Sulfenyl Bromide Research Articles

C–S barrier and vibrational analyses of (halocarbonyl)sulfenyl halides XCO-SX (X = F, Cl, and Br)

The structural stability of (halocarbonyl)sulfenyl halides XCO-SX (X is F, Cl, and Br) was investigated by DFT-B3LYP and ab initio MP2 calculations using 6–311 + G ** basis set. From the calculations the molecules were found to exist predominantly in the trans conformation (two halogen atoms are trans to each other). Full energy optimizations were carried out for the minima and the transition states (TS) at the two levels, from which the rotational barriers about CS bond in the three molecules were calculated to be about 12–13 kcal mol −1. The vibrational frequencies of (fluorocarbonyl)sulfenyl fluoride (FCO-SF), (chlorocarbonyl)-sulfenyl chloride (ClCO-SCl), and (bromocarbonyl)-sulfenyl bromide (BrCO-SBr) were computed at the DFT-B3LYP level and the vibrational assignments for the normal modes of the stable forms of the compounds were made on the basis of normal coordinate calculations and experimental data of the chloride.

4′-Methylazobenzene-2-sulfenyl cyanide

The title compound [systematic name: 2-(p-tolyldiazenyl)phenyl isothiocyanate], C14H11N3S, is non-ionic in nature. Highly electronegative atoms like Br or Cl in sulfenyl halides make the S atom sufficiently electron deficient for strong ortho azo–sulfur interaction in sulfenyl bromides or chlorides of ortho mercaptoazo compounds; this leads to a planar thia­diazo­lium structure, in which the S atom interacts with the ortho azo group. However, in case of the 4′-Me title compound, the S atom is not sufficiently electron deficient, and no intramolecular ortho azo–sulfur interaction exists. The mol­ecule is almost planar. There are no hydrogen bonds and the crystal structure is stabilized by van der Waals interactions.

ChemInform Abstract: (Bromocarbonyl)sulfenyl Bromide, BrC(O)SBr: A Novel Carbonyl Sulfenyl Compound Formed by the Photochemical Reaction Between Br2 and OCS Isolated Together in an Ar Matrix.

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(Bromocarbonyl)sulfenyl bromide, BrC(O)SBr: a novel carbonyl sulfenyl compound formed by the photochemical reaction between Br2 and OCS isolated together in an Ar matrix

Download options Please wait... Article information DOI https://doi.org/10.1039/B108218C Article type Communication Submitted 10 Sep 2001 Accepted 29 Oct 2001 First published 20 Nov 2001 Download Citation Chem. Commun., 2001, 2638-2639 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions (Bromocarbonyl)sulfenyl bromide, BrC(O)SBr: a novel carbonyl sulfenyl compound formed by the photochemical reaction between Br2 and OCS isolated together in an Ar matrix R. M. Romano, C. O. Della Védova and A. J. Downs, Chem. Commun., 2001, 2638 DOI: 10.1039/B108218C To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author Rosana M. Romano Carlos O. Della Védova Anthony J. Downs

Matrix photochemistry of syn-(chlorocarbonyl)sulfenyl bromide, syn-ClC(O)SBr: precursor to the novel species anti-ClC(O)SBr, syn-BrC(O)SCl, and BrSCl.

The vapor of (chlorocarbonyl)sulfenyl bromide, ClC(O)SBr, was isolated in solid Ar, Kr, N(2), and Ar doped with 5% CO at 15 K, and the matrix was subsequently irradiated with broad-band UV--visible light (200 < or = lambda < or = 800 nm), the changes being followed by reference to the IR spectrum of the matrix. The initial spectrum showed the vapor of ClC(O)SBr to consist of more than 99% of the syn form (with the C==O bond syn with respect to the S--Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)S-containing compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs (35)Cl/(37)Cl and (79)Br/(81)Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations.

