Arylsulfenyl Chlorides Research Articles

Chalcogenation/pyrrolo(pyrido)annulation of 2-(3-butenyl)quinazolin-4(3H)-ones by arylsulfenyl(selenyl) chlorides

Arylsulfenyl chlorides react with 2-(3-butenyl)quinazolinones in dichloromethane by the AdE addition mechanism to give 2-(3-arylthio-4-chlorobutyl)quinazolin-4 (3Н)-ones, which, when heated in the presence of sodium acetate, cyclize to 8-arylthio-6,7,8,9-tetrahydropyrido [2,1-b]quinazolin-11-ones. Arylsulfenylation (selenylation) of 2-(3-butenyl)quinazolinones conducted in nitromethane in the presence of an equimolar amount of lithium perchlorate proceeds as an electrophilic 5-exo-trig cyclization involving either of the nitrogen atoms of the quinazolone nucleus to yield 1-arylthio (selenyl)methyl substituted angular-annulated 2,3-dihydropyrrolo [1,2-a]quinazolin-5(1H)-ones as major products and isomeric linear-annulated 2,3-dihydropyrrolo [2,1-b]quinazolin-9(1H)-one derivatives as minor products.

Fused pyrimidine systems: XVII. Arylsulfenylation of 5-allylpyrimidine-4(3H)-one derivatives. Synthesis of arylsulfanyl-substituted 5,6-dihydrofuro[2,3-d]- and 6,7-dihydro-5H-pyrano[2,3-d]pyrimidines

5-Allylpyrimidine-4-ones react with arylsulfenyl chlorides in dichloromethane with the formation of 5-[(2-arylsulfanyl)-3-chloropropyl]-pyrimidine-4-ones that under the action of sodium acetate undergo cyclization into 6-arylsulfanyl-6,7-dihydro-5H-pyrano[2,3-d]pyrimidines. At performing similar reactions in nitromethane an intramolecular electrophilic cyclization occurs affording 6-[(arylsulfanyl)methyl]-5,6-dihydrofuro[2,3-d]pyrimidines.

Fused pyrimidine systems: XVI. Electrophilic intramolecular cyclization of 2-(alkenylsulfanyl)pteridin-4(3H)-ones

2-[Allyl(but-3-en-1-yl, pent-4-en-1-yl)sulfanyl]pteridin-4(3Н)-ones at heating in polyphosphoric acid undergo an intramolecular cyclization affording respectively 9-methyl-8,9-dihydro-5H-[1,3]thiazolo[3,2-a] pteridin-5-one and 10-methyl(ethyl)-9,10-dihydro-5Н,8Н-[1,3]thiazino[3,2-a]pteridin-5-ones of angular structure. The cyclization of 2-(alkenylsulfanyl)pteridin-4(3Н)-ones under the action of iodine or arylsulfenyl chlorides afforded iodo(arylsulfanyl) derivatives of angularly fuzed thiazolo- and thiazinopteridines.

Electrophilic intramolecular cyclization of functional dervatives of unsaturated compounds: VII. Synthesis of 5-arylsulfanyl-6-phenylpiperidin-2-ones in the absence of salt additives and their selective reduction and oxidation

Cinnamylacetamides reacted with arylsulfenyl chlorides in chloroform in the absence of LiClO4 affording 5-(arylsulfanyl)-6-phenylpiperidin-2-ones. Their reduction with a system LiAlH4-AlCl3 resulted in 3-(tolylsulfanyl)-1,2-diphenylpiperidine, and with Raney nickel, in 1-aryl-6-phenylpiperidin-2-ones. The latter treated with LiAlH4-AlCl3 were converted into 1-aryl-2-phenyl-piperidines. The oxidation of 5-(arylsulfanyl)-6-phenylpiperidin-2-ones with hydrogen peroxide in acetone led to the formation of 5-sulfinyl-, and with oxone, to 5-sulfonyl derivatives.

ChemInform Abstract: Electrophilic Intramolecular Cyclization of Functional Derivatives of Unsaturated Compounds. Part 4. Cyclosulfenylation of 5‐Hexenoic Acid Amides and Nucleophilic Cleavage of Reaction Products.

AbstractCompounds (I) react with arylsulfenyl chlorides (II) to give products of electrophilic cyclization (III).

