Sulphenyl Chlorides Research Articles

Synthesis of mixed phosphorotrithioates via thiol coupling with bis(diisopropylamino)chlorophosphine and sulphenyl chloride.

In this study, we report a novel and efficient one-pot synthesis of mixed phosphorotrithioates under mild conditions at ambient temperature, obviating the requirement for supplementary additives. The method's versatility stems from its utilization of diverse thiols as nucleophilic reactants, 1-chloro-N,N,N',N'-tetraisopropylphosphanediamine [bis(diisopropylamino)chlorophosphine] as the phosphorus precursor, and various sulphenyl chlorides as sources of electrophilic sulfur. Notably, our investigation extends beyond mixed phosphorotrithioates to encompass the synthesis of phosphoroselenodithioates, underscoring the broad applicability of this synthetic protocol.

Functionalization of alkenes by polyfluorinated α,β-unsaturated sulphenyl chlorides Dual reactivity of perfluoro-2-methyl-2-penten-3-yl sulphenyl chloride in reactions with activated olefins

A dual reactivity of perfluoro-2-methyl-2-penten-3-yl sulphenyl chloride ( 1) in reactions with alkenes is described. Whereas 1 interacts with 3,3-dimethyl-1-butene and styrene in nitromethane solution in the sulphenyl chloride form, reactions with olefins that have mobile hydrogen atoms in an allylic position (e.g. allyl- and p-methoxyallyl-benzenes) occur through the tautomeric thioketone form −2-chloroperfluoro-2-methylpentanethione-3 ( 3) — with the formation of products by ene rearrangement. Chlorotropism in the system 1 ⇌ 3 in the presence of nucleophilic solvents or catalysts is responsible for the dual reactivity of 1 in the above reactions.

Addition of sulphenyl halides and thiocyanates to alkenyl-metal compounds. Structures of [1-chloro-2-(4-methyl-2-nitrophenyl)ethyl]-triphenylstannane and [2-(2-nitrophenyl)-1-thiocyanatoethyl]triphenylstannane

The crystal and molecular structures of Ph 3SnCHClCH 2SC 6H 3NO 2-2-Y-4 (II, Y  Me) and Ph 3SnCH(SCN)CH 2SC 6H 4NO 2- o (III) have been determined. Compounds II and Ill are adducts of Ph 3SnCHCH 2 and the appropriate sulphenyl chloride and thiocyanate. Both compounds are monomeric and contain slightly distorted tetrahedral tin atoms. The intra-molecular SnS(R) distances in II (Y  Me) and III are 3.67 and 3.58 Å, respectively. The solid state conformations are staggered and have dihedral angles SnCCS of 56.6 and 57.4° in II (Y  Me) and III, respectively, and ClCCS in II and SCCS in III 176.0° and 174.1°, respectively. From 3 J(HH) and 3 J( 119Sn 1H) values, the solid state conformation of II (Y  Me) is calculated to be populated in solution for approximately 1/3rd of the time at 25°C.

Trifluoromethylsulphenyl chloride in synthesis of some heterocyclic systems

The presented work deals with the utility of trifluoromethyl sulphenyl chloride in synthesis of pyridine and pyrazine derivatives. Pyridine derivatives substituted at position 5 by trifluoromethylthio group were synthesised in the reaction between 4,4-Dicyano-3-phenyl-N-phenyl-3-enamide and trifluoromethyl sulphenyl chloride. On the other hand a new route of ring closure of 3-pyrazine -5-thione system with simultaneous introduction of the fluoromethylthio group via nickel complex of β-aminocinnamic acid anilide was investigated. The structure of the obtained compounds was established on the basis of their spectroscopic data.

Organic heterocyclothiazenes. Part 13. Rational synthesis and chemistry of 1,3,5,2,4-trithiadiazines

1,3,5,2,4-Trithiadiazines, previously formed from tetrasulphur tetranitride and diazoalkanes, are syn-thesised from 1,1-bis-sulphenyl chlorides (1; R = H, Cl), (5), (11) and bis(trimethylsilyl)sulphurdiimide (2), and this reaction extends to trithiadiazines with functional groups on carbon. Bissulphenyl chlorides (5a–d) are formed in one step from malonic esters and amides and sulphur dichloride. Pentathiepane (lenthionine)(14), prepared from di-iodomethane and disodium di-sulphide, gives methanebis(sulphenyl chloride) on chlorinolysis and hence, with (2), the parent trithiadiazine (3; R = H). Similarly the pentathiepane (16) is converted into bis-sulphenyl chloride (11) and the spirotrithiadiazine (12). The sensitivity of the heterocyclic ring towards strongly polar reagents precluded the generation of the trithiadiazine cation (17) and anion (19), but the radical (18) is formed on treatment with benzoyl peroxide and benzoyl t-butyl nitroxide (22), resulting in the benzoyloxy and amino-oxy derivatives (21) and (24). m-Chloroperbenzoic acid or nitrogen tetroxide convert trithiadiazine into the S-oxide (25).

