(+/-)-1a,2,3,7b-tetrahydro-(1aα,2β,3α,7bα)-naphth<1,2-b>oxirene-2,3-diol | 69222-27-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (+/-)-1a,2,3,7b-tetrahydro-(1aα,2β,3α,7bα)-naphth<1,2-b>oxirene-2,3-diol
• 英文别名: (+/-)-1a,2,3,7b-tetrahydro-(1aβ,2β,3α,7bβ)naphth[1,2-b]oxirene-2,3-diol；(+/-)-1β,2α-Dihydroxy-3β,4β-epoxy-1,2,3,4-tetrahydro-naphthalin；(1aS,2R,3S,7bR)-1a,2,3,7b-tetrahydronaphtho[3,4-b]oxirene-2,3-diol
• CAS: 69222-27-1
• 化学式: C₁₀H₁₀O₃
• 分子量: 178.188
• InChiKey: XDSJRQRRQDAPNL-JLIMGVALSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  53
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-1a,2,3,7b-tetrahydro-(1aα,2β,3α,7bα)-naphth<1,2-b>oxirene-2,3-diol 在 serpentine 、 铂 1,5-dihydrolumiflavin 、 氢气 作用下， 以 1,4-二氧六环 为溶剂， 以63%的产率得到(+/-)-1,2,3,4-tetrahydro-(1α,2β,3α)-naphthalene-1,2,3-triol
  参考文献：
  名称：

  二氢黄素-四氢萘环氧化物加合物的二氢黄素还原裂解的机理研究。

  摘要：

  二氢黄素是容易的还原剂和有效的亲核试剂。通过与四氢萘环氧化物形成共价黄素加合物的速率测量的二氢黄素亲核反应性与硫醇根阴离子的亲核反应性相当（YT Lee和JF Fisher（1993）J. Org。Chem。58，3712）。在这些反应中，在被二氢黄素亲核裂解环氧化物之后，出现了与这些环氧化物的形式氢化物还原产物（在苄基碳上）相对应的产物。因此，（+/-）-1a，2,3,7b-四氢-（1aalpha，2alpha，3beta，7balpha）-萘[1,2-b]环氧乙烷-2,3-二醇的反应（1），（ +/-）-1a，2,3,7b-四氢-（1aalpha，2beta，3alpha，7balpha）-萘[1,2-b]环氧乙烷-2、3-二醇（2）和（+/-）在9：1（v / v）的Tris缓冲液-二恶烷水溶液中的-1a，2,3,7b-四氢-（1aalpha，7balpha）-萘[1,2-b]环氧乙

  DOI：

  10.1006/bioo.2000.1171
• 作为产物：
  描述：

  [(1S,2R,3R,4R)-4-acetyloxy-2-hydroxy-3-(4-methylphenyl)sulfonyloxy-1,2,3,4-tetrahydronaphthalen-1-yl] acetate 、 disodium;carbonate 、 甲醇 以90%的产率得到
  参考文献：
  名称：

  SCHMIDT R. R.; ANGERBAUER R., ANGEW. CHEM., 1979, 91, NO 4, 325-326

  摘要：

  DOI：

文献信息

• Chemistry of anti- and syn-1,2:3,4-naphthalene dioxides and their potential relevance as metabolic intermediates
  作者：Wing Sum Tsang、Gary W. Griffin、M. G. Horning、W. G. Stillwell

  DOI：10.1021/jo00148a021

  日期：1982.12
• The mechanism of adduct formation between reduced flavins and arene epoxides
  作者：Yong T. Lee、Jed F. Fisher

  DOI：10.1021/jo00066a025

  日期：1993.7

  The mechanism of nucleophilic epoxide opening by reduced flavins, a potentially relevant transformation to the carcinogenesis of polycyclic aromatic hydrocarbons, was investigated. In the spontaneous epoxide hydrolysis pH region, the reaction pathway between the epoxide and the dihydroflavin is bimolecular epoxide opening. Chromatographic analysis of the reaction of (+/-)-1a,2,3,7b-tetrahydro-(1aalpha,2alpha,3beta,7balpha)-naphth[1,2-b]oxirene-2,3-diol (1) with 5,10-dihydro-7,8,10-trimethylbenzo[g]pteridine-2,4(1H,3H)-dione (LFH2, dihydrolumiflavin) in 9/1 (v/v) aqueous pH 7.86 Tris buffer-dioxane yielded the flavin N(5) adduct 8 as the only major product. Under the same conditions, (+/-)-1a,2,3,7b-tetrahydro-(1aalpha,2beta,3alpha,7balpha)-naphth[1,2-b]oxirene-2,3-diol (2) gave the N(5) adduct 10, N(3) adducts (the stereoisomers 11a and 12a), and an unknown adduct (possibly the C(4a) adduct), each in similar yields. The tetrahydronaphthalene oxide, (+/-)-1a,2,3,7b-tetrahydro-(1aalpha,7balpha)-naphth[1,2-b]oxirene (3), gave the N(5) adduct 14 and the C(4a) adduct 16, in approximately a 2/1 ratio. The C(4a) adduct was not stable, however, and was transformed to a secondary adduct. A comparison of the absorption spectra indicated that the outcome of 1 and 3 with FMNH2 Was similar to that for LFH2. The reaction of 2 with FMNH2 gave an adduct, assigned to that of a C(4a) adduct, in addition to the N(5) and N(3) adducts. While the reactions of 1 (pH 5.1) and 2 (pH 4.3) with LFH2 under acidic conditions gave only the N(5) adducts, that of 3 at pH 6.6 gave the same adducts as observed at pH 7.86. Most of these adducts have been isolated. All of the adducts (except 12a) exhibited trans stereochemistry with respect to epoxide opening. Rate constants for these reactions were determined by chromatographic monitoring of the epoxide disappearance and for these epoxides in the spontaneous region (pH approximately 7.5) are in the range of 0.1-0.9 M-1 s-1. The magnitude of these rate constants indicates that the rate constant for nucleophilic, bimolecular attack by the dihydroflavin on these epoxides is comparable to that of the thiolate anion (rate constants for the 2-thioethanol thiolate opening of 1 and 2 are 0.27 and 0.85 M-1 s-1, respectively, under conditions comparable to this study: Becker, A. R.; Janusz, J. M.; Bruice, T. C. J. Am. Chem. Soc. 1979, 101, 5679-5687). The behavior of the epoxides with the dihydroflavins provides one of the few quantitative estimates of the nucleophilic capacity of the dihydroflavin and confirms the perception of the dihydroflavin as an exceptionally reactive nucleophile.