Sulfenyl Chlorides Research Articles

Six Membered Heterocycles in the Reaction of Sulfenyl Chlorides with Dialkyl 2-Chloro-2(1-cyclohexenyl)-ethenylphosphonates

Abstract In the reaction of dialkyl 2-chloro-2(1-cyclohexenyl)ethenyl-phosphonates with methyl- and arylsulfenyl chlorides, a hetero-cyclization of the 1,3-dienylphosphonate system of double bonds (O˭P‒C˭C‒C˭C) occurs leading to the formation of six-membered heterocycles - hexahidrobenz-2H-1,2-oxaphosphorines:

ChemInform Abstract: Reaction of Dialkoxythioxaphosphoranesulfenyl Chlorides with Dialkyl Trimethylsilyl Phosphites. New Stereoselective Route to the Unsymmetrical Tetraalkyl Dithiopyrophosphates. Preparation of Diastereoisomeric 2‐Trimethylsilyloxy‐4‐methyl‐1,3,2‐dioxaphosphorinanes.

AbstractThe sulfenyl chlorides (I) react with the trimethylsilylphosphites (II) to yield the dithiopyrophosphates (III).

ChemInform Abstract: The Use of Sulfenyl Halides in the Synthesis of Mercapturic Acids and Their Esters.

AbstractSolutions of the generally rather unstable title reagents (III) are obtained by treating (I) or (II) with NCS or Br2, respectively.

ChemInform Abstract: Cyclization Reactions of βγ‐Unsaturated Derivatives of Carbonic Acid. Part 11. Investigation of the Stereochemistry of the Cyclofunctionalization of βγ‐Unsaturated Carbamic Acid Esters.

AbstractThe urethane (I) reacts with the sulfenyl chloride (II) to afford the racemic oxazolidines (III) with (5S,6R)‐ and (5R,6S)‐configuration.

A New Approach towards Organophosphorus Sulfenyl and Selenyl Halides

Abstract We describe new highly effective methods leading to compounds of general formula 1 and 2 including chiral diaste-reoisomeric systems 1, (Y=S, X=Cl) containing the asymmetric phosphorus center. Some aspects of the reaction between organophosphorus dithioacids and halogens are also discussed.

ChemInform Abstract: A Novel Class of Nitrile Ylide.

AbstractThe sulfenyl chlorides (I) are coupled with the isonitrile (II), yielding the nitrile ylides (IV).

Reactions of sulfonhydrazides with benzeneseleninic acid, selenium halides, and sulfur halides. A convenient preparation of selenosulfonates and thiosulfonates

The oxidation of sulfonhydrazides with benzeneseleninic acid provides an efficient and convenient preparation of selenosulfonates. Se-Phenyl p-tolueneselenosulfonate was also produced in good to excellent yield from the reaction of p-toluenesulfonhydrazide with PhSeCl, PhSeBr3, or PhSeCl3. Sulfonhydrazides react with sulfenyl halides or with PhSBr3 to produce thiosulfonates in generally high yield. The treatment of p-toluenesulfonhydrazide with benzenetellurinic acid, PhTeCl3, or PhTeBr3 afforded only diphenyl ditelluride and not the corresponding tellurosulfonate.

Versuche zur Synthese sterisch gehinderter Thiazylarene und deren Beziehung zu Arylsulfenylnitrenen

Attempts to Synthesize Sterically Hindered Thiazyl Arenes and Their Relationship to Arylsulfenyl NitrenesUp till now all attempts to synthesize organic thiazyl compounds in substance failed. Stabilization leads to the corresponding disulfide 2, the thioaminyl radical 7 and the sulphur diimide 8. Formally thiazyl compounds 1 and sulfenyl nitrenes 1 were resonance structures. Via sulfenyl nitrenes 1 the formation of 2, 7, 8 can be discussed. An in situ preparation of sulfenyl nitrene 1a via the sulfenyl chloride 5a, synthesized by chlorination of the disulfide 2a, and the sulfenyl azide 6a is described in detail. 1a can also be prepared from the sulfenyl amide 4a by oxidation. The structures of the radicals 7a–f and 12f are discussed.

ChemInform Abstract: Bis(sulfonyl)cyclopentadienes.

AbstractAddition of the sulfenyl chlorides (I) to cyclopentadiene (II) and subsequent oxidation by H2O2 according to method A) or by MCPBA yields the dichloro‐1,3‐bis(sulfonyl)cyclopentanes (V), (XIII) or (XIV), the regio and stereoselectivity of these reactions depending on the sequence of the steps.

