アリルアルコール 化学特性,用途語,生産方法
外観
無色澄明の液体
性質
アリルアルコールは、分子量が58.08の無色透明な液体で、強い刺激臭があります。密度は0.854g/cm3、融点は-129℃、沸点は97℃、引火点は21℃、発火温度が443℃、屈折率は1.4134です。
水に極めて溶けやすく、、、エーテル等に可溶、引火しやすい性質があります。アリルアルコールの蒸気を吸入すると、主に眼や鼻への影響が強く、化管法の第一種指定化学物質、毒劇物取締法の毒物として指定されています。
また、引火性も高いため、消防法の危険物第4類第2石油類水溶に分類されており、取扱いと保管数量が制限されています。この他、労働安全衛生法の引火性危険物、名称等を表示・通知すべき危険物及び有害物に指定されています。
溶解性
水、エタノール及びジエチルエーテルに極めて溶けやすい。
解説
2-propen-1-ol．CH2=CHCH2OH(58.08)．プロペンを高温塩素化して塩化アリルをつくり，これをアルカリ加水分解すると70～80％ の収率で得られる．また，プロペンオキシドをリン酸リチウムの存在下，気相で異性化させてつくる．刺激臭のある無色の軽い液体．沸点97 ℃．引火点32 ℃(開放)，22 ℃(密閉)．d2040.852．n20D1.413．アリルアルコール, アルケンとしての付加反応，アルコールとしての縮合反応をするほか，金属酸化物の高温接触反応によってプロピオンアルデヒドに異性化し，酸化によってアクリルアルデヒド，さらにアクリル酸にかわる．数年間放置すると水に不溶の重合物が生成する。酸化すればアクロレイン，グリセリン，さらにギ酸，シュウ酸などに変わる。酸化アルミニウム，酸化亜鉛，銅などの高温接触作用によってプロピオンアルデヒドCH3CH2CHOに異性化する。森北出版「化学辞典（第2版）
用途
アリルグリシジルエーテル?エピクロロヒドリン合成原料、ジアリルフタレート樹脂合成原料、医薬品?香料?難燃化剤合成原料、ジアリルフタレート樹脂?医薬?香料?難燃化剤などの原料
用途
アリルアルコールは，グリセリンの製造原料，合成樹脂，香料，化学薬品の合成中間体として重要であり，また，溶剤，そのほかに用いられる．
化学的特性
Allyl alcohol is a flammable, colorless liquid. It has a pungent, mustard-like odor. It is used in making drugs, organic chemicals, pesticides, in the manufacture of allyl esters, and as monomers and prepolymers for the manufacture of resins and plastics. It has a large use in the preparation of pharmaceutical products, in organic synthesis, and as a fungicide and herbicide. Occupational workers engaged in industries such as the manufacture of drugs, pesticides, allyl esters, organic chemicals, resins, war gas, and plasticizers, are often exposed to this alcohol.
物理的性質
Colorless, mobile liquid with a pungent, mustard-like odor at high concentrations. At low
concentrations, odor resembles that of ethyl alcohol. Katz and Talbert (1930) and Dravnieks
(1974) reported experimental detection odor threshold concentrations of 3.3 mg/m
3 (1.4 ppm
v) and
5 mg/m
3 (2.1 ppm
v), respectively.
使用
Allyl alcohol is used as an intermediate compound for synthesizing raw materials such as epichlorohydrin C3H5ClO and 1,4- butanediol C4H10O2, and this development is bringing about expansion of the range of uses of allyl alcohol. The term allyl of allyl compounds is derived from allium, the Latin word for garlic. It is also used to induce a mouse model of liver damage that has been used to study the mechanisms of hepatotoxicity and hepatic stem cell-mediated repair.
