Sulfur chlorides

Condensation of (chloroformyl)-sulfur chloride with 2-aminOthiazole gives a product (170) whose structure was established by X-ray analysis (Scheme 108) (352-354). 

Trichlorothiazole, which behaves as an insecticide, can be prepared by the reaction at 150 to 200°C of sulfur with either 1.2.2.2-tetrachlorethylisocyanide dichloride (103), JV-(l,2,2,2-tetrachlor-ethyl)formimidine (104), or by the reaction of sulfur chlorides at... 

Chemical Properties. The chemistry of the sulfur chlorides has been reviewed (141,142). Sulfur monochloride is stable at ambient temperature but undergoes exchange with dissolved sulfur at 100°C, indicating reversible dissociation. When distilled at its atmospheric boiling point, it undergoes some decomposition to the dichloride, but decomposition is avoided with distillation at ca 6.7 kPa (50 mm Hg). At above 300°C, substantial dissociation to S2 and CI2 occurs. Sulfur monochloride is noncombustible at ambient temperature, but at elevated temperatures it decomposes to chlorine and sulfur (137). The sulfur then is capable of burning to sulfur dioxide and a small proportion of sulfur trioxide. 

Some metallic oxides and sulfides are chlorinated by sulfur chlorides ... 

Ma.nufa.cture. Sulfur monochloride is made commercially by direct chlorination of sulfur, usually in a heel of sulfur chloride from a previous batch. The chlorination appears to proceed stepwise through higher sulfur chlorides (S Cl2, where x > 2). If conducted too quickly, the chlorination may yield products containing SCI2 and S Cl2 as well as S2CI2. A catalyst, eg, iron, iodine, or a trace of ferric chloride, faciUtates the reaction. The manufacture in the absence of Fe and Fe salts at 32—100°C has also been reported (149—151). 

When the batch is completed, a slight excess of oleum and chlorine is added to reduce to a minimum the residual SCI2. Because thionyl chloride combines readily with sulfur trioxide to form the relatively stable pyrosulfuryl chloride, it is necessary to maintain the concentration of sulfur trioxide in the reaction mass at a low level hence, the addition of oleum to sulfur chloride rather than the reverse. When all of the reactants are added, heat is appHed to the jacket of the reactor and the batch is refluxed until most of the sulfur dioxide, hydrogen chloride, and chlorine are eliminated. The thionyl chloride is then distilled from the reactor. 

A number of processes have been devised for purifying thionyl chloride. A recommended laboratory method involves distillation from quinoline and boiled linseed oil. Commercial processes involve adding various high boiling olefins such as styrene (qv) to react with the sulfur chlorides to form adducts that remain in the distillation residue when the thionyl chloride is redistilled (179). Alternatively, sulfur can be fed into the top of the distillation column to react with the sulfur dichloride (180). Commercial thionyl chloride has a purity of 98—99.6% minimum, having sulfur dioxide, sulfur chlorides, and sulfuryl chloride as possible impurities. These can be determined by gas chromatography (181). 

Sulfur Chlorides, Bulletin B-11317-75, Stauffer Chemical Co., Industrial Chemical Division, Westport, Coim., 1975. 

Sulfur Products Handbook on Sulfur Monochloride and Sulfur Chloride, Bulletin SPE-SUL-HB 10/9, Oxychem Basic Chemicals Group, Occidental Chemical Corp., Dallas, Tex., 1993, p. 3. 

E. J. Diaan and J. E. Bieron,M Survey ofPeactions of Ehionyl Chloride, Sulfuryl Chloride and Sulfur Chlorides, Occidental Chemical Corp., Niagara EaUs, N.Y., 1990. 

The sulfur chlorides give higher xanthate sulfides. For example, the following product is obtained from sulfur monochloride and an ether suspension at room temperature ... 

Inorga.nicNIa.teria.ls. These include acids (sulfuric, nitric, hydrochloric, and phosphoric), bases (caustic soda, caustic potash, soda ash, sodium carbonate, ammonia, and lime), salts (sodium chloride, sodium nitrite, and sodium sulfide) and other substances such as chlorine, bromine, phosphoms chlorides, and sulfur chlorides. The important point is that there is a significant usage of at least one inorganic material in all processes, and the overall toimage used by, and therefore the cost to, the dye industry is high. 

