每周分子 | Molecule of the Week

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

收录于合集 #每周分子 110个

每周分子：氯氟磺酰

Molecule of the Week:

Sulfuryl chloride fluoride

氯氟磺酰(SO₂ClF)为强路易斯酸，可作为溶剂和试剂使用。如危害信息表所示，在处理氯氟磺酰的过程中，必须小心。氯氟磺酰的沸点范围使其既可以是气体，也可以是液体。

20世纪30年代，美国西储大学(克利夫兰；后来的凯斯西储大学)的Harold Simmons Booth和Carl V. Herrmann对SO₂ClF进行了开创性的研究。他们在五氯化锑(SbCl₅)存在下，通过硫酰氯 (SO₂Cl₂) 和三氟化锑(SbF₃)的反应合成了SO₂ClF。他们还测量了SO₂ClF的一些特性，包括沸点、熔点、液体密度、-89到+9ºC的蒸汽压、蒸发热和表面张力。

但研究SO₂ClF的真正冠军是1994年的化学诺贝尔奖得主George A. Olah。Olah和Joachim Lukas于1967年在美国凯斯西储大学使用溶剂系统SO₂ClF- FSO₃H-SbF₅生成了稳定的烷基碳正离子(现在称为碳正离子)——从简单的如Me₃C+和Me₂EtC+到含有多达9个碳原子的阳离子。他们所用的这种酸混合物后来被称为超强酸。

1976年，Olah、Mark R. Bruce和John Welch在温和条件下向氟化氢吡啶聚合物中添加SO₂Cl₂，改进了SO₂ClF的合成。到20世纪80年代早期，Olah和他的同事们(现在在美国南加州大学)开发了一种多功能的SO₂ClF试剂。一些SO₂ClF的应用包括：

一种用于将醛肟转化为腈的脱水剂；
与三乙胺结合使用，一种用于从羧酸和伯胺制备酰胺、从羧酸和醇制备酯的试剂；
与三氧化硫结合使用，一种用于将叔膦和胂转化为其相应氧化物的氧化剂；
与SO₂Cl₂结合使用，一种用于将烯醇硅醚转化为α-氯酮的试剂。

最后，在1992年，美国南加州大学的V. Prakash Reddy、Donald R. Bellew和G. K. Surya Prakash报道了另一种有用的合成SO₂ClF的方法，在三氟乙酸存在下从SO₂Cl₂和氟化铵或氟化钾制备SO₂ClF。Surya Prakash是Olah的学生，为其南加州大学Loker碳氢化合物研究所所长继任者，Olah的碳正离子研究主要在该研究所完成。

氯氟磺酰信息速览

CAS 登记号	13637-84-8
SciFinder命名	Sulfuryl chloride fluoride
分子式	ClFO₂S
摩尔质量	118.52 g/mol
外观	无色气体，无色或者浅黄液体
熔点	7.1 ºC
水溶性	发生反应

氯氟磺酰危害信息

GHS*分类：高压气体，液化气
H280-含高压气体；如果加热可能爆炸
GHS分类：急性毒性，口服，分类3
H301-吞食有毒
GHS分类：皮肤，分类3
H311-与皮肤接触有毒
GHS分类：皮肤腐蚀/刺激，分类1B
H314-导致严重的皮肤烧伤和眼睛损伤
GHS分类：严重眼睛损害/眼睛刺激，分类1
H318-引起严重眼睛损害
GHS分类：急性毒性，吸入，分类3
H331-吸入有毒
GHS分类：特定靶器官毒性，单次暴露，呼吸道刺激，分类3
H335-引起呼吸道刺激
GHS分类：简单窒息，分类1
H380-可能取代氧气并导致快速窒息

【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。

Sulfuryl chloride fluoride (SO₂ClF) is a strong Lewis acid and a useful solvent and reagent. As shown in the hazard information table, it must be handled with care. Its boiling point is in the range that allows its use as a gas or a liquid.

In the 1930s, Harold Simmons Booth and Carl V. Herrmann at Western Reserve University (Cleveland; later Case Western Reserve University) performed pioneering work on SO₂ClF. They synthesized it via the reaction of sulfuryl chloride (SO₂Cl₂) and antimony trifluoride (SbF₃) in the presence of antimony pentachloride (SbCl₅). They also measured several properties of SO₂ClF, including boiling point, melting point, liquid density, vapor pressure from –89 to +9 ºC, heat of vaporization, and surface tension.

But the real champion of SO2ClF was the 1994 chemistry Nobelist George A. Olah. In 1967, also at Case Western, Olah and Joachim Lukas used the solvent system SO₂ClF–fluorosulfonic acid (FSO₃H)–antimony pentafluoride (SbF₅) to generate stable alkylcarbonium ions (now called carbocations)—from simple ones such as Me₃C+ and Me₂EtC+ through cations containing as many as nine carbon atoms. Acid mixtures like the ones they used came to be known as superacids.

In 1976, Olah, Mark R. Bruce, and John Welch developed an improved synthesis of SO₂ClF by adding SO₂Cl₂ to pyridinium poly(hydrogen fluoride) under mild conditions. By the early 1980s, now at the University of Southern California (Los Angeles), Olah and co-workers developed SO₂ClF as a versatile reagent. Some SO₂ClF applications include.

a dehydrating agent for converting aldoximes to nitriles;
in combination with triethylamine, a reagent for making amides from carboxylic acids and primary amines and esters from carboxylic acids and alcohols;
in combination with sulfur trioxide, an oxidant for converting tertiary phosphines and arsines to their corresponding oxides; and
in combination with SO2Cl2, a reagent for converting enol silyl ethers to α-chloro ketones.

Finally, in 1992, V. Prakash Reddy, Donald R. Bellew, and G. K. Surya Prakash at USC reported another useful synthesis of SO₂ClF, from SO₂Cl₂ and ammonium or potassium fluoride in the presence of trifluoroacetic acid. Surya Prakash was a student of Olah and is his successor as the director of USC’s Loker Hydrocarbon Research Institute, the location of much of Olah’s carbocation research.

Sulfuryl chloride fluoridefast facts

CAS Reg. No.	13637-84-8
SciFinder nomenclature	Sulfuryl chloride fluoride
Empirical formula	ClFO₂S
Molar mass	118.52 g/mol
Appearance	Colorless gas or colorless to light yellow liquid
Melting point	7.1 ºC
Water solubility	Miscible

Sulfuryl chloride fluoride hazard information

Gases under pressure, liquefied gas
H280-Contains gas under pressure; may explode if heated
Acute toxicity, oral, category 3
H301-Toxic if swallowed
Acute toxicity, dermal, category 3
H314-Toxic in contact with skin
Skin corrosion/irritation, category 1B
H314-Causes severe skin burns and eye damage
Serious eye damage/eye irritation, category 1
H318-Causes serious eye damage
Acute toxicity, inhalation, category 3
H331-Toxic if inhaled
Specific target organ toxicity, single exposure, respiratory tract irritation, category 3
H335-May cause respiratory irritation
Simple asphyxiation, category 1
H380-May displace oxygen and cause rapid suffocation

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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