Consecutive Thiophene-Annulation Approach to π-Extended Thienoacene-Based Organic Semiconductors with [1]Benzothieno[3,2-b][1]benzothiophene (BTBT) Substructure

We describe a new synthetic route to the [1]benzothieno[3,2-b][1]benzothiophene (BTBT) substructure featuring two consecutive thiophene-annulation reactions from o-ethynyl-thioanisole substrates and arylsulfenyl chloride reagents that can be easily derived from arylthiols. The method is particularly suitable for the synthesis of unsymmetrical derivatives, e.g., [1]benzothieno[3,2-b]naphtho[2,3-b]thiophene, [1]benzothieno[3,2-b]anthra[2,3-b]thiophene, and naphtho[3,2-b]thieno[3,2-b]anthra[2,3-b]thiophene, a selenium-containing derivative, [1]benzothieno[3,2-b][1]benzoselenophene. It also allows us to access largely π-extended derivatives with two BTBT substructures, e.g., bis[1]benzothieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene and bis[1]benzothieno[2,3-d:2',3'-d']naphtho[2,3-b:6,7-b']dithiophene (BBTNDT). It should be emphasized that these new BTBT derivatives are otherwise difficult to be synthesized. In addition, since various substrates and reagents, o-ethynyl-thioanisoles and arylthiols, respectively, can be combined, the method can be regarded as a versatile tool for the development of thienoacene-based organic semiconductors in this class. Among the newly synthesized materials, highly π-extended BBTNDT afforded very high mobility (>5 cm(2) V(-1) s(-1)) in its vapor-deposited organic field-effect transistors (OFETs), which is among the highest for unsubstituted acene- or thienoacenes-based organic semiconductors. In fact, the structural analyses of BBTNDT both in the single crystal and thin-film state indicated that an interactive two-dimensional molecular array is realized in the solid state, which rationalize the higher carrier mobility in the BBTNDT-based OFETs.

Electrophilic intramolecular cyclization of functional derivatives of unsaturated compounds: IV. Cyclosulfenylation of 5-hexenoic acid amides and nucleophilic cleavage of reaction products

Anilides of 5-hexenoic acid react with arylsulfenyl chlorides in nitromethane in the presence of lithium perchlorate affording products of electrophilic cyclization, N-{6-[(arylsulfanyl)methyl]tetrahydro-2H-pyran-2-ylidene}anilinium perchlorates. The treatment of the latter with sodium acetate or secondary cycloalkylamines in the presence of water results in the opening of the tetrahydropyran ring and provides anilides or cycloalkylamides of 6-arylsulfanyl-5-hydroxyhexanoic acid.

ChemInform Abstract: Intramolecular Electrophilic Cyclization of Functional Derivatives of Unsaturated Compounds. Part 2. Synthesis and Transformation of N‐{(2Z)‐5‐ [(Arylsulfanyl)methyl]dihydrofuran‐2(3H)‐ylidene}‐N‐alkyl(aryl)aminium Perchlorates.

AbstractThe cyclization of amides (I) with arylsulfenyl chlorides (II) in the presence of LiClO4 gives rise to perchlorates (III), which are used as starting compounds in the synthesis of lactones (V), amides (VII), and sulfones (VIII).

Intramolecular electrophilic cyclization of functional derivatives of unsaturated compounds: II. Synthesis and transformation of N-{(2Z)-5-[(arylsulfanyl)methyl]dihydrofuran-2(3H)-ylidene}-N-alkyl(aryl)aminium perchlorates

N-Alkyl(aryl)amides of allylacetic acid when reacting with arylsulfenyl chlorides in acetic acid in the presence of lithium perchlorate undergo a selective cyclization to form N-{(2Z)-5-[(arylsulfanyl)methyl] dihydrofuran-2(3H)-ylidene}-N-alkyl-(aryl)aminium perchlorates. Treating of the latter with sodium acetate leads to the formation of the corresponding 5-[(arylsulfanyl)methyl]lactones, and with sodium ethylate, to 5-[(arylsulfanyl) methyl]-2-iminolactones. In reaction with secondary cycloalkylamines in the presence of water a transamidation and tetrahydrofuran ring opening occurs to afford 5-arylsulfanyl-4-hydroxypentanoic acid amides.

ChemInform Abstract: Intramolecular Electrophilic Cyclization of Functional Derivatives of Unsaturated Compounds. Part 1. Synthesis of 5‐Arylsulfanyl‐6‐phenylpiperidin‐2‐ones from Cinnamylacetamides and Arylsulfenyl Chlorides.

AbstractSterically nonhindered amides (I) in the reaction with arylsulfenyl chlorides (II) undergo a selective cyclization into piperidinones (III), whereas sterically hindered amides (IV) under similar conditions lead to tetrahydropyrano‐2‐iminium perchlorates (V).

Intramolecular electrophilic cyclization of functional derivatives of unsaturated Compounds: I. Synthesis of 5-arylsulfanyl-6-phenylpiperidin-2-ones from cinnamylacetamides and arylsulfenyl chlorides

Sterically nonhindered N-alkyl(aryl)amides of cinnamylacetic acid in the reaction with phenyl(4- tolyl)sulfenyl chlorides in acetic acid in the presence of lithium perchlorate undergo a selective cyclization into 5-arylsulfanyl-6-phenylpiperidin-2-ones. Under similar conditions the reaction with arylsulfenyl chlorides of amides containing bulky substituents at the nitrogen atom resulted in 5-arylsulfanyl-6-phenyltetrahydropyran-2- iminium perchlorates, which by treatment with aqueous ethanol were converted into the corresponding derivatives of pyran-2-ones. DOI: 10.1134/S1070428011080057

