(5S,6S)-5,6-Dihydroxy-5-methyldihydro-2,4(1H,3H)-pyrimidinedione | 57968-49-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (5S,6S)-5,6-Dihydroxy-5-methyldihydro-2,4(1H,3H)-pyrimidinedione
• 英文别名: 5,6-dihydroxy-5-methyl-dihydro-pyrimidine-2,4-dione；cis-5,6-Dihydroxy-dihydro-thymin
• CAS: 57968-49-7
• 化学式: C₅H₈N₂O₄
• 分子量: 160.13
• InChiKey: GUKSGXOLJNWRLZ-MVHIGOERSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  98.7
• 氢给体数：
  4
• 氢受体数：
  4

文献信息

• Products of Thymine Oxygenation by a Non-heme Oxygenation Model, Fe<sup>II</sup>(MeCN)<sub>6</sub><sup>2+</sup>–Ac<sub>2</sub>O–H<sub>2</sub>O<sub>2</sub>, and the Transition State Model between Oxoiron and Thymine
  作者：Shigeki Kobayashi、Akihiko Takagi、Toshiyuki Chikuma、Osamu Tamura、Eiichi Kotani、Takao Katase

  DOI：10.1248/cpb.58.775

  日期：——

  Oxidative thymine damage was investigated using a new non-heme oxygenation model, Fe(MeCN)62+–H2O2–Ac2O, based on high-spin Fe(MeCN)62+ in a non-aqueous solution, Ac2O–MeCN. Thymine and 1,3-dimethylthymine oxidized by the system gave the corresponding trans-thymine glycol derivatives in good yield. Thymineglycol is equivalent to an oxidative product as a measure of oxidative DNA damage in living cells. It is suggested that the activation of Fe(MeCN)62+–H2O2–Ac2O in Ac2O–MeCN forms the oxoiron O=FeIV(AcO)(MeCN)4+ as an active species via a hetelolytic two-electron mechanism, not a Haber–Weiss–Fenton-type reaction with a one-electron process by treatment with a radical scavenger. In addition, we also demonstrated the transition state (TS) for the interaction between thymine and O=FeIV(AcO)(MeCN)4+ in the triplet spin (spin multiplicity; M=3). This model of oxidative thymine damage may provide new insight into the oxidative mechanism of thymine glycol production in non-aqueous reactions of thymine.

  利用一种新的非血红素氧化模型，即基于非水溶液Ac2O-MeCN中的高自旋Fe(MeCN)6^2+的Fe(MeCN)6^2+-H2O2-Ac2O体系，研究了胸腺嘧啶的氧化损伤。在该体系中，胸腺嘧啶和1,3-二甲基胸腺嘧啶被氧化生成相应的反式胸腺嘧啶二醇衍生物，产率良好。胸腺嘧啶二醇相当于一种氧化产物，可作为活细胞中氧化DNA损伤的衡量标准。研究表明，在Ac2O-MeCN中Fe(MeCN)6^2+-H2O2-Ac2O的活化通过异裂双电子机制形成活性物种O=FeIV(AcO)(MeCN)4+，而不是通过自由基清除剂处理时的Haber-Weiss-Fenton型单电子反应。此外，我们还阐明了胸腺嘧啶与O=FeIV(AcO)(MeCN)4+在三重态自旋（自旋多重性；M=3）中的相互作用过渡态(TS)。这一胸腺嘧啶氧化损伤模型可能为胸腺嘧啶在非水反应中生成胸腺嘧啶二醇的氧化机制提供新的见解。
• Reduction of Hydroperoxythymines with Glutathione and Glutathione Peroxidase
  作者：Toshio Itahara

  DOI：10.1246/cl.1987.1943

  日期：1987.10.5

  Glutathione peroxidase exerted acceleration effect on reduction of cis-6-hydroperoxy-5-hydroxy-5,6-dihydrothymine with glutathione, whereas it exerted little effect on reduction of trans-5-chloro-6-hydroperoxy-5,6-dihydrothymine with glutathione.