ChemInform Abstract: The Reaction of 9‐(2′,3′‐Dideoxy‐β‐D‐glycero‐pent‐2‐enofuranosyl)‐adenine Derivatives with Arene‐ and Alkanesulfenyl Chlorides. An Unusual Ring Opening Reaction of Thiiranium Ions.

AbstractThe nucleoside derivative (I) reacts with sulfenyl chlorides (II) to give mixtures of the isomeric adducts (III)‐(V).

ChemInform Abstract: Synthesis of Cyclopropylsulfides and Cyclopropylsulfones by Sulfenylchlorination of 3,3‐Disubstituted Cyclopropenes.

AbstractDie Addition der Sulfenylchloride (II) an die Cyclopropene (I) führt zu den Addukten (III), deren Isomerenverhältnis von der Lösungsmittelpolarität abhängt.

Reactions at a dimolybdenum(V) sulfur bridge. Formation of disulfide (S22-), monosubstituted organic disulfide (RSS-) and tetrasulfide (S42-) bridges

Compounds of the general form (Mo/sub 2/(NAr)/sub 2/(S/sub 2/P(OC/sub 2/H/sub 5/)/sub 2/)/sub 2/S(O/sub 2/CR))/sub 2/(S/sub 2/) (Ar = C/sub 6/H/sub 5/, p-C/sub 6/H/sub 4/CH/sub 3/; R = alkyl, aryl) were prepared by the reaction of (Mo(NAr)(S/sub 2/P(OC/sub 2/H/sub 5/)/sub 2/)S)/sub 4/ with H/sub 2/O/sub 2/ in the presence of a carboxylic acid. The compounds contain a disulfide linkage bridging in inter- and intradimer fashion, formed by the oxidation of two Mo/sub 2/S/sub 2//sup 6 +/ cores to give SMo/sub 2/SSMo/sub 2/S, formally equivalent to SMo/sub 2/S thiyl radical coupling. Mixed dimer-organic disulfides were prepared by the reaction of (Mo/sub 2/-(NC/sub 6/H/sub 4/CH/sub 3/)/sub 2/(S/sub 2/P(OC/sub 2/H/sub 5/)/sub 2/)/sub 2/S/sub 2/(O/sub 2/CCH/sub 3/))/sup -/ with sulfenyl chlorides, R'SCl (R' = alkyl, aryl). The products, (Mo/sub 2/-(NC/sub 6/H/sub 4/CH/sub 3/)/sub 2/(S/sub 2/P(OC/sub 2/H/sub 5/)/sub 2/)/sub 2/S(O/sub 2/CCH/sub 3/)(SSR')), contain an unusual R'SS/sup -/ linkage to the two Mo(V) sites within the dimer, representable by SMo/sub 2/SSR', wherein the monosubstituted organic disulfide ion bridges by its ..beta..-sulfur. A bridge tetrasulfide, (Mo/sub 2/(NC/sub 6/H/sub 4/CH/sub 3/)/sub 2/(S/sub 2/P(OC/sub 2/H/sub 5/)/sub 2/)/sub 2/S(O/sub 2/CCH/sub 3/))/sub 2/(S/sub 4/), was prepared by the reaction of (Mo/sub 2/(NC/sub 6/H/sub 4/CH/sub 3/)/sub 2/(S/sub 2/P(OC/sub 2/H/sub 5/)/sub 2/)/sub 2/S/sub 2/(O/submore » 2/CCH/sub 3/))/sup -/ with S/sub 2/Cl/sub 2/ and contains the SMo/sub 2/SSSSMo/sub 2/S unit, in which the tetrasulfide bridges also in inter- and intradimer fashion via its terminal sulfur atoms. Most of the compounds show stereoisomers related by bridge sulfur inversion. Reactions with triphenylphosphine gave either desulfurization or reduction.« less

ChemInform Abstract: Synthesis, Structure, and Reactions of Thiocarbonic Acid Derivatives.

AbstractNovel pentathiodipercarbonates (IIa)‐(IId) have been synthesized by reaction of sulfenyl chlorides (I) with trithiocarbonates; the heptathio analog (IIe) was prepared similarly.