Reactions of 2-[(Phenylthio)methylene]tetralin-1-thione

Abstract Hetero Diels–Alder reactions of 2-[(phenylthio)methylene]tetralin-1-thione (1) with methyl acrylate, methyl vinyl ketone, acrylonitrile, and other electron-poor dienophiles afford the corresponding cycloadducts (2), from which thiophenol is eliminated by the treatment with sodium alkoxide to give the corresponding 2H-thiopyran derivatives (3). The cycloadducts 2 with styrene and indene do not undergo elimination. The reactions of thioketone 1 with cycloalkenones give both the cycloadducts and the elimination products, even in the absence of a base. The reactions of 1 with acryloyl, crotonoyl, cinnamoyl, and 3-methyl-2-butenoyl chlorides give dienecarbothioic S-esters, in good yields, which are converted into stable dienecarbodithioic esters by the treatment with Lawesson’s reagent. In the reaction of 1 with methyl 2-bromoacrylate, elimination of sulfenyl bromide takes place to afford the elimination product 3.

Reaction of thioxophosphorane sulfenyl bromides with ethyl vinyl ether: Mechanistic and synthetic aspects

The mechanistic and synthetic aspects of the addition reaction of thioxophosphorane sulfenyl bromide with ethyl vinyl ether were studied in detail by NMR techniques. It has been found that the regiospecific, primary product of the reaction, 1-bromo-1-ethoxy-2S(dialkoxythiophosphoryl)ethane I, is unstable and undergoes slow decomposition to give four compounds. The formation of thiophosphoryl derivatives, vinyl ethers II and III, aldehyde IV, and the symmetrical hemiacetal anhydride V, has been considered in terms of a carbocation intermediate. By choice of the appropriate reaction conditions, the aldehyde IV can be obtained in very high yield.

The preparation and some physical properties of ten methyl dithiastearate isomers

Ten methyl dithiastearate isomers, containing 0–4 methylene groups between the two sulfur atoms in each of the molecules, were synthesized using a one-pot synthesis approach. The preparation of the tetra-methylene ( 3,4), tri-methylene ( 5,6) and di-methylene ( 7,8) interrupted methyl dithiastearate isomers involved the asymmetric coupling of n-bromoalkanes, alkanedithiols and ω-bromoalkanoic acids. The mono-methylene interrupted isomers ( 9,10) were prepared from dibromethane, which was allowed to couple with n-alkanethiols and ω-mercaptoalkanoic acids. For the non-methylene interrupted isomers ( 11,12), n-alkanethiols were initially converted to the sulfenyl bromide and reacted with ω-merchaptolaklanoc acids. These sulfur-containing fatty ester analogues were found to be more polar and with longer retention times than methyl stearate when analyzed by TLC (silica) and GC (SE-30) respectively. In the 1H-NMR analysis the shifts of the protons of CH 2 groups adjacent to the sulfur atoms in 3–6 appeared at 2.50–2.60 (t) δ, while the tri-methylene interrupted isomers ( 5,6) furnished an additional characteristics signal at 1.84 (quintet) δ arising from the protons of the β-positioned CH 2 between the sulfur atoms. Compounds 7–8 gave a singlet at 2.70 δ, while 9,10 also gave a singlet at 3.64–3.65 δ for the protons of the CH 2 group situated between the sulfur atoms. In compounds 11,12 the shift of the protons of the CH 2 adjacent to the sulfur atom appeared at 2.68 δ, while the remaining isomers gave a distorted triplet at 0.88 δ. In the 13C-NMR analysis the shift of the carbon atoms adjacent to thye sulfur atoms compounds 3–8 appeared between 30.7–34.4 ppm. The shift for the carbon of the methylene group between th sulfur atoms in the mono-methylene interrupted somers ( 9,10 was found at 35.5–35.7 ppm, while the shifts for the methylene carbons adjacent to the disulfane group (SS) in 11,12 were found at 38.6–41.2 ppm. From the results of the 1H and 13C-NMR analyses, it was possible to characterize each isomer by either one of these two techniques.

SYNTHESIS OF THE SULFUR ANALOG OF Δ6-PGI1

Abstract A synthesis of the sulfur analog of Δ6-PGI1 with potent inhibitory activity in platelet aggregation is described. The synthesis starting from the suitably protected Corey lactone includes the hydroxylation of the lactone and the novel intramolecular addition of the sulfenyl bromide.

