- A practical, one-step synthesis of primary thiols under mild and neutral conditions using bis(triorganotin) sulfides
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Thiols are obtained from primary organic halides and bis(triaryl/alkyltin) sulfides in the presence of fluoride ion in CH3CN/H2O at 20°C. This simple one-step methodology involving fluorodestannylation is carried out under mild and neutral conditions, in sharp contrast to virtually all known methods. Some attempts at utilizing triorganotin and triorganogermanium mercaptans for the same purpose are reported.
- Gingras,Harpp
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- Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided Mo-Ni/Al2O3 catalysts
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The thioetherification reaction of 1-butanethiol and 1-hexene dissolved in n-hexane was investigatedover sulfided Mo-Ni/Al2O3catalysts. The experimental results showed the catalysts have good cat-alytic performance for thioetherification reaction, but the isomerization and hydrogenation reactions of olefins over the catalysts can inhibit thioetherification reaction. As reaction temperature increases,the isomerization and hydrogenation reactions of olefins increase rapidly, however, the inhibition of thioetherification reaction also increases. The sulfur distribution and molecular structures of sulfurcompounds in the products were analyzed by the gas chromatograph with sulfur chemiluminescencedetector (GC-SCD) and the gas chromatograph/mass spectra spectrometry (GC/MS). Two possible routesof thioetherification reaction could be observed. At low temperature, the major pathway involves a directaddition of 1-butanethiol to the terminal carbon of double bond of 1-hexene. In this mechanism, the mainproduct is anti-Markovnikov adduct. At a higher temperature, the C S bond of 1-butanethiol can be sub-sequently cleaved, and the adsorbed -SH species can be formed on the catalysts. On the same time,abundant 1-hexene can be absorbed on the catalysts, as well. Therefore, the adsorbed SH species canthen recombine with adsorbed 1-hexene to form new hexyl-mercaptans, which can continue to produceanother kind of thioether (di-hexyl sulfide) with adsorbed 1-hexene. Similar with the first reaction route,the thioether of the anti-Markonikov adduct still dominates in the product.
- Shen, Zhibing,Ke, Ming,Yu, Pei,Hu, Haiqiang,Song, Zhaozheng,Jiang, Qingzhe
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- Catalytic Hydrogenation of Thioesters, Thiocarbamates, and Thioamides
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Direct hydrogenation of thioesters with H2 provides a facile and waste-free method to access alcohols and thiols. However, no report of this reaction is documented, possibly because of the incompatibility of the generated thiol with typical hydrogenation catalysts. Here, we report an efficient and selective hydrogenation of thioesters. The reaction is catalyzed by an acridine-based ruthenium complex without additives. Various thioesters were fully hydrogenated to the corresponding alcohols and thiols with excellent tolerance for amide, ester, and carboxylic acid groups. Thiocarbamates and thioamides also undergo hydrogenation under similar conditions, substantially extending the application of hydrogenation of organosulfur compounds.
- Luo, Jie,Rauch, Michael,Avram, Liat,Ben-David, Yehoshoa,Milstein, David
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supporting information
p. 21628 - 21633
(2021/01/11)
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- Characterization of initial reaction intermediates in heated model systems of glucose, glutathione, and aliphatic aldehydes
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To understand the effect of lipid degradation on Maillard formation of meaty flavors, initial reaction intermediates in model systems of glucose–glutathione with hexanal, (E)-2-heptenal, or (E,E)-2,4-decadienal were identified by HPLC–MS and by NMR. Besides Amadori compounds, hemiacetals and thiazolidines via addition of sulfhydryl to carbonyl or to the conjugated olefinic bond were found. Concentrations of all intermediates increased with reaction time while degradation of the intermediates with a glutathione moiety helped formation of thiazolidines with cysteinylglycine. The unsaturated aldehydes (E)-2-heptenal and (E,E)-2,4-decadienal exhibited high reactivity against glucose for glutathione, yielding higher levels of intermediate compounds than from glucose. Heating prepared intermediates reversibly released the original aldehydes, which caused various compounds formed by retro-aldol, oxidation, etc. to react with H2S and NH3. Among them, formation pathways including 3-nonen-2-one, 2-hexanoylfuran, and six dialkylthiophenes (e.g., 2-ethyl-5-(1-methylbutyl)thiophene) were proposed for the first time.
