塩化チオニル (約1mol/Lジクロロメタン溶液) 化学特性,用途語,生産方法
外観
無色～黄色, 澄明の液体
溶解性
水, エタノールに分解, ベンベン, エーテルに可溶。
解説
SOCl2(118.97)．IUPAC命名法で許される慣用名は二塩化チオニル．付加方式体系名はジクロリドオキシド硫黄．S2Cl2またはSCl2とSO3との反応や，PCl5とSO2との反応などで合成される．室温では，無色，発煙性の刺激臭のある液体．密度1.66 g cm－3(20 ℃)．気体分子はSを頂点とする三方すい型で，S-O1.48 Å，S-Cl2.07 Å．∠Cl-S-O108.0°，∠Cl-S-Cl97.0°．融点－105 ℃，沸点78.8 ℃．140 ℃ 以上で分解してS2Cl2，SO2，Cl2 になる．水とははげしく反応してSO2とHClになる．ベンゼン，クロロホルムなどに可溶．有機合成で，酸化剤や塩素化剤として使われる．たとえば，-OHや-SH基を-Cl基にかえて塩化アシルをつくったり，グリニャール試薬をスルホキシドにかえる作用をする．皮膚，粘膜などをおかす．「塩化チオニル及びこれを含有する製剤」は毒物及び劇物取締法・劇物，「塩化チオニル」は労働安全衛生法・名称等を通知すべき危険物及び有害物，化学兵器禁止法・第2種指定物質-原料物質である．[CAS 7719-09-7]
森北出版「化学辞典（第2版）
用途
有機合成(和光試薬時報Vol.63 No.3,p.27(1995))。
用途
クロル化剤(アルコール性水酸基のクロル化、カルボン酸のクロル化、酸無水物のクロル化、有機スルホン酸?ニトロ化合物のクロル置換)、脱水作用(二重結合の生成、酸無水物の生成、ニトリルの生成)、分子内閉環(トリアジン生成、ピロリドン生成、アミド生成)、クロロスルホン化剤、ベックマン転位
使用上の注意
水で分解し、亜硫酸及び塩酸を生じる。
化学的特性
Colorless to slightly yellow liquid
化学的特性
Thionyl chloride is a pale yellow to reddish liquid. Suffocating odor like sulfur dioxide. Fumes form when exposed to moist air.
物理的性質
Pale yellow to red fuming liquid; suffocating odor; refractive index 1.517 at 20°C; density 1.631 g/mL at 20°C; freezes at -101°C; boils at 75.6°C; decomposes at 140°C; decomposes in water; soluble in benzene, chloroform, and carbon tetrachloride.
使用
Thionyl chloride (SOCl2) is used as a chlorinating agent in
manufacturing organic compounds. It is also used as a
solvent in high-energy lithium batteries.
使用
In the manufacture of
lithium batteries; in the synthesis of herbicides,
surfactants, drugs, vitamins, and dyestuffs.
使用
For making acyl chlorides, to replace OH or SH groups with chlorine atoms; reacts with Grignard reagents to form the corresponding sulfoxides. Review of use in organic synthesis: J. S. Pizey, Synthetic Reagents vol. 1 (John Wiley, New York, 1974) pp 321-357.
製造方法
Sulfurous oxychloride can be prepared by oxidation of sulfur dichloride with sulfur trioxide: SCl
2 + SO
3 → SOCl
2 + SO
2 Also, the compound can be prepared by reacting sulfur dioxide with phosphorus pentachloride: SO
2 + PCl
5 → SOCl
2 + POCl
3.
一般的な説明
A colorless to yellow fuming liquid with a suffocating pungent odor. Boiling point 79°C. A lachrymator. Highly corrosive and toxic. Long-term inhalation of low concentrations or short-term inhalation of high concentrations has adverse health effects.
反応プロフィール
Thionyl chloride reacts, potentially explosively, with dimethyl sulfoxide or dimethylformamide containing traces of iron or zinc [Spitulnik, M. J., Chem. Eng. News, 1977, 55(31), p. 31]. Undergoes violent reactions with bases (ammonia, sodium hydroxide, potassium hydroxide, amines), alkali metals (sodium, potassium), esters (ethyl acetate), toluene mixed with ethanol / water [Bretherick, 5th ed., 1995, p. 1325]. Has an expansion ratio from gas to liquid of nearly 1000:1. Hence may cause an explosion if heated while contained [MCA Case History No. 1808]. 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]. Perchloric acid ignites on contact with sulfinyl chloride. (Bailar, 1973, Vol. 2, 1442). SOCl2 reacts with esters, such as ethyl acetate, forming toxic SO2 gas and water soluble/toxic acyl chlorides, catalyzed by Fe or Zn (Spagnuolo, C.J. et al. 1992. Chemical and Engineering News 70(22):2.).
危険性
Strong irritant to skin, tissue, and upper
respiratory tract.
健康ハザード
CORROSIVE and/or TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. Fire will produce irritating, corrosive and/or toxic gases. Reaction with water may generate much heat that will increase the concentration of fumes in the air. Contact with molten substance may cause severe burns to skin and eyes. Runoff from fire control or dilution water may cause pollution.
