Trichloromethanesulfenyl Chloride Research Articles

Inhibition of DNA polymerase β activity in isolated bovine liver nuclei by captan and related compounds

The effects on DNA synthesis of the fungicide captan and several structurally related compounds were investigated in isolated bovine liver nuclei. Captan, folpet, captafol, and trichloromethanesulfenyl chloride inhibited DNA synthesis to the same degree with ID 50 values of approximately 50 μ M in a 40-min assay. The inhibition is concentration dependent and the degree of inhibition increases with time. Studies with structural analogs of captan indicated that inhibition of DNA synthesis by captan is mediated through the trichloromethylthio moiety of the captan molecule. In addition, the data indicate thiophosgene is probably not the toxic species involved in the inhibition of DNA synthesis. The isolated nuclei used in this study were shown to exhibit only a single DNA polymerase activity which was determined to be of the β or low-molecular-weight type. In addition to its inhibition in intact nuclei, captan inhibited the activity of the β polymerase in nuclear extracts as well as in partially purified enzyme preparations. These results indicate that captan inhibits DNA synthesis in our preparation of isolated nuclei by acting directly on the DNA polymerase-catalyzed reaction rather than by causing a nonspecific or indirect effect in the nuclear system such as alterations in the nuclear membrane or aggregation of the nuclei. The site of captan's inhibitory action is the DNA polymerase molecule. The interaction of captan with the polymerase results in irreversible inhibition of the enzyme. Interaction of captan with the template, if it occurs, does not appear to be involved in mediating the inhibition.

ChemInform Abstract: THE UTILIZATION OF SULFUR, SULFENYL, SELENENYL, AND SELENINYL CHLORIDES IN THE CONVERSION OF ALDOXIMES TO NITRILES

AbstractUntersucht wird die Dehydratisierung der Aldoxime R‐CH=N‐OH mit R: ‐Ph, 4‐Methoxy‐phenyl, V‐Pr, n‐Hexyl durch a) Cl‐S‐Cl, Cl‐S‐S‐Cl, CCl3‐S‐Cl und b) Ph‐S‐Cl, Ph‐Se‐Cl und Ph‐SeO‐Cl in Gegenwart von Et3N in Ether oder Chloroform.

ChemInform Abstract: STUDIES ON FURAN DERIVATIVES. III. SYNTHESIS OF 4‐SUBSTITUTED 5‐(5‐NITRO‐2‐FURYL)THIAZOL‐2‐ONES AND SOME OF THEIR DERIVATIVES

Seven kinds of 4-substituted 5-(5-nitro-2-furyl) thiazol-2-ones were obtained by the reaction of α-substituted β-(5-nitro-2-furyl) vinylamines (Ia-g) with chlorocarbonylsulfenyl chloride. Reaction of Ia and c with trichloromethylsulfenyl chloride gave 3-sub-stituted 4-(5-nitro-2-furyl)-5-chloroisothiazoles.

The Utilization of Sulfur, Sulfenyl, Selenenyl, and Seleninyl Chlorides in the Conversion of Aldoximes to Nitriles

Abstract The comparative usefulness of six sulfur, sulfenyl, selenenyl, and seleninyl chlorides towards aldoximes in the presence of a base were examined under similar reaction condi-tions. The reactions of aromatic aldoximes with either sulfur dichloride (1), sulfur mono-chloride (2), or trichloromethane sulfenyl chloride (3) in either ether or chloroform at 23-35 °C after one hour resulted in 60-84% yields of nitriles. Under the same conditions, the reactions of aliphatic aldoximes with either 1, 2, or 3 gave mixtures of products, while at -40 to -30 °C, 15-22% yields of aliphatic nitriles were obtained. The reactions of aliphatic and aromatic oximes with either benzenesulfenyl chloride (4), benzene-selenenyl chloride (5), or benzeneseleninyl chloride (6) produced after fifteen minutes to three hours the corresponding nitriles in 71-96% yields at 23-35 °C.

Studies on furan derivatives. III. Synthesis of 4-substituted 5-(5-nitro-2-furyl)thiazol-2-ones and some of their derivatives.

Seven kinds of 4-substituted 5-(5-nitro-2-furyl) thiazol-2-ones were obtained by the reaction of α-substituted β-(5-nitro-2-furyl) vinylamines (Ia-g) with chlorocarbonylsulfenyl chloride. Reaction of Ia and c with trichloromethylsulfenyl chloride gave 3-sub-stituted 4-(5-nitro-2-furyl)-5-chloroisothiazoles.