- Wang, Tianze,Zhen, Dawei,Tan, Jia,Xie, Jianchun,Cheng, Jie,Zhao, Jian
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- Phosphorus pentasulfide mediated conversion of organic thiocyanates to thiols
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In this paper we report an efficient and mild procedure for the conversion of organic thiocyanates to thiols in the presence of phosphorus pentasulfide (P2S5) in refluxing toluene. The method avoids the use of expensive and hazardous transition metals and harsh reducing agents, as required by reported methods, and provides an attractive alternative to the existing methods for the conversion of organic thiocyanates to thiols.
- Maurya, Chandra Kant,Mazumder, Avik,Gupta, Pradeep Kumar
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supporting information
p. 1184 - 1188
(2017/07/03)
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- Two-step three-component process for one-pot synthesis of 8-alkylmercaptocaffeine derivatives
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A highly efficient, odourless and two-step three-component process for one-pot synthesis of some 8-alkylmercaptocaffeine derivatives has been described. The catalyst-free three-component reaction of alkyl bromides, thiourea, and 8-bromocaffeine gave 8-alkylmercaptocaffeine products in excellent to quantitative yields. In addition, the impact of parameters on sample reaction is discussed.
- Rad, M. N. Soltani,Maghsoudi
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p. 70335 - 70342
(2016/08/06)
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- A rhodium(i)-oxygen adduct as a selective catalyst for one-pot sequential alkyne dimerization-hydrothiolation tandem reactions
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An air-stable rhodium(i)-oxygen adduct featuring a CNC-pincer ligand, based on 1,2,3-triazol-5-ylidenes, catalyzes the homo-dimerization and hydrothiolation of alkynes, affording the gem-enyne and α-vinyl sulfide isomers, respectively, with excellent selectivity. A one-pot stepwise strategy allows the selective catalytic preparation of non-symmetric bis-vinyl sulfides, as well as the alkyne dimerization-hydrothiolation tandem reactions.
- Kleinhans, George,Guisado-Barrios, Gregorio,Liles, David C.,Bertrand, Guy,Bezuidenhout, Daniela I.
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supporting information
p. 3504 - 3507
(2016/03/04)
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- A method of manufacturing a thiolcarboxylic compd.
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PROBLEM TO BE SOLVED: To provide a method of production, obtaining a thiol compound in a high yield by using a hydroxy compound and hydrogen sulfide as raw materials. SOLUTION: This method of production includes reacting the hydroxy compound with hydrogen sulfide in the presence of a metal oxide catalyst selected from a complex metal oxide containing zirconia, acid-carrying zirconia or silica/titania having mesoporous pores, under gas phase heating, and it is especially useful for the production of an aromatic thiol compound such as thiophenol. COPYRIGHT: (C)2011,JPOandINPIT
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Paragraph 0026-0027
(2017/09/29)
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- Electromediators based on the Ni(II) and Cr(III) complexes with the redox-active ligands in the synthesis of sulfur-containing organic compounds
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The chromium(III) tris-o-semiquinolate complex Cr(LSQ) 3 (LSQ is 3,6-di-tert-butyl-o-semiquinone) and the monoanionic paramagnetic nickel(II) complex [n-Bu4N][Ni(L S SQ)(L S DT)] (L S SQ is o-thiosemiquinone, L S DT is benzene-1,2-dithiolate) are considered as electromediators of hydrogen sulfide oxidation in the presence of various organic substrates (hex-1-ene, oct-1-ene, benzene, toluene, and benzoic acid). It is revealed that the electrolysis of hydrogen sulfide at the oxidation potential of the mediators in the presence of the substrates affords the corresponding aliphatic and aromatic thiols in a yield of 62-75%.
