Vapor thionyl chloride

Health nd Safety Factors. Thionyl chloride is a reactive acid chloride which can cause severe bums to the skin and eyes and acute respiratory tract injury upon vapor inhalation. The hydrolysis products, ie, hydrogen chloride and sulfur dioxide, are beheved to be the primary irritants. Depending on the extent of inhalation exposure, symptoms can range from coughing to pulmonary edema (182). The LC q (rat, inhalation) is 500 ppm (1 h), the DOT label is Corrosive, Poison, and the OSHA PEL is 1 ppm (183). The safety aspects of lithium batteries (qv) containing thionyl chloride have been reviewed (184,185). 

The reaction involves two electrons per thionyl chloride [7719-09-7] molecule (40). Also, one of the products, SO2, is a Hquid under the internal pressure of the cell, facihtating a more complete use of the reactant. Finally, no cosolvent is required for the solution, because thionyl chloride is a Hquid having only a modest vapor pressure at room temperature. The electrolyte salt most commonly used is lithium aluminum chloride [14024-11-4] LiAlCl. Initially, the sulfur product is also soluble in the electrolyte, but as the composition changes to a higher SO2 concentration and sulfur [7704-34-9] huA.ds up, a saturation point is reached and the sulfur precipitates. 

In a i-l. three-necked flask are mixed 150 g. (r.63 moles) of /3-hydroxyethyl methyl sulfide (p. 54) (Note i) and 200 g. of dry chloroform (Note 2). The flask is placed on a steam bath and is fitted with a dropping funnel, a mechanical stirrer, and a condenser. The condenser is fitted with a trap to remove the vapors of hydrogen chloride and sulfur dioxide (page 2). A solution of 204 g. (1.7 moles) (Note 3) of thionyl chloride in 200 g. (135 cc.) of dry chloroform is added dropwise to the /3-hydroxyethyl methyl sulfide over a period of about two hours (Note 4). The reaction mixture is stirred vigorously during this addition and for about four hours after the addition is complete. The chloroform is distilled on the steam bath and the residue is distilled under reduced pressure. The yield is 135-153 g- (75 5 per cent of the theoretical amount) of a product boiling at 55-s6°/3o mm- (Note 5). 

Cholesterol, glycyrrhetic acid acetate Apply sample solution and moisten with anhydrous benzene, subject for 4 h to the vapors of thionyl chloride — benzene (1 -I-1) in a desiccator, then dry and develop. A chlorinated cholesterol or the chloride of 3- -acetoxyglycyrrhetic acid are formed. [16]... 

Reacts with vapors of sodium with luminescence at about 260°C. Reacts explosively with thionyl chloride or potassium reacts violently with hexafluoro isopropylidene, amino lithium, ammonia, and strong acids reacts with tert-butyl azidoformate to form explosive carbide reacts with 24-hexadiyn-l, 6-diol to form 2, 4-hexadiyn-l, 6-bischloro-formate, a shock-sensitive compound reacts with isopropyl alcohol to form isopropyl chloroformate and hydrogen chloride thermal decomposition may occur in the presents of iron salts and result in explosion. 

Seventy grams (0.25 mole) of oleic acid (Note 1) is placed in the dropping funnel H of the tangential apparatus (Fig. 2 Note 2). The thionyl chloride distillation is started and regulated (Note 2) the upper part of the column should be filled with the vapor, and reflux should be constant and steady. The acid is dropped in at the top of the column over a period of 35 minutes (120 g. per hour). The product that collects in the receiver I contains about 25-27% of thionyl chloride (Note 2) if the heated lower leg K is employed. The product in... 

The silanol groups which had not been esterified on reaction with methanol did still react with thionyl chloride. Gok9ek (231) found that the sum of methoxy content (after reaction with methanol vapor at various temperatures) and chloride formation remained nearly constant. 

Esterification of Aerosil with Methanol Vapor at ca. 0.1 mm Hg and Subsequent Reaction with Thionyl Chloride [after Qokfek (231)]... 