Thiophosgene in Organic Synthesis

The synthetic utility of thiophosgene has recently been widely explored. Besides use in the classical preparations of isothiocyanates, thiocarbamates,thiocarbonates, and thioureas, it can also be successfully used in the synthesis of nitriles, alkenes, thietanes, a wide variety of thioxo-substituted heterocyclic compounds, and inorganic complexes. Thiophosgene is a readily available chemical but can also be conveniently prepared in the laboratory by reductive dechlorination of trichloromethanesulfenyl chloride. The present survey of the literature on thiophosgene is intended to encourage better use of the reagent in future organic syntheses. 1. Introduction 2. Synthesis of Thiophosgene 3. Reactions at a Nitrogen Centre 3.1. Reactions with Primary Amines 3.2. Reactions with Amides 3.3. Reactions with Secondary Amines 3.4. Reactions with Tertiary Amines 3.5. Reactions with Imines 3.6. Reactions with Hydrazines 3.7. Reactions with Diazo Compounds and Azides 4. Reactions at an Oxygen Centre 4.1. Reactions with Alcohols 4.2. Reactions with Phenols 4.3. Reactions with Thiolactones 4.4. Reactions with Oximes 5. Reactions at a Sulfur Centre 5.1. Reactions with Thiols 5.2. Reactions with Dithiolactone Derivatives 6. Reactions at a Carbon Centre 7. Reactions with Organometallic and Inorganic Compounds 8. Miscellaneous Reactions 9. Conclusions

ChemInform Abstract: BIS(TRICHLOROMETHANESULFENYL)AMINE FROM THE REACTION OF NITROGEN TRICHLORIDE WITH DIMETHYL DISULFIDE‐ SYNTHESIS AND REACTIONS

AbstractDie Reaktion des Disulfids (I) mit Stickstofftrichlorid liefert das Sulfenylamin (II), das mit Trichlormethan‐ bzw. Trifluormethansulfenylchlorid in die Amine (III) bzw. (IV) übergeht.

Bis(trichloromethanesulfenyl)amine from the reaction of nitrogen trichloride with dimethyl disulfide: Synthesis and reactions

AbstractReaction of nitrogen trichloride with dimethyl disulfide in chloroform solution affords bis(trichloromethanesulfenyl)amine (2). Compound 2 is converted by trichloromethanesulfenyl chloride into tris(trichloromethanesulfenyl)amine (3) and by trifluoromethanesulfenyl chloride into bis‐(trichloromethanesulfenyl)trifluoromethanesulfenyl amine (4). Acylation of 2 with acetyl chloride and with benzoyl chloride respectively, is described The reaction of 2 with thionyl chloride affords sulfinyl‐(trichloromethanesulfenyl)amine (7).

Essais de Chloration Dirigée. XII. Photochloration d'Acétates d'Alkyles Par Agents Chlorants [1

AbstractPhotochemical chlorination of several alkylacetates. CH3–CO–O–R (with R = n.C3H7, n.C4H9, i.C4H9, n.C5H11), was performed, using trichloromethane‐sulfenyl chloride (TCSE) as chlorinating agent, both with and without benzene as solvent.As in our previous works, chlorination was limited in order to get a mixture of monochlorinated isomers. Experimental results, expressed in terms of relative reactivity, r.r. (alb), of two hydrogen atoms, were correlated by the equation: magnified image.The reaction constants ρ*(−1,28) and h (0,112), compared with analogous values obtained in direct chlorination (ρ* = − 084, h = 0,034) show an important increase selectivity.Reactions were also performed at different temperatures and results are discussed. Some experiments were also made with amyl acetate and trichloromethane‐sulfonyl chloride (TCSO) as chlorinating agent.

Electron-diffraction study of the structure of the trichloromethylsulfenyl chloride molecule

Electron-diffraction study of the structure of the trichloromethylsulfenyl chloride molecule

The reactions of trichloromethanesulfenyl chloride and its derivatives. VII. Solvolysis of aryl esters of trichloromethanesulfenic acid

The reactions of trichloromethanesulfenyl chloride and its derivatives. VII. Solvolysis of aryl esters of trichloromethanesulfenic acid

The chemistry of sulfenyl halides: Part III: Photochlorination of alkyl chlorides with trichloromethylsulfenyl chloride

AbstractThe photochlorination of some alkyl chlorides with trichloromethylsulfenyl chloride has been investigated. Product distributions and reactivities relative to alkanes were determined. The results show the importance of polar effects and can be correlated with the polar substituent constants σ*. A chlorine atom reduces the reactivity of a neighbouring carbon‐hydrogen bond by a factor of 45. The reactivities at other positions correspond to a loss factor of 1.6. A methyl group exerts a slight activating polar effect.A correlation with NMR chemical shifts suggests that the differences in reactivity of methylene groups in hydrocarbons, as reported in Part II 2, are also due to polar effects.