Reaction of tryptophan derivatives with phenylsulphenyl chloride and phenylselenenyl bromide

Treatment of Nb protected tryptophan methyl esters with phenyl sulphenyl chloride and phenylselenenyl bromide results in substitution at the indole 2-position and not in the anticipated tetrahydropyrrolo[2,3-b]indoles.

Electrophilic Sulphenylation of Silyl Ketene Acetals Derived from 3-Hydroxyesters. Diastereoselective Synthesis of Protected Epoxyalcohols

Abstract Anti-3-Hydroxy-2-phenylsulphenyl esters are stereoselectively synthesized by reaction between silyl ketene acetals and phenyl sulphenyl chloride. Subsequent elaboration leads to protected epoxyalcohols.

A new route to 1,3,4-thiadiazolines. Part 3. Consequences of the aza-enamine concept

N,N-Disubstituted hydrazones react with sulphenyl chlorides, sulphur dichloride, and disulphur dichloride to give C-sulphenyl products. N,N-Tetramethylenehydrazones with SCl2 or S2Cl2 give the novel pyrrolo[2,1-b]-1,3,4-thiadiazole ring system. Studies of the site selectivity in reaction of these hydrazones with sulphur(II) electrophiles by the semiempirical CNDO and MNDO methods are reported.

ChemInform Abstract: Organic Heterocyclothiazenes. Part 3. Synthesis and Structure of 1,3,5,2,4‐Trithiadiazepines.

AbstractThe trithiadiazepine (III) is best prepared by reaction of the trichloro compound (Ic) (obtained from chlorination of (Ia) at 0 °C) with the reagent (II).

ChemInform Abstract: Conversion of Indole into 3‐S‐(Cysteinyl)indoles and 2‐S‐(Cysteinyl)tryptophans. An Approach to Tryptathionines.

AbstractIndole (I) reacts with the sulphenyl chlorides (II), which have been prepared in situ from the corresponding L‐cystine derivatives and SOCl2, to form the 3‐S‐(cysteinyl)indoles (III).

Organic heterocyclothiazenes. Part 3. Synthesis and structure of 1,3,5,2,4-trithiadiazepines

1,3λ4δ2,5,2,4-Trithiadiazepine (10) has been prepared from 1-chloroethane–1,2-bis(sulphenyl chloride)(11) and bis(trimethylsilyl)sulphurdi-imide (3) and also by dehydrogenation of the 6,7-dihydro derivative (9). Trithiadiazepine (10) is a planar, delocalised, stable 10π aromatic system. Its benzo derivative (4), an analogous 14π aromatic system, has been prepared from benzene–1,2-bis(sulphenyl chloride)(2) and sulphurdi-imide (3). In 6,7-dihydro-1,3λ4δ2,5,2,4-trithiadiazepine (9), similarly prepared from ethane–1,2-bis(sulphenyl chloride)(8) and sulphurdi-imide (3), the five heteroatoms are accurately co-planar, with the out of plane methylene protons rapidly interconverting at room temperature. Reaction of S4N4 with di-t-butyl acetylenedicarboxylate in boiling toluene gave di-t-butyl 1,3λ4δ2,5,2,4-trithiadiazepine-6,7-dicarboxylate (14) and t-butyl 1,3λ4δ2,5,2,4,6-trithiatiazepine-7-carboxylate (15) in low yield.

1,3,5,2,4-Trithiadiazines; a new ring system

Diazoalkanes react with tetrasulphur tetranitride to give red crystalline, 1,3λ4δ2,5,2,4-trithiadiazines [(3), (7), (8)], representatives of a new ring system with a nearly planar S3N2 unit; the parent compound (3) was independently synthesised from methanebis(sulphenyl chloride)(11) and sulphur bis(trimethylsilyl)diimide (12).

