Benzenesulfonyl chloride

Description

Benzenesulfonyl chloride is a colorless oilyliquid with a pungent odor. Molecular weight= 176.6;Specific gravity= 1.3842 at 15℃; Boilingpoint = 251- 252℃ (decomposes); Freezing/Meltingpoint= 15℃; Vapor pressure= 1 mmHg at 20℃; Relativevapor density (air=1) = 6.12; Flash point =130℃;Autoignition point = 460℃. Hazard Identification (based onNFPA-704 M Rating System): Health 3, Flammability 1,Reactivity 1. Moderately soluble in water.

Chemical properties

Benzenesulfonyl chloride is a colorless oily liquid with a pungent odor. Insoluble in water, soluble in ethanol and ether. Can react with ammonia, amine and alcohol to produce benzenesulfonamide and benzene sulfonate respectively. It is toxic, irritates skin, eyes and mucous membranes, corrosive, and can cause burns. Oral LD50 1960mg/kg in rats.

The Uses of Benzenesulfonyl chloride

Benzenesulfonyl chloride reacts with Grignard reagents to form oxindoles from N-unsubstituted indoles. It is widely used to check the assay of thiamine in different food products. It is involved in the synthesis of alpha-disulfones, sulfonamides and sulfoante esters as precursor. It is a derivatization reagent for the determination of various amines in waste water and surface water at the sub-ppb level by gas chromatography-mass spectrometry. It is common reagent used in Hinsberg test for detection and distinguishing the type of amines as primary, secondary and tertiary amines.

The Uses of Benzenesulfonyl chloride

Benzenesulfonyl chloride may be used in thiamine assay for determination of thiamine in different food products.

The Uses of Benzenesulfonyl chloride

Intermediates of Liquid Crystals

Production Methods

The most convenient method for the production of benzenesulfonyl chlorides is the chlorosulfonation reaction of benzene or substituted benzene with chlorosulfuric acid. Sulfonation and formation of the sulfonyl chlo- ride take place in one reaction sequence:
Ar-H+Cl-SO₃H→ArSO₃H+HCl
ArSO₃H+Cl-SO₃H=ArSO₂Cl+H₂SO₄
Sulfone is formed in a side reaction of the chlorosulfonation. The amount of sulfone formation can be reduced by diluting with a solvent, by using a large excess of chlorosulfuric acid, or by adding sulfone-inhibiting substances, e.g., alkali metal and ammonium salts, acetic acid, phosphoric acid, dimethylformamide, or amidosulfuric acid.
For industrial chlorosulfonation the chlorosulfuric acid is introduced into a cast-steel or enameled steel vessel and 10 – 25 mol% of the aromatic compound is stirred in at 25 – 30 ℃, whereupon sulfonation of the aromatic compound and HCl formation occur. The formation of sulfonyl chloride is initiated by heating the reactants to 50 – 80 ℃. The reaction is exothermic. The sulfonyl chloride is isolated by draining the reaction mass onto water and simultaneous cooling. Excess chlorosulfuric acid is decomposed, and the sulfonyl chloride either precipitates or separates as an organic liquid phase. The quality of the chlorosulfuric acid affects the yield.
Other chlorinating agents, such as phosgene, thionyl chloride, sulfuryl chloride, or phosphorus pentachloride, can be used instead of chlorosulfu- ricacid. When thionyl chloride is used the sulfonyl chloride is obtained from the sulfonic acid in high yield and without formation of sulfuric acid.

General Description

A colorless to slightly yellow solid that melts at approximately 40°F. Very irritating to skin, eyes and mucous membranes. May emit toxic fumes when heated to high temperatures. Used to make dyes and other chemicals.

Air & Water Reactions

Insoluble and stable in cold water [Merck]. Decomposes in hot water to produce corrosive and toxic hydrochloric acid and benzenesulfonic acid. Rate of reaction decreases as temperature decreases.

Reactivity Profile

Benzenesulfonyl chloride is incompatible with strong oxidizing agents and bases, including amines. Corrodes metals in the presence of water due to slow formation of hydrochloric acid and benzenesulfonic acid [USCG, 1999]. May react vigorously or explosively if mixed with diisopropyl ether or other ethers in the presence of trace amounts of metal salts [J. Haz. Mat., 1981, 4, 291].

Health Hazard

May be fatal if inhaled, swallowed or absorbed through skin. Contact may cause skin and eye burns. Irritating to eyes, skin and mucous membranes. INGESTION: May cause abdominal spasm and vomiting.

Safety Profile

Poison by intraperitoneal route. Adangerous storage hazard. It may explode in a sealedbottle. Explosive reaction with dimethyl sulfoxide. Reactsvigorously with methyl formamide. When heated todecomposition it emits toxic fumes of Cl^- and SO

Potential Exposure

It is used as a chemical intermediate for benzenesulfonamides, thiophenol, glybuzole (hypoglycemic agent), N-2-chloroehtylamides, benzonitrile; for its esters-useful as insecticides, and miticides.

First aid

If this chemical gets into the eyes, remove anycontact lenses at once and irrigate immediately for at least15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts theskin, remove contaminated clothing and wash immediatelywith soap and water. Seek medical attention immediately. Ifthis chemical has been inhaled, remove from exposure,begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR ifheart action has stopped. Transfer promptly to a medicalfacility. When this chemical has been swallowed, get medical attention. Do not induce vomiting. Medical observationis recommended for 24-
48 h after breathing overexposure,as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a corticosteroid spray.

storage

Color Code—Blue: Health Hazard/Poison: Storein a secure poison location. Store in tightly closed containers in a cool, well-ventilated area. Metal containers involving the transfer of this chemical should be grounded andbonded. Drums must be equipped with self-closing valves,pressure vacuum bungs, and flame arresters. Use only nonsparking tools and equipment, especially when opening andclosing containers of this chemical. Sources of ignition,such as smoking and open flames, are prohibited where thischemical is used, handled, or stored in a manner that couldcreate a potential fire or explosion hazard.

Shipping

UN2225 Benzene sulfonyl chloride, Hazard class: 8; Labels: 8—Corrosive material.

Purification Methods

Distil the sulfonyl chloride, then treat it with 3mole % each of toluene and AlCl3, and allow it to stand overnight. The sulfonyl chloride is distilled off at 1mm pressure and then carefully fractionally distilled at 10mm in an all-glass column. [Adams & Marvel Org Synth Coll Vol I 84 1941, Jensen & Brown J Am Chem Soc 80 4042 1958, Beilstein 11 IV 49.] It is TOXIC.

Incompatibilities

Violent reaction with strong oxidizers, dimethyl sulfoxide, and methyl formamide. It is very reactive with bases and many organic compounds. Incompatible with ammonia, aliphatic amines. Water contact forms hydrochloric and chlorosulfonic acids. Aqueous solutions of this chemical are strong acids that react violently with bases. Attacks metals in presence of moisture.