- Okhlobystin,Smolyaninov,Okhlobystina,Berberova,Koldaeva, Yu. Yu.,Abdulaeva
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- Synthesis and antifungal activities of alkyl N-(1,2,3-thiadiazole-4-carbonyl) carbamates and S-alkyl N-(1,2,3-thiadiazole-4-carbonyl) carbamothioates
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A series of alkyl N-(1,2,3-thiadiazole-4-carbonyl) carbamates and S-alkyl N-(1,2,3-thiadiazole-4-carbonyl) carbamothioates with unsubstituted or monobrominated straight chain alkyl groups were synthesized and evaluated as fungistatic agents against Gibberella zeae and Altemaria kikuchiana. These compounds showed variable antifungal activities at concentrations of 5 and 50 μg/mL The results showed that antifungal activities depended on the length of the alkyl chain with the optimal chain length of 6-11 carbons. Carbamic acid, (1,2,3-thiadiazole-4-ylcarbonyl)-, hexyl ester (4) showed a strong fungistatic activity against A. kikuchiana at both concentrations, with 90.7 and 54% growth inhibition at 50 and 5 μg/mL, respectively. Carbamic acid, (1,2,3-thiadiazole-4-ylcarbonyl)-, heptyl ester (5); Carbamic acid, (1,2,3-thiadiazole-4-ylcarbonyl)-, octyl ester (6); and Carbamic acid, (1,2,3-thiadiazole-4-ylcarbonyl)-, undecyl ester (9) showed strong fungistatic activity against G. zeae at both concentrations. Their growth inhibitions against G. zeae at the concentration of 5 μg/mL were 78, 63, and 59%, respectively.
- Li, Zaifeng,Wu, Zengru,Luo, Fuying
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p. 3872 - 3876
(2007/10/03)
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- Mild and efficient desulfurization of alkyl sulfides with sodium
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The reactions of dialkyl mono- and disulfides and functionalized alkylthio compounds with sodium in refluxing hydrocarbon solvent (tetradecane mositylene or toluene) resulted in sulfur-free products in very high yields.
- Yu, Zhengkun,Verkade, John G.
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p. 2671 - 2674
(2007/10/03)
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- Mechanism of the Solution-Phase Reaction of Alkyl Sulfides Atomic Hydrogen. Reduction via a 9-S-3 Radical Intermediate
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The low selectivity of benzyl alkyl sulfide fragmentation subsequent to its reaction with atomic hydrogen is indicative of a reaction that proceeds via an early transition state. The competitive reduction of a series of substituted-benzyl alkyl sulfides was insensitive to the substituent on the aromatic ring (ρ = -0.13, r = 0.99). The relative rates of fragmentation of a series of the substituted-benzyl alkyl sulfides gave a V-shaped Hammett plot. Both electron-donating and electron-withdrawing groups destabilized the transition state (ρ = +0.99, r = 0.999; ρ = -0.82, r = 0.992). Since the relative rates of disappearance of the alkyl benzyl sulfides are not substituent dependent, but the relative rates of fragmentation are, a 9-S-3 intermediate is preferred as the structure leading to products.
- Tanner, Dennis D.,Koppula, Sudha,Kandanarachchi, Pramod
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p. 4210 - 4215
(2007/10/03)
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- Convenient one-pot synthesis of β-alkylthio acid derivatives from thioacetates and the corresponding α,β-unsaturated compounds
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Various β-alkylthio acid derivatives were prepared conveniently from thioacetates and α,β-unsaturated compounds through borohydride exchange resin (BER)-Pd catalyzed transesterification of thioacetates to the corresponding thiols and Michael addition of the resulting thiols to α,β-unsaturated compounds.
- Lee,Choi,Yoon
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p. 2189 - 2196
(2007/10/03)
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- Low pressure hydrogenation of unsaturated sulphides with homogeneous and heterogeneous ruthenium catalysts
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Ru2O·nH2O and [Ru3O(AcO)6(H2O)3]+AcO- were examined for catalytic activity in the hydrogenation of a series of unsaturated sulphides under heterogeneous and homogeneous conditions, respectively. By the appropriate combination of these two methodologies, a number of saturated sulphides could be synthesized in satisfactory to good yields, thus minimizing side reactions.