Kinkead ER, Einhaus RL Acute toxicity of thionyl chloride vapor for rats. Govt Reports Announcements Index (GRA I) Issue 7, 1985... 

The compound is produced by evaporating hydrochloric acid solutions of polonium (IV) 6, 26, 74), by heating the dioxide in carbon tetrachloride vapor 74), in hydrogen chloride, thionyl chloride or with phosphorus pentachloride 6) and by heating the metal in dry chlorine at 200°C (6, 25, 74). It is hygroscopic and hydrolyzes in moist air to a white solid, possibly a basic chloride (7)). The tetrachloride is soluble in thionyl chloride and in water with hydrolysis, and is moderately soluble in ethanol, acetone, and... 

Fifty-five grams of tin (IV) chloride 5-hydrate are refluxed in an all-glass apparatus with lOOg of thionyl chloride for 3-4 hours [hood]. Moisture is excluded during this operation the reaction is over when no more acid vapors escape from the drying tube at the top of the condenser. The product is then fractionally distilled to remove the excess thionyl chloride which is collected up to 110°G the material boiling at 110-115°C must be colorless, otherwise a redistillation is necessary. 

B. 4 - Chloromethyl-3-ethyl-5 -methylisoxazole. Caution The following reaction should be carried out in a fume hood to avoid thionyl chloride vapors. 

Improved versions of OLGA (versions II and III) enabled the applications of corrosive gases such as hydrogen chloride or hydrogen bromide, chlorine, thionyl chloride or boron tribromide vapor etc. This made it possible to synthesize volatile halides and measure their retention times in isothermal quartz columns. 

Since the two esters I and II are not available commercially, they will be synthesized by a procedure that is basically that of Jeffeiy and Vogel. The starting materials for the syntheses are the free acids, cyclopropanecarboxylic acid and cyclohexanecarboxylic acid. Each is first converted to the acid chloride with thionyl chloride, and the acid chloride is then allowed to react with the appropriate alcohol to form the ester. Alternatively the acid chlorides can be obtained commercially from Aldrich Chemical Co., Inc., Milwaukee, Wisconsin, and the first part of the syntheses can be dropped. The purity of the two esters is checked by refractometry, infrared spectroscopy, and vapor-phase chromatography and the heats of combustion are determined with a bomb calorimeter. It is suggested that each student in the team synthesize and check the purity of one of the esters and that both work together on the calorimetric measurements. 

Refractor vapor-phase chromatograph infrared spectrometer fume hood steam bath pump for reduced pressure distillation thionyl chloride (30 g) cyclopropanecarbox-ylic acid (7 g) and cyclohexanecarboxylic acid (8 g) or cyclopropanecarboxylic acid chloride (8 g) and cyclohexanecarboxylic acid chloride (9 g) o-butanol (6 g) methanol (4 g) ethyl ether (175 mL) saturated aqueous NaffC03 solution (40 mL) MgS04 CCI4. 

Thionyl chloride is frequently the reagent of choice for the dehydration of higher-molecular-weight amides, since the secondary products are gaseous and the nitrile is more readily purified. Oftentimes, the higher fatty acids are converted to the nitriles in a single operation via the intermediate ammonium salts and amides. For this purpose, dry ammonia gas is passed into the molten acids at 290-300° the yields of nitriles are excellent (80-85%). A small amount of 85% phosphoric acid appreciably reduces the reaction time. Another procedure consists in passing the acid vapors mixed with ammonia over silica gel at 500°. This technique... 

The most satisfactory method, which can also be used to prepare gram quantities, is to heat the vacuum-dried hydrous oxide in a sealed, evacuated Pyrex reaction vessel with thionyl chloride vapor at 350°-500°C, the volatile, yellow pentachloride (m.p. 306°C) being obtained in better than 95% yield (47). Thermal decomposition of SO(PaCl6)2 is less satisfactory (15) and only gives a partial yield of the pentachloride, leaving an unidentified black residue. 

