Sulfur Monochloride Research Articles

Addition Copolymerization of Sulfur Dichloride and Sulfur Monochloride with 1,3-Butadiene

Abstract Poly(dichlorobutane sulfide) I and poly(dichlorobutane disulfide) II have been prepared in 97% yield by addition copolymerization of butadiene with sulfur dichloride and sulfur monochloride, respectively. The polymers were characterized by elemental analysis, infrared spectrum, inherent viscosity, and thermogravimetric analysis. The reactions of several dienes with sulfur dichloride (but not with sulfur monochloride) have been reported in the literature. All were reported to give mainly the intramolecular addition products. However, it has very recently been found that diolefins with double bonds rigidly separated from each other, or with double bonds so situated that intramolecular reaction is thermodynamically unfavorable, preferentially undergo polymerization with sulfur monochloride or sulfur dichloride. In the case of butadiene, polymerization is thermodynamically more feasible than intramolecular addition due to the dipole repulsion and eclipsing chain which would be present in the intramol...

Polysulfide chelates—I. The reaction of sulfur monochloride with a nickel(II) mercaptide

Evidence is presented for the preparation of a macrocyclic nickel(II) complex containing a tetrasulfide chelate ring. Preparation of the tetrasulfide ring was via a template mechanism by reacting (1, 10-dithia-4,7-diaza-5, 6-dimethyldeca-4,6-diene)nickel(II) with sulfur monochloride. Analysis of the product is consistent with the composition of dichloro-(1,2,3,4-tetrathia-7, 10-diaza-8,9-dimethylcyclododeca-7,9-diene)-nickel(II). A hydrochloride of this complex was also prepared. The magnetic moment of the products is 3·1 B.M., indicative of an octahedral configuration for nickel (II). Molar conductivity in D.M.F. solution shows the product to be a weak electrolyte, approaching a uni-univalent electrolyte at infinite dilution. Infrared spectral data are consistent with the proposed structure. The electronic spectrum was also examined. The reaction of several other complexes with sulfur monochloride is reported.

ヨウ素を触媒とするカルボン酸と一塩化イオウとの反応

ヨウ素を触媒とするカルボン酸と一塩化イオウとの反応

7,15,17,19-Tetra-alkoxy-2,3,4,5,10,11,12,13-octathiatricyclo[12,2,2,26,9]eicosa-6,8,14,16,17,19-hexaene

The catalysed reaction of sulphur monochloride and 1,4-diethoxybenzene gives the unexpected novel macrocyclic polysulphur compound mentioned in the title.

Mean Amplitudes of Vibration in Molecules with Internal Rotation. IV. Theory with Application to Disulfur Dichloride

A normal-coordinate analysis has been performed for disulfur dichloride, and used to calculate the mean amplitudes of vibration. A generalized definition of framework mean amplitudes is proposed, and is applicable to cases where the torsional mode (for internal rotation) is kinematically coupled with other normal modes of vibration. According to this definition the total mean-square amplitude is composed of a sum of the framework mean-square amplitude and the torsional mean-square amplitude; the latter quantity contains all contributions where the torsional coordinate is involved. Numerical results of framework and torsional mean amplitudes are reported for S2Cl2 at various temperatures as functions of the angle of rotation θ. The approximate formula for framework mean-square amplitudes, 〈Δρ2〉frm = (α + β cosθ + γ cos2θ) / ρ2, has been subjected to detailed studies. The α, β, and γ coefficients were evaluated in terms of certain mean-square amplitude quantities, and the following statement was deduced from the properties of their classical limits at high temperatures: α(θ, T), β(θ, T), and γ(θ, T) approach θ-independent values when T → ∞. Furthermore, it is explained why the above formula with constant coefficients may give a very good approximation even at low temperatures when the conditions of classical limits are not fulfilled. This feature was actually found for S2Cl2 even at absolute zero.