Synthesis of 3-Sulfenyl- and 3-Selenylindoles by the Pd/Cu-Catalyzed Coupling of N,N-Dialkyl-2-iodoanilines and Terminal Alkynes, Followed by n-Bu4NI-Induced Electrophilic Cyclization

3-Sulfenyl- and 3-selenylindoles are readily synthesized by a two-step process involving the palladium/copper-catalyzed crossing coupling of N,N-dialkyl-ortho-iodoanilines and terminal alkynes and subsequent electrophilic cyclization of the resulting N,N-dialkyl-ortho-(1-alkynyl)anilines with arylsulfenyl chlorides or arylselenyl chlorides. The presence of a stoichiometric amount of n-Bu(4)NI is crucial to the success of the electrophilic cyclization. A variety of 3-sulfenyl- and 3-selenylindole derivatives bearing alkyl, vinylic, aryl, and heteroaryl substituents have been prepared in good to excellent yields (up to 99%). By employing N,N-dibenzyl-ortho-iodoanilines, a 3-sulfenyl-N-H-indole has been successfully prepared. In addition, 3-sulfonyl- and 3-sulfinylindoles have also been successfully prepared by facile oxidation of the corresponding 3-sulfenylindoles.

A Novel Synthetic Route to 3-Sulfenyl- and 3-Selenylindoles by n-Bu4NI-Induced Electrophilic Cyclization

3-Sulfenyl- and 3-selenylindoles are prepared in excellent yields by the palladium/copper-catalyzed crossing coupling of N,N-dialkyl-o-iodoanilines and terminal alkynes, followed by electrophilic cyclization with arylsulfenyl chlorides and arylselenyl chlorides in the presence of a stoichiometric amount of n-Bu(4)NI.

Volume of electrostriction of the solvate-separated ions of lithium perchlorate and contact ion pair of the transition state in sulfenyl insertion

The volumes of electrostriction of the ions of lithium perchlorate are in a linear relation with the solvent electrostriction parameter ∂(1/ ɛ )/∂ p but the volume changes of ion pair transition state of electrophilic addition of aryl sulfenyl chloride to styrene and cyclohexene have the slope about 20 times less.

Reactions of 2-(2-propynylsulfanyl)-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]pyrimidin-4(3H)-one with arylsulfenyl chlorides

2-(2-propynylsulfanyl)-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]pyrimidin-4(3H)-one with arylsulfenyl chlorides in chloroform gave products of anti-Markownikoff Ad E-addition. The use of nitromethane as solvent in the presence of lithium perchlorate additives favored intramolecular electrophilic cyclization into 1-arylsulfanyl-1,2,6,7,8,9-hexahydro-4H-benzo[4,5]thieno[3,2-e][1,3]thiazolo[3,2-a]-pyrimidin-5-one.

A facile stereoselective synthesis of (E)-1-arylseleno-2-arylsulfanylethenes via hydrozirconation of arylselenoethynes

Hydrozirconation of arylselenoethynes 1 gave ( E)-2-arylselenovinylzirconium(IV) complexes 2, which reacted with arylsulfenyl chlorides 3 stereoselectively to afford ( E)-1-arylseleno-2-arylsulfanylethenes 4 in good yields. ( E)-1-Arylseleno-2-arylsulfanylethenes 4 could undergo a cross-coupling reaction with Grignard reagents stereoselectively in the presence of a nickel-phosphine complex to give ( E)-vinylic sulfides 5.

β‐Arylthio‐α‐chloroalkyl Ethers — Novel 1,1‐Bis‐electrophiles for Geminal Alkylation.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

β‐Arylthio‐α‐chloroalkyl Ethers — Novel 1,1‐Bis‐electrophiles for Geminal Alkylation

AbstractA novel protocol for geminal alkylation is suggested based upon the consecutive generation of two cationoid intermediates from the easily prepared adducts of arylsulfenyl chlorides and vinyl ethers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Stereoselective Synthesis of (Z)-α-Arylsulfenylvinyl Tellurides Via Hydrozirconation of Alkynyltellurides

Hydrozirconation of alkynyltellurides 1 in THF at room temperature gave ( Z)-α- tellurenylvinylzirconium complexes 2, which were reacted with arylsulfenyl chlorides 3 to afford stereoselectively ( Z)-α-arylsulfenylvinyl tellurides 4 in good yields.

A Facile Stereoselective Synthesis of (E)-1,2-disubstituted Vinyl Sulfides via Hydromagnesiation of Alkylarylacetylenes

Hydromagnesiation of alkylarylacetylenes 1 in diethyl ether gave (E)-α-arylvinyl Grignards reagents 2, which reacted with arylsulfenyl chlorides 3 to afford stereoselectively (E)-1,2-disubstituted vinyl sulfides 4 in good yields.