オピエットの14-水酸化:コデニオンの14-ヒドロキシコデニオンの触媒的直接オート酸化を14-ヒドロキシコデニオンの14-ヒドロキシコデニオンの直接オート酸化とする
Qibo Zhang1, Joseph O Rich, Ian C Cotterill
1Albany Molecular Research, Inc., Bioscience Division, Albany, New York 12212-5098, USA.
Journal of the American Chemical Society
|May 19, 2005
まとめ
研究者らは14-ヒドロキシル化オピエット薬剤を合成する新しい方法を開発した. このプロセスは,コデインオンの14-ヒドロキシコデインオンの触媒的空気酸化を使用して,豊富なコデインから直接合成を可能にします.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 薬用化学 薬用化学について
- バイオカタリシス バイオカタリシス
背景:
- 14ヒドロキシル化オピエット薬の合成は,通常,発端材料としてセバインに依存します.
- 微生物の変換に関する研究では,コデインの14-ヒドロキシル化が酵素的ステップではなく,化学的ステップを伴う可能性があることが明らかになりました.
研究 の 目的:
- コデインオンから14-ヒドロキシコデインオンの直接的かつ効率的な化学合成を開発する.
- 14ヒドロキシル化オピエット合成のためのよりアクセシブルな前駆体としてコデインの使用を調査する.
主な方法:
- コデインオンの水溶液中の触媒性空気酸化.
- 単純マンガンと銅の塩 (例えば,MnSO4,KMnO4,CuSO4) を触媒として利用する.
- ペロキシド中間物質の管理のために,硫酸ナトリウムチオスルフェートなどの還元剤を加える.
主要な成果:
- コデインオンは,触媒的な空気酸化によって14-ヒドロキシコデインオンに効率的に変換されました.
- マンガンと銅の塩は,この変換の触媒として有効性を示しました.
- 反応は水溶液で進行し,潜在的によりグリーンな合成経路を提供します.
結論:
- この方法は,14-ヒドロキシコデインオンへの直接的な経路を提供し,バインの中間物質の必要性を回避します.
- これは,より豊富な前駆体であるコデインを14-水酸化オピエット薬の合成のために利用することを可能にします.
- この発見は,コデイン14-水酸化の酵素性に関する以前の仮定に異議を唱え,その化学的基礎を強調しています.
関連する概念動画
02:23Autoxidation of Ethers to Peroxides and Hydroperoxides
Ethers represent a class of chemical compounds that become more dangerous with prolonged storage because they tend to form explosive peroxides when standing in the air. Autoxidation is the spontaneous oxidation of a compound in air. In the presence of oxygen, ethers slowly oxidize to form hydroperoxides and dialkyl peroxides.
02:35Free-Radical Chain Reaction and Polymerization of Alkenes
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
01:17Oxidation of Phenols to Quinones
In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox property is crucial in...
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox property is crucial in...
01:20Radical Autoxidation
The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
01:29Chain Reactions
Chain reactions involve highly reactive transient species, such as atoms or free radicals, as intermediates. These intermediates facilitate rapid reactions over an extended period. The process includes a series of steps: a reactive intermediate is consumed, reactants are converted to products, and the intermediate is regenerated. This cycle enables continuous repetition, amplifying the production of products with a small amount of intermediate. Chain reactions often utilize free radicals as...
01:30Spontaneous and Induced Mutations
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