Reaction of polynitroalkane salts with some divalent sulfur derivatives

The reaction of polynitroalkane anions with sulfenyl bromides leads to the C-sulfenylation products, whereas the main direction of the reaction is O-sulfenylation when sulfenium salts are used.

Reactions of tetra- O-acetyl-β- D-glucopyranosylsulfenyl bromide

Tetra- O-acetyl-β- D-glucopyranosylsulfenyl bromide ( 2) has a bivalent sulfur atom that exhibits electrophilic character. With such sulfur nucleophiles as benzenethiol and α-toluenethiol, the sulfenyl bromide 2 reacts to give mixed disulfides ( 5 and 6, respectively) and, with such arylamines as aniline or o-chloroaniline, the sulfur atom of 2 attacks the nucleophilic nitrogen atom to give sulfenamides ( 7 and 8, respectively). Addition of 2 to the double bond of cyclohexene gives trans-2-bromo-1-(tetra- O-acetyl-β- D-glucopyranosylthio)cyclohexane ( 3); the 3′,3′,6′,6′-tetradeuterated analog was prepared by use of cyclohexene- 3,3,6,6-d 4. With N,N-dimethylaniline, the sulfenyl bromide 2 reacts by attack at the para position to give p-(dimethylamino)-phenyl tetra- O-acetyl-1-thio-β- D-glucopyranoside ( 1), although a concurrent, major reaction-pathway gives bis(tetra- O-acetyl-β- D-glucopyranosyl) disulfide ( 4). With phenol and various enolizable ketones, the sulfenyl bromide 2 reacts to give the disulfide 4 in high yield. The structures assigned to the products were confirmed by n.m.r. spectroscopy. Such glycosylsulfenyl halides as 2 thus offer a potential route to a wide range of thio sugar derivatives by reactions with thiols, amines, and alkenes.

The action of bromine on tetra- O-acetyl-1- S-acetyl-1-thio-β- D-glucopyranose. Formation and decomposition of tetra- O-acetyl-β- D-glucopyranosylsulfenyl bromide

Treatment of either tetra- O-acetyl-1- S-acetyl-1-thio-β- D-glucopyranose ( 1) or tert-butyl tetra- O-acetyl-1-thio-β- D-glucopyranoside ( 6) with a >3-molar excess of bromine in carbon tetrachloride or pure chloroform, at 10° for 1-3 min, gives tetra- O-acetyl-β- D-glucopyranosylsulfenyl bromide ( 2) in quantitative yield; prolonged exposure to bromine at room temperature converts the product 2 into tetra- O-acetyl-α- D-glucopyranosyl bromide ( 3). Slow addition of bromine to the 1-thioglycoside 6 in carbon tetrachloride, or bromination of the thiolacetate 1 in reagent-grade chloroform, gives bis(tetra- O-acetyl-β- D-glucopyranosyl) disulfide ( 4), also obtainable by treating the sulfenyl bromide 2 with dry ethanol or with the 1-thioglycoside 6. Oxidation of the disulfide 4 with m-chloroperoxybenzoic acid gives a mono-oxide derivative 5, also obtainable by treating the sulfenyl bromide 2 with water or 95% ethanol. The disulfide 4 and its mono-oxide 5 were both converted into the bromide 3 by prolonged exposure to bromine at room temperature.

Synthesis of α.α′‐dibromomethyl sulfid and some reactions

Abstractα.α′‐Dibromomethyl sulfide was obtained by reacting sym‐trithiane with bromine. Bromomethyl sulfenyl bromide was postulated as an intermediate in this reaction. The latter substance also condenses with ethylene to produce α.α′‐dibromomethyl ethyl sulfide. α.ω Dibromopolythimethylene was obtained by treating sym‐trithiane in bulk at 180°C with α.α′‐dibromomethyl sulfide. Polythiomethylene was obtained by treating α.α′‐dibromomethyl sulfide with water.