Cyclisierungsreaktionen β,γ‐ungesättigter Kohlensäurederivate. X. Reaktionen von N‐Cinnamylcarbamidsäureestern mit Sulfenylchloriden‐Synthese von 3, 5‐disubstituierten Oxazolidin‐2‐onen

Cyclization Reactions of β,γ‐Unsaturated Derivatives of Carbonic Acid. X. Reaction of N‐Cinnamyl Carbamic Acid Esters with Sulfenyl Chlorides—Synthesis of 3,5‐Disubstituted Oxazolidine‐2‐onesN‐Cinnamyl urethanes 1 have been cyclized to 3,5‐disubstituted oxazolidine‐2‐ones 3 by aromatic sulfenyl chlorides in methylene chloride. The tetrahydro‐2H‐1,3‐oxazine‐2‐ones 6 were obtained by reaction of 5‐bromotetrahydro‐2H‐1,3‐oxazine‐2‐ones 8 with thiophenols.

The use of sulfenyl halides in the synthesis of mercapturic acids and their esters

AbstractA new method for the synthesis of mercapturic acids (N‐acetyl‐S‐substituted‐L‐cysteines), based on the addition of sulfenyl halides to olefins, is described. Alkenes and alkynes of widely different structure have been converted in this way into fully characterized mercapturic acids and their methyl esters.

Conversion of indole into 3-s-(cysteinyl)indoles and 2-s-(cysteinyl) tryptophans. an approach to tryptathionines

The 3-S-(cysteinyl)indoles 8a and 8b, easily derived (ca 95% yield) from indole and the sulfenyl chlorides 7a and 7b, respectively, have been converted (ca 50%) into oximino derivatives of tryptophan 9a,b. Reduction gave a mixture of two diastereomeric 2-S-(cysteinyl)tryptophan derivatives - i.e. 10 and its H 2N-C(α)epimer - which could be separated. One of these is a derivative of tryptathionine, the characteristic structural element of toxic principles (e.g. Phalloin ( 5)) of members of the genus Amanita.

Charakterisierung und photochemie von (dihalogenmethylen)sulfoxiden, XYCSO

Abstract Dihalogenomethylene sulfoxides (dihalogenosulfines) 2a – c were generated by flash vacuum pyrolysis of 2,2,4,4-tetrahalogeno-1,3-dithietane 1,3-dioxides 1a – c and trapping the pyrolysis products in argon at 10 K. At room temperature unstable difluorosulfine ( 2a ) and chlorofluorosulfine ( 2b ) were identified by i.r. spectroscopy, and the photochemistry of the sulfines was investigated. Chlorofluorosulfine ( 2b ) exists in two geometrical isomers. Photolysis of 2a leads to fragmentation to give CF 2 and SO, photolysis of the chlorine containing sulfines 2b and 2c to rearrangement to give the sulfenyl chlorides 6 and 8 . This is explained by different migratory tendencies of fluorine and chlorine and the stability of the CF bond.

Cyclisierungsreaktionen β,γ‐ungesättigter Kohlensäurederivate. XI [1] Untersuchungen zur Stereochemie der Cyclofunktionalisierung β,γ‐ungesättigter Carbamidsäureester

Cyclization Reactions of β,γ‐Unsaturated Derivatives of Carbonic Acid. XI. Investigation of Stereochemistry of the Cyclofunctionalization of β,γ‐Unsaturated Carbamic Acid EstersN, N‐Disubstituted β,γ‐unsaturated urethanes 1 have been cyclized to 3,5‐disubstituted oxazolidine‐2‐ones 3 by aromatic sulfenyl chlorides 2. The stereochemistry of the products and the cyclofunctionalization reaction were investigated.

ChemInform Abstract: A NEW SIMPLE METHOD FOR THE PRODUCTION AND SOME CONVERSIONS OF BORON‐SULFUR BOND‐CONTAINING O‐ AND M‐CARBORANYL

AbstractAus m‐Carboran (I) bzw. o‐Carboran (IV) werden mit S2 C12 die Thiole (l lla) bzw. (Va) hergestellt, die nach prinzipiell bekannten Methoden in die Derivate (IIIb)‐(IIIi) und (Vb), (Vc) übergefuhrt werden.

C-2-side chain modification of 2-methyl-3-alkylindoles via 3-methylthioindolenines: a new approach to pyrrolo[1,2-a]indoles

A strategy for side chain alkylation of 2-methyl-3-alkylindoles, involving deprotonation of 3-methylthioindolenines, derived from 2-methyl-3-alkylindoles by reaction with methane sulfenyl chloride, reaction with carbon electrophiles and reduction, is outlined and applied to the synthesis of pyrrolo[1,2-a] indoles.