ニトロベンゼン 化学特性,用途語,生産方法
外観
無色～うすい黄色, 澄明の液体
溶解性
水に微溶 (0.2g/100ml水), アルコール, ベンゼンに易溶。エタノール及びジエチルエーテルには極めて溶けやすく、水にはほとんど溶けない。
反応
ニトロベンゼンは濃硫酸と発煙硝酸によってさらにニトロ化され、メタ-ジニトロベンゼン（1,3-）となります。また、ニトロベンゼンを酸性で還元するととなります。応用例として、ニトロベンゼン、、アニリン、からが生成する反応があり、Skraupキノリン合成と呼ばれています。
解説
C6H5NO2(123.11)．ベンゼンを混酸でニトロ化すると得られる．芳香族ニトロ化合物の一つ。ニトロベンゾールともいう。アーモンドのような甘い香気をもつ淡黄色の液体で、水に難溶、有機溶媒に可溶。過剰のベンゼンを混酸（硝酸28％、硫酸57％、水15％）と70℃以下で反応させれば得られる。淡黄色の油．融点5.7 ℃，沸点210.9 ℃．d420"1.20．nD20"1.55296．蒸気および液体はヒトに有毒で，チアノーゼを起こす．大部分の有機溶媒とまざるが，水に難溶．酸性および中性で還元すればアニリンが，アルカリ性で還元すればアゾキシベンゼン，アゾベンゼンを経てヒドラゾベンゼンが得られる．森北出版「化学辞典（第2版）
用途
アニリン原料,M-ジニトロベンゼン原料,M-クロロニトロベンゼン原料,M-ニトロベンゼンスルホン酸原料,染料?香料中間体 (NITE CHRIP)
用途
化学品の製造用途。化学品製造工程の中間生成物.
用途
染料中間体原料、香料中間体原料
用途
染料工業において，アニリンの原料として重要性をもつ．また，極性溶媒として，ときには穏やかな酸化剤として用いられることもある．皮膚からの吸収が速く，蒸気も毒性が強い．水には溶けにくいが大部分の有機溶剤に溶ける。吸湿性が強く、水蒸気とともに蒸発する。蒸気は有毒。還元するとアニリンなどになる。アニリンの製造原料として重用されるほか、染料中間体の原料、有機溶剤などに用いられる。ニトロベンゾール。ミルバン油。LD50 640 mg/kg(ラット，経口)．
説明
Nitrobenzene is a greenish-yellow crystal or yellow oily liquid, and is slightly soluble in water. The primary hazard of nitrobenzene is toxicity; however, it is also combustible. The boiling point is about 410°F, the flash point is 190°F, and the ignition temperature is 900°F. The specific gravity is 1.2, which is heavier than water, and the material will sink to the bottom. The vapor density is 4.3, which is heavier than air. Nitrobenzene is toxic by ingestion, inhalation, and skin absorption, with a TLV of 1 ppm in air. The four-digit UN identification number is 1652. The NFPA 704 designation is health 3, flammability 2, and reactivity 1. Nitrobenzene is a nitro hydrocarbon derivative, but it is not very explosive. The primary uses are as a solvent, an ingredient of metal polishes and shoe polishes, and in the manufacture of aniline.
化学的特性
Nitrobenzene is a pale yellow to dark brown
oily liquid whose odor resembles bitter almonds (or black
paste shoe polish).
物理的性質
Clear, light yellow to brown, oily liquid with an almond-like or shoe polish odor. May darken on
exposure to air. An experimentally determined odor threshold concentration of 4.7 ppb
v was
reported by Leonardos et al. (1969). A detection odor threshold concentration of 9.6 mg/m
3 (1.9
ppmv) was determined by Katz and Talbert (1930).
使用
Nitrobenzene is an organic compound used a standard for detection and analyses as well as its removal from the environment. The compound’s cytotoxic effects have been studied in a hepatocarcinoma cell line.
定義
nitrobenzene: A yellow oily liquid,C
6H
5NO
2; r.d. 1.2; m.p. 6°C; b.p.211°C. It is made by the nitration ofbenzene using a mixture of nitricand sulphuric acids.
調製方法
Nitrobenzene is produced by the direct nitration of benzene with a mixture of
sulfuric and nitric acids. U.S. capacity for nitrobenzene production is approximately
1.5 billion pounds . The most important use for
nitrobenzene is in the production of aniline. Nearly 98% of the nitrobenzene
produced in the U.S. is converted to aniline.
製造方法
Nitrobenzene is produced commercially by the exothermic nitration of benzene with fuming nitric acid in the presence of a sulfuric acid catalyst at 50 to 65℃. The crude nitrobenzene is passed through washer-separators to remove residual acid and is then distilled to remove benzene and water.
空気と水の反応
Very slightly soluble in water.