主な応用
Allyl alcohol is used to produce glyceroland acrolein and other allylic compounds. It is also used in the manufacture of militarypoison gas. The ester derivatives are used inresins and plasticizers.Allyl alcohol is an intermediate in the production of polymerizable allyl ethers and esters, especially diallyl phthalate. The bulk of the allyl alcohol produced commercially is consumed in the production of glycerol. Polymeric allyl alcohol reacts with unsaturated fatty acids to give drying oils. Sulfur dioxide and allyl alcohol yield polymeric allylsulfonic acids, which have been proposed as intermediates for plasticizers and textile auxiliaries. Allyl alcohol can be copolymerized with other monomers and then used as an intermediate in the production of flame-resistant materials or as a nematocide, fungicide, or preservative.
定義
ChEBI: Allyl alcohol is a propenol in which the C=C bond connects C-2 and C-3. It is has been found in garlic (Allium sativum). Formerly used as a herbicide for the control of various grass and weed seeds. It has a role as an insecticide, a herbicide, an antibacterial agent, a fungicide and a plant metabolite. It is a primary allylic alcohol and a propenol.
調製方法
Allyl alcohol is prepared by several different processes, the original is alkaline hydrolysis of allyl chloride
by steam injection at high temperatures. A more recent
commercial process used oxidation of propylene to acrolein,
which in turn reacts with a secondary alcohol to yield
allyl alcohol and a ketone. In this process, allyl alcohol is
not isolated, but its aqueous stream is converted directly to
glycerol. The most recent commercial process is isomerization
of propylene oxide over a lithium phosphate catalyst.
Origin
Allyl alcohol was first prepared in 1856 by A. CAHOURS and A. W. HOFMANN by saponification of allyl iodide.
一般的な説明
Allyl alcohol appears as a clear colorless liquid with a mustard-like odor. Flash point 70°F. Very toxic by inhalation and ingestion. Less dense than water (7.1 lb / gal). Vapors are heavier than air. Prolonged exposure to low concentrations or short exposure to high concentrations may have adverse health effects from inhalation.
空気と水の反応
Highly flammable. Water soluble.
反応プロフィール
Allyl alcohol presents a dangerous fire and explosion hazard when exposed to heat, flame, or oxidizing agents. Reacts violently or explosively with sulfuric acid, strong bases. Reacts violently with 2,4,6-trichloro-1,3,5-triazine and 2,4,6-tris(bromoamino)-1,3,5-triazine. Reacts with carbon tetrachloride to produce explosively unstable products [Lewis]. Mixing Allyl alcohol in equal molar portions with any of the following substances in a closed container caused the temperature and pressure to increase: chlorosulfonic acid, nitric acid, oleum, sulfuric acid [NFPA 491M. 1991].
危険性
Toxic by skin absorption. Eye and upper
respiratory tract irritant. Questionable carcinogen.
健康ハザード
The toxicity of allyl alcohol is moderately high, affecting primarily the eyes. The other target organs are the skin and respiratory system. Inhalation causes eyeirritation and tissue damage. A 25-ppmexposure level is reported to produce asevere eye irritation. It may cause atemporary lacrimatory effect, manifested by photophobia and blurred vision, for some hours after exposure. Occasional exposure of a person to allyl alcohol does not indicate chronic or cumulative toxicity. Dogterom and associates (1988) investigated the toxicity of allyl alcohol in isolated rathepatocytes. The toxicity was independent of lipid peroxidation, and acrylate was found to be the toxic metabolite Ingestion of this compound may cause irritation of the intestinal tract. The oral LD50 value in rats is 64 mg/kg (NIOSH 1986).
火災危険
Allyl alcohol vapor may explode if ignited in confined areas. Combustion products may be poisonous. The vapor is heavier than air and flashback along vapor trail may occur. Gives off toxic fumes when heated. May react vigorously with oxidizing materials, carbon tetrachloride, acids, oleum, sodium hydroxide, diallyl phosphite, potassium chloride, or tri-n-bromomelamine.
