每周分子 | Molecule of the Week

每周分子： 甲基肼

Molecule of the Week: 

Methylhydrazine

本期的每周分子甲基肼(MMH)具有矛盾的两面性，如危害信息表所示，其对人类和环境非常不友好，但它是在自然界中被发现的。

甲基肼至少在1888年就已为人所知，当时德国化学家Gustav von Brüning发表了一系列关于它的文章。1890年，Gustav von Brüning报道了甲基肼的合成方法，首先用硝酸甲基脲和亚硝酸钠制备1-亚硝基-1-甲基脲。然后用锌粉在乙酸中还原亚硝基化合物，再经过大量的后处理后生成了甲基肼。

1954年，伊利诺伊大学(厄巴纳-香槟分校，美国)的L.F.Audrieth和L.H.Diamond报道了一种更简洁的合成方法，即通过甲胺与氯胺的反应来制备甲基肼和其他单取代肼。该工艺被用于甲基肼的现代工业生产。甲基肼主要被用作火箭推进剂和合成高级肼衍生物和其他有机化学品。

自然界中的哪些地方会存在甲基肼？甲基肼是毒蘑菇中最致命的化合物之一。甲基肼还存在于 赭鹿花菌 ( Gyromitra spp. )植物中，由原生毒素鹿花菌素 ¹ (gyromitrin)水解时形成。其他致命的蘑菇毒物包括α-鹅膏菌素 ² (α-amanitin)，奥来毒素 ³ (orellanine)和麦角胺 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.

甲基肼信息速览

甲基肼危害信息

【 关于每周分子 】

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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