Thionyl Chloride and Sulfuryl Chloride

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Presentation on Thionyl Chloride and Sulfuryl Chloride reagents used in chemistry.

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Thionyl Chloride and Sulfuryl Chloride

Thionyl Chloride and Sulfuryl ChlorideCompiled By-Karishma Singh12CHY20166-Nov-131Contents:What is Thionyl Chloride?Preparation Method Of Thionyl ChlorideApplicationsMSDSWhat is Sulfuryl Chloride?

6-Nov-132Preparation Method Of Sulfuryl ChlorideApplicationsMSDS

6-Nov-133What is Thionyl Chloride?It is an inorganic compound.It is a colorless liquid with a nauseating pungent smell.Often confused with sulfuryl chloride.Miscible with CCl3,benzene etc.Pyramidal lone pair of electrons at the top

6-Nov-134Preparation Methods Oldest methods of thionyl chloride preparation : reacting PCl5 and SO2 (Scheme 1)

Hallowell and Vaalas process: SO2 and CCl4 or CHCl3, and a Friedel-Crafts catalyst,extreme temperatures (140 to 400 C) and pressure (15 to 200 atm) (Scheme2).

Schudel, J. G.; United States Patent Office, 1931. (No 1.788.959) Hallowell, A. T.; Vaala, G. T.; United States Patent Office, 1946. (No 2.393.247) 6-Nov-135

Pechkas, A.; United States Patent Office, 1947. (No 2.431.823)

Pechkas, A.; United States Patent Office, 1947. (No 2.431.823)

Cicha, W. V.; Manzer, L. E.; United States Patent Office, 1999. (No 5.879.652)6-Nov-136John E. Hill proposed an integrated process that reuses waste from other manufacturing processes and monitors the steps of the industrial production of SOCl2

Hill, J. E.; United States Patent Office, 1996. (No 5.498.400) 6-Nov-137ApplicationsThe most common uses of Thionyl Chloride in chemistry are:the production of acyl chloride and sulfuryl chloride,using the corresponding carboxylic acids and sulphonic acids as a raw material.

6-Nov-138

Mechanism:6-Nov-139Formation of heterocyclic biaryls:

As a condensing agent: Acetanilides react with dialkylformamides 401 in the presence of thionyl chloride as a condensing agent to give the formamidines 402, which are used as acaricides and/or insecticides

J.S. Pizey, K. Symeonides. Phosphorus Sulfur, 8, 1 (1980).

W. Ried, H. Schinzel. Liebigs Ann. Chem., 1569 (1982).6-Nov-1310Formation of sulfides:

Chlorination: The mechanism by which thionyl chloride acts as a chlorinating agent is not fully understood. One possible explanation is that thionyl chloride undergoes oxidation in the presence of atmospheric oxygen to sulfuryl chloride, which is a well known chlorinating agent for organic substances

B.G. Lenz, H. Regling, B. Zwanenburg. Tetrahedron Lett., 25, 5947 (1984).A. Rahman, H. Ila, H. Junjappa. Synthesis, 250 (1984).6-Nov-1311Thionyl Chloride (1) is also used in thionyl chloride-lithium (Li-SOCl2) batteries. In these batteries, the metallic lithium is the anode and the cathode is porous carbon filled with 1. The Li-SOCl2 batteries presents as advantages long storage periods and a service life longer than 10 years.

6-Nov-1312MSDSVery hazardous in case of skin contact (irritant, corrosive, permeator), of eye contact (irritant, corrosive), of ingestion, of inhalation. Skin contact may produce burns. Liquid or spray mist may produce tissue damage particularly on mucous membranes of eyes, mouth and respiratory tract. Inhalation of the spray mist may produce severe irritation of respiratory tract, characterized by coughing, choking, or shortness of breath. Severe overexposure can result in death. Skin inflammation is characterized by itching, scaling, reddening, or occasionally, blistering.6-Nov-1313Precautions:Keep container dry. Keep away from heat ,sources of ignition, direct sunlight or strong incandescent light. Do not ingest/ breathe gas/fumes/ vapour/spray. Never add water to this product. Avoid shock and friction.Keep away from incompatibles such as metals, acids, alkalis, moisture.

