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外観
無色～うすい黄色透明液体
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性質
トルイジンはアニリン誘導体の1つで、芳香族アミンの1種です。トルイジンには、o-トルイジンm-トルイジン、および p-トルイジンの3つの異性体が存在します。これらの異性体は、メチル基がアニリン環の異なる位置に結合していることで区別されます。
トルイジンは化学式C7H9N、分子量107.15g/molで表され、水に若干溶ける程度の溶解性を持ちますが、エタノールやエーテル、アセトン等の有機溶媒には良好に溶けます。純粋なトルイジンは、無色または微黄色の結晶または液体ですが、空気中で酸化されると茶色に変色する場合があります。
異性体によって融点と沸点は異なり、常温常圧でo-トルイジンとm-トルイジンは液体、p-トルイジンは固体です。
- o-トルイジン: 融点-23℃、沸点200℃
- m-トルイジン: 融点-30℃、沸点203℃
- p-トルイジン: 融点43℃、沸点200℃
o-トルイジンは発がん性や変異原性が指摘されており、取り扱いに注意が必要です。
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解説
トルイジンとは、ベンゼン環にアミノ基とメチル基がついた構造の芳香族化合物です。
アニリン誘導体の1つで、芳香族アミンの1種です。アミノ基とメチル基の位置関係によってo-トルイジン、m-トルイジン、p-トルイジンの3種類の異性体があります。常温常圧でo-トルイジンとm-トルイジンは液体、p-トルイジンは固体です。
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用途
染料、溶剤
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構造
トルイジンは、アニリン (C6H5NH2) の誘導体であり、芳香族アミンの一種です。化学式はC6H4(CH3)NH2です。
トルイジンには3つの異性体 (o-トルイジン、m-トルイジン、p-トルイジン) が存在します。これらの異性体は、ベンゼン環上の異なる位置にメチル基が結合していることで区別されます。また、ベンゼン環上におけるメチル基とアミノ基の相対的な位置によって、物理的および化学的性質が異なります。
しかし、すべてのトルイジン異性体は芳香族アミンの特性を持ち、酸と反応して塩を形成したり、酸化剤や還元剤と反応したりする性質があります。
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化学的特性
O-Toluidine is a light yellow to reddish brown liquid. On exposure to light and atmospheric air, the compound quickly turns a dark color. The compound has extensive use in a large number of industries around the world. For instance, as an intermediate in the manufacture of azo and indigo dyes, pigments, sulfur dyes, pesticides, pharmaceutical products, rubber and vulcanizing chemicals, and similar products.
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物理的性質
Colorless to pale yellow liquid with an aromatic, aniline-like odor. Becomes reddish-brown on
exposure to air and light. Odor threshold concentration is 250 ppb (quoted, Amoore and Hautala,
1983).
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天然物の起源
O-Toluidine has been reported to be a component of tar produced by low-temperature carbonization of coal and has been detected in gasoline fractions from arlan petroleum, tobacco leaf extracts, and in the aroma components of black tea (Anon. 1972). Patrianakos and Hoffmann (1979) detected it in tobacco smoke. It is a metabolite of prilocaine anesthetic in rats (Akerman et al 1966) and humans (Hjelm et al 1972; Struck et al 1969). It is a possible contaminant of bootleg methaqualone (Goldfarb and Finelli 1974) but is not a methaqualone metabolite (Nowak et al 1966). It is also a metabolite of the dye Poncean 3R (Lindstrom et al 1969).O-Toluidine has been detected as a contaminant in injectables stored in polystyrene (Ahmad, 1982).
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使用
A carcinogenic and toxic aromatic amine contained in hair dye, henna and dyed hair samples.
o-Toluidine, is a methemoglobin-inducing chemical and a human carcinogen. Commercial production of o-toluidine was first reported in the United States in 1922. o-Toluidine and its hydrochloride salt are used primarily as intermediates in the manufacture of dyes and pigments for printing textiles, in color photography, and as biologic stains. In addition, o-toluidine is used as an intermediate for rubber vulcanizing chemicals, pharmaceuticals, and pesticides. Other minor uses include intermediate for organic synthesis and clinical laboratory reagent for glucose analysis (IARC, 2000, 2010; Woo and Lai, 2012).
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定義
ChEBI: An aminotoluene in which the amino substituent is ortho to the methyl group.
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調製方法
The production of O-toluidine is based on the catalytic hydrogenation of O-nitrotoluene or the amination of toluene with methylhydroxylamine in the presence of aluminum trichloride (Windholz 1983). It is available as a technical grade with a minimum of 99.5% purity containing m-toluidine (0.4% maximum) and/or ptoluidine (0.1% maximum) as impurities (Anon. 1978). The stabilized technical grade may also contain less than 0.5% of unidentified stabilizing agents to prevent darkening.