The chemistry of sulfenyl halides: Part II: Photochlorination of alkanes with trichloromethylsulfenyl chloride

AbstractWhen solutions of trichloromethylsulfenyl chloride, Cl3CSCl, in alkanes are exposed to sunlight, alkyl chlorides, hydrogen chloride and hexachlorodimethyl disulfide are formed: An advantage of this novel chlorination method is the high selectivity, which is even further increased in the presence of benzene. The disulfide may be reconverted to the sulfenyl chloride by molecular chlorine in a separate step.A radical chain mechanism is proposed for the reaction in which trichloromethylthiyl and alkyl are the chain‐carrying radicals.

(Dichloro‐fluoromethyl)sulfenyl chloride

AbstractEvidence is presented that the compound obtained from trichloromethylsulfenyl chloride and mercuric fluoride is dichlorofluoromethylsulfenyl chloride.

Derivatives of Sulfenic Acids. XXXIII. Studies of Thioperoxides. Part 4. Reactions of Trichloromethanesulfenyl Chloride with 1,2-Epoxides and Alcohols

Abstract : Trichloromethane sulfenyl chloride (I) reacts with 1,2epoxides and with meso-butadiene dioxide to form betachloroalkyl trichloromethane sulfenates. The reaction is catalyzed by t-amines and identical products are obtained by substituting appropriate beta-chloro alcohols for the epoxides. The results agree with the mechanism which postulates trans opening of the epoxide rings, as previously suggested for the similar reactions of 2,4-dinitrobenzene sulfenyl chloride. The new products from reaction of I with epoxides and certain alcohols are reported. (Author)

STUDIES ON THE FUNGICIDAL ACTION OF N–(TRICHLOROMETHYLTHIO)–4–CYCLOHEXENE–1,2–DICARBOXIMIDE (CAPTAN)

N(trichloromethylthio) -4-cyclohexene-1, 2-dicarboximide (captan)3 is an important member of a class of organic fungicides which has been synthesized by the reaction of perchlorome-thyl mercaptan with certain imides, amides, and hydantoins (Kittleson, 1952). All the compounds of this class have in common the N-trichloromethylthio group to which their activity has been attributed (Kittleson, 1953). Captan is currently used extensively in the control of certain fungus diseases of plants. Studies of certain effects of captan on fungus metabolism reported in this paper were undertaken to elucidate the mode of action of this fungicide. MATERIALS AND METHODS.-Captan 4 was purified from a technical sample by precipitation from acetone with water and had an uncorrected melting point of 172?C. Inasmuch as captan is of limited solubility in water, a wetting agent 5 was used to prepare fine suspensions which could be pipetted accurately: The final concentration of wetting agent (0.00125 per cent) had no measurable effect on the biological materials used. The fungus, Fusarium roseum Lk., was used as a test organism and was grown on a medium containing: maltose, 10 g.; proteose peptone, 5 g.; KH2PO4, 0.5 g-; MgSO4. 7H20, 0.5 g.; FeSO4. 71120, 0.03 g-; agar, 20 g.; and distilled water, 1 1. Conidia were harvested by washing them from the surface of cultures which were 7 days old. The conidial suspensions were freed, of mycelial fragments by passage through several layers of cheese cloth, and the conidia were washed 3 times by alternate centrifugation and resuspension. For use in manometric experiments, the conidia were suspended in a basal solution containing: 0.002 M MgSO4 7H20 and 0.0001 M FeSO4 7H20 and potassium phosphate buffer (0.04 M

The infrared spectrum of perchloromethyl mercaptan (trichloromethane sulphenyl chloride) CCl3SCl: Fermi‐splitting and isotope effect in the spectrum of carbon tetrachloride

AbstractThe infrared spectrum of liquid CSCl4 has been measured from 3‐25μ. The experimental results are discussed and a complete analysis of the spectrum is given.Although some corrections in his vibrational assignment had to be made, the spectrum supports the structure proposed by Duchesne1), i.e. CCl4 with a chlorine atom replaced by sulphur and a chlorine atom attached to the sulphur at an angle to the CS bond.One of the fundamental frequencies shows Fermi‐splitting with a combination frequency. The difference between vapour and liquid state spectrum is used to prove the interpretation given. For comparison the shape of the Fermi‐doublet observed in the infrared spectrum of carbon tetrachloride is studied in the vapour and the liquid phase.