A. Preparation of Thiocarbonyl Per chloride.—In a 5-I. bottle arranged for cooling by running water is placed 500 g. (6.58 moles) of dry carbon disulfide (Note i) to which 0.5 g. of iodine has been added. Dry chlorine is passed into the cooled carbon disulfide at such a rate that the temperature does not rise above 25°, until the liquid weighs 1770 g. (17.9 moles chlorine) (Note 2). The time required is about forty hours. The product is a deep red liquid, a mixture of impure thiocarbonyl perchloride and sulfur chloride. 

If the addition is much more rapid than this, the sulfur chloride is not all decomposed. 

Diphenyl sulfide can best be prepared by treating benzene and aluminum chloride with sulfur chloride, sulfur dichloride, or sulfur. In addition to diphenyl sulfide there are found traces of thiophenol and varying amounts of thianthrene. 

The first large-scale use of chlorine was for bleaching paper and cotton textiles it also is widely used as a germicide for public water supplies. Presently it is used principally in production of the chemical compounds sulfur chloride, thionyl chloride, phosgene, aluminum chloride, iron(ni) chloride, titaniura(IV) chloride, tin(IV) chloride, and potassium chlorate. 

Sulfur and Sulfur Compounds, 123 Sulfur chloride, 123 Sulfur dioxide, 123 Sulfur hexafluoride, 123 Sulfur tetrafluoride, 124 Sulfur trioxide, 124 Sulfuric acid, 123 Sulfurous acid, 124 Sulfuryl fluoride, 124 Sulphamic acid, 124 Sulprofos, 124... 

Carboxylic Thionyl acid chloride Acyl Sulfur chloride dioxide Hydrogen chloride... 

T. Tonoba, Poly(Sulfur-Nitr ogen) Heterocycles via Sulfur Chlorides and Nitrogen Reagents, J. Prakt. Chem., 341, 99 (1999). 

Sulfur diamides (diaminosulfanes) are obtained by the action of sulfur chlorides with an aliphatic secondary amine (Eq. 10.10). ° The monoselanes Se(NR2)2 (R = Me, Et) have also been prepared. Polyselanes Scx(NR2)2 (x = 2 - 4, NR2 = morpholinyl x = 4, NR2 = piperidinyl) are formed in the reaction of elemental selenium with the boiling amine in the presence of Pb304. ... 

Chlor-siure, /. chloric acid. -sMureanhydrid, n. chloric anhydride, chlorine(V) oxide, -schwefel, n. sulfur chloride (esp. the monochloride). -silber, n. silver chloride, -sili-cium, n. silicon tetrachloride, -soda, /. = Chlornatron. -stickstoff, m. nitrogen chloride. -Strom, m. stream of chlorine, -strontium, n. strontium chloride, -suifonsaure, /. chlorosulfonic acid, chlorosulfuric acid, -toluol, n. chlorotoluene. -fibertrager, m. chlorine carrier. 

Sulfur, as catalyst, 17, 18 Sulfur chloride, 14, 36 Sulfur dioxide, 16, 3g... 

When SNG is made from coal, the methanation feed gas can contain various trace constituents which could affect performance. The coal can contain various amounts of sulfur, chloride, and nitrogen. These components will mostly be converted to H2S, HC1, NO, and NH3 (the NH3... 

Parkes Absorbent for Nitroglycerin. Materials patented in 1898 by Parkes, manufd by Chem-ische Fabrik at Winkel-on-Rhine, Ger, for use in Dynamites as absorbents for NG in lieu of the previously used kieselguhr. The absorbents were rubber-llke materials, prepd by the action of sulfur chloride, S2C12, on vegetable oils. It was claimed at the time that Dynamites prepd with Parkes absorbent were so insensitive, they could be used for loading shells... 

Sulfur hexafluoride is a thermally stable, nontoxic gas that is a good insulator sulfur chlorides are toxic liquids. 

There are a number of other methods to prepare crude sulfane oils, e.g., from hquid H2S and elemental chlorine or bromine [10] or by reaction of H2S with sulfur fluorides [10] or sulfur chlorides [20] but these processes are of httle practical importance. 

The sulfur chloride (S2C12) volatilizes along with the ferric chloride (FeCl3) and the cupric chloride (CuCl2) remains in the residue. When the reaction is conducted at 600 °C with a limited supply of chlorine, the products are different ... 

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