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一般的な説明
A clear colorless or light yellow liquid. May become reddish brown on exposure to air and light. Flash point 185°F. Has about the same density as water and is very slightly soluble in water. Vapors are heavier than air. Confirmed carcinogen.
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空気と水の反応
Becomes reddish brown upon exposure to air and light [Hawley]. Slightly soluble in water.
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反応プロフィール
o-Toluidine neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides. Emits very toxic oxides of nitrogen when heated to decomposition. Undergoes a hypergolic reaction with red fuming nitric acid [Kit and Evered, 1960, p. 239, 242].
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健康ハザード
Exposures to O-toluidine cause toxicity and poisoning to animals and occupational workers. It is highly toxic to animals and humans and is rapidly absorbed by oral, dermal, and inhalation by mammals. The acute oral LD50 to rats ranges from 900 to 940 mg/kg. The compound is known to cause adverse effects in workers, which include headache, irritation of skin, eye, kidneys, bladder, and hematuria. O-Toluidine has caused hepatocellular adenoma and carcinoma in experimental laboratory mice and rats. Occupational workers exposed to O-toluidine have also demonstrated bladder cancer although the role of aniline cannot be ruled out. However, the IARC working group, because of insuffi cient data, classify O-toluidine as a Group 2B agent, meaning possibly carcinogenic to humans, while the NIOSH classify this compound as an occupational carcinogen, and the ACGIH label it as a suspected human carcinogen under A2 class.
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火災危険
Special Hazards of Combustion Products: Toxic oxides of nitrogen and flammable vapors may form in fire.
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規制
トルイジンの規制
o-トルイジン
- 労働安全衛生法: 特定化学物質第2類
- 労働基準法: 疾病化学物質
- 毒物及び劇物取締法: 劇物
- PRTR法: 第1種指定化学物質
p-トルイジン
- 労働安全衛生法: 名称等を表示・通知すべき危険物及び有害物
- 毒物及び劇物取締法: 劇物
- PRTR法: 第1種指定化学物質
m-トルイジン
- 労働安全衛生法: 名称等を通知・表示すべき危険物及び有害物質
- 労働基準法: 疾病化学物質
- 毒物及び劇物取締法: 劇物
- 消防法: 第4類引火性液体・第三石油類非水溶性液体
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使用用途
トルイジンは、主に化学合成の中間体として使用され、さまざまな産業分野で応用されます。
例えば、o-トルイジンはトルイジンブルーという染料の原料として用いられます。トルイジンブルーはo-トルイジン、チアジン、を原料とした青色の塩基性染料です。
繊維の染色には不向きですが、負の電荷を帯びた物質を染色しやすく、生体材料の染色に用いられます。特に、軟骨細胞の染色や多糖類の染色にはトルイジンブルーが用いられることが多いです。また、植物の染色に用いられることも多く、維管束の観察などの際にはトルイジンブルーが用いられます。
その他、医薬品合成、ゴム加硫剤などの原料としても有用です。
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化学反応性
Reactivity with Water: No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
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工業用途
O-Toluidine is used as an intermediate of the manufacturing of triphenylmethane dyes and safranine colors (Northcott 1978; Windholz 1983). It is an antioxidant in rubber manufacturing and a pharmaceutical intermediate. It has been used as a laboratory reagent in glucose analysis and also used in the preparation of ion exchange resins and making various colors fast to acid.
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安全性プロファイル
Confirmed carcinogen
with experimental neoplastigenic and
tumorigenic data. Poison by ingestion and
intraperitoneal routes. Moderately toxic by
skin contact. Human systemic effects by
inhalation: urine volume increase, hematuria,
and blood methemoglobinemiacarboxyhemoglobinemia.
An experimental
teratogen. Human mutation data reported. A
skin and severe eye irritant. Human mucous
membrane effects. Can produce severe
systemic disturbances. The main portal of
entry into the body is the respiratory tract,
particularly in cases of industrial exposure.
The symptoms produced are headache,
weakness, difficulty in breathing, air hunger,
psychic dsturbances, and marked irritation
of the kidneys and bladder. The literature
does not yield any good data for comparing
the toxicity of the o-, m-, and p-isomers.
Their behavior is generally comparable to
that of aniline. It has been determined
experimentally that a concentration of about
100 ppm is the maximum endurable for 1
hour without serious consequences and that
6-23 ppm is endurable for several hours
without serious disturbances.
Flammable when exposed to heat or
flame. Hypergolic reaction with red fuming
nitric acid. Can react with oxidizing
materials. To fight fire, use foam, CO2, dry
chemical. When heated to decomposition it
emits highly toxic fumes of NOx. See also
ANILINE.
