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氢负理论与氧化还原反应

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化学制药工艺的研究中,氧化还原反应尚存在诸多含混不清的问题。笔者通过对硼氢化钠的来源、还原机制和还原能力等现象进行思考,提出"氢负(H-)"的概念,进而推广至其他金属还原剂,比如LiAlH4、Red-Al、DIBAL-H、Et3SiH,分析指出其还原性都是由于硼(B)、铝(Al)、硅(Si)与氢(H)的电负性差导致氢负的产生。在传统催化氢化的自由基理论基础上提出了另外一种极性反应假说,并对生物催化氧化还原反应中的羰基还原过程进行了详细解释,进一步证实氢负理论的合理性。同时,笔者在氢负还原剂的基础上推导出氧化剂大多是氢氧正(HO+)或活性氧(+O-),揭示了氧化剂的共性特点,还对生物酶催化氧化反应案例剖析,结果显示氧化反应总是伴随还原反应。在氢负理论的指导下,笔者对多种涉及氧化还原的人名反应进行重新解读,修正或提出了更合理的机理假说,初步探讨了催化剂在氧化还原反应中的作用。最后,本文对氧化还原反应进行了精准定义,把极性反应划分为取代反应和氧化还原反应,揭示了氧化还原的本质特点在于发生"极性颠倒"。
Hydrogen Negative Theory and Redox Reaction
In the research of chemical pharmaceutical processes,there are still many seemingly ambiguous issues regarding redox reactions.Author proposed the concept of"hydrogen negative(H-)"by considering the sources,reduction mechanisms,and reducing abilities of sodium borohydride,and then extended it to other metal reducing agents such as LiAlH4,Red-Al,DIBAL-H,Et3SiH.The analysis indicated that their reducibility stems from the disparity in electronegativity between B,Al,Si,and H,which led to the generation of hydrogen negativity.Building upon the free radical theory of traditional catalytic hydrogenation,another polar reaction hypothesis was proposed,and the carbonyl reduction process in biocatalytic oxidation-reduction reactions was explained in detail,further confirming the rationality of the hydrogen negative theory.Meanwhile,based on the hydrogen negative reducing agent,it was inferred that the majority of oxidants were hydrogen oxygen positive(HO+)or reactive oxygen species(+O-),thereby revealing the shared characteristics of oxidants.Furthermore,an analysis was conducted on instances of enzymatic oxidation reactions which consistently demonstrates their association with reduction reactions.Guided by the theory of hydrogen negativity,various reactions involving oxidation-reduction had been reinterpreted,and more reasonable mechanistic hypotheses had been revised or proposed.The role of catalysts in oxidation-reduction reactions had been preliminarily explored.Finally,a precise definition of oxidation-reduction reactions was provided,dividing polarity reactions into substitution reactions and oxidation-reduction reactions,while elucidating that the fundamental characteristic of oxidation-reduction lies in the occurrence of"polarity reversal".

hydrogen negative theoryoxidation-reduction reactionpolar reaction

张福利

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中国医药工业研究总院,上海医药工业研究院,上海 201203

氢负理论 氧化还原反应 极性反应

2024

中国现代应用药学
中国药学会

中国现代应用药学

CSTPCD北大核心
影响因子:0.877
ISSN:1007-7693
年,卷(期):2024.41(20)