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外観
無色澄明の液体
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溶解性
水及びエタノールと任意の割合で混和する。
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解説
トリメチルアミン天然に広く存在し，動物，植物質が分解するときに生じる．その母体としては，グリシンベタイン，コリン，またはレシチンなどが考えられる．ギ酸アンモニウムをホルムアルデヒドと熱して製造する．魚類の腐敗臭をもつ無色の気体．融点－124.0 ℃，沸点3.5 ℃．d40"0.6709．nD0"1.3631．Ka25 7.4×10－5．[CAS 75-50-3]
森北出版「化学辞典（第2版）
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用途
有機合成原料。
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用途
医薬農薬原料等
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用途
塩化コリン原料、逆性石けん?イオン交換樹脂原料、医薬?農薬?カチオン活性剤原料
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使用する
トリメチルアミンは水とほとんどの有機溶媒に可溶です．塩基性が強い．悪臭防止法による指定物質で，発生源は畜産農業，複合肥料製造業，魚腸骨処理場，水産缶詰製造業など．
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化学的特性
Trimethylamine is compressed gas or liquid.
Flammable gas. Shipped as a compressed gas, it may be
present in an aqueous solution. It has a strong, fishy, ammoniacal
odor. The Odor Threshold is 0.00011-0.87 ppm.
Warning: The Odor Threshold range is so broad that odor
alone should not be used as a warning of potentially
hazardous exposures.
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物理的性質
Trimethylamine has a pungent, fishy, ammoniacal odor at low concentration.It's a colourless liquid with a boiling point around 3.5°C, compared with the higher melting point of 224-226°C for the more polar Me3NO, which presumably has dipole-dipole intermolecular forces.
Trimethylamine is a base, like ammonia. Also like ammonia, it has a trigonal pyramidal structure. The C-N-C bond angle is 110.9°, compared with 107.2° in NH3, presumably due to greater repulsions between the methyl groups. This angle is reduced to 109.0° in Me3NO.
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天然物の起源
TMA is widely distributed in the environment as a normal constituent of animal and plant tissue and as a result of its formation during the decay of organic matter in plants, animals, fish, sewage and animal waste (Graedel 1978; Hippe et al 1977; Oremland et al 1982). The amine is formed primarily as the result of microbial degradation of the plant and animal constituents betaine and choline and from bacterial reduction of trimethylamine oxide, a common constituent of aquatic organisms. It also occurs naturally in a variety of foodstuffs and in tobacco smoke and these are the most likely sources of human exposure (HSDB 1988).
Numerous strains of bacteria isolated from various sources have been found capable of growing on TMA (HSDB 1988). Degradation products formed under anaerobic conditions include dimethylamine, formaldehyde, formate and C02, while under aerobic conditions, TMA is converted to dimethylamine, ammonia and methane.
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使用
Trimethylamine is used as a warning agent for natural gas, a synthetic flavor (fish) ingredient, and in the synthesis of photochemicals, choline salts, flotation agents, dyes, pesticides, ion-exchange resins, cationic starches, and intense sweeteners (HSDB 2006).
Organic synthesis, especially of choline salts, warning agent for natural gas, manufacture of disinfectants, flotation agent, insect attractant, quaternary ammonium compounds, plastics.
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定義
ChEBI: Trimethylamine is a tertiary amine that is ammonia in which each hydrogen atom is substituted by an methyl group. It has a role as a human xenobiotic metabolite and an Escherichia coli metabolite. It is a tertiary amine and a member of methylamines. It is a conjugate base of a trimethylammonium.
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調製方法
Trimethylamine (TMA) is produced by several methods: from the reaction of ammonia and methanol; from paraformaldehyde and ammonium chloride; by the action of formaldehyde and formic acid on ammonia; and by the interaction of methanol and ammonia over a catalyst at high temperature (Hawley 1981; HSDB 1988). TMA is sold as an aqueous solution or as a liquefied gas (Windholz et al 1983) in which the aqueous solution is available as 25, 30, and 40% and anhydrous as 99% minimum. The impurities consist of ammonia at no more than 0.2% by weight of solution and formaldehyde at no more than 0.3% by wt. of solution (Rick 1985). U.S. production was estimated to be approximately 15,322 tons in 1984 (HSDB 1988).
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製造方法
Trimethylamine can be synthesized from paraformaldehyde and ammonium chloride, by the reaction of formic acid, formaldehyde, and ammonia, and by interaction of methanol and ammonia with a catalyst at high temperature.