- Cere, Vanda,Massaccesi, Franco,Pollicino, Salvatore,Ricci, Alfredo
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p. 899 - 907
(2007/10/03)
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- β-carboxy sulfonamide ACAT inhibitors
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β-Carboxy sulfonyl compounds of the formula STR1 wherein R1 is aryl, R3 is hydrogen or alkyl, R3 and R4 are hydrogen or alkyl, Y is --O--, --S--, or --NR2 --, and R5 is alkyl or aryl are potent inhibitors of the enzyme acyl CoA:cholesterol acyltransferase (ACAT) and are thus useful for treating hypercholesterolemia and atherosclerosis.
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- The Regioselective Reaction of Atomic Hydrogen with Unsymmetric Disulfides and Sulfides
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Unsymmetrical disulfides undergo solution phase reduction with atomic hydrogen regioselectively by displacement at the least hindered sulfur atom.The cleavage of the sulfur-sulfur bond forms mixtures of two thiol and two thiyl radicals.At the temperature at which the reactions are carried out, the thiyl radicals form symmetric disulfides by thiyl-thiyl radical coupling and not by thiyl radical displacement on the starting material.The reaction of atomic hydrogen with an unsymmetric sulfide is a cleavage that favors the formation of the most stable radical.The reaction of phenyl cyclohexyl sulfide produces benzene, cyclohexane, cyclohexyl thiol, and thiophenol.Benzene and cyclohexyl thiol produced from the cleavage of the phenyl-sulfur bond are proposed to arise from the α-scission of an intermediate formed by ipso-addition of atomic hydrogen to the benzene ring.
- Tanner, Dennis D.,Zhang, Liying,Vigneswaran, Markandu,Kandanarachchi, Pramod
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p. 4481 - 4487
(2007/10/02)
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- PREPARATION OF THIOLS USING α-TRIMETHYLSILOXY DERIVATIVES
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Aliphatic thiols (1) can be prepared under the mildest conditions presently available by desilylation of the appropriate α-trimethylsiloxy sulfide (3).Sulfides 3 are generated by either alkylation of the corresponding alkyl halide or by standard literature methods.
- Harpp, David N.,Kobayashi, Michio
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p. 3975 - 3978
(2007/10/02)
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- ONE POT CONVERSION OF ALKYL HALIDES INTO THIOLS UNDER MILD CONDITIONS
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Alkyl halides are converted into the corresponding thiols in good yields at room temperature under neutral conditions by reaction with 1-(2-hydroxyethyl)-4,6-diphenylpyridine-2-thione.
- Molina, P.,Alajarin, M.,Vilaplana, M. J.,Katritzky, A. R.