反応プロフィール
Aluminum chloride added to Nitrobenzene containing about 5% phenol caused a violent explosion [Chem. Eng. News 31:4915. 1953]. Heating a mixture of Nitrobenzene, flake sodium hydroxide and a little water led to an explosion, discussed in [Bretherick's 5th ed. 1995]. Mixed with oxidants, i.e. dinitrogen tetraoxide, fluorodinitromethane, nitric acid, peroxodisulfuric acid, sodium chlorate, tetranitromethane, uranium perchlorate, etc., forms highly sensitive explosive, [Bretherick 5th ed, 1995]. Heated mixtures of Nitrobenzene and tin(IV) chloride produce exothermic decomposition with gas production [Bretherick, 5th Ed., 1995].
危険性
Toxic by ingestion, inhalation, and skin
absorption. Methemoglobinemia. Possible carcinogen.
健康ハザード
The routes of entry of nitrobenzene intothe body are the inhalation of its vaporsor absorption of the liquid or the vaporthrough the skin and, to a much lesserextent, ingestion. The target organs are theblood, liver, kidneys, and cardiovascular system. Piotrowski (1967) estimated that in anexposure period of 6 hours to a concentration of 5 mg/m
3, 18 mg of nitrobenzene wasabsorbed through the lungs and 7 mg throughthe skin in humans. Furthermore, about 80%of inhaled vapor is retained in the respiratorytract. The dermal absorption rate at this concentration level is reported as 1 mg/h, whilethe subcutaneous absorption of the liquidis between 0.2 and 0.3 mg/cm3/h (ACGIH1986).
The symptoms of acute toxicity are headache, dizziness, nausea, vomiting, and dyspnea. Subacute and chronic exposure cancause anemia. Nitrobenzene effects the conversion of hemoglobin to methemoglobin. Itis metabolized to aminophenols and nitrophenols to about 30%, which are excreted.
火災危険
Moderate explosion hazard when exposed to heat or flame. Reacts violently with nitric acid, aluminum trichloride plus phenol, aniline plus glycerine, silver perchlorate and nitrogen tetroxide. Avoid aluminum trichloride; aniline; gycerol; sulfuric acid; oxidants; phosphorus pentachloride; potassium; potassium hydroxide. Avoid sunlight, physical damage to container, freezing, and intense heat.
生成
ニトロベンゼンは、濃硫酸と濃硝酸によって調整された混酸をと反応させて合成可能であり、ニトロ化と呼ばれている。反応段階として、まず混酸によってニトロニウムイオン(NO2+)が活性種として生じ、これがベンゼンと反応することでニトロベンゼンが合成される。この反応は大きな発熱反応を伴い、非常に危険な化学反応の一つである。
使用用途
本物質の主な用途は、医薬、農薬、染料、香料、ゴムなどの合成中間体（アニリン、ベンジジン、キノリン、アゾ 色素）です。酸性および中性で還元すればアニリンが，アルカリ性で還元すればアゾキシベンゼン，を経てヒドラゾベンゼンが得られます。また、ガス（アダムサイト）の原料にもなります。極性溶媒として利用されることもあり，ときには穏やかな酸化剤として用いられることもあります。
生体への影響
毒性は高くはありませんが、液体、蒸気ともに有毒で皮膚からも吸収し、神経系と肝臓の障害および貧血が発生させる恐れがあります。17か月間、職業的に本物質に暴露された結果、頭痛、吐き気、眩暈、脱力感、 足のしびれ感、手足の痛覚過敏、チアノーゼ、低血圧、脾臓腫張、肝臓腫張と圧痛、黄疸な どの神経、肝臓への影響ならびにメトヘモグロビン血症がみられたことが報告されている。
工業用途
Nitrobenzene is mainly utilized for aniline production. The aniline is used primarily
for the manufacture of 4,4'-methylenebis (phenyl isocyanate) and polymers
thereof (50%). The second largest use of aniline is in the manufacture of chemicals
for rubber production (30%). Dyes and dye intermediates, hydroquinone and drugs
account for about 8% of the aniline produced, while 10% of the aniline is
converted to agricultural products such as pesticides and defoliants (Northcott
1978). It also is used as a solvent for cellulose ethers and an ingredient in polishes
for metals and shoes (HSDB 1988).
安全性プロファイル
Confirmed carcinogen.
Human poison by an unspecified route.
Poison experimentally by subcutaneous and
intravenous routes. Moderately toxic by
ingestion, skin contact, and intraperitoneal
routes. Human systemic effects by ingestion:
general anesthetic, respiratory stimulation,
and vascular changes. An experimental
teratogen. Experimental reproductive
effects. Mutation data reported. An eye and
skin irritant. Can cause cyanosis due to
formation of methemoglobin. It is absorbed
rapidly through the skin. The vapors are
hazardous.
to heat and flame. Moderate explosion
hazard when exposed to heat or flame.
