Dimerization of methyl isothiocyanate to the 2-mercapto-1-methylimidazole-5(4H)-thione anion under the action of a superbase

Dimerization of methyl isothiocyanate under the action of potassium diisopropylamide followed by alkylation of the intermediate dithiolate gives 2,5-bis(alkylthio)-1-methylimidazoles in 71–74% yields. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 186–187, January, 1998.     

Reactions of 4-Methoxy-3-quinolinyl and 1,4-Dihydro-4-oxo-3-quino-linyl Sulfides Aiming at the Synthesis of 4-Chloro-3-Quinolinyl Sulfides

The preparation of 1,4-dihydro-4-oxo-3′-alkylthio-3,4′-diquinolinyl sulfides 3 or 1,4-dihydro-4-oxo-3-(alkylthio)quinolines 4 by acid catalysed hydrolysis of 4-methoxy-3′-alkylthio-3,4′-diquinolinyl sulfides 1 or 4-methoxy-3-(alkylthio)-quinolines 2 is described. The reactions of 4-methoxy-3′-alkylthio-3,4′-diquinolinyl sulfides 1 or 1,4-dihydro-4-oxo-3′-alkylthio-3,4′-diquinolinyl sulfides 3 with phosphoryl chloride in DMF afforded 4-chloro-3′-alkylthio-3,4′-diquinolinyl sulfides 5 . Treatment of the title compounds 1 or 3 with boiling phosphoryl chloride systems:leads to 4-chloro-3-(alkylthio)quinolines 6 and thioquinanthrene but those of alkoxy- or oxo-quinolines 2 or 4 lead to 4-chloro-3-(alkylthio)quinolines 6 . The reactions of N-methyl-4(1H)-quinolinones 3n and 4n with phosphoryl chloride directed to 4-chloro-3-(alkylthio)quinolines 6 were studied as well.     

Syntheses of fluorine‐containing enamines,ketenedithioacetals, and acetylene sulfoxides from 1‐alkythio‐3,3‐difluoropropynes‐1

Convenient methods of synthesis of fluorocontaining N,N‐dimethylenamines by the reactions of 1,1‐dihydrotetrafluoropropyl sulfides with KOH in dimethylformamide and of fluoro‐containing 1,4‐dienes by the cycloaddition reactions of 1‐(alkylsulfinyl)‐difluoropropynes with dimethylbutadiene or cyclopentadiene are described. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:383–386, 2000     

(Organylthio)chloroacetylenes: VII. Hydrochlorination of (Alkylthio)chloroacetylenes

(Alkylthio)chloroacetylenes are readily hydrochlorinated with hydrogen chloride in dioxane to form a mixture of (E)- and (Z)-1-(alkylthio)-1,2-dichloroethenes, as well as 1-(alkylthio)-1,1,2-trichloroethanes.     

Reactions of 6-Alkoxy(alkylthio)carbonylamino-4-hydroxy-2H-pyran-2-ones with Some Electrophilic Reagents

Alkoxy(alkylthio)-4-hydroxy-2H-pyran-2-ones readily react with electrophiles to give substitution products at C³. Hard electrophilic reagents replace hydrogen both in position 3 and in position 5 of the pyran ring. Methylation of 6-alkoxy(alkylthio)-4-hydroxy-2H-pyran-2-ones with diazomethane leads to formation of O- and N-methyl derivatives.     

Differentiation and electron ionization-induced isomerization of 4,5-Bis(alkylthio)-1,3-dithiole-2-thiones and 1,2-dithiole-3-thiones

The electron impact ionization mass spectra of 4,5-bis(alkylthio)-1,3-dithiole-2-thiones and their 1,2-dithiole-3-thione isomers were studied by accurate mass measurements and linked scans. The relative abundance of ions formed following the extrusion of S₂, CS or CS₂ allows an unambiguous isomer differentiation. Isomerization of molecular ions was studied by means of metastable ion analysis and collision-induced dissociation. The order of reactivity was analogous to that observed in isomerization under photochemical conditions.     

Oxidation of 1,3,4,6-tetrakis(alkylthio)thieno[3,4-c]-thiophenes with iodine in the presence of aniline

1,3,4,6-Tetrakis(alkylthio)thieno[3,4-c]thiophenes were oxidized by iodine in the presence of aniline in dry benzene to give 1,4,6-tris(alkylthio)thieno[3,4-c]thiophen-3(1H)-imines in high yields through the intermediary formation of their cation radicals.     

