3-methyl-10-(1'-naphthyl)isoalloxazine | 116138-29-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 蝶啶及其衍生物
• 英文名称: 3-methyl-10-(1'-naphthyl)isoalloxazine
• 英文别名: 3-methyl-10-(1-naphthyl)isoalloxazine；3-Methyl-10-(naphthalen-1-yl)benzo[g]pteridine-2,4(3H,10H)-dione；3-methyl-10-naphthalen-1-ylbenzo[g]pteridine-2,4-dione
• CAS: 116138-29-5；116138-30-8；160510-39-4
• 化学式: C₂₁H₁₄N₄O₂
• 分子量: 354.368
• InChiKey: KZTIJQTVMZTPHL-UHFFFAOYSA-N

物化性质

• 沸点：
  553.3±33.0 °C(Predicted)
• 密度：
  1.40±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  27
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  65.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-methyl-10-(1'-naphthyl)isoalloxazine 生成 3-methyl-10-naphthalen-1-yl-1,5-dihydrobenzo[g]pteridine-2,4-dione
  参考文献：
  名称：

  SHINKAI, SEIJI;NAKAO, HIDEKI;KUWAHARA, ITSUKO;MIYAMOTO, MEGUMI;YAMAGUCHI,+, J. CHEM. SOC. PERKIN TRANS.,(1988) N 2, 313-319

  摘要：

  DOI：
• 作为产物：
  描述：

  3-Methyl-6-(naphthalen-1-ylamino)-1H-pyrimidine-2,4-dione 生成 3-methyl-10-(1'-naphthyl)isoalloxazine
  参考文献：
  名称：

  SHINKAI, SEIJI;NAKAO, HIDEKI;KUWAHARA, ITSUKO;MIYAMOTO, MEGUMI;YAMAGUCHI,+, J. CHEM. SOC. PERKIN TRANS.,(1988) N 2, 313-319

  摘要：

  DOI：

文献信息

• Flavin Activation by Intramolecular Acid Catalysis at N(1) Position
  作者：Seiji Shinkai、Sayuri Kawanabe、Akito Kawase、Toshiro Yamaguchi、Osamu Manabe、Shigeharu Harada、Hideki Nakamura、Nobutami Kasai

  DOI：10.1246/bcsj.61.2095

  日期：1988.6

  In order to assess the effect of intramolecular acid catalysis on the specific flavin reactivities, 3-methyl-10-(2-hydroxyphenyl)isoalloxazine (1(2OH)) and 3-methyl-10-(2-hydroxy-1-naphthyl)isoalloxazine (2(2OH)) were synthesized and the redox properties were compared with those of reference flavins such as 3-methyl-10-(2-methoxyphenyl)isoalloxazine (1(2OMe)) and 3-methyl-10-(2-methoxy-1-naphthyl)isoalloxazine (2(2OMe)). The pKa values for 1(2OH) and 2(2OH) were determined to be 7.7 and 7.0, respectively, which were lower than that of 3-methyl-10-(4-hydroxyphenyl)isoalloxazine (1(4OH): pKa 8.6). It is thus unlikely that 2′-OH and N(1) form a hydrogen bond at the initial state of the reaction (i.e., at the oxidized state). The X-ray crystallographic studies indicated that the phenyl ring makes an angle of 79.7° with the isoalloxazine ring and the 2′-OH group forms a hydrogen bond with methanol included in the crystal lattice. In acetonitrile at 30 °C 1-benzyl-1,4-dihydronicotinamide was not oxidized by 1(2OMe), 1(4OH), and 2(2OMe). On the other hand, the oxidation took place with 1(2OH) and 2(2OH) which have an acidic OH group at the 2′-position of the 10-aryl substituent. The presence of the intramolecular acid catalysis suggests that 2′-OH and N(1) can interact at least at the transition state or at the final state of the reaction (i.e., at the reduced state). In general, the oxidized flavin adopts a “planar” structure which is sterically tense while the reduced flavin adopts a “bent” structure which is sterically relaxed. As the structure of the transition state is more or less similar to the reduced form, the hydrogen-bonding interaction could increase on going from the tense initial state to the relaxed transition state. This is a novel example for acid catalysis in flavin-mediated reactions.