6-Nov-1314Storage:Keep container tightly closed. Keep container in a cool.Keep in a well-ventilated area.

Note: It will explode in presence of severalchemicals:Azidoacetylacid,Chlorylperchlorate, N,N-Dimethylformaide,Dimethylsulfoxide etc.6-Nov-1315What is Sulfuryl Chloride?Itis an inorganic compound with the formula SO2Cl2. It is a colourless liquid with a pungent odour. Sulfuryl chloride is not found in nature, as can be inferred from its rapidhydrolysis.sulfuryl chloride is a source ofchlorinewhereas thionyl chloride is a source ofchlorideionsIUPAC name issulfuroyl dichloride.

6-Nov-1316Preparation MethodsItis prepared by the reaction of sulfur dioxide and chlorine in the presence of a catalyst, such as activated carbon.The crude product can be purified by fractional distillation. It is uncommon to prepare SO2Cl2in the laboratory because it is commercially available. Sulfuryl chloride can also be considered a derivative of sulfuric acid.

6-Nov-1317Attack of Sulfuryl Chloride via. Free Radical Mechanism

6-Nov-1318ApplicationsIt is used as a chlorinating and sulfonating agent. Acylation of alcohols and amines, the conversion of carboxylic acid salts to acid chlorides and anhydridesFacilitates of various condensation reactionsIt can be used in asymmetric catalysis.6-Nov-1319Chlorination of Aromatic Nuclei: Although sulfuryl chloride readily chlorinates the more reactive benzenoid derivatives, of which the phenols and amines

Production Of Sulfenyl Chloride: Sulfenyl chlorides are used in the production of agents used in thevulcanizationof rubber.

Silberrad, O., Silberrad, C. A., and Parke, B., Ibki., 127, 1724

Organic ChemistryBy Jonathan Clayden, Nick Greeves, Stuart Warren6-Nov-1320Asymmetric Catalysis: The given Diol is converted into protected amino group using sulfuryl chloride and this also be done using thionyl chloride.

Organic ChemistryBy Jonathan Clayden, Nick Greeves, Stuart Warren6-Nov-1321MSDSExtremely hazardous in case of skin contact (corrosive, irritant, sensitizer), of eye contact (irritant), of ingestion, of inhalation.Liquid or spray mist may produce tissue damage particularly on mucous membranes of eyes, mouth and respiratory tract. Repeated or prolonged exposure to the substance can produce target organs damage6-Nov-1322PrecautionKeep container dry. Do not breathe gas/fumes/ vapour/spray. In case of insufficient ventilation,wear suitable respiratory equipment.Itis toxic and corrosive. Acts as alachrymator.It can form fuming mixtures with water, as well as donor solvents such asDMSOandDMF.6-Nov-1323References:Schudel, J. G.; United States Patent Office, 1931. (No 1.788.959)Hallowell, A. T.; Vaala, G. T.; United States Patent Office, 1946. (No 2.393.247)Pechkas, A.; United States Patent Office, 1947. (No 2.431.823)Cicha, W. V.; Manzer, L. E.; United States Patent Office, 1999. (No 5.879.652)Hill, J. E.; United States Patent Office, 1996. (No 5.498.400

6-Nov-1324J.S. Pizey, K. Symeonides. Phosphorus Sulfur, 8, 1 (1980)W. Ried, H. Schinzel. Liebigs Ann. Chem., 1569 (1982).A. Rahman, H. Ila, H. Junjappa. Synthesis, 250 (1984).B.G. Lenz, H. Regling, B. Zwanenburg. Tetrahedron Lett., 25, 5947 (1984).Silberrad, O., Silberrad, C. A., and Parke, B., Ibki., 127, 1724 Organic Chemistry-By Jonathan Clayden, Nick Greeves, Stuart WarrenIndustrial Preparation Methods of Chemical Solvents and Reagents Virtual Journal of Chemistry ISSN 1984-6835 Volume XX Issue XX

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