1,4-ジオキサン

外観

無色澄明の液体

溶解性

水及びエタノールに極めて溶けやすい。

解説

ジオキサン,淡い香気のある無色の液体．融点11.8 ℃，沸点101 ℃．d₂₀²⁵1.0356．n_D²⁰1.422．可燃性で，引火点8 ℃．水および多くの有機溶媒とまざる．水20％ を含む共沸混合物(沸点88 ℃)をつくる．無水状態では爆発性の過酸化物をつくることがある．金属塩化物，硫酸などと結晶性付加物をつくる．高分子化合物ならびに無機物質の溶媒としてきわめて広く用いられる．また，リチウム塩の抽出分離に使われる．

森北出版「化学辞典（第2版）

用途

汎用試薬、溶剤、有機合成原料。

用途

溶剤( アセチルセルロース等) 、洗浄剤、医薬農薬の抽出剤

用途

紫外、可視及び蛍光スペクトル分析。

用途

汎用試薬(溶媒)。

用途

液体クロマトグラフ用溶離液及び溶離液調製用。

用途

非水滴定用溶媒。

用途

精密分析、個人専用試薬、用途専用試薬等。

用途

セルロースエステル類、セルロースエーテル類の溶剤、有機合成反応?抽出溶剤、トランジスター用?合成皮革溶剤、塗料?医薬品の合成原料、試薬用、塩素系有機溶剤の安定剤、洗浄剤の調整用溶剤、繊維処理?染色?印刷時の分散?潤滑剤、パルプ精製時の溶剤等。

製造

1,4-ジオキサン：エチレングリコールまたはポリエチレングリコールを濃硫酸などの触媒の存在下で蒸留するか，エチレンオキシドを水酸化ナトリウムと加熱して合成される．

毒性

やや毒性があり，皮膚や粘膜を刺激する。

使用上の注意

不活性ガス封入

説明

1,4-dioxane is a clear liquid with ether-like odour. It is highly flammable and forms explosive peroxides in storage (rate of formation increased by heating, evaporation, or exposure to light). 1,4-Dioxane is incompatible with oxidising agents, oxygen, halogens, reducing agents, and moisture. Industrial applications of 1,4-dioxane are extensive, for instance, as solvent for cellulose acetate, ethyl cellulose, benzyl cellulose, resins, oils, waxes, and some dyes; as a solvent for paper, cotton, and textile processing; and for various organic and inorganic compounds and products. It is also used in automotive coolant liquid and in shampoos and other cosmetics as a degreasing agent and as a component of paint and varnish. Human exposures to 1,4-dioxane have been traced to multiple occupations and breathing of contaminated workplace air and drinking polluted water. Industrial uses of 1,4-dioxane are very many. For instance, it is used as solvent for celluloses, resins, lacquers, synthetic rubbers, adhesives, sealants, fats, oils, dyes, and protective coatings; as a stabiliser for chlorinated solvents and printing inks; and as a wetting and dispersing agent in textile processing agrochemicals and pharmaceuticals, in different processing of solvent-extraction processes, and in the preparation and manufacture of detergents.

化学的特性

1,4-Dioxane is a colorless, stable liquid with a faint, pleasant odor. Although it has been known as far back as 1863, it was not until 1929 that is became commercially available. It is chemically a di-ether obtained by the loss of water from two molecules of ethylene glycol. It is completely soluble in water, as well as most organic solvents. It is freely soluble in mineral, vegetable, blown and heat-bodied oils, and oil soluble dyes. Most waxes are more readily soluble in dioxane when heated and examples of these are beeswax, carnauba, montan, paraffin, gilsonite, and Japan wax.

物理的性質

Clear, colorless, very flammable, volatile liquid with a faint pleasant, ether-like odor. Experimentally determined detection and recognition odor threshold concentrations were 2.9 mg/m³ (800 ppb_v) and 6.5 mg/m³ (1.8 ppm_v), respectively (Hellman and Small, 1974).

使用

1,4-Dioxane, the six-member cyclic diether, is used as an aluminum inhibitor in chlorinated solvents like 1,1,1-trichloroethane and as a solvent for certain resins and polymers.

定義

ChEBI: A dioxane with oxygen atoms at positions 1 and 4.

一般的な説明

A clear colorless liquid with a faint ethereal odor. Flash point 55°F. Slightly denser than water and soluble in water. Vapors heavier than air. Susceptible to autooxidation to form peroxides.

空気と水の反応

Highly flammable. When exposed to air 1,4-Dioxane undergoes autooxidation with formation of peroxides. In the distillation process peroxides will concentrate causing violent explosion. Water soluble.