For chlorination in the liquid phase, chlorine gas is led into the liquid and is dispersed in the form of fine bubbles. In most chlorina-tions heat and a catalyst are employed. Phosphorus and its halides, sulfur and its halides, iron, aluminum chloride, antimony chloride, and iodine are among the common catalysts used for chlorinations. For laboratory use red phosphorus, iron, and thionyl chloride give good results. Aluminum chloride (or aluminum-mercury couple), although a very efficient catalyst, clogs the disperser. The use of actinic light is sometimes used to promote chlorination in the liquid phase, and is extensively used in the vapor phase. The action of the catalysts is assumed to activate a few chlorine molecules which initiate chain reactions. For example, in the chlorination of benzene the reaction begins with the dissociation of a few molecules of chlorine to atoms ... 

Manufacture Pure sulfur trioxide is industrially produced from oleum by distillation in stainless steel falling film evaporators or forced circulation evaporators and liquefaction of the vapor, in which a minimum temperature of 27 °C must be respected to prevent solidification of sulfur trioxide. The formation of solid sulfur trioxide modifications during longer transport times is hindered by the removal of water and the addition of stabilizers such as thionyl chloride or oxalyl chloride. 

Hygroscopic, bright yellow, cryst solid. Monoclinic or triclinic. Hydrolyzed by moist air, forming a white solid of indefinite composition, mp ca 300 (in chlorine), turns scarlet red at 350. bp 390. Vapors are purple-brown, turning blue-green above 500. Sol in water (fairly slow hydrolysis). Freely sol in hydochloric acid, thionyl chloride. Moderately sol in ethanol, acetone. Dec by dil nitric acid. Forms s complex with two moles of tributyl phosphate. 

The cells of lithium-sulfur dioxide system are largely similar to thionyl chloride-lithium cells. Similar to thionyl chloride, liquefied SO2 can simultaneously play the role of an oxidant and a solvent. However, the vapor pressure over liquefied SO2 is much higher than the vapor pressure over thionyl chloride, and dielectric permeability of SO2 is, on the contrary, lower than that of thionyl chloride. It is for this reason that the solvent used is not pure SO2, but its mixture with acetonitrile or acetonitrile and propylene carbonate. The lithium salt used is commonly bromide and, in some variants, chloroaluminate, perchlorate, tetrafluoroborate, orhexafluoroarsenate. 

Place 1.81 g (0.0133 mol) of m-toluic acid (3-methybenzoic acid, MW = 136.1) into a dry 25-mL round-bottom flask. Add 1 mL of anhydrous diethyl ether to wet the solid (it will not dissolve), and place a stir bar in the flask. In a hood, carefully add 2.0 mL of thionyl chloride (0.0275 mol, density = 1.64 g/mL, MW 118.9) from a plastic Pasteur pipette. Thionyl chloride is a nasty substance, so be careful not to breathe in the vapors Add 5 drops of pyridine. At this point, you should observe a rapid reaction with evolution of gases. Lightly stopper the flask. The reaction will liberate sulfur dioxide and hydrogen chloride, so make sure that the flask is kept in a well-ventilated hood. Stir the mixture for about 10 minutes. During the course of the reaction period, the solid... 

The thionyl chloride is kept in a hood. Do not breathe the vapors of this noxious and corrosive chemical. Use dry equipment when handling this material because it reacts violently with water. Do not get it on your skin. 

A typical use of these reagents is the reaction of 1-heptanol (101) with thionyl chloride. After refluxing for 4 hours, 1-chloroheptane (102) is isolated in 77% yield,and the by-products of the reaction are HCI and srdfur dioxide (SO2). This is clearly a substitution reaction in which the OH unit is replaced by Cl. The term reflux indicates that the reaction is heated at the boiling point of the mixture, and the vapors are condensed and returned to the flask rather than condensed and removed as in a normal distillation. Clearly, the Cl comes from SOCI2, but the substitution requires loss of the OH unit. Presumably, OH is converted to a leaving group. 

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