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職業ばく露
o-Toluidine is used as an intermediate in the manufacture of dyes; as an intermediate in pharmaceutical manufacture; in textile printing; in rubber accelerators; in production of o-aminoazotoluene
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発がん性
o-Toluidine and o-toluidine hydrochloride are reasonably anticipatedto be human carcinogens based on sufficient evidence of carcinogenicity from studies in experimental animals.
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製造方法
トルイジンの製造方法
トルイジンは、主に以下の方法で製造されます。
ニトロトルエンの還元
トルイジンの製造の一般的な方法は、ニトロトルエンの還元です。ニトロトルエンの還元は、鉄粉や亜鉛粉と酸を用いた化学還元、あるいは触媒を用いた水素化還元によって行われます。
アニリンからの合成
トルイジンは、アニリンからも合成することができます。アニリンにフリーデル・クラフツ縮合反応を利用してアルキル基を導入することで、トルイジンが得られます。
この方法では、触媒としてアルミニウムクロリド (AlCl3) や鉄 (III) クロリド (FeCl3) が用いられます。また、反応には適切なアルキル化剤が必要で、例えば塩化メチル (CH3Cl) や塩化エチル (C2H5Cl) が使用されます。
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環境運命予測
Biological. Heukelekian and Rand (1955) reported a 5-d BOD value of 1.40 g/g which is 55.1%
of the ThOD value of 2.54 g/g.
Chemical/Physical. Kanno et al. (1982) studied the aqueous reaction of o-toluidine and other
substituted aromatic hydrocarbons (aniline, toluidine, 1- and 2-naphthylamine, phenol, cresol,
pyrocatechol, resorcinol, hydroquinone, and 1-naphthol) with hypochlorous acid in the presence of
ammonium ion. They reported that the aromatic ring was not chlorinated as expected but was
cleaved by chloramine forming cyanogen chloride. As the pH was lowered, the amount of
cyanogen chloride formed increased (Kanno et al., 1982).
o-Toluidine will not hydrolyze because it does not contain a hydrolyzable functional group
(Kollig, 1993).
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代謝
Absorption of O-toluidine from the gastrointestinal tract in rats is rapid with peak blood values at 1 h; blood values were near zero in 24 h (Sencyuk and Rucinska 1984a). The urine was the main excretory route; > 92% in 24 h (Cheever et al 1980). At an oral dose of 20 mg/kg, 26% was excreted in the urine in 24 h as O-toluidine (Senczuk and Rucinska 1984b). Kulkarni et al (1983) demonstrated that N-hydroxy-O-toluidine and O-nitrosotoluene are urinary metabolites of otoluidine. Other urinary metabolites in rats have included conjugated aminomethylphenols (Cheever et al 1980), azoxytoluene, N-acetyl-O-toluidine, N-acetyl-oaminobenzylalcohol, 4-amino-m-cresol, N-acetyl-4-amino-m-cresol, anthranilic acid, N-acetylanthranilic acid (Son et al 1980). Sulfate conjugates predominate over glucuronides by a ratio of 6:1. Thus, in rats, the major metabolic routes are N-acetylation and 4-hydroxylation. Human urinary metabolites (after administration of prilocaine) included O-toluidine,P-hydroxy-O-toluidine, and O-hydroxy-toluidine (Hjelm et al 1972). The primary metabolism of O-toluidine takes place in the endoplasmic reticulum. Exposure to O-toluidine enhances the microsomal activity of aryl hydrocarbon hydroxylase (particularly in kidney), NADPH-cyto-chrome c reductase and the content of cytochrome P-450 (Gnojkowski et al 1984).
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輸送方法
UN1708 Toluidines, liquid, Hazard Class: 6.1; Labels: 6.1-Poisonous materials.
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純化方法
In general, methods similar to those for purifying aniline can be used, e.g. distillation from zinc dust, at reduced pressure, under nitrogen. Berliner and May [J Am Chem Soc 49 1007 1927] purified it via the oxalate. Twice-distilled o-toluidine is dissolved in four times its volume of diethyl ether, and the equivalent amount of oxalic acid needed to form the dioxalate is added as its solution in diethyl ether. (If p-toluidine is present, its oxalate precipitates and can be removed by filtration.) Evaporation of the ethereal solution gives crystals of o-toluidine dioxalate [Beilstein 12 III 1494, 12 IV 1817]. These are filtered off, recrystallised five times from water containing a small amount of oxalic acid (to prevent hydrolysis), then treated with dilute aqueous Na2CO3 to liberate the amine which is separated, dried (CaCl2) and distilled under reduced pressure. The benzoyl derivative has m 144o (from EtOH). [Beilstein 12 H 772, 12 I 372, 12 II 429, 12 III 1837, 12 IV 1744.]
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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.
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廃棄物の処理
Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Controlled incineration (oxides of nitrogen are removed from the effluent gas by scrubbers and/or thermal devices).