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反応性
Trimethylamine (TMA) has been used in the preparation of poly[9,9′-bis(6′-N,N,N-trimethylammonium)hexyl)fluorene-co-alt-4,7-(2,1,3-benzothiadiazole) dibromide] (PFBT), a water-soluble, cationic conjugated polymer used in label-free DNA microarrays. It can also be used to prepare benzyltrimethylammonium chloride, which then reacts with sodium ethoxide to form benzyltrimethylammonium ethoxide.The adsorption of TMA on the gold surface of trimethylsilylated barium nitrate-gold/titanosilicate catalyst acts as a promoter for the propylene epoxidation with oxygen and hydrogen.
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安全性
トリメチルアミンはガスまたは水溶液として販売、利用されており、性状だけでなく、安全性や適用法規が異なります。水溶液でも引火性は高く、消防法で「第4類引火性液体・第一石油類・水溶性液体」に該当します。同様に労働安全衛生法、船舶安全法、航空法においても引火性液体となっています。
ガス、水溶液に共通する点としては、両方とも悪臭防止法の特定悪臭物質に該当します。また、燃焼すると分解して有毒ガスであるを生成します。
その他、以下のような危険性があるため、取扱いには注意が必要です。
- 強酸化剤、酸、酸化エチレンと激しく反応する。
- 、、に対して腐食性を示す。
- 水銀との反応で衝撃に敏感な化合物を生成する。
- 亜硝酸塩やと反応して、極めて有毒なニトロソアミンを生成する
参考文献
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一般的な説明
A colorless gas with a fishlike odor at low concentrations changing to ammonia-like odor at higher concentrations. Shipped as a liquid under its own vapor pressure. Contact with the unconfined liquid can cause frostbite from evaporative cooling or chemical type burns. The gasis corrosive and dissolves in water to form flammable, corrosive solutions. Gas is an asphyxiate by the displacement of air. Produces toxic oxides of nitrogen during combustion. Prolonged exposure to heat can cause the containers to rupture violently and rocket. Long-term inhalation of low concentrations or short -term inhalation of high concentrations has adverse health effects.
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空気と水の反応
Highly flammable and easily ignited. Water soluble.
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反応プロフィール
TRIMETHYLAMINE 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. Contamination of an ethylene oxide tank with trimethylamine caused an explosion [BCISC Quart. Safety Summ., 1966, 37, 44].
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健康ハザード
TMA is formed naturally from the biodegradation of plants, fish and animal products, and is ingested in foods such as fish, or from foods containing TMA precursors [e.g. trimethylamine oxide (TMAO), choline, and L-carnitine], which are metabolized to TMA by enterobacteria (Bain et al. 2005). Human exposure to TMA vapor has caused respiratory and eye irritation and corneal lesions. Effects in laboratory animals consisted of respiratory tract toxicity (gasping, labored breathing, lung lesions), eye lesions, neurotoxicity (apathy, splayed hind- or forelimbs, uncoordinated movements, convulsions, brain lesions), and some studies also found pathological changes of the liver, spleen, and kidneys.
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化学性质
常温で気体であり，水に微溶
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使用用途
トリメチルアミンは、多くのものに使用されていますが、一般的に気体の状態ではなく、水に溶かして30~40%程度の水溶液状態で使用されることが多いです。水との溶解性は高く、水とは任意の比率で混和します。
具体的には、の原料や、繊維油剤、逆性せっけん、医薬品の原料として使用されます。また、身近なものでは、するめいか、にしん、ぼらなどの脂肪分の少ない魚の加工品、すずき等の生魚の食品中に元から存在しており、欧米においては、菓子類、肉製品、冷凍乳製品、清涼飲料等の様々な食品に香り付け、風味の向上を目的に食品添加物として使用されることも多いです。
日本国内での扱いは、食品衛生法において添加物として使用することは差し支えないが、香りを付ける目的以外には使用してはならないとされています。
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安全性プロファイル
Poison by intravenous
route. Moderately toxic by subcutaneous
and rectal routes. Mildly toxic by inhalation.
A very dangerous fire hazard when exposed
to heat or flame. Self-reactive. Moderately
explosive in the form of vapor when
exposed to heat or flame. Can react with
oxidizing materials. To fight fire, stop flow
of gas. Potentially explosive reaction with
bromine + heat, ethylene oxide,
triethynylaluminum. When heated to
decomposition it emits toxic fumes of NOx.
See also AMINES.
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職業ばく露
Trimethylamine is used as a chemical
intermediate in organic synthesis of quaternary ammonium
com pounds; as an insect attractant; as a warning agent in
natural gas; flotation agent.