火災危険
EXCEPT FOR ACETIC ANHYDRIDE (UN1715), THAT IS FLAMMABLE, some of these materials may burn, but none ignite readily. May ignite combustibles (wood, paper, oil, clothing, etc.). Substance will react with water (some violently), releasing corrosive and/or toxic gases and runoff. Flammable/toxic gases may accumulate in confined areas (basement, tanks, hopper/tank cars, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated or if contaminated with water. Substance may be transported in a molten form.
安全性プロファイル
Moderately toxic by
inhalation. The material itself is more toxic
than sulfur dioxide. Has a pungent odor
similar to that of sulfur dioxide; it fumes
upon exposure to air. Violent reaction with
water releases hydrogen chloride and sulfur
dioxide. Both these decomposition products
constitute serious toxicity hazards. A
corrosive irritant that causes burns to the
skin and eyes. A powerful chlorinating
agent. Potentially explosive reaction with
ammonia, bis(dimethy1amino)sulfoxide -
(above 80℃), chloryl perchlorate, 1,2,3-
cyclohexanetrione trioxime + sulfur dioxide,
dimethyl sulfoxide, hexafluoroisopropylideneaminolithium.
Violent reaction or
ignition with 2,4-hexadiyn-1-6-di01, onitrobenzoyl
acetic acid, o-nitrophenylacetic
acid, sodum (ignites at 300℃).
Incompatible with ammonia, dimethyl
formamide + trace iron or zinc, linseed oil +
quinoline, toluene + ethanol + water. When
heated to decomposition it emits toxic
fumes of SOx and Cl-. See also
HYDROGEN CHLORIDE and SULFUR
DIOXIDE.
職業ばく露
Thionyl chloride is used as specialty chlorinating agent, particularly in preparation of organic acid chlorides; in organic synthesis; as a catalyst.
輸送方法
UN1836 Thionyl chloride, Hazard class: 8; Labels: 8-Corrosive material.
純化方法
Crude SOCl2 can be freed from sulfuryl chloride, sulfur monochloride and sulfur dichloride by refluxing it with sulfur and then fractionally distilling twice. [The SOCl2 is converted to SO2 and sulfur chlorides. The S2Cl2 (b 135.6o) is left in the residue, whereas SCl2 (b 59o) passes over in the forerun.] The usual purification is to distil it from quinoline (50g SOCl2 to 10g quinoline) to remove acid impurities, followed by distillation from boiled linseed oil (50g SOCl2 to 20g of oil). Precautions must be taken to exclude moisture. Thionyl chloride is used extensively in organic syntheses and can be prepared by distillation of technical SOCl2 in the presence of diterpene (12g/250mL SOCl2), and avoiding overheating. Further purification is achieved by redistillation from linseed oil (1-2%) [Rigby Chem Ind (London) 1508 1969]. Gas chromatographically pure material is obtained by distillation from 10% (w/w) triphenyl phosphite [Friedman & Wetter J Chem Soc (A) 36 1967, Larsen et al. J Am Chem Soc 108 6950 1986]. HARMFUL VAPOURS.
不和合性
Reacts violently with water releasing sulfur dioxide and hydrogen chloride. Keep away from water, acids, alcohols, alkalis, ammonia, chloryl perchlorate.
廃棄物の処理
Spray on a thick layer of a (1:1) mixture of dry soda ash and slaked lime behind a shield. After mixing, spray water from an atomizer with great precaution. Transfer slowly into a large amount of water. Neutralize and drain into the sewer with sufficient water.
塩化チオニル (約1mol/Lジクロロメタン溶液) 上流と下流の製品情報
原材料
準備製品
シクロペンタンカルボン酸クロリド
ピリジン-2,6-ジカルボン酸ジクロリド
1-フェノキシ-2-クロロプロパン
塩化5,6-ジクロロピリジン-3-カルボニル
3-フェニル-2-プロペンアミド
クロロメチレンジメチルイミニウムクロリド
スミフィックスターコイズブルーG
o-[1-(1H-イミダゾール-1-イル)ビニル]フェノール
2-ヒドロキシベンゼン酢酸メチル
5,5'-ジクロロ-3,3'-ジニトロビフェニル-2,2'-ジオール
4-エチルベンゾイルクロリド
ピロリジン‐2‐カルボン酸メチル塩酸塩
(2-メチルフェニル)メタンスルホニルクロリド
3,4,5-トリクロロチオフェン-2-カルボニルクロリド
3-アミノ安息香酸メチル
6,8-ジクロロオクタン酸エチルエステル
2-ナフトイルクロリド
3-チオフェンカルボン酸クロリド
2-クロロエチルメチルスルフィド
N,N-ビス(2-クロロエチル)-4-メチルベンゼンスルホンアミド
4-クロロ-2-メチル-N-(ジメチルアミノメチレン)アニリン
6,8-ジクロロオクタン酸エチル
3-クロロプロパン-1-スルホン酸クロリド
(2-フルオロフェニル)メタンスルホニルクロリド
二塩化5アミノ2，4，6トリヨ-ドイソフタロイル
2,5-ジメトキシベンゼン酢酸クロリド
1-ナフトイルクロリド
4-フルオロフェニルアセチルクロリド
3-オキソ-2-[2-(ジエチルアミノ)エチル]酪酸エチル