  为了评估分子内酸催化对特定黄素反应性的影响，合成了3-甲基-10-(2-羟基苯基)异黄素（1(2OH)）和3-甲基-10-(2-羟基-1-萘基)异黄素（2(2OH)），并将其氧化还原性质与参考黄素如3-甲基-10-(2-甲氧基苯基)异黄素（1(2OMe)）和3-甲基-10-(2-甲氧基-1-萘基)异黄素（2(2OMe)）进行了比较。1(2OH)和2(2OH)的pKa值分别为7.7和7.0，均低于3-甲基-10-(4-羟基苯基)异黄素（1(4OH)：pKa 8.6）。因此，在反应的初始状态（即氧化状态）下，2′-OH和N(1)形成氢键的可能性较小。X射线晶体学研究表明，苯环与异黄素环之间的夹角为79.7°，而2′-OH基团与晶体格中包含的甲醇形成氢键。在30 °C的乙腈中，1-苯基-1,4-二氢烟酰胺未被1(2OMe)、1(4OH)和2(2OMe)氧化。另一方面，1(2OH)和2(2OH)（在10-芳基取代基的2′位置具有酸性OH基团）发生了氧化。分子内酸催化的存在表明，2′-OH和N(1)至少可以在反应的过渡态或最终状态（即还原状态）下相互作用。一般来说，氧化的黄素采用“平面”结构，立体张力较大，而还原的黄素则采用“弯曲”结构，立体张力较小。由于过渡态的结构或多或少与还原形式相似，因此在从紧张的初始状态转变为放松的过渡状态时，氢键相互作用可能会增强。这是黄素介导反应中酸催化的新颖例子。
• Novel Racemization of Atropisomeric Flavins and 5-Deazaflavins via Adduct Formation
  作者：Seiji Shinkai、Hideki Nakao、Toshiro Yamaguchi、Osamu Manabe

  DOI：10.1246/bcsj.61.307

  日期：1988.1

  The molecular structures of covalent adducts derived from flavins and 5-deazaflavins are discussed on the basis of racemization of atropisomeric flavins and 5-deazaflavins. The 5-adducts with SO32− and CN− underwent facile racemization, indicating that the molecular structure changes from the “tense” planar state to the “relaxed” bent state. On the other hand, the 4a-adduct prepared by the photo-alkylation method did not racemize at room temperature. This indicates that the structure of the 4a-adduct is different from the bent 5-adduct. These results provide an information useful to discuss the reduced state of flavoproteins.

  基于旋光异构黄素和5-脱氮黄素的消旋化，讨论了黄素和5-脱氮黄素共价加合物的分子结构。5-加合物与SO32−和CN−发生简单的消旋化，表明分子结构从“紧张”的平面状态转变为“松弛”的弯曲状态。另一方面，通过光烷基化方法制备的4a-加合物在室温下不会发生消旋化。这表明4a-加合物的结构不同于弯曲的5-加合物。这些结果为讨论黄素蛋白的还原状态提供了有用的信息。
• Staab, Heinz A.; Kirsch, Peer; Zipplies, Matthias F., Chemische Berichte, 1994, vol. 127, # 9, p. 1653 - 1666
  作者：Staab, Heinz A.、Kirsch, Peer、Zipplies, Matthias F.、Weinges, Alexa、Krieger, Claus

  DOI：——

  日期：——
• Shinkai, Seiji; Nakao, Hideki; Kuwahara, Itsuko, Journal of the Chemical Society. Perkin transactions I, 1988, p. 313 - 320
  作者：Shinkai, Seiji、Nakao, Hideki、Kuwahara, Itsuko、Miyamoto, Megumi、Yamaguchi, Toshiro、Manabe, Osamu

  DOI：——

  日期：——
• SHINKAI, SEIJI;NAKAO, HIDEKI;KUWAHARA, ITSUKO;MIYAMOTO, MEGUMI;YAMAGUCHI,+, J. CHEM. SOC. PERKIN TRANS.,(1988) N 2, 313-319
  作者：SHINKAI, SEIJI、NAKAO, HIDEKI、KUWAHARA, ITSUKO、MIYAMOTO, MEGUMI、YAMAGUCHI,+

  DOI：——

  日期：——