Copolymerization of sulfur monochloride with cyclopentadiene

Copolymerization of sulfur monochloride with cyclopentadiene

A novel copolymerization reaction

AbstractA new addition polymerization reaction is described which involves the copolymerization of sulfur dichloride or sulfur monochloride with a diolefin. Sulfur dichloride copolymerizes with bis(1,2,3,6‐tetrahydrophthalimide) (A) to form poly[N,N′‐m‐phenylenebis(3,4‐dicarboxy‐6‐chlorocyclohexyl) sulfide imide] (I). Sulfur monochloride copolymerizes with A to form poly[N,N′‐m‐phenylenebis(3,4‐dicarboxy‐6‐chlorocyclohexyl) disulfide imide] (II). The polyimides, I and II were characterized by elemental analysis, infrared spectroscopy, and inherent viscosity. The mechanism of polymerization is discussed.

Studies on Isothiazoles. III. A Novel Ring Closure to Isothiazoles by the Reaction of α-Amino Ketones with Thionyl Chloride or Sulfur Monochloride

Abstract New compounds, 4-hydroxyisothiazoles, have been prepared by the reaction of α-amino ketones with thionyl chloride or sulfur monochloride, which is a novel procedure for cyclization to an isothiazole ring. Polar solvents, especially dimethylformamide (DMF), were preferable for this cyclization. The reaction hardly proceeded in a nonpolar solvent such as benzene, but was accelerated by an addition of a small amount of DMF.

Studies on Isothiazoles. IV. A New Synthetic Route to 4-Cyanoisothiazoles

Abstract 4-Cyanoisothiazoles have been prepared by a novel procedure which comprises the reacreaction of β-cyano enamines with thionyl chloride or sulfur monochloride. The reaction proceeds favorably in nonpolar solvents or in the absence of solvent. However, the cyclization did not occur in dimethylformamide and instead an amidine derivative was isolated. The preparations of the corresponding isothiazole-4-carboxylic acids are also described briefly.

Reactivity of the residual allyl group in poly(allyl methacrylate)

AbstractCompletely soluble linear allyl methacrylate polymers with pendant allyl groups were prepared, in high conversion, by the lithium‐initiated polymerization of allyl methacrylate in tetrahydrofuran. Three reactions typical of olefinic double bonds (i.e., crosslinking with benzoyl peroxide or with azobisisobutyronitrile, vulcanization with sulfur or with sulfur monochloride, and epoxidation with perbenzoic acid) were found to proceed smoothly for the remaining allyl groups in the polymers. In its reactivities toward these reagents the allylic double bond in the polymer compares with the terminal double bond of an olefinic hydrocarbon but is inferior to an internal double bond. Effects of the separations of the pendant allyl groups with inert monomer units by copolymerization are also recognized.

Sydnones—III: Some reactions of lithium phenylsydnone with acid and non-metallic chlorides

The reactions of lithium phenylsydnone with the acid chloride of 3-phenylsydnonyl 4-carboxylic acid, as well as with acetyl, valerianyl, benzoyl, oxalyl chlorides and with phosphorous trichloride, phosphorous oxychloride, sulphur monochloride and thionyl chloride, are described.

Polyfluoroaryl organometallic compounds—VI : Some reactions of pentafluorophenyl- and ortho-bromotetrafluorophenyl-organometallic compounds

Pentafluoropehenyl-lithium and ortho-bromotetrafluorophenyl-lithium react with sulphur dichloride, in ether-hexane, to give the corresponding aryl sulphides; various polyfluoroaryl sulphides are reported, including the new heterocycle octafluorothianthren. Reaction of the lithium reagents with sulphur monochloride or with organic disulphides leads to SS bond cleavage; and a nucleophilic displacement of CF − 3 from sulphur is reported. Cleavage of pentafluorophenyl- and ortho-bromotetrafluorophenyl-tin compounds occurs with iodide ion but is not a useful route to polyfluorobenzynes.