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発がん性
No studies were found that examined the carcinogenicity of Trimethylamine in humans. Because mechanisms have been proposed by which the known carcinogen N47 nitrosodimethylamine can be formed from Trimethylamine and TMAO (Bain 2005) in the presence of nitrosating agents, there is some concern about the neoplastic potential of Trimethylamine. Thus, the German exposure guidelines warn that co-exposure to Trimethylamine and nitrosating agents should be minimized (see Section 8.2.). However, a 2-year mouse and rat inhalation study with the related amine DMA, which can also potentially form N-nitrosodimethylamine, showed no tumor formation despite severe chronic nasal lesions (CIIT 1990).
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特徴
トリメチルアミンの構造式は (CH3)3Nで、構造式からもわかるように、アンモニア (NH3) の水素がすべてメチル基に置換された構造をしています。分子量は59.11、密度が0.67g/ml (0℃) 、融点が-117.1℃、沸点が2.9℃であり、常温で無色透明の気体です。
極めて可燃性、引火性の高いガスで、吸入や付着による有害性も認められている物質です。トリメチルアミンは、強烈な魚の臭いであることが特徴ですが、アルカリ物質であるため、酸性のものと反応させると無臭化できることも知られており、アミン系の悪臭には酸性の消臭剤を使用することが一般的です。
悪臭防止法の規制対象であり、特定悪臭物質に登録されています。特定悪臭物質とは不快な臭いの原因となり、生活環境を損なうおそれのある物質です。現在、22物質しか指定されていないことから、その臭いの強さが分かると思います。
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製造方法
1. トリメチルアミンの製造方法
トリメチルアミンは、最も基本的な第3級アミンで、工業的にはとを脱水触媒の存在下で反応させて製造します。
1. メチルアミンの合成
まずは、メタノールとアンモニアの混合物を、1.0~2.1MPaの加圧下で、などの脱水触媒に450~500℃で通し、モノメチルアミン、、トリメチルアミンの3種類のメチルアミンの混合物を合成します。
- モノメチルアミンの生成
CH3OH + NH3 → CH3NH2 + H2O
- ジメチルアミンの生成
2CH3OH + NH3 → (CH3)2NH2 + 2H2O
- トリメチルアミンの生成
3CH3OH + NH3 → (CH3)3NH2 + 3H2O
2. 脱水・蒸留によるトリメチルアミンの分離
生成物を加圧下で蒸留して、原料のメタノールと生成した水を分離した後、アンモニアとトリメチルアミンの共沸混合物を留出させることで、モノメチルアミンとジメチルアミンを分離させます。最後に、アンモニアとトリメチルアミンの共沸混合物を抽出蒸留してトリメチルアミンを回収します。
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合成方法
メタノールとアンモニアの混合物を加圧下，脱水触媒に450?500℃で通しトリメチルアミンを得る
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純化方法
Dry triethylamine by passing the gas through a tower filled with solid KOH. Water and impurities containing labile hydrogen were removed by treatment with freshly sublimed, ground, P2O5. It has been refluxed with acetic anhydride, and then distilled through a tube packed with HgO and BaO. [Comyns J Chem Soc 1557 1955.] For more extensive purification, trimethylamine is converted to the hydrochloride, crystallised (see below), and regenerated by treating the hydrochloride with excess aqueous 50% KOH, the gas is passed through a CaSO4 column into a steel cylinder containing sodium ribbon. After 1-2 days, the cylinder is cooled to -78o and hydrogen and air are removed by pumping. [Day & Felsing J Am Chem Soc 72 1698 1950.] Me3N has been distlled from trap-to-trap and degassed by freeze-pump-thaw [Halpern et al. J Am Chem Soc 108 3907 1986]. It is commercially supplied in a pressure tin. [Beilstein 4 H 43, 4 I 322, 4 II 553, 4 III 99, 4 IV 134.]
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不和合性
A medium strong base. Violent reaction
with strong oxidizers (such as chlorine, bromine, fluorine),
ethylene oxide; nitrosating agents, for example, nitrites,
sodium nitrite, nitrous gases, nitrous acid) capable of
releasing carcinogenic nitrosamines.); keep away from mercury,
strong acids. Corrosive to many metals, for example,
zinc, brass, aluminum, copper, tin, and their alloys.
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廃棄物の処理
Return refillable compressed
gas cylinders to supplier. Nonrefillable cylinders should be
disposed of in accordance with local, state and federal regulations.
Allow remaining gas to vent slowly into atmosphere
in an unconfined area or exhaust hood. Refillabletype
cylinders should be returned to original supplier with
any valve caps and outlet plugs secured and valve protection
caps in place.
