チオケテンS酸化物から分離可能なチアレン-2-チオン (アルファ-ディチオラクトン) の合成
Kentaro Okuma1, Toshiyuki Shigetomi, Yoshinori Nibu
1Department of Chemistry, Faculty of Science, Fukuoka University, Jonan-ku, Fukuoka 814-0180, Japan. kokuma@fukuoka-u.ac.jp
Journal of the American Chemical Society
|August 5, 2004
まとめ
研究者は,Lawesson反応剤とdi-tert-butyl thioketene S-oxideを使用して3,3-di-tert-butylthiirane-2-thioneを合成しました. 更に酸化することで,対応するS-オキシドが得られ,チアラン-チオン反応性を詳細に示した.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 硫黄化学 硫黄の化学について
背景:
- チオケテンおよびその誘導体は,反応性中間物質である.
- チアラン誘導体は,独特の化学特性を持つ硫黄を含むヘテロサイクルである.
研究 の 目的:
- 新型チアレン誘導体を合成するために.
- チアレン-2-チオーンとそのS酸化物の反応性を調査する.
主な方法:
- ディテルト・ブチルチオケテンS酸化物とローエソン反応剤の反応.
- m-塩素ベンゾ酸を用いて,生成されたチアレン-2-チオンの酸化.
主要な成果:
- 3,3-di-tert-butylthiirane-2-thioneの合成に成功し,88%の生産率を達成しました.
- 3,3-di-tert-butylthiirane-2-thione S-オキシドの酸化による準備.
- 反応産物の特徴とチアラン・チオンの化学反応の記述.
結論:
- ディ-テルト-ブチルチオケテンS酸化物は,チアレン-2-チオン合成の有効な前駆体である.
- チアレン-2-チオンは,選択的に酸化され,S-オキシドにすることができます.
- この研究は,チアラン-チオン化合物の既知の反応を拡張しています.
関連する概念動画
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
Oxidative Cleavage of Alkenes: Ozonolysis
In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Oxidation of Alcohols
In this lesson, the oxidation of alcohols is discussed in depth. The various reagents used for oxidation of primary and secondary alcohols are detailed, and their mechanism of action is provided.
The process of oxidation in a chemical reaction is observed in any of the three forms:
The process of oxidation in a chemical reaction is observed in any of the three forms:
Preparation and Reactions of Thiols
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Aldol Condensation with β-Diesters: Knoevenagel Condensation
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.


