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Thionyl Chloride and Sulfuryl

ChlorideCompiled By-

Karishma Singh

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Contents:

• What is Thionyl Chloride?

• Preparation Method Of Thionyl Chloride

• Applications………

• MSDS

• What is Sulfuryl Chloride?

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• Preparation Method Of Sulfuryl Chloride

• Applications………

• MSDS

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What 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

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Preparation Methods

1. Oldest methods of thionyl chloride preparation : reacting PCl5 and SO2 (Scheme 1)

2. Hallowell and Vaala’s 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)

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• Using sulfur chloride (SCl2), Cl2, and sulfuric acid (H2SO4), drawbacks are the formation of SO2 and hydrochloric acid (HCl) (Scheme 4)

• Reacting SO, Cl2 and S2Cl2 or SCl2, activated carbon as catalyst (Scheme 5).

• SO2, Cl2 and different carbon sources (e.g., wood, bone, coal, and sugar), containing activated metals after treatment with hydrochloric acid as a catalyst, SO2can be produced in good yields (Scheme 6).

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)

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• John 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)

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Applications……

• The 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.

R

O

OH

S

O

Cl Cl

R

O

ClSO2 HCl

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O

RO

H

ClS

Cl

O O

R OS

Cl

OH

Cl

O

OS

Cl

O

R

O

ORS

O

Cl

H Cl

O

OS

O

Cl

R

H

Cl

O

OS

O

Cl

RCl

H

R

ClO

H Cl

S

OO

unstable intermediate

Mechanism:

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• Formation 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

S Li SOCl2

S STHF

195K,15min 30%

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

O

HN R3Ar

O CH

NR1

R2

SOCL2

70-90%N C

HAr N

R1

R2

a;Ar=2,4-Me(Cl)C6H3, Ph;R1=R2=Meb;Ar=2,4-Cl2C6H3;R1=CH2SMe;R2=Me

c;Ar=2MeC6H4;R1=Et;R2=H;R3=Me,CH2ClW. Ried, H. Schinzel. Liebigs Ann. Chem., 1569 (1982). 6-Nov-13

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• Formation 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

N

N

NN

N

N

NN ClSOCl2

N

N

NN Cl

Cl

85%

63%

SOCl2

O

HN

S

SOCl2

O

N

S O

N

benzene(dry)

B.G. Lenz, H. Regling, B. Zwanenburg. Tetrahedron Lett., 25, 5947 (1984).

A. Rahman, H. Ila, H. Junjappa. Synthesis, 250 (1984).

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• Thionyl 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.

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MSDS

• Very 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.

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Precautions:

• 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.

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Storage:

• 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.

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What is Sulfuryl Chloride?

• It is 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 rapid hydrolysis.

• sulfuryl chloride is a source of chlorine whereas thionyl chloride is a source of chloride ions

• IUPAC name is sulfuroyl dichloride.6-Nov-13

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Preparation Methods

• It is 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 SO2Cl2 in the laboratory because it is commercially available.

• Sulfuryl chloride can also be considered a derivative of sulfuric acid.

SO2 + Cl2 SO2Cl26-Nov-13

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Attack of Sulfuryl Chloride via. Free Radical Mechanism

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Applications……………

• It is used as a chlorinating and sulfonating agent.

• Acylation of alcohols and amines, the conversion of carboxylic acid salts to acid chlorides and anhydrides

• Facilitates of various condensation reactions

• It can be used in asymmetric catalysis.

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• Chlorination 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 the vulcanization of rubber.

CH3

OH

CH3

OH

ClCl2SO2Cl2

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

Organic Chemistry By Jonathan Clayden, Nick Greeves, Stuart Warren

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• Asymmetric Catalysis: The given Diol is converted into protected amino group using sulfuryl chloride and this also be done using thionyl chloride.

Organic Chemistry By Jonathan Clayden, Nick Greeves, Stuart Warren

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MSDS

• Extremely 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 damage

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Precaution

• Keep container dry.

• Do not breathe gas/fumes/ vapour/spray.

• In case of insufficient ventilation,wear suitable respiratory equipment.

• It is toxic and corrosive.

• Acts as a lachrymator.

• It can form fuming mixtures with water, as well as donor solvents such as DMSO and DMF.

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References:

• 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

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• J.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 Warren

• Industrial Preparation Methods of Chemical Solvents and Reagents Virtual Journal of Chemistry ISSN 1984-6835 Volume XX Issue XX

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