Two pathways for the protolysis of 1-(alkythio)-1-buten-3-ynes and the effect of cis-trans isomerism

Conclusions We have used a spectrophotometric method to examine the kinetics of the hydrolysis of 1-(alkylthio)-1-buten-3-ynes to (alkylthio)butenones and acetoacetaldehyde; the rate of reaction depends markedly on the reactant configuration.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 153–159, January, 1978.     

Complexes wits a Thioalkyl-Bridged M-P-Bond from Metallo(Alkylthio)Phosphanes

Abstract

Metallation of alkylthio(ch1oro)phosphanes ClP(R′)S-R (R = i-Pr, tBu; R′ = tBu, St-Bu) and Cl₂P-S-tBu with Na[M(CO)₃Cp] (M = Cr, Mo, W) yields the metallo-(alkylthio) chloro-, metallo-bis(alkylthio)-, metallo-(alkylthio) (alkyl) phosphanes (la-f) or the bis(metallo)(alkylthiol phosphane (lg) respectively.     

Novel Rearrangements of 2,3-Dimercapto-1-propanol Derivatives: Formation of Dialkyl Sulfide, Dialkyl Disulfide, and 1,2,3-Tris(alkylthio)propane

The base alkylation of 2,3-dimercapto-1-propanol with alkyl halides leads in good yield to 2,3-bis(alkylthio)-1-propanol and dialkyl sulfide. The reaction of 2,3-bis(alkylthio)-1-propanol with catalytic concentrated sulfuric acid proceeds with rearrangement to give 1,2,3-tris(alkylthio)propane and dialkyl disulfide. The rearrangement reaction takes place through a common intermediate thiaranium intermediate 8.     

Formation of cyclic ions in the electron impact induced fragmentation of 1,n-bis-(alkylthio) alkanes

Fragmentation of molecular ions of 1,n-bis(alkylthio)alkanes (R¹-S-(CH₂)_n-S-R²) occurs mainly by α- or β-cleavage to a sulphur atom. The ratio of fragments derived by α- or β-cleavage depends on the number of methylene groups (n) between the two sulphur atoms and on the alkyl groups R¹ and R². Generally β-cleavage induced fragmentation dominates for 1,2-bis(alkylthio)ethanes (n=2) leading to formation of thiiranium ions. Fragmentations derived by α-cleavage are predominant for all compounds with n=3; base peaks corresponding to [M-(R)]⁺ or [M-(2R)+(H)]⁺ are found which gives evidence for formation of five membered cyclic ions. Such fragmenss are less intense in compounds with n=4 whereas m all other compounds β-cleavage predominates if R = methyl, ethyl, n-propyl.     

Heteroatomic derivatives of aziridine. 15. Reaction of 1-(triethylsilyl)- and 1-[2-(trialkylsilyl)ethyl]-aziridines with thiols

The reaction of 1-(triethylsilyl)aziridine with alkanethiols proceeds with splitting out of aziridine and the formation of (alkylthio)triethylsilanes. The reaction of 1-(triethylsilyl)aziridine with 2-mercaptoethanol leads to 2-(triethylsilyloxy)ethanethiol; the same reaction in a closed system leads to [2-(2-aminoethylthiol)ethoxy]triethylsilane. 1-[2-(Trialkylsilyl)ethyl]aziridines react with 2-mercaptoethanol and with mercapto carboyxlic acids with opening of the aziridine ring.See [1] for Communication 14.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 891–893, July, 1988.     

1,2,4-triazines and condensed derivatives—XIV : Thermal and acid catalysed degradations of 3-alkylthio-6,7-dihydro-[1.2.4]Triazino[1.6-c]quinazolin-5-ium-1-olates

3 - Alkylthio - 6,7 - dihydro - [1.2.4]triazino - [1.6-c]quinazolin - 5 - ium - 1 - olates (3), prepared by condensation of 3 - alkylthio -6-(2- aminophenyl) - 1,2,4 - triazin - 5(2H) - ones (1) with aldehydes, ketones or their equivalents are transformed by thermolysis and/or acid treatment into 3 - alkylthio - [1.2.4]triazino[5.6-b]indoles (4) and/or 4-(5- alkylthio - s - triazol -3-yl)- quinolines (5). Alkylation and acylation reactions of the compounds 5 are discussed, as well as their NMR and UV spectra and those of their alkylation and acylation products.     

