每周分子： 甲基肼

Molecule of the Week: 

Methylhydrazine

本期的每周分子甲基肼(MMH)具有矛盾的兩面性，如危害信息表所示，其對(duì)人類和環(huán)境非常不友好，但它是在自然界中被發(fā)現(xiàn)的。

甲基肼至少在1888年就已為人所知，當(dāng)時(shí)德國(guó)化學(xué)家Gustav von Brüning發(fā)表了一系列關(guān)于它的文章。1890年，Gustav von Brüning報(bào)道了甲基肼的合成方法，首先用硝酸甲基脲和亞硝酸鈉制備1-亞硝基-1-甲基脲。然后用鋅粉在乙酸中還原亞硝基化合物，再經(jīng)過大量的后處理后生成了甲基肼。

1954年，伊利諾伊大學(xué)(厄巴納-香檳分校，美國(guó))的L.F.Audrieth和L.H.Diamond報(bào)道了一種更簡(jiǎn)潔的合成方法，即通過甲胺與氯胺的反應(yīng)來制備甲基肼和其他單取代肼。該工藝被用于甲基肼的現(xiàn)代工業(yè)生產(chǎn)。甲基肼主要被用作火箭推進(jìn)劑和合成高級(jí)肼衍生物和其他有機(jī)化學(xué)品。

自然界中的哪些地方會(huì)存在甲基肼？甲基肼是毒蘑菇中最致命的化合物之一。甲基肼還存在于 赭鹿花菌 ( Gyromitra spp. )植物中，由原生毒素鹿花菌素 ¹ (gyromitrin)水解時(shí)形成。其他致命的蘑菇毒物包括α-鵝膏菌素 ² (α-amanitin)，奧來毒素 ³ (orellanine)和麥角胺 ⁴ (ergotamine)。

1. CAS Reg. No. 16568-02-8. 2. CAS Reg. No. 23109-05-9. 3. CAS Reg. No. 37338-80-0. 4. CAS Reg. No. 113-15-5.

甲基肼信息速覽

甲基肼危害信息

【 關(guān)于每周分子 】

We begin 2023 with the nasty molecule methylhydrazine. As shown in the hazard information table, the compound, also called monomethylhydrazine (MMH), is deadly to humans and environmentally harmful. It is, unexpectedly, found in nature.

Methylhydrazine has been known since at least 1888, when German chemist Gustav von Brüning initiated a series of articles on the molecule. In 1890, he reported a synthesis of MMH that began with the preparation of 1-nitroso-1-methylurea from methylurea nitrate and sodium nitrite. The nitroso compound was then reduced with zinc dust in acetic acid to produce MMH after an extensive workup procedure.

In 1954, L. F. Audrieth and L. H. Diamond at the University of Illinois (Urbana–Champaign) reported a more concise synthesis: They prepared methylhydrazine and other monosubstituted hydrazines via the reaction of methylamine with chloramine. This process is used for the modern industrial production of MMH. The compound’s main uses are in rocket propellants and the synthesis of higher hydrazine derivatives and other organic chemicals.

Where does methylhydrazine turn up in nature? It is one of the deadliest compounds in poisonous mushrooms. It is found in  Gyromitra spp. , in which it is formed when the native toxin gyromitrin ¹  hydrolyzes. Other lethal mushroom poisons include α-amanitin ² , orellanine ³ , and ergotamine ⁴ .

1. CAS Reg. No. 16568-02-8. 2. CAS Reg. No. 23109-05-9. 3. CAS Reg. No. 37338-80-0. 4. CAS Reg. No. 113-15-5.

Methylhydrazine fast facts

Methylhydrazine hazard information

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