ジエチルアミン 化学特性,用途語,生産方法
外観
無色澄明の液体
性質
1. 物理的性質
ジエチルアミンは、化学式C4H11N、分子量73.14、CAS番号109-89-7の有機化合物です。無色の液体で、アンモニアのような特徴的な臭気を持ちます。pHは強塩基性で、粘度は 0.319cp (25℃) 、比重は0.707です。
融点-50℃、引火点-26℃以下 (密閉系) 、 沸点・初留点及び沸騰範囲55.5℃、爆発範囲下限 1.8vol％ 、上限 10.1vol％、自然発火温度312℃の引火性液体です。
2. 化学的性質
ジエチルアミンは、水と混和し、アルコール、四塩化炭素、クロロホルムに可溶です。通常状態において安定ですが、加熱や燃焼により分解し、一酸化炭素や窒素酸化物などの、有毒なヒュームを生じます。
混触危険物質には、酸化剤とニトロシアノフラザンが指定されています。酸化剤と反応すると、火災や爆発の危険があります。また、ニトロシアノフラザンに触れると即時に爆発するため、混触危険物質と接触しないよう取り扱いに注意が必要です。
溶解性
水, アルコール, アセトンに易溶。水、エタノール及びアセトンに極めて溶けやすい。
解説
ジエチルアミン，第二級アミンの一つ．ヨウ化エチルとアンモニアとの反応で生成する．p-ニトロソジエチルアニリンをアルカリ溶液と加熱しても生成する．アンモニアに似た臭気をもつ無色の可燃性液体．融点－50 ℃，沸点56 ℃．0.7067．1.3867．共役酸はpKa 10.98．強い塩基性をもつ．亜硝酸の作用によりN-ニトロソアミンを生成する．皮膚，粘膜を刺激する．
用途
医薬品、染料中間体、ゴム薬品、農薬(除草剤)、界面活性剤、塗料
説明
Diethylamine is a colourless, strongly alkaline, fish odour liquid, and highly inflammable. It has an ammonia-like odour and is completely soluble in water. On burning, diethylamine releases ammonia, carbon monoxide, carbon dioxide, and nitrogen oxides. Diethylamine is used in the production of pesticides. It is used in a mixture for the production of DEET which goes into the repellents that are found readily in supermarkets for general use.
物理的性質
Colorless liquid with a fishy, ammonia-like odor. Experimentally determined detection and recognition odor threshold concentrations were 60 μg/m3 (20 ppbv) and 180 μg/m3 (60 ppbv), respectively (Hellman and Small, 1974). Diethylamine is a very strong base in aqueous solution (pKb = 3.0). Its chemistry is governed by the unshared electron pair on the nitrogen, thus it tends to react with acids to form salts.
天然物の起源
Diethylamine occurs in low concentrations in food and other biological materials.
Concentrations (in p.p.m.) in fresh products include: spinach (15), apples (3), butterbeans
(2.4), shelled peas (0.1), bean salad (1.5) and red cabbage (2.4) (HSDB
1989). Pickled vegetables contain 0-3.2 p.p.m. diethylamine while concentrations
(in p.p.m.) in other materials include herring (0-5.2), barley (5.7), hops (3.1), boiled
beef (2), tobacco leaf (0.1-35) and cigarette smoke concentrate (0-0.4). Interest in
the occurrence of diethylamine in foods arises in part because of its possible formation
of a carcinogenic N-nitroso derivative (Neurath et al 1977). Diethylamine has
been reported in the exhaust from a gasoline engine (Hampton et al 1982).
使用
Diethylamine is manufactured by heating ethyl chloride and
alcoholic ammonia under pressure or by hydrogenation of
aziridines in the presence of catalysts. DEA is used as a
solvent, as a rubber accelerator, in the organic synthesis of
resins, dyes, pesticides, and pharmaceuticals, in electroplating,
and as a polymerization inhibitor. Other
applications include uses as a corrosion inhibitor. It was
reported noneffective as a skin depigmentator.
定義
ChEBI: Diethylamine is a secondary aliphatic amine where both N-substituents are ethyl. It is a conjugate base of a diethylammonium.
調製方法
Diethylamine is produced using the three methods also used for the manufacture of ethylamine with very slight modification.
