Arenesulfenyl Chlorides Research Articles

Sulfanyl chloride induced heterocyclization of N-(pyrazolyl)styrylacetamides

Heterocyclization of N-(pyrazol-3-yl)styrylacetamides with arenesulfenyl chlorides yields the corresponding tetrahydrofuran-2-iminium perchlorates isolable after chromatography as trans-5-aryl-4-(arylthio)tetrahydrofuran-2-ones and 5-aryl-4-(arylthio)-1-(pyrazol-3-yl)pyrrolidin-2-ones, with the latter predominating. N-(Pyrazol-4-yl)styrylacetamides react under analogous conditions to give 5-aryl-4-(arylthio)-1-(pyrazol-4-yl)pyrrolidin-2-ones, 4-aryl-3-(arylthio)-4-chloro-N-(1-methylpyrazol-4-yl)butanamides, and tetrahydrofuran-2-iminium perchlorates which, when chromatographed, produce 5-aryl-4-(arylthio)dihydrofuran-2(3H)-ones and 4-aryl-3-(arylthio)-4-methoxy-N-(1-methyl-1H-pyrazol-4-yl)butanamides.

ChemInform Abstract: Synthesis of 7‐Iodo(arylsulfanyl)methyl‐7,8‐dihydro[1,3]thiazolo[2,3‐i]purinium Pentaiodide (Perchlorates) and Their Transformation into 4‐Amino‐5‐(1,3‐thiazol‐2‐yl)imidazole Derivatives.

AbstractThe intramolecular electrophilic cyclization of 6‐allylsulfanylpurine (I) with iodine and arenesulfenyl chlorides, respectively and the subsequent behavior of the resulting fused heterocycles toward nucleophiles is explored.

ChemInform Abstract: Intramolecular Electrophilic Cyclization of Functional Derivatives of Unsaturated Compounds. Part 3. Reaction of N,4‐Diarylbut‐3‐enamides with Arenesulfenyl Chlorides. Synthesis of 5‐Aryl‐4‐arylsulfanyl‐2,3,4,5‐tetrahydro‐1H‐1‐benzazepin‐2‐ones.

AbstractThe reaction of N,4‐diarylbut‐3‐enamides (I), (IV), and (VI) with arenesulfenyl chlorides (II) is studied and the different underlaying mechanisms are discussed.

Synthesis of 7-iodo(arylsulfanyl)methyl-7,8-dihydro-[1,3]thiazolo[2,3-i]purinium pentaiodide (perchlorates) and their transformation into 4-amino-5-(1,3-thiazol-2-yl)imidazole derivatives

Intramolecular electrophilic cyclization of 6-allylsulfanylpurine by the action of iodine and arenesulfenyl chlorides gave 7-iodomethyl-7,8-dihydro[1,3]thiazolo[2,3-i]purin-6-ium pentaiodide and 7-arylsulfanylmethyl-7,8-dihydro[1,3]thiazolo[2,3-i]purin-6-ium perchlorates, respectively. 7-Iodomethyl-7,8-dihydro-[1,3]thiazolo[2,3-i]purin-6-ium iodide reacted with sodium and potassium alkoxides to produce alkyl N-[5-(4-methyl-1,3-thiazol-2-yl)-1H-imidazol-4-yl]formimidates, and its reaction with secondary cyclic amines afforded 5-(4-methyl-1,3-thiazol-2-yl)-N-[morpholin-4-yl(or piperidin-1-yl)methylidene]-1H-imidazol-4-amines. Successive treatment of 7-arylsulfanylmethyl-7,8-dihydro[1,3]thiazolo[2,3-i]purin-6-ium perchlorates with sodium acetate and morpholine led to the formation of 5-(4-arylsulfanylmethyl-4,5-dihydro-1,3-thiazol-2-yl)-N-(morpholin-4-ylmethylidene)-1H-imidazol-4-amines.

Intramolecular electrophilic cyclization of functional derivatives of unsaturated compounds: III. Reaction of N,4-Diarylbut-3-enamides with arenesulfenyl chlorides. Synthesis of 5-aryl-4-arylsulfanyl-2,3,4,5-tetrahydro-1H-1-benzazepin-2-ones

N-Aryl-4-phenylbut-3-enamides reacted with arenesulfenyl chlorides in chloroform to give N,4-diaryl-3-arylsulfanyl-4-chlorobutanamides, whereas in acetic acid in the presence of lithium perchlorate N-[4-arylsulfanyl-5-phenyltetrahydrofuran-2-ylidene]arenaminium perchlorates were obtained. Reactions of arenesulfenyl chlorides with N,4-diarylbut-3-enamides having strong electron-donating groups in positions 3 and 4 of the N-aryl substituent afforded 5-aryl-4-arylsulfanyl-2,3,4,5-tetrahydro-1H-1-benzazepin-2-ones.