Transient species in the photolysis of sulphur monochloride, including S2(a 1? g ).

A number of transient spectra have been detected by kinetic spectroscopy in absorption following the photolysis of sulphur monochloride. Vibrationally excited S2 in the ground electronic state with up to eight vibrational quanta have been observed together with the spectra of the optically metastable S2(a1Δg) and the sulphur atom. A number of transient diffuse spectra were observed, one of these being characterized by regular structure. It is proposed that this may be assigned to the SCl radical. The kinetic behaviour of these transient intermediates has been investigated and the basis of a mechanism describing the photolysis of S2Cl2 is given.

A route to sulfur-nitrogen polymers containing eight-membered rings

The condensation of disulfur dichloride with any one of the three positional isomers of hexasulfur diimide gives rise to linear polymers in which eight-membered sulfur–nitrogen rings derived from the diimide are coupled together by S2 groups. From the 1,5-diimide a single homologous series arises; we have isolated its first four members. Rings derived from the 1,3-diimide can couple cis- or trans- to one another; we have isolated cis- and trans-forms of the two-ring coupling product and observed their spontaneous interconversion. Rings of the 1,4-diimide are optically asymmetric; we have isolated diastereoisomers of the corresponding two-ring coupling product, and a mixture of isomers of the three-ring homolog.

The action of sulphur monochloride on 2-acyl-1,1-dimethylhydrazines; the formation of tetrazans and oxadiazolines

Tetrazans are the main products of the action of sulphur monochloride on 2-acyl-1,1-dimethylhydrazines. In some cases 1,3,4-oxadiazoline-2-thiones are also formed, in smaller yields.

The action of sulphur monochloride on aromatic primary amines: the Herz reaction

1,3,2-Benzothiazathiolium chlorides are obtained by the action of sulphur monochloride on a primary aromatic amine, its salts, or N-acyl derivatives. Four reactions are involved, (i) the formation of the heterocyclic ring, (ii) the chlorination of the aromatic ring, (iii) replacement of electron-attracting groups in the ortho- and para-positions by chlorine, and (iv) the oxidation of the sulphur atom in position 2. A likely sequence of reactions is considered, and experimental evidence is given in support of each stage.

The action of sulphur monochloride on o-nitroanilines and o-phenylenediamines: the formation of 2,1,3-benzothiadiazoles

o-Phenylenediamines react with sulphur monochloride forming 2,1,3-benzothiadiazoles. In acid solution the nitro-group of o-nitroanilines oxidises sulphur monochloride to thionyl chloride, and the phenylenediamine thus formed reacts with these sulphur compounds giving the corresponding benzothiadiazole.

Determination of sulphur monochloride by oxidation with chloramine-T

A rapid method is described for the determination of sulphur monochloride by adding excess of chloramine-T and determining the excess iodometrically.

Radiochlorine Exchange Reactions in Sulfur Monochloride

Chloride lability in the solvent sulfur monochloride was investigated by studying radiochlorine exchange rates between the solvent and the four solutes tetraethylammonium chloride, antimony tri- and pentachlorides, and thionyl chloride. Exchange is rapid and complete in the first three cases and, at best, very slow in the last. The results suggest a ready dissociation of solvent chloride in the presence of (and only in the presence of) a strong chloride acceptor, none being evident with thionyl chloride. It is inferred that the ready exchange observed with the ionic substance, tetraethylammonium chloride, probably goes via a bimolecular process or an association equilibrium. The experiments appear to imply a limited general importance for chloride dissociation in this medium. (auth)

595. The reactions of some aminosilanes and disiazanes with di-sulphur dichloride, sulphur dichloride, thionyl chloride, sulphuryl chloride, and sulphonyl chlorides

595. The reactions of some aminosilanes and disiazanes with di-sulphur dichloride, sulphur dichloride, thionyl chloride, sulphuryl chloride, and sulphonyl chlorides