使用用途
アリルアルコールは、各種合成原料としてさまざまな分野で使用されています。化学分野では、、アリルグリシジルエーテル、プロパンスルトンを合成をするための中間体として有用です。
また、ジアリルフタレート樹脂の原料、樹脂添加剤や等のアリル化合物の原料として使用されています。その他、医薬品、香料、農薬、殺菌剤、難燃化剤などの原料としても使用されます。
安全性プロファイル
Suspected carcinogen. Poison by inhalation, ingestion, skin contact, subcutaneous, intraperitoneal, and possibly other routes. A slim, severe eye (human), and systemic irritant. Mutation data reported. Dangerous fire and explosion hazard when exposed to heat, flame, or oxidizers.
職業ばく露
Allyl alcohol is a colorless water soluble liquid. The melting point, boiling point, vapor pressure, and the octanol–water partition coefficient (log Kow) are 129°C, 97°°C, 26.1mmHg at 25°C, and 0.17, respectively. The Henry’s law constant is 4.99×10-6 atm-m3 mol-1. Allyl alcohol’s production, its use as an industrial solvent and as a raw material/intermediate in the preparation of pharmaceuticals, polymers, organic chemicals, in the manufacture of glycerol and acrolein, and in the production of insecticides and herbicides, may result in its release to the environment.
発がん性
Male and female F344 rats were
given allyl alcohol in the drinking water at a concentration of
0 or 300 mg/L for 106 weeks. The incidence of tumors was
similar to that in controls . Male and female hamsters
were administered 2 mg allyl alcohol by oral gavage once a
week for 60 weeks. The incidence of tumors did not increase
significantly compared to controls.
製造方法
工業的には、プロピレンオキサイドの異性化、プロピレンを直接酸化する方法が行われています。
プロピレンオキサイドの異性化
CH2CH(CH3)O → CH2＝CHCH2OH
酸化プロピレンを、硫酸カリウムアルミニウムの存在下で加熱することで、異性化してアリルアルコールが生成します
プロピレンの直接酸化
CH3CH=CH2 + CH3COOH + 1/2O2 → CH2= CHCH2OCOCH3 + H2O
CH2= CHCH2OCOCH3 ＋ H2O → CH2＝CHCH2OH + CH3COOH
プロピレン、酢酸、酸素が反応して、アリルアルコールが生成する反応です。この反応は、プロピレンからアリルアルコールを直接的に合成する方法の1つであり、反応条件の最適化によって、高収率でアリルアルコールを得ることができます。
輸送方法
UN1098 Allyl alcohol Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable liquids, Inhalation Hazard Zone B.
純化方法
It can be dried with K2CO3 or CaSO4, or by azeotropic distillation with *benzene followed by distillation under nitrogen. It is difficult to obtain it free of peroxide. It has also been refluxed with magnesium and fractionally distilled [Hands & Norman Ind Chem 21 307 1945]. [Beilstein 1 IV 2079.]
環境運命予測
The vapor pressure of allyl alcohol, 26.1mmHg at 25°C, indicates that if released in the air, it will exist mainly as a vapor in the ambient atmosphere. If released to soil, allyl alcohol is expected to have very high mobility based upon an estimated Koc of 1.3 and will be distributed mainly in the water and soil. If released into water, allyl alcohol will stay in the water and is not expected to adsorb to suspended solids and sediments. Allyl alcohol is stable in water since it lacks functional groups that hydrolyze under environmental conditions and hence hydrolysis is not expected to be an important environmental fate process. In an aerobic biodegradation study, allyl alcohol was found to readily degradable (82–86%) in 14 days. The estimated bioconcentration factor of 3.2 based on the low log Kow indicates that the potential to bioaccumulate in aquatic organisms is expected to be low.
不和合性
May form explosive mixture with air. Reacts explosively with carbon tetrachloride, strong bases. Also incompatible with strong acids. 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. Polymerization may be caused by heat above 99 C, peroxides, or oxidizers.
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. Incineration after dilution with a flammable solvent.
予防処置
Occupational workers should be careful during handling and use of allyl alcohol and wear
アリルアルコール 上流と下流の製品情報
原材料
準備製品