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p. 469 - 472
(2007/10/02)
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- Rate Constants and Equilibrium Constants for Thiol-Disulphide Interchange Reactions Involving Oxidized Glutathione
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The rate of reduction of oxidized glutathione (GSSG) to glutathione (GSH) by thiolate (RS-) follows a Broensted relation in pKas of the conjugate thiols (RSH): βnuc ca. 0.5.This value is similar to that for reduction of Ellman's reagent: βnuc ca. 0.4 - 0.5.Analysis of a number of rate and equilibrium data, taken both from this work and from the literature, indicates that rate constants, k, for a range of thiolate-disulphide interchange reactions are correlated well by equations of the form log k = C + βnucpKanuc + βcpKac + βlgpKalg ( nuc = nucleophile, c = central, and lg = leaving group sulfur): eq 36 - 38 give representative values of the Broensted coefficients.The values of these Bronsted coefficients are not sharply defined by the available experimental data, although eq 36 - 38 provide useful kinetic models for rates of thiolate-disulfide interchange reactions.The uncertainty in these parameters is such that their detailed mechanistic interpretation is not worthwhile, but their qualitative interpretation - that all three sulphur atoms experience a significant effective negative charge in the transition state, but that the charge is concentrated on the terminal sulfurs - is justified.Equilibrium constants for reduction of GSSG using α,ω-dithiols have been measured.The reducing potential of the dithiol is strongly influenced by the size of the cyclic disulfide formed on its oxidation: the most strongly reducing dithiols are those which can form six-membered cyclic disulfides.Separate equilibrium constants for thiolate anion-disulphide interchange (KS-) and for thiol-disufide interchange (KSH) have been estimated from literature data: KS- is roughly proportional to 2ΔpKa is the difference between the pKas of the two thiols involved in the interchange.The contributions of thiol pKa values to the observed equilibrium constants for reduction of GSSG with α,ω-dithiols appear to be much smaller than those ascribable to the influence of structure on intramolecular ring formation.These equilibrium and rate constants are helpful in choosing dithiols for use as antioxidants in solutions containing proteines: dithiothreitol (DTT), 1,3-dimercapto-2-propanol (DMP), and 2-mercaptoethanol have especially useful properties.
- Szajewski, Richard P.,Whitesides, George M.
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p. 2011 - 2026
(2007/10/02)
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- Metalation of 1,3-Dithiolanes. Mercaptan Synthesis and Carbonyl Transposition
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The reaction of 1,3-dithiolanes with n-butyllithium results in fragmentation to the corresponding thiocarbonyl compound followed by furhter reaction with n-butyllithium.All four types of thiocarbonyl reactions are observed: reduction, S-addition, C-addition, double addition.Synthetic applications of this reaction for the synthesis of secondary mercaptans and 1,2-carbonyl transposition (23 -> 24a-c) are described.
- Wilson, Stephen R.,Georgiadis, Gregory M.,Khatri, Hiralal N.,Bartmess, John E.
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p. 3577 - 3583
(2007/10/02)
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- Antimicrobial composition and method containing N-(3,5-dihalophenyl)-imide compounds
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Novel N-(3,5-dihalophenyl)imide compounds, which exhibit a strong antimicrobial activity against microorganisms including phytopathogenic fungi, parasites of industrial products and pathogenic microorganisms, represented by the formula, STR1 wherein X and X' each represent halogens and A represents a substituted ethylene such as chloroethylene, C1 - C4 alkylthioethylene, C1 - C2 alkyl-ethylene or 1,2-di-C1 - C2 -alkyl-ethylene, a cyclopropylene such as 1,3-dimethylcyclopropylene, trimethylene, a cyclohexylene-1,2-, cyclohexenylene-1,2-, cyclohexadienylene-1,2- or o-phenylene. The N-(3,5-dihalophenyl)imide compounds can be obtained by any of methods which produce imide compounds or reaction of an N-(3,5-dihalophenyl)maleimide compound with a mercaptan, a hydrogen halide, phosphorus chloride or thionylchloride.
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- Method of preparing primary aliphatic mercaptans
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Primary aliphatic (preferably alkyl) mercaptans are prepared by heating a phosphorus-sulfur compound, preferably a primary aliphatic phosphorodithioic acid, with a basic nitrogen compound. The preferred basic nitrogen compounds are amines and particularly aliphatic primary and secondary amines, especially alkylene polyamines.
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- 3-Aryl-2-halothiopropionic acid s-esters
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Novel 3-aryl-2-halothiopropionic acid compounds of the formula STR1 wherein X is chlorine or bromine, R1 is hydrogen, a salt-forming cation, an aliphatic radical or a substituted aliphatic radical wherein the substituent is halogen, haloalkyl, hydroxy, alkoxy, alkoxy-carbonyl or aryl, R2 is hydrogen, halogen or alkyl R3 is hydrogen or alkyl n is an integer from 0 to 3; and R4 is halogen, alkyl, haloalkyl or nitro and wherein the radical R4, when n is 2 or 3, may be the same or different, Are outstandingly effective herbicides, exhibiting particularly selective action.
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