每周分子 | Molecule of the Week

Original ACS 美国化学会 ACS美国化学会 2022-07-01

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每周分子：1,2-二氧环丁烷二酮

Molecule of the Week:

1,2-Dioxetanedione

1,2-二氧环丁烷二酮是一种高应变的四元环分子，可被认为是草酸的过氧酸酐或二氧化碳的二聚体。它因具有高应变性而非常不稳定，在-93°c的温度下即分解。

1,2-二氧环丁烷二酮除了具有独特的结构，还有另一个出名的原因：它参与了一个引起化学发光的反应序列，这是一个通过化学反应产生光的过程。草酰氯或草酸酯与过氧化氢在活性染料存的条件下引起化学发光的反应，已经被研究了近60年，但直到最近1,2-二氧环丁烷二酮才被证明是其中关键的高能中间体(HEI)。

在2021年，Wilhelm J. Baader及其在巴西São Paulo大学和ABC联邦大学(巴西Santo André)的同事们有力地证明了其中的HEI确实是1,2-二氧环丁烷二酮。利用各种芳基过氧草酸酯生成HEI，并进行精确的动力学和热力学测定后，研究人员得出结论：1,2-二氧环丁烷二酮的平面结构和电子受体性质使其成为唯一能够参与该反应序列的HEI。他们的实验排除了其他不具备足够驱动发光反应步骤能量的已知中间体，如过草酸和1,2-二氧乙酮。

1,2-二氧环丁烷二酮以及化学发光的实际应用是什么呢？名气最大的当然要属发光棒这种当时的新奇产品了。早在20世纪60年代，当时的美国氰胺公司(现已不存在，当时位于美国新泽西州韦恩)的一位研发经理注意到贝尔实验室(位于美国新泽西州默里山，现为诺基亚贝尔实验室)的Edwin a . Chandross在其发表的一篇文章中首次描述了这种现象。美国氰胺公司的化学家将Chandross的反应序列完善并开发成了发光棒商品，是其衍生公司Cyalume Technologies(位于美国马萨诸塞州西斯普林菲尔德)开发相关产品的基础。

大概在同一时间，美国国防部和军方开发了用在训练设备和救生浮力背心上等用途的发光棒。此后，Cyalume公司推出了化学发光寿命从30秒到24小时、工作温度从-50°C到+50°C不等的发光棒创新产品。

1,2-二氧环丁烷二酮信息速览

CAS 登记号	26974-08-3
SciFinder命名	1,2-Dioxetane-3,4-dione
分子式	C2O4
摩尔质量	88.02 g/mol
外观	N/A
熔点/沸点	–93 °C (dec.)
水溶性	N/A

【关于每周分子】

自2001年以来，“每周分子”已成为广受欢迎的栏目。多数分子由读者推荐。每个结构都经由科学家审查，并以3-D和平面图像的形式显示，同时附有该分子简介。可以通过美国化学文摘社 (CAS) 提供的SciFinder中的CAS REGISTRY获取“每周分子”的更多信息。CAS REGISTRY中的每条物质信息都展示了物质的CAS登记号、索引名、通用名、商品名、书目信息等其他更多信息。发送邮件至motw@acs.org推荐您感兴趣的分子吧。

1,2-Dioxetanedione is a highly strained four-memberedring molecule that can be thought of as a peroxy anhydride of oxalic acid or asa dimer of carbon dioxide. Because of its high strain, it is quite unstable,decomposing at temperatures above –93 °C.

Other than its unique structure, 1,2-dioxetanedionehas another claim to fame: its participation in a reaction sequence that leadsto chemiluminescence, a process that produces light via a chemical reaction.Chemiluminescence that results from the reaction between oxalyl chloride or anoxalate ester and hydrogen peroxide in the presence of an activator dye hasbeen studied for almost 60 years, but only recently was it demonstrated that1,2-dioxetanedione is the key high-energy intermediate (HEI).

In 2021, Wilhelm J. Baader at the University of SãoPaulo (Brazil) and colleagues there and at the Federal University of ABC (SantoAndré, Brazil) conclusively showed that the HEI is indeed 1,2-dioxetanedione. Using various arylperoxyoxalate esters to generate the HEI and precisekinetic and thermodynamic measurements, the researchers concluded that1,2-dioxetanedione’s planar structure and electron-acceptor properties made itthe only participant in the reaction sequence capable of being the HEI. Theirexperiments eliminated other known intermediates, such as peroxalic acids and1,2-dioxetanones, from having enough energy to drive the luminescence step.

What are the practical applications of1,2-dioxetanedione and chemiluminescence? Certainly, the best known are thenovelty products known as glowsticks. Back in the 1960s, a research manager atthe now-defunct American Cyanamid (Wayne, NJ) noticed an article by Edwin A.Chandross at Bell Laboratories (Murray Hill, NJ; now Nokia Bell Labs) that first describedthe phenomenon. Cyanamid chemists refined Chandross’s reactionsequence into commercial glowsticks, which were the basis for a spinoffcompany, Cyalume Technologies (West Springfield, MA).

At about the same time, the US Department of Defenseand the military developed glowsticks for such uses as training devices andlife-saving flotation vests. Innovations atCyalume since then have brought forth glowsticks with chemiluminescencelifetimes from 30 sec to 24 h and with operating temperatures ranging from –50to +50 °C.

1,2-Dioxetanedionefast facts

CAS Reg. No.	26974-08-3
SciFinder nomenclature	1,2-Dioxetane-3,4-dione
Empirical formula	C₂O₄
Molar mass	88.02 g/mol
Appearance	N/A
Melting / Boiling point	-93°C (dec.)
Water solubility	N/A soluble

About Molecule of the Week

MOTW has been a popular feature on ACS website since 2001. Many molecules are suggested by our website visitors. Every structure is reviewed by a scientist and displayed in 3-D and flat images with a brief description. Each week’s molecule also links to a sample record from the CAS REGISTRY, which is searched using SciFinder. Each record displays the registry number, index name and synonyms, bibliographic information, and more. Send us a molecule suggestion at motw@acs.org.

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