  谷胱甘肽过氧化物酶对顺式-6-羟过氧-5-羟基-5,6-二氢胸腺嘧啶与谷胱甘肽的还原作用具有促进效果，而对反式-5-氯-6-羟过氧-5,6-二氢胸腺嘧啶与谷胱甘肽的还原作用影响甚微。
• An unusual reaction of cis-6-hydroperoxy-5-hydroxy-5,6-dihydrothymine with ascorbic acid
  作者：Toshio Itahara

  DOI：10.1016/s0040-4039(01)83866-1

  日期：1987.1

  When two solutions of cis-6-hydroperoxy-5-hydroxy-5,6-dihydrothymine and ascorbic acid in deuterium oxide were mixed, chemically induced dynamic nuclear polarization was observed. The reaction gave N-formyl-N′-pyruvylurea.

  将顺式-6-氢过氧-5-羟基-5,6-二氢胸腺嘧啶和抗坏血酸在氧化氘中的两种溶液混合时，观察到化学诱导的动态核极化。反应得到N-甲酰基-N'-丙酮酰脲。
• Photosensitization of DNA bases by 4(5)-nitroimidazole: a steady state and flash photolysis study
  作者：Maitrayee Basu Roy、Parikshit C. Mandal、Samita Basu、Sudhindra N. Bhattacharyya

  DOI：10.1039/ft9959101191

  日期：——

  UV photolysis and laser flash photolysis of 4(5)-nitroimidazole in the presence of thymine and/or uracil generates the respective glycols under conditions where the bases do not absorb any light. The reaction is mediated through the triplet state of 4(5)-nitroimidazole which generates a highly oxidizing N-centred radical. The radical has an absorption maximum at ca. 350 nm and reacts efficiently with the DNA bases resulting in the formation of glycols. The rate constant of reaction of the radical with the DNA bases and nucleosides is of the order of ca. 108 dm3 mol–1 s–1, the rate being slower with the nucleosides than with the free bases.

  在存在胸腺嘧啶和/或尿嘧啶的情况下，4(5)-硝基咪唑的UV光解和激光闪光光解反应在嘧啶碱不吸收任何光线的条件下产生了相应的甘醇。这一反应是通过4(5)-硝基咪唑的激发三重态介导的，该三重态产生了一个高度氧化的N中心自由基。该自由基在约350 nm处有最大吸收，并且能高效地与DNA碱基反应，导致甘醇的形成。该自由基与DNA碱基和核苷的反应速率常数大约为10的8次方 dm3 mol–1 s–1，与自由碱基相比，与核苷的反应速度较慢。
• Effect of Fe(III) Ions on the γ-Radiolysis of Thymine
  作者：S. N. Bhattacharyya、P. C. Mandal、S. Chakrabarti

  DOI：10.1246/bcsj.63.3001

  日期：1990.10

  Aqueous solutions of thymine (T) in the presence of Fe(III) were irradiated under deaerated conditions at pH ≈2. The products of radiolysis were separated by two dimensional thin-layer chromatography. In the absence of any metal ion, the G(-T) is 2.6 but when Fe(III) is present during radiolysis, the G(-T) increases significantly and reaches a limiting value of 3.2. The yields of the hydroxylated products

  胸腺嘧啶 (T) 在 Fe(III) 存在下的水溶液在 pH ≈2 的脱气条件下进行辐照。辐射分解产物通过二维薄层色谱分离。在没有任何金属离子的情况下，G(-T) 为 2.6，但当在辐射分解过程中存在 Fe(III) 时，G(-T) 显着增加并达到 3.2 的极限值。在 Fe(III) 存在下，胸腺嘧啶的羟基化产物的产率也会增加。结果由一种机制解释，该机制涉及 Fe(III) 与胸腺嘧啶的瞬态加合物的相互作用。