ベンゼンスルホニルクロリド 化学特性,用途語,生産方法
外観
無色～わずかにうすい黄色, 澄明の液体
溶解性
水に難溶, エタノール, アセトンに易溶。エタノール及びアセトンに極めて溶けやすく、水にほとんど溶けない。
用途
ベンゼンスルホニル化剤および第一、第二、第三アミン類のヒンスベルク(HINSBERG)分離に用る。
使用上の注意
アルゴン封入
化学的特性
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.
使用
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.
調製方法
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-SO
3H→ArSO
3H+HCl
ArSO
3H+Cl-SO
3H=ArSO
2Cl+H
2SO
4
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.
一般的な説明
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.
空気と水の反応
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.
反応プロフィール
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].
健康ハザード
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.
安全性プロファイル
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
職業ばく露
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.
輸送方法
UN2225 Benzene sulfonyl chloride, Hazard
class: 8; Labels: 8—Corrosive material.
純化方法
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.
不和合性
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.
ベンゼンスルホニルクロリド 上流と下流の製品情報
原材料
準備製品
2-(2,3-Dihydro-1benzenesulfonyl-pyrrolo[2,3-b]pyridin-3-yl)ethanamine
スルファサラジン
2-メチル-4-ニトロベンゼンジアゾニウム
(トリフルオロメチル)トリメチルシラン
17-ヒドロキシプレグナ-4,9(11)-ジエン-3,20-ジオン
2-(2-クロロエトキシ)ベンゼンスルホンアミド
ジベンゼンスルホンイミド
スルファキノキサリン
ベンゼンチオール
16α,17α-エポキシプレグナ-4,9(11)-ジエン-3,20-ジオン
ベンゼンスルホンアミド
2-メチル-3-ニトロアニリン
ベンゼンスルホニルヒドラジド
ベンゼンチオスルホン酸S-ナトリウム
ジチオりん酸=O-エチル=S,S-ジフェニル
2,4-ジクロロ-5-スルファモイル安息香酸
dimethyl p-octadecyl phenylsulfonyl amino propyl ammoium propylsulfonate
p-トルエンスルホニルクロリド
Acid Yellow 79
2-メチル-4-ニトロアニリン
2-(2,3-Dihydro-1-benzenesulfonyl-pyrrolo[2,3-b]pyridin-3-yl)acetonitrile
8,18-ジクロロ-5,15-ジエチル-5,15-ジヒドロジインドロ[3,2-b:3',2'-m]トリフェノジオキサジン
リュープロレリン
(フェニルスルホニル)アザイド
1-(フェニルスルホニル)-1H-インドール-2-カルバルデヒド
4-ベンゼンスルフィン酸ナトリウム
4-メチル-2-ニトロアニリン
2,5-ジクロロピリジン