Diethylamine Synthesis
1. N,N-Diethyl-3-methylbenzamide + Ethylene Glycol + NaOH + Heat
2. Ethylchloride + Ammonia (forms diethylamine HCL)
3. Ethanol + Ammonia + Sulfuric Acid
The most widely used method is the passing of ammonia and ethanol over a catalyst such as alumina or silica (Schweizer et al 1978). Diethylamine can be separated from the mixture by selective distillations and extractions.
安全性
引火性の高い液体及び蒸気を発生させ、皮膚との接触 (経皮) 、吸引 (蒸気) 、飲み込む (経口) と有害です。また、眼に入ると、重篤な損傷を起こします。
単回ばく露では、呼吸器系、肝臓障害の恐れがあり、反復ばく露では、呼吸器系、腎臓障害の恐れがあります。また、水性生物への有害性が確認されており、廃棄時は関連法規、地方自治体の基準に従って処理する必要があります。
一般的な説明
A clear colorless liquid with an ammonia-like odor. Density 5.9 lb / gal. Flash point -15°F. A respiratory irritant. Corrosive to the eyes and skin. Vapors heavier than air. Toxic oxides of nitrogen produced during combustion.
空気と水の反応
Highly flammable. Soluble in water. Sensitive to heat. May be sensitive to prolonged exposure to air.
反応プロフィール
It is incompatible with several chemical substances such as strong oxidisers, acids, cellulose nitrate, some metals, and dicyanofuroxan. N-nitrosamines, many of which are known to be potent carcinogens, may be formed when diethylamine comes in contact with nitrous acid, nitrates, or atmospheres with high nitrous oxide concentrations.
健康ハザード
Diethylamine can be harmful if it is inhaled, swallowed, or in contact with skin.
Vapors can irritate the eyes and cause irritation of the respiratory tract, leading to
coughing and chest pain. Liquid diethylamine can cause severe burns to the eyes
and skin. Vision became misty and halos appeared several hours after workmen
were exposed to the vapors of amines such as diethylamine (Grant 1986). The
edema of the corneal epithelium, which is principally responsible for the disturbances
in vision, clears after one or more days, depending on the severity of
exposure. Photophobia and discomfort from roughness of the corneal surface also
can occur after greater exposure to the amine.
応急処置
吸引、皮膚への付着、眼への付着、経口摂取した際は、いずれの場合も直ちに医療機関に連絡します。吸引した際は、空気が新鮮な場所で、半座位で安静にします。
皮膚に付着した場合は、 少なくとも15分間多量の水で洗い流した後、ジエチルアミンが付着し衣服を脱がせ、再度洗い流すことが重要です。
眼に付着した場合は多量の水で洗い流し、コンタクトレンズの場合は可能であればはずします。経口摂取した場合は、無理に吐かせず、口をすすぎ、医師の指示に従います。
取扱方法
取扱いの際は、適切な呼吸器系保護具、保護手袋 (ネオプレン推奨) 、顔面保護具、必要に応じて全身の化学用保護衣 (耐酸スーツなど) を着用します。作業後はよく手を洗い、眼や皮膚等に付着しないよう注意します。
設備は防爆の電気、換気、照明機器を使用し、静電気放電に対する予防措置を行います。また、貯蔵、取扱場所には、洗眼器と安全シャワーを設置します。
高熱工程でミストが発生する場合は、空気汚染物質を管理濃度・許容濃度以下に保つため、換気装置を設置する必要があります。
消火方法
粉末消火薬剤、アルコール耐性泡消火薬剤、大量の水、二酸化炭素を使用し、消火を行います。 火災を予防するためには、裸火、火花との接触を避け、作業場所は禁煙にする必要があります。
また、作業場所は密閉系、もしくは換気設備のある場所で取り扱います。充填、取り出し、取り扱い時に圧縮空気を使用しないよう注意が必要です。
使用用途
ジエチルアミンは、医薬品、染料中間体、ゴム薬品、除草剤、殺虫剤、界面活性剤、塗料、合成樹脂などの原料として幅広く利用されています。また、化学分析の試薬としても用いられています。ジエチルアミン-銅法は、物質の濃度を定量的に分析する吸光光度法です。
このほか、電気めっき浴の材料、自動重合を防ぐ目的でモノマーに添加する重合遅延剤 (あるいは重合阻害剤ともいう) 、pH調整剤も用途として挙げられます。
化学反応性
Reactivity with Water No reaction; Reactivity with Common Materials: No hazardous reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
工業用途
Diethylamine, like many of the other short chain aliphatic amines, has achieved
widespread industrial use as an intermediate in the manufacture of a number of
commercial products. Among these are included insecticides, pharmaceuticals,
textile finishing agents, and corrosion inhibitors (Hawley 1981; Schweizer et al
1978). It is used as a polymerization inhibitor and/or catalyst in the polymer
industry and in the manufacture of surfactants and rubber processing accelerators.