反応プロフィール

1,4-Dioxane is a flammable liquid; when exposed to air 1,4-Dioxane undergoes autooxidation with formation of peroxides. In the distillation process peroxides will concentrate causing violent explosion. The addition complex with sulfur trioxide (1:1) sometimes decomposes violently on storing at room temperature [Sisler, H. H. et al., Inorg. Synth., 1947, 2, p. 174]. Evaporation of boron trifluoride in aqueous 1,4-Dioxane with nitric acid led to an explosion upon addition of perchloric acid [MCA Guide, 1972, p. 312]. Explosive reaction with Raney nickel catalyst above 210° C {Mozingo R., Org. Synth., 1955, Coll. Vol. 3, p. 182].

健康ハザード

The toxicity of 1,4-dioxane is low in testanimals by all routes of exposure. However,in humans the toxicity of this compoundis severe. The target organs are theliver, kidneys, lungs, skin, and eyes. Exposureto its vapors as well as the absorptionthrough the skin or ingestion can cause poisoning,the symptoms of which include drowsiness,headache, respiratory distress, nausea,and vomiting. It causes depression of centralnervous system. There are reports of humandeaths from subacute and chronic exposures todioxane vapors at concentration levels rangingbetween 500 and 1000 ppm. Serious healthhazards may arise from its injurious effects onthe liver, kidneys, and brain. Rabbits died ofkidney injury resulting from repeated inhalationof 1,4-dioxane vapors for 30 days (Smyth1956). It is an irritant to the eyes, nose, skin,and lungs. In humans, a 1-minute exposure to5000-ppm vapors can cause lacrimation.
LC50 value, inhalation (rats): 13,000 ppm/2 h
LD50 value, oral (mice): 5700 mg/kg
1,4-Dioxane is an animal carcinogen oflow potential. Ingestion of high concentrationsof this compound at a level of7000–18,000 ppm in drinking water for14–23 months caused nasal and liver tumorsin rats (ACGIH 1986). Guinea pigs developedlung tumors.

燃焼性と爆発性

Dioxane is a highly flammable liquid (NFPA rating = 3). Its vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back. Dioxane vapor forms explosive mixtures with air at concentrations of 2 to 22% (by volume). Fires involving dioxane should be extinguished with carbon dioxide or dry powder extinguishers.
Dioxane can form shock- and heat-sensitive peroxides that may explode on concentration by distillation or evaporation. Samples of this substance should always be tested for the presence of peroxides before distilling or allowing to evaporate. Dioxane should never be distilled to dryness.

安全性プロファイル

Confirmed carcinogen with experimental carcinogenic, neoplastigenic, tumorigenic, and teratogenicdata. Poison by intraperitoneal route. Moderately toxic by ingestion and inhalation. Mildly toxic by skin contact. Human systemic effects by inhalation: lachrymation, conjunctiva irritation, convulsions, hgh blood pressure, unspecified respiratory and gastrointestinal system effects. Mutation data reported. An eye and slun irritant. The irritant effects probably provide sufficient warning, in acute exposures, to enable a worker to leave exposure before being seriously affected. Repeated exposure to low concentrations has resulted in human fatahties, the organs chefly affected being the liver and kidneys. A very dangerous fire and explosion hazard when exposed to heat or flame; can react vigorously with oxidizing materials. Violent reaction with (H2 + Raney Ni), AgClO4. Can form dangerous peroxides when exposed to air. Potentially explosive reaction with nitric acid + perchloric acid, Raney nickel catalyst (above 210°C). Forms explosive mixtures with decaborane (impactsensitive), triethynylaluminum (sensitive to heating or drying). Violent reaction with sulfur trioxide. Incompatible with sulfur trioxide. To fight fire, use alcohol foam, CO2, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes. See also GLYCOL ETHERS.

発がん性

1,4-Dioxane is reasonably anticipated to be a human carcinogen basedon sufficient evidence of carcinogenicity from studies in experimental animals.

貯蔵

dioxane should be used only in areas free of ignition sources, and quantities greater than 1 liter should be stored in tightly sealed metal containers in areas separate from oxidizers. Containers of dioxane should be dated when opened and tested periodically for the presence of peroxides.

不和合性

Dioxane can form potentially explosive peroxides upon long exposure to air. Dioxane may react violently with Raney nickel catalyst, nitric and perchloric acids, sulfur trioxide, and strong oxidizing reagents.

廃棄物の処理

Excess dioxane and waste material containing this substance should be placed in an appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines.

予防処置

Workers Should be careful during handling of 1,4-Dioxane and avoid open flames, sparks and smoking. Workers should wear proper protectives since 1,4-Dioxane in known as hazardous, cause damage to eyes, respiratory tract, liver and kidney.