Reactions of dithioxo-1,3,2λ5,4λ5-dithiadiphosphetanes with triorganolead derivatives

The reactions of Lawesson's reagent 1a and its 4-ethoxy homologue 1b with triethyl- and triphenyl(alkoxy)plumbanes 2a,b and -(alkylthio)plumbanes 4a,b were studied. On the basis of these reactions, novel, advantageous methods of synthesizing S-triethyl and triphenylplumbyl derivatives of aryldithio- and trithiophosphonic acids 3a–d and 5a,b were developed. © 1997 John Wiley & Sons, Inc.     

Synthesis of a new conformationally defined serotonin homologue by intramolecular [4+2] cycloaddition

Treatment of 1-[(p-methoxyphenyl)sulfonyl]-2-methyl-3-[N-allyl-N-methyl-3-(2,6-dichlorobenzoyl)propylamino]indole 3 with triethylamine in chlorobenzene at 135°C results in the formation of 1,2,3,4,4a,5,6,11c-octahydro-7-[(p-methoxypyhenyl)-sulfonyl]-3-methyl-7H-pyrido[3,4-c]carbazole 1b in 58% yield. The reaction is selective in giving predominantly the trans isomer.     

Copper-catalyzed aerobic oxidative dehydrogenation for conversion of 2-(alkylthio)-1,4-dihydropyrimidines to 2-(alkylthio)pyrimidines

A simple and efficient aerobic oxidative dehydrogenation reaction method for the conversion of 2-(alkylthio)-1,4-dihydropyrimidines to 2-(alkylthio)pyrimidines using copper catalyst with no additives, such as an oxidant, acid, or base, has been developed. The reaction was successful with a wide range of 2-(alkylthio)-1,4-dihydropyrimidine substrates.     

REACTION OF (ORGANYLTHIO)CHLOROACETYLENES WITH ALIPHATIC 1,2-DITHIOLS: A ROUTE TO FUNCTIONALIZED 1,3-DITHIOLANES

(Organylthio)chloroacetylenes react with aliphatic 1,2-dithiols in dimethyl sulfoxide at 20–25°C in the presence of a two-fold molar excess of alkali to form 2-[(alkylthio)methyliden]-1,3-dithiolanes in up to 66% yield.     

Ouverture acide de bis-(alkylthio)-2,2 cyclopropanols: Une nouvelle methode d'homologation et d'extension de cycle

Solvolysis of 2,2-bis(alkylthio) cyclopropanols by aqueous trifluoroacetic acid occurs easily to yield conjugated α-alkylthio emone and/or β-oxo-S alkylthioesters. The formation of the former most probably involves a disrotary rink opening concerted with the departure of the alkylthio group trans to hydoxyl, or, alternatively with monocyclic compounds, a 1,2-emigration of the same akylthio group synchronous with OH departure and cleavage. A nucleophilic substitution at the thioacetal centre followed by oxidative opening of the intermediate cyclopropandiol accounts for the formation latter. In 70% aqueous perchloric acid the formation of enones in favoured.     

Reductive cleavage of ether and thioether bonds on 1,3-benzodioxole and 1,3-benzoxathiole derivatives

The reaction of lithium and sodium diethylamide with 1,3-benzodioxoles and 1,3-benzoxathioles is here reported. 1,3-Benzodioxoles exhibit selective cleavage of the ether bond with formation of alkoxyphenols; 1,3-benzoxathioles when reacting with sodium diethylamide lead to 2-alkoxybenzenethiols while with lithium diethylamide give 2-alkoxybenzenethiols together with 2-(alkylthio)phenols.     

Tetrakis(alkylthio)thieno[3,4-c]thiophene: Synthesis,stability, and reactivity

The synthesis of tetrakis(alkylthio)thieno[3,4-c]thiophenes la-e by the dimerization reaction of bis(alkylthio)cyclopropenethiones is described. The remarkable thermodynamic and kinetic stability suggests the significant electron-accepting conjugation of the alkylthio substituents to the carbanionic 1, 3, 4, and 6 carbons in the framework. The isopropylthio- and ethylthio-substituted thienothiophenes 1d and 1e undergo cycloaddition reactions with dienophiles such as N-phenylmaleimide and dimethyl acetylenedicarboxylate to give the cycloadducts in moderate yields.