This amine also is useful as a depilatory agent for animal skins, as a selective
solvent for the removal of impurities from oils, fats, and waxes, and as a flotation
agent in the petroleum industry (NIOSH/OSHA 1981; HSDB 1989).
毒性学
Exposure to low vapor concentrations are reported to transiently impair vision in humans (reduction of sensitivity to light): no-effect threshold 0.022 – 0.028 mL/m3 ( 0.08mg/m3 ). The odor threshold in air is ca. 0.02 – 0.3 mL/m3 ( 0.9 mg/m3 ). Transient physiological effects in rats after 90-d exposure to vapors were reported to already be visible at 0.37 – 4.19 mg/m3 with no effects at 0.05 mg/m3 , but with morphological, apparently reversible changes in the lung and cerebral neurons at the highest concentration. On the other hand, 50 mL/m3 (150 mg/m3 ) was the lowest concentration to show mild, but signifi- cant effects in the lung and liver of rabbits on prolonged inhalation. There were no visible signs of toxicity following exposure of rats to 25 mL/m3 (75 mg/m3 ) for 120 d, but a moderate, bronchiolar hyperplasia of lymphoid cells. It was assumed that diethylamine may exert a certain neurotoxic effect, which, however, was not confirmed by others.
安全性プロファイル
Moderately toxic by
ingestion, inhalation, and skin contact. A
skin and severe eye irritant. Exposure to
strong vapor can cause severe cough and
chest pains. Contact with liquid can damage
eyes, possibly permanently; contact with
skin causes necrosis and vesciculation. A
very dangerous fire hazard when exposed to
heat, flame, or oxidizers. To fight fire, use
alcohol foam, CO2, dry chemical. Explodes
on contact with dicyanofurazan. Violent
reaction with sulfuric acid. Ignites on
contact with cellulose nitrate of sufficiently
high surface area. When heated to
decomposition it emits toxic fumes of NOx.
See also MINES.
概要
ジエチルアミンとは、二級アミンの有機窒素化合物です。
また、腐食性を持ち、皮膚に触れると重度の皮膚熱傷を引き起こします。
ジエチルアミンは、エチルアルコールのアミノ化、もしくはとの還元アミノ化反応により製造されています。いずれの方法も、、ジエチルアミン、の3種が同時に生成することから、蒸留法により、それぞれに分離・精製しています。
発がん性
No evidence of mutagenicity was seen
in Ames bacterial assays.8 Diethylamine has
an ammonia-like odor that is detectable at
0.13ppm.
The 2003 ACGIH threshold limit valuetime-
weighted average (TLV-TWA) for
diethylamine is 5ppm (15mg/m3) with
a short-term excursion limit of 15ppm
(45mg/m3) and an A4-not classifiable as a
human carcinogen designation; there is a notation
for skin absorption.
環境運命予測
Photolytic. Low et al. (1991) reported that the photooxidation of aqueous secondary amine
solutions by UV light in the presence of titanium dioxide resulted in the formation of ammonium
and nitrate ions.
Chemical/Physical. Diethylamine reacted with NOx in the dark forming diethylnitrosamine. In
an outdoor chamber, photooxidation by natural sunlight yielded the following products:
diethylnitramine, diethylformamide, diethylacetamide, ethylacetamide, ozone, acetaldehyde, and
peroxyacetyl nitrate (Pitts et al., 1978).
Reacts with mineral acids forming water-soluble salts (Morrison and Boyd, 1971).
代謝
Little information is available regarding the metabolism of diethylamine. The
amine can be readily absorbed from the respiratory and gastrointestinal tract. It has
been reported that following oral administration of diethylamine hydrochloride to
humans, much of the amine was recovered in the urine (Beard and Noe 1978). This
suggests that it is not readily metabolized and, therefore, may not be a substrate for
monoamine oxidase. When administered intraperitoneally to rats, it was moderately
inhibitory with respect to liver monoamine oxidase (Valiev 1974). Diethylamine
may serve as a precursor for the formation of the reportedly carcinogenic
N-nitrosoamines and, indeed, when a diethylamine containing liquid was examined
for nitrosation reactions under simulated conditions of the human stomach,
N-nitrosodiethylamine was formed (Ziebarth 1985).
