,2,4-triazole 21 and 1-alkyl-1,2,4-triazoles 22a,b, resp. N.N-Dimethylcyanacetamide (32) reacts with 3 and the orthoamide 4a, resp., to give a mixture of the formylated compound 34 and the amidine 33. The reaction conditions are of low influence on the ratio in which 33 and 34 are formed. The orthoamide 4b and 32 react to afford a mixture of the amidine 35 and the enamine 36. Hydrogen-sulfide acts on 3 giving N,N-dimethylthioformamide (37). From 3 and 1-alkynes 41 can be prepared the amidines 42. Hydrolysis of 42b affords phenylpropiolaldehyde (43). The alkylation of the aminalester 3 gives rise to the formation of vinylogous amidinium salts 1c and 1d, resp., additionally is formed the amide acetal 2a. The salt 1d can also be prepared from 3 and borontrifluoride-ether. Iodide reacts with N,N-dimethylformamide acetals 12a,b in an unclear, complicated manner giving orthoesters 53, N,N-dimethylformamide, alkyliodides, alcohols, ammonium iodides 46 and carbondioxide. The action of halogens on 3 affords the salts 1a,b,c,e,f depending on the chosen stoichiometric ratio. Aromatic aldehydes are suited for trapping azavinylogous carbenes formed on thermolysis of 3; 1,3-oxazoles 69 are the reaction products. From 3 and propionaldehyde the amidine 65 can be obtained with low yield. Carbondisulfide transforms 3 to the azavinylogous salt 66. The preparation of the azavinylogous orthoamide 4a is described. The thermolysis of 3 and 4a, resp., gives rise to the formation of the triaminopyrimidine 67. Treatment of 1a with lithium diisopropylamide affords the triaminopyrazine 68, which can also be obtained by thermolysis of 3 in the presence of sodium hydride. Azavinylogous carbenes are thought to be the intermediates. Wiley-VCH Verlag GmbH, 2000.
- Kantlehner, Willi,Hauber, Michael,Haug, Erwin,Schallenmueller, Claus,Regele, Claudia
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p. 682 - 699
(2007/10/03)
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- Microwave-accelerated solvent-free synthesis of thioketones, thiolactones, thioamides, thionoesters, and thioflavonoids
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Formula presented An expeditious, solvent-free, and high yield conversion of ketones, flavones, isoflavones, lactones, amides, and esters to the corresponding thio analogues is described utilizing Lawesson's reagent in a process that circumvents the use of dry solvents and excess of the reagent.
- Varma, Rajender S.,Kumar, Dalip
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p. 697 - 700
(2008/02/11)
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- A Facile Conversion of Amides and Lactams to Thioamides and Thiolactams using Tetrathiomolybdate
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Chloro iminium salts generated in situ from amides and lactams using (COCl)2 or POCl3 reacted very readily with the new sulfur transfer reagent, benzyltriethylammonium tetrathiomolybdate to afford the corresponding thioamides and thiolactams in excellent yields under mild reaction conditions.
- Ilankumaran, Palanichamy,Ramesha, A. R.,Chandrasekaran, Srinivasan
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p. 8311 - 8314
(2007/10/02)
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- 2-amino-3-aroyl-benzo[β]thiophenes and methods for preparing and using same to produce 6-hydroxy-2-(4-hydroxyphenyl)-3-]benzo[4-(2-aminoethoxy)-benzoyl[β]thiophenes
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A group of 2-amino-3-aroyl-benzo[β]thiophenes are prepared by preparing an α-hydroxy thioacetamide by silyl mediated condensation of an aldehyde with an anion of dialkylamino thioformamide, cyclizing the α-hydroxy thioamide, and subsequently acylating the benzo[β]thiophene to yield the 2-amino-3-aryl derivative. These compounds may be treated with suitable phenyl Grignard reagents, and after deprotection, yield 6-hydroxy-2-(4-hydroxyphenyl)-3-[4-(2-piperidinoethoxy)benzoyl]benzo[β]thiophene.
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- In Situ Reagent for Thionation of Amides, Peptides and Lactams
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An in situ reagent 1A for thionation of amides, peptides and lactams is prepared from phosphorus decasulfide/sodium carbonate (1:1 ratio) in THF at 25 deg C.
- Brillon, Denis
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p. 3085 - 3095
(2007/10/02)
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- THE REACTION OF C-(N,N-DIALKYLAMINO)PHOSPHAALKENES AND THEIR DIMERS WITH SULFUR
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The nature of the dialkylamino group has a significant effect on the reactivity of C-(N,N-dialkylamino)phosphaalkenes upon their reaction with sulfur.
- Ionkin, A. S.,Ignat'eva, S. N.,Arbuzov, B. A.
