ジアゾ酢酸エチル

解説

C4H6N2O2(114.11)．N2CHCOOC2H5．ジアゾ酢酸エチルは，グリシンエチルエステルの塩酸塩に亜硝酸カリウムを作用させてつくる．刺激臭のある黄色の液体．融点－22 ℃，沸点141 ℃(96 kPa，不純なものは分解する)，84 ℃(8.1 kPa)．d²⁰1.083．エタノール，ベンゼン，エーテル，リグロインなどに可溶，水に難溶．非常に反応性に富み，加熱や濃塩酸，濃硫酸によって爆発的に分解する．また，水と煮沸するか，痕跡の硫酸の作用でグリコール酸エステルとなる．フェーリング液や硝酸銀を還元する．非常に多くの有機化学反応および合成に利用されている．なお，遊離のジアゾ酢酸(N2CHCOOH)はまだ知られていない．森北出版「化学辞典（第2版）

化学的特性

Liquid.

使用

Reagent for ruthenium-catalyzed asymmetric cyclopropanation of alkenes.1

危険性

Flammable liquid that explodes when heated.

安全性プロファイル

Poison by ingestion and intravenous routes. Questionable carcinogen with experimental carcinogenic and tumorigenic data. Can explode. Explodes on contact with tris(dimethy1amino) antimony. When heated to decomposition it emits toxic fumes of NOx. See also ESTERS.

純化方法

It is a very volatile yellow oil with a strong pungent odour. EXPLOSIVE [distillation even under reduced pressure is dangerous and may result in an explosion — TAKE ALL THE NECESSARY PRECAUTIONS IF DISTILLATION IS TO BE CARRIED OUT]. It explodes in contact with conc H2SO4-trace acid causes rapid decomposition. It is slightly soluble in H2O, but is miscible with EtOH, *C6H6, pet ether and Et2O. To purify, dissolve it in Et2O [using CH2Cl2 instead of Et2O, protects the ester from acid], wash it with 10% aqueous Na2CO3, dry (MgSO4), filter and repeat as many times as possible until the Et2O layer loses its yellow colour, then remove the solvent below 20o (vacuum). Note that prolonged heating may lead to rapid decomposition and low yields. It can also be purified by steam distillation under reduced pressure but with considerable loss in yield. Place the residual oil in a brown bottle, keep below 10o, and use as soon as possible without distilling. For preparing esters usually the ethereal solution is used directly without purification. [Womack & Nelson Org Synth Coll Vol III 392 1955, UV: Miller & White J Am Chem Soc 79 5974 1957, Fieser 1 367 1967, Beilstein 3 IV 1495.]