貯蔵
Diethylamine should be protected from physical damage. It should be kept stored in a
cool, dry, well-ventilated location, away from incompatible chemical substances and away
from fi re hazard and smoking areas. The containers should be bonded and grounded for
transfer to avoid static sparks. Storage and use areas should be no smoking areas.
純化方法
Dry diethylamine with LiAlH4 or KOH pellets. Reflux with, and distil it from, BaO or KOH. Convert it to the p-toluenesulfonamide and crystallise to constant melting point from dry pet ether (b 90-120o), then hydrolyse with HCl, excess NaOH is added, and the amine is passed through a column of activated alumina. Redistil the amine and dry it with activated alumina before use [Swift J Am Chem Soc 64 115 1942]. [Beilstein 4 III 313.] § A polystyrene diethylaminomethyl supported version is commercially available.
予防処置
Occupational workers and users should be very careful during the use and chemical management
of diethylamine. Workers should wear impervious protective clothing, including
boots, gloves, a laboratory coat, apron or coveralls, as appropriate, to prevent skin contact. The chemical is very hazardous, corrosive, and harmful, and is a very flammable liquid
and vapor. Exposures to vapor may cause fl ash fi re. It causes burns and adverse effects
to the cardiovascular system. Workers should use chemical safety goggles and a full-face
shield to avoid splashing of the chemical substance. An eye-wash fountain and quickdrench
facilities in the work area should be maintained by the chemical management unit.
ジエチルアミン 上流と下流の製品情報
原材料
準備製品
N,N-ジエチルシアナミド
テトラエチルチウラムジスルフィド
トラピジル
2-(N,N-DIETHYLAMINOCARBONYL)PHENYLBORONIC ACID
ジエチルアミノアセトニトリル
ESFENVALERATE FREE ACID METABOLITE
ジエチルジチオカルバミン酸亜鉛
5-アミノ-3-メチル-チオフェン-2,4-ジカルボン酸ジメチルエステル
5-[(ジエチルアミノ)スルホニル]-2-メトキシベンゼンジアゾニウム
2-AMINO-6-METHYL-4,5,6,7-TETRAHYDRO-1-BENZOTHIOPHENE-3-CARBONITRILE
1,4,6-Trimethyl-1H-pyrazolo[3,4-b]pyridin-3-ylamine ,97%
2-AMINO-5,6-DIHYDRO-4H-CYCLOPENTA[B]THIOPHENE-3-CARBONITRILE
2-アミノ-4,5,6,7-テトラヒドロベンゾ[b]チオフェン-3-カルボニトリル
2-アミノ-4,5-ジメチルチオフェン-3-カルボニトリル
サリチル酸ベンジル
4'-ヨードアセトフェノン
N,N-ジエチルニコチンアミド
リドカイン注射液
ジエチルジチオカルバミン酸ジエチルアンモニウム
3-(DIETHYLAMINO)PROPANOIC ACID
2-クロロ-N,N-ジエチルプロパンアミド
エタンシラート
1,2-ジヒドロ-4,6-ジメチル-2-オキソ-3-ピリジンカルボニトリル
5-ブロモ-N,N-ジエチルピリミジン-2-アミン
プロカイン塩酸塩
ジエチルアミン 塩酸塩
1-[(4-メチルフェニル)スルホニル]-4-フェニル-4-ピペリジンカルボン酸
モンテルカスト
ビス(ジエチルアミノ)クロロホスフィン
けい皮酸ベンジル
2-クロロ-4,6-ジメチルピリジン-3-カルボニトリル
1,1-ジエチルグアニジン塩酸塩
ジエチルカルバミン酸 クロリド
ファスト レッド ITR
N,N-ジエチル-m-トルアミド
3 - ジエチルアミノプロピルアミン
coating adhesive tiemao 102
ジエチルカルバマジン
トリス(ジエチルアミノ)ホスフィン
4,6-ジメチル-1H-ピラゾロ[3,4-B]ピリジン-3-イルアミン