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p. 1052 - 1054
(2007/10/02)
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- Thermolysis of Polyazapentadienes. Part 11. Concerted and Free Radical Mechanisms in 2-Aza Enone and 2-Aza Enthione Pyrolyses: Crystal and Molecular Structures of 3-Dimethylamino-1-p-tolyl-2-azaprop-2-en-1-one and 3-Dimethylamino-1-phenyl-2-azaprop-2-ene-1-thione
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Flash vacuum pyrolysis of the dimethylamino-azapropenones (7)-(9) and -azapropenethione (12) gives nitriles and amides (or thioamide) in yields of ca. 30percent by an electrocyclisation-ring cleavage mechanism.This is a minor pathway for the triarylazapropenones (14) and (15) for which homolytic cleavage of the C-N bond gives rise to the major products.The X-ray crystal structures of (10) and (12) show that the conjugated systems are almost planar in the s-Z conformation, as required for the electrocyclic ring closure.
- Blake, Alexander J.,McNab, Hamish,Murray, M. Elizabeth-Ann
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p. 589 - 595
(2007/10/02)
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- Thiono and Dithio Esters, 41. - Reaction of Dithiono Malonic Esters with Electrophiles
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Dithiono malonic esters 1 react with alkali alkoxides to form the stable alkali salts 2.According to an X-ray analysis for the N,N,N',N'-tetramethylformamidinium salt 18 their anions adopt a trans,s-trans configuration in the crystalline state.By NOE experiments the same configuration is confirmed for solutions (DMSO or D2O).Alkylation of 2, however, gives rise to the Z-configurated thiono acrylic esters 4.By oxidation of 1a with tert.-butyl hypochlorite or iodine the 1,2-dithiolium salts 5 and 7 were obtained.The reaction of 1a with N,N-dimethyl formamidediethylacetal (8) in ethanol leads to the formation of the dimethylaminomethylene compound 12, in ether the formamidinium salt 18 precipitates.The latter decomposes to N,N-dimethylformamide 20 and the thiono acrylic ester 21.
- Mueller, Hans-Georg,Hartke, Klaus,Kaempchen, Thomas,Massa, Werner,Hahn, Friedemann
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p. 873 - 878
(2007/10/02)
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- STUDIES ON ORGANOPHOSPHORUS COMPOUNDS XLVII PREPARATION OF THIATED SYNTHONS OF AMIDES, LACTAMS AND IMIDES BY USE OF SOME NEW P,S-CONTAINING REAGENTS
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The thionation properties of 2,4-bismethylthio-1,3,2,4-dithiadiphosphetane 2,4-disulfide, 1, 2,4-bis(4-phenoxyphenyl)-1,3,2,4-dithiaphosphetane 2,4-disulfide, 2, 2,4-bis(4-phenylthiophenyl)-1,3,2,4-dithiaphosphetane 2,4-disulfide, 3, and 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiaphosphetane 2,4-disulfide (LR), 4, have been investigated on a series of amides, lactams and imides.The most remarkable feature is that 2, 3 and 4 thionate most amides and lactams in THF at room temperature (reaction time 5 min) to give the corresponding thionated compounds.Imides are easily thionated by 2, 3 and 4 in DME at 60 oC.The reactions of 1 with amides, imides and most lactams are run at 60 oC to give good yields of the corresponding thionated compounds.
- Yde, B.,Yousif, N. M.,Pedersen, U.,Thomsen, I.,Lawesson, S. -O.
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p. 2047 - 2052
(2007/10/02)
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- SYNTHESIS OF THE FIRST STABLE METADITHIOPHOSPHONATE
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Evidence for the formation of the first stable metadithiophosphonate is given.
- Navech, J.,Majoral, J. P.,Kraemer, R.
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p. 5885 - 5886
(2007/10/02)
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- Note on the Preparation of N,N-Disubstituted Aliphatic Thiocarboxamides, N-Substituted Thiolactames, and Aromatic Thiocarboxylates
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Hydrogen sulfide reacts with the N,N-dimethylformamide acetal 1 to give N,N-(dimethyl)thioformamide (2a).The thioamides 2a-e and the thiolactams 2f,g are prepared by thiolysis of the nitriles 3a-g.The action of hydrogen sulfide on nitriles 5a-f affords the O-ethyl thiocarboxylates 6a-f.The preparation of the nitriles 3g and 5a-f is described.
- Kantlehner, Willi,Haug, Erwin,Farkas, Michael
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p. 1582 - 1587
(2007/10/02)
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- 10. Nucleophile Aminoalkylierung mit Thiopivalamiden
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Of the twelwe thioamides 7a-e and 8a-g, only N,N-dimethylthiopivalamide (7a) could be metallated at the CH-group in α-position to the N-atom.The reagent 9 thus obtained (Table 1) reacts in high yields with primary haloalkanes, with aldehydes, and with non-enolizable ketones (Table 2).As shown in Scheme 1, the products can be hydrolyzed to pivalamides, cleaved to secondary amines, or reduced to neopentylamines (see 18/19, 15/equation (4) and (5), and 16/20, respectively).
- Lubosch, Winfried,Seebach, Dieter
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p. 102 - 116
(2007/10/02)
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