Nitro-Substituted Arene Sulfenyl Chlorides as Precursors to the Formation of Aromatic SAMs

The formation of aromatic SAMs on Au(111) using three nitro-substituted arene sulfenyl chlorides (4-nitrophenyl sulfenyl chloride (1), 2-nitrophenyl sulfenyl chloride (2), and 2,4-dinitrophenyl sulfenyl chloride (3)) is studied. The formation of SAMs and their quality are investigated as a function of the position of the nitro substituent(s) on the aromatic ring. The modified surfaces are characterized by X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), polarization modulation infrared reflection absorption spectroscopy (PMIRRAS), and cyclic voltammetry (CV). The results show that all three compounds are deposited on Au within very short times. The corresponding coverages are determined using CV. However, only compound 1 forms stable, long-range, well-ordered SAMs. The 4-nitrophenyl thiolate is adsorbed nearly vertically on the Au surface. Compounds 2 and 3 both form lower-quality SAMs where the adsorbed nitro-phenyl thiolates are more tilted. These SAMs are less stable than the ones obtained with the 4-nitrosubsituted precursor and decompose with time, leaving only sulfur on the gold surface.

ChemInform Abstract: Cyclofunctionalization of 6‐Alkenylsulfanylpyrazolo[3,4‐d]pyrimidin‐4(5H)‐ones with Arenesulfenyl Chlorides.

AbstractReactions of the title alkenyl thioethers with arenesulfenyl chlorides in CHCl3 affords products of addition at the exocyclic double bond, while analogous reactions in acetic acid in the presence of LiClO4 are accompanied by an intramolecular electrophilic cyclization involving the N7 atom.

ChemInform Abstract: Sequence of Reactions of Arenesulfenyl Chloride + Alkoxyalkene-I + Alkoxyalkene-II + Allylmagnesium or Allylboron Derivatives as a New Method for the Directed Synthesis of Polyfunctional Compounds.

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ChemInform Abstract: Triorganogermanium Selenocarboxylates: Synthesis and Reactions.

A series of triphenylgermanium selenocarboxylates 3 were synthesized and characterized. The esters 3 are thermally stable, but labile towards moisture and oxygen. They react with arenesulfenyl chlorides and areneselenenyl bromides at room temperature to afford the corresponding acyl arenesulfenyl selenides and acyl aryl diselenides in moderate yields.

A novel approach towards the preparation of functionalized alkyne derivatives via ArS-mediated Ad E reaction of cobaltcarbonyl complexed conjugated enynes

A unified protocol of three-component coupling of arenesulfenyl chloride, dicobalthexacarbonyl complexed conjugated enynes, and nucleophiles of π-donor type is applied for the synthesis of functionalized alkynes.

10.1007/s11178-008-2008-5

Advantages and shortcomings were discussed of three procedures for preparation N-arylsulfinyl-1,4-benzoquinone imines: the reaction of arenesulfenyl chlorides with 1,4-benzoquinone oximes, the oxidation of N-arylthio-1,4-benzoquinone imines, and the reaction of arylsulfinyl chlorides with p-aminophenols followed by oxidation. A series of new N-arylsulfinyl-1,4-benzoquinone imines was obtained.

Cyclofunctionalization of 6-alkenylsulfanylpyrazolo[3,4-d]-pyrimidin-4(5H)-ones with arenesulfenyl chlorides

Reactions of 6-allylsulfanylpyrazolo[3,4-d]pyrimidin-4(5H)-one with arenesulfenyl chlorides in chloroform gave products of addition of the latter at the exocyclic double bond, while analogous reactions in acetic acid in the presence of LiClO4 were accompanied by intramolecular electrophilic cyclization involving the N7 atom. 6-Cinnamylsulfanylpyrazolo[3,4-d]pyrimidin-4(5H)-one reacted with arenesulfenyl chlorides in acetic acid in the absence of electrolyte to produce fused pyrazolo[4′,3′: 5,6]pyrimido[2,1-b][1,3]thiazine derivatives. Introduction of a bulky phenyl group into position 1 of the pyrazolo[3,4-d]pyrimidine system reduces the yield of the corresponding intramolecular cyclization product at N7 as a result of concurrent formation of acyclic addition product. DOI

New direction in sulfenylation of dimethyl endo,endo-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate

It is known1 that the reaction of dimethyl endo,endo bicyclo[2.2.2]oct 5 ene 2,3 dicarboxylate (1) with arene sulfenyl chlorides leads exclusively to the products of trans annullar cyclization involving the oxygen atom of the methoxy group, viz., γ and δ lactones, the ratio of which varies widely depending on the electronic characteristics of substituents in the arene ring of the sulfur containing electrophile. We found that the reactions of compound 1 with 3 methoxycarbonylpyridine 2 and 1,3 benzothiazole 2 sulfenyl chlorides (2 and 3), containing potentially nu cleophilic nitrogen atom in the hetaryl fragment, in ni tromethane in the presence of lithium perchlorate proceed by the mechanism of polar cycloaddition of the sulfenylat ing agent to the multiple bond.2—7 In these electrophilic processes, the nitrogen atoms of the hetaryl fragment of the starting agent are involved into the ring closure to form the polycyclic systems 4 and 5 in 87 and 84% yields, re spectively (Scheme 1). The structures of compounds obtained were con firmed by 1H and 13C NMR spectroscopy and elemen tal analysis data. The assignment of signals in the NMR spectra was made using COSY, HSQC, HMBC, and NOESY experiments. In the NOESY spectra of com pounds 4 and 5, the correlation peaks for the protons of the methoxy groups of the bicyclooctane framework with the protons H(2), H(10) and H(2), H(13), respec tively, are observed. At the same time, in the NOESY spectra the correlation peaks for the following pairs of protons are absent: H(2), H(14) and H(10), H(15) (in the spectrum of compound 4); H(2), H(17) and H(13), H(18) (in the spectrum of compound 5). These data indi cate the exo cis cycloaddition of the sulfenylating agent to the double bond.

Comparison of preparation methods of N-arylsulfinyl-1,4-benzoquinone monoimines

Advantages and shortcomings were discussed of three procedures for preparation N-arylsulfinyl-1,4-benzoquinone imines: the reaction of arenesulfenyl chlorides with 1,4-benzoquinone oximes, the oxidation of N-arylthio-1,4-benzoquinone imines, and the reaction of arylsulfinyl chlorides with p-aminophenols followed by oxidation. A series of new N-arylsulfinyl-1,4-benzoquinone imines was obtained.

Moderate Generation of Sulfenylnitrenes from Novel N‐Sulfenylsulfodiimides.

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Radical/Ion Pair Formation in the Electrochemical Reduction of Arene Sulfenyl Chlorides.

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Moderate generation of sulfenylnitrenes from novel N-sulfenylsulfodiimides

N-Sulfenylated sulfodiimides were first prepared by the reaction of S, S-diphenyl- N-tosylsulfodiimide with arenesulfenyl chlorides under the basic conditions. Thermolysis of S, S-diphenyl- N-(2-nitrophenylsulfenyl)- and S, S-diphenyl- N-(2,4-dinitrophenylsulfenyl)sulfodiimides in the presence of olefins proceeded at 50–80 °C to give the corresponding deiminated S, S-diphenyl- N-tosylsulfimide and N-sulfenylaziridines in very good yields. 2,4-Dinitrophenyl-sulfenylnitrene was trapped by trans- and cis-1-phenylpropenes stereospecifically. The thermolysis temperature of the N-sulfenylsulfodiimides was found to be lower than N-sulfenylsulfoximide and higher than N-sulfenyliminosulfonium salt and very effective to trap the sulfenylnitrene to give the N-sulfenylaziridines in very good yields.

Radical/Ion Pair Formation in the Electrochemical Reduction of Arene Sulfenyl Chlorides

Important aspects of the electrochemical reduction of a series of substituted arene sulfenyl chlorides are investigated. A striking change is observed in the reductive cleavage mechanism as a function of the substituent on the aryl ring of the arene sulfenyl chloride. With p-substituted phenyl chlorides a "sticky" dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With o-nitropheyl sulfenyl substituted chlorides a stepwise mechanism is observed where through space S...O interactions play an important role stabilizing both the neutral molecules and their reduced forms. Disulfides are generated through a nucleophilic reaction of the two-electron reduction produced anion (arenethiolate) on the parent molecule. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with the gas phase chemical quantum calculations results helped rationalize both the observed change in the ET mechanism and the occurrence of the "sticky dissociative" ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in gas phase. This study shows that despite the low magnitude of in-cage interactions in acetonitrile as compared to in the gas phase, their existence strongly affects the kinetics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents.

N‐Arylsulfinyl‐1,4‐benzoquinonimines.

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ArS-Mediated Ad E Reaction of the Cobaltcarbonyl-Complexed Conjugated Enynes

A novel approach to the synthesis of functionalized enynes is elaborated based on the protocol of the three-component coupling of arenesulfenyl chlorides, dicobalthexacarbonyl complexes of the conjugated enynes, and nucleophiles of the π-donor type and a possibility to employ the 1,6-enyne derivatives thus prepared as the substrates for the intramolecular Pauson–Khand cyclization is demonstrated.