ChemInform Abstract: Reactions of Chloropolyfluoroalkylsulphenyl Chlorides with Monosubstituted Ethenes.

AbstractThe reactions between the polyfluorinated sulphenyl chlorides (I) and the vinyl compounds (II), (IV) and (VI) produce the adducts (III), (V) and (VII), respectively.

ChemInform Abstract: Reaction of Chlororhodan and Dirhodan with Cyclopropene Hydrocarbons.

AbstractThe reactions of dirhodan (Ia) and of chlororhodan (Ib) with the cyclopropenes (II) and (IV) and with propene (VIII) are investigated for a comparison with the known results of the reactions of sulphenyl chlorides with these hydrocarbons.

ChemInform Abstract: Reaction of Tetrafluorobenzobarrelene with Arylsulphenyl Chlorides in the Nitromethanel Lithium Perchlorate System.

AbstractThe reaction of tetrafluorobenzobarrelene (I) with the sulphenyl chlorides (II) in a 1:2 molar ratio in the presence of MeNOz/Li‐ ClO4 yields the thionium compounds (III).

ChemInform Abstract: Selective Functionalisation of 1,3‐Dienes via Organosulphur Intermediates.

The 1,2-adducts from 1,3-dienes and sulphenyl chlorides are shown to be useful intermediates by their conversion into a variety of functionalised alkenes.

Metastable enthiols and α,β-unsaturated sulphenyl chlorides. Rearrangements in a triad ‘carbon-carbon-sulphur’

As was shown for the first time, sterically unhindered tautomeric systems (enthiol-thioketone and α,β-unsaturated sulphenyl chloride-thioketone) with negligibly small rates of tautomeric conversions under normal conditions may be found among polyfluorinated monothiocarbonyl compounds. Metastable in these systems are respectively enthiols and α,β-unsaturated sulphenyl chlorides which are highly stable kinetically. Enthiols and α,β-unsaturated sulphenyl chlorides do not convert spontaneously into the corresponding thioketones. However, basic catalysts or thermal treatment can isomerize enthiol (I) into thioketone (II). The reverse reaction cannot be carried out. ▪ A tautomeric system—α,β-unsaturated sulphenyl chloride (III) + thioketone (IV)—in the presence of a weakly basic catalyst acquires a state of equilibrium with a low activation barrier of the form interconversions; in other words chlorotropy—migration of the chlorine in the triad ‘carbon-carbon-sulphur’ —is observed for the first time. In the absence of catalysts both forms are stable. ▪

ChemInform Abstract: 1,3,5,2,4‐TRITHIADIAZEPINE

AbstractStabile Trithiadiazepine (III) bzw. (VI) erhält man ‐ durch Reaktion der Bis‐sulfenylchloride (I) bzw. (VII) mit dem Schwefeldiimid (II).

Preparation, crystal and molecular structures of Ph2CNSNSO and a comparison of the —SNSO and —SNSS chromophores

The sulphenyl chloride, Ph2CNSCl, prepared insitu from Ph2CNSiMe3 and sulphur dichloride, has been employed in the synthesis of Ph2CNSNSO and Ph2CNSNSNSNCPh2 by reaction with Me3SiNSO and Me3SiNSNSiMe3, respectively. An X-ray structural determination of Ph2CNSNSO shows it to consist of a planar cis-trans chain. The crystals are triclinic and belong to the space group[Formula: see text], a = 9.9078(8), b = 10.0967(9), c = 15.1682(14) Å, α = 78.646(7), β = 71.065(7), γ = 63.449(7)°, V = 1281.5(5) Å3, Z = 4. The final R and Rw values were 0.033 and 0.027, respectively. The π* → π* excitation energies for the RSNSO and RSNSS chromophores are compared for different R groups and discussed in the light of MNDO calculations on the model compounds HSNSX (X = S, O). The thermal decomposition of both Ph2CNSNSO and Ph2CNSNSNSNCPh2 produced S4N4 and Ph2CO or (Ph2CN)2S, respectively.

Study of the thermal degradation of elastomers modified with sulphenyl chlorides

The behaviour of modified elastomers containing various functional groups has been investigated under conditions of high temperature degradation in an inert medium and in air. It was found that dissimilarities in thermal stability observed for the modified polymers are due to the nature of the elastomer matrices, and to the influence of functional groups in polymer backbones. It has been established that sulphenyl chlorides (in amounts of up to 5 mole %) have a stabilizing influence on thermal degradation of the elastomers.