Explosive reaction with solid or
concentrated alkali + heat (e.g., sodium
hydroxide or potassium hydroxide),
aluminum chloride + phenol (at 12O°C),
aniline + glycerol + sulfuric acid, nitric +
sulfuric acid + heat. Forms explosive
mixtures with aluminum chloride, oxidants
(e.g., fluorodinitromethane, uranium
perchlorate, tetranitromethane, sodium
chlorate, nitric acid, nitric acid + water,
peroxodsulfuric acid, dinitrogen
tetraoxide), phosphorus pentachloride,
potassium, sulfuric acid. Reacts violently
with aniline + glycerin, N20, AgCLO4. To
fight fne, use water, foam, CO2, dry
chemical. Incompatible with potassium
hydroxide. When heated to decomposition it
emits toxic fumes of NOx. See also NITRO
COMPOUNDS OF AROMATIC
HYDROCARBONS.
職業ばく露
Nitrobenzene is used in the manufacture
of explosives and aniline dyes and as solvent and intermediate.
It is also used in floor polishes; leather dressings
and polished; and paint solvents, and to mask other
unpleasant odors. Substitution reactions with nitrobenzene
are used to form m-derivatives. Pregnant women may be
especially at risk with respect to nitrobenzene as with many
other chemical compounds, due to transplacental passage
of the agent. Individuals with glucose-6-phosphate dehydrogenase
deficiency may also be special risk groups.
Additionally, because alcohol ingestion or chronic alcoholism
can lower the lethal or toxic dose of nitrobenzene,
individuals consuming alcoholic beverages may be at risk.
発がん性
Nitrobenzene is reasonably anticipated to be a human carcinogenbased on sufficient evidence of carcinogenicity from studies in experimental animals.
輸送方法
UN1662 Nitrobenzene, Hazard Class: 6.1;
Labels: 6.1-Poisonous materials.
純化方法
Common impurities include nitrotoluene, dinitrothiophene, dinitrobenzene and aniline. Most impurities can be removed by steam distillation in the presence of dilute H2SO4, followed by drying with CaCl2, and shaking with, then distilling at low pressure from BaO, P2O5, AlCl3 or activated alumina. It can also be purified by fractional crystallisation from absolute EtOH (by refrigeration). Another purification process includes extraction with aqueous 2M NaOH, then water, dilute HCl, and water, followed by drying (CaCl2, MgSO4 or CaSO4) and fractional distillation under reduced pressure. The pure material is stored in a brown bottle, in contact with silica gel or CaH2. It is very hygroscopic. [Beilstein 5 H 233, 5 I 124, 5 II 171, 5 III 591, 5 IV 708.]
不和合性
Concentrated nitric acid, nitrogen tetroxide;
caustics; phosphorus pentachloride; chemically-active
metals, such as tin or zinc. Violent reaction with strong oxidizers
and reducing agents. Attacks many plastics. Forms
thermally unstable compounds with many organic and inorganic
compounds.
廃棄物の処理
Incineration (982℃, 2.0 seconds
minimum) with scrubbing for nitrogen oxides abatement
. 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.
ニトロベンゼン 上流と下流の製品情報
原材料
準備製品
2-(キノリン-6-イル)酢酸メチル
4-(2-チエニル)ブタン酸
3-アミノベンゼンスルホンアミド
6,10,12-トリクロロナフト[2,3-c]アクリジン-5,8,14(13H)-トリオン
polythiniren
8-クロロキノリン
4,4'-ジアミノジフェニルエーテル
1,5-ナフチリジン-2-カルボン酸
16,17-ジメトキシジナフト[1,2,3-cd:3',2',1'-lm]ペリレン-5,10-ジオン
3-Hydroxy-4-methoxybenzaldehyde
1-クロロフタラジン
プルンバギン
6-メトキシ-2-ナフトエ酸
3-ニトロベンゼンスルホン酸ナトリウム
4-(4-メトキシフェニル)酪酸
ジミジウムブロミド
4-ニトロカテコール
ペンタクロロニトロベンゼン
6-メトキシ-8-アミノキノリン
3-アミノベンゼンスルホン酸ナトリウム
ソルベントブラック5
3-METHYL-1H-PYRAZOLO[3,4-C]PYRIDAZINE-4,5-DIOL
3-アミノベンゼンスルホン酸
アニリン
6-ブロモキノリン-3-オール
2(3H)-ベンゾチアゾロン
セリトンブルーGF-3R
(6-METHYL-BENZOFURAN-3-YL)-ACETIC ACID
4'-ヒドロキシバレロフェノン
2-アセチル-6-メトキシナフタレン
4'-ヒドロキシ-3',5'-ジメトキシアセトフェノン
N,N'-ジフェニル-N,N'-ジ(m-トリル)ベンジジン
3-ニトロアニリン
2-フェノキシ-1-アミノ-4-ヒドロキシアントラセン-9,10-ジオン
1,3-ジクロロベンゼン
3-アミノフェノール
アゾイックジアゾコンポーネント22
ニグロシン (水溶性)
FUCHSIN BASIC
1,3-ジニトロベンゼン