イソチオシアン酸アリル

外観

無色～黄褐色, 澄明の液体

溶解性

水に難溶。エタノール, アセトン, 有機溶媒に易溶。エタノール及びアセトンに極めて溶けやすく、水に溶けにくい。

解説

C4H5NS(99.15)．CH2=CHCH2N=C=S．天然のカラシ油の主成分であり，タマネギの辛味の成分でもある．p-トルエンスルホン酸アリルエステルにチオシアン酸カリウムを作用させると得られる．一般には，塩化アリルとチオシアン酸カリウムより合成されるチオシアン酸アリルの転位反応により得られる．凝固点－80 ℃，沸点152 ℃．d²⁰ 1.015．n²⁰_D 1.526．水に難溶，有機溶媒に易溶．活性なイソチオシアナート基(-N=C=S)をもつので，各種の求核剤と反応する．アンモニアを付加すると，チオ尿素誘導体となる．調味料，防腐剤として広く利用され，医薬品にも使用される．LD50 339 mg/kg(ラット，経口)．[CAS 57-06-7]
森北出版「化学辞典（第2版）

用途

マスタードの揮発性油の主要成分。戦争ガス。

効能

忌避剤

使用上の注意

不活性ガス封入

化学的特性

Allyl Isothiocyanate is the main component of mustard oil (>95%). It is a highly flammable, colorless to pale yellow, oily liquid with a typical mustard odor. Exposure to air might cause it to darken. It has a pungent, irritating smell and a bitter taste that can cause lacrimatory. It can be synthesized by reacting allyl chloride with alkaline-earth or alkali rhodanides.

天然物の起源

In the essential oil from seeds of Brassica nigra Koch, Brassica juncea Hook. and Thoms., and Thlaspi arvense; in the essential oil from roots of Cochlearia armoracia; in the seeds and roots of Alliaria officinalis; in onion juice; and in the seeds of various Cruciferae. Reported found in pineapple (Anans comoscus), raw cabbage, cooked cabbage, sauerkraut, milk, heated beans, horseradish (Armoracia lapathifolia), raw cauliflower, Brussels sprouts, turnip, Chinese cabbage, wasabi (Japanese horseradish) (Wasabi japonica).

使用

Allyl isothiocyanate, also known as mustard oil, is a synthetic flavoring agent that is used as an artificial oil of mustard and as an imitation horseradish flavor with application in condiments, meats, and pickles at 87 ppm. It has additional applications as an antiseptic, antiamebic, manufacture of flavors and war gas.

製造方法

By distillation of sodium thiocyanate and allyl chloride

一般的な説明

A colorless to pale-yellow oily liquid with an irritating odor. Flash point 135°F. Boiling point 300°F. Poisonous by ingestion and skin absorption. Emits toxic fumes when heated to high temperature. Insoluble in water and slightly denser than water. Hence sinks in water. Used to make other chemicals and as a fumigant. It should be stored in glass containers.

空気と水の反応

Flammable. Insoluble in water.

反応プロフィール

A routine preparation by interaction of allyl chloride and sodium thiocyanate in an autoclave at 5.5 bar exploded violently at the end of the reaction. Peroxides were not present or involved and no other cause could be found, but extensive decomposition occurred when allyl isothiocyanate was heated to 250°C. in glass ampoules [Ind. Eng. Chem. 1941:19 1408].

危険性

Toxic via ingestion, inhalation, skin con- tact; fire risk. Questionable carcinogen.

健康ハザード

TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. Bromoacetates and chloroacetates are extremely irritating/lachrymators. Reaction with water or moist air will release toxic, corrosive or flammable gases. Reaction with water may generate much heat that will increase the concentration of fumes in the air. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

火災危険

HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapors may travel to source of ignition and flash back. Substance will react with water (some violently) releasing flammable, toxic or corrosive gases and runoff. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated or if contaminated with water.

接触アレルゲン

Allyl isothiocyanate is generated by enzymatic hydrolysis of the glucoside sinigrin, present in Cruciferae- Brassicaceae, mainly the oil from black mustard seed (Brassica nigra Koch). It may induce irritant and sometimes allergic contact dermatitis, mimicking the “tulip finger” dermatitis.

抗がん研究

This compound was tested on Ehrlich ascites tumor cells transplanted in Swissalbino mice using HEK293 cells as control. There was a significantly reduced ascitessecretion and tumor cell proliferation. Also the vascular endothelial growth factorexpression was inhibited. The apoptosis was induced in tumor cells, and cellcycle was arrested at G1 phase (Ichwan et al. 2014).

安全性プロファイル

Suspected carcinogen with experimental neoplastigenic and tumorigenic data. Poison by ingestion, skin contact, intravenous, subcutaneous, and intraperitoneal routes. Experimental teratogenic and reproductive effects. An eye irritant. An allergen. May cause contact dermatitis. Mutation data reported. A flammable liquid. Highly reactive. When heated to decomposition (above 250') or on contact with acid or acid fumes it emits highly toxic fumes of CN-, SO,, and NOx. To fight fire, use foam, CO2, dry chemical. See also ALLYL COMPOUNDS and ESTERS.

職業ばく露

Used in fumigants, veterinary drugs, ointments and counter irritants, mustard plasters, and as a flavoring agent.

輸送方法

UN1545 Allyl isothiocyanate, stabilized, Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 3 flammable liquids.

純化方法

Fractionate the isothiocyanate using an efficient column, preferably in a vacuum. It is a yellow pungent, irritating and TOXIC (suspected CARCINOGEN) liquid. Store it in a sealed tube under N2. The N'-benzylthiourea derivative has m 94.5o (from aqueous EtOH) [Weller et al. J Am Chem Soc 74 1104 1952]. [Beilstein 4 IV 1081.]

不和合性

Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides, alcohols, amines