(+/-)-1a,2,3,7b-tetrahydro-(1aα,2α,3β,7bα)-naphth<1,2-b>oxirene-2,3-diol | 69222-28-2

• 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,2α,3β,7bα)-naphth<1,2-b>oxirene-2,3-diol
• 英文别名: (+/-)-1a,2,3,7b-tetrahydro-(1aα,2β,3α,7bα)naphth[1,2-b]oxirene-2,3-diol；3α,4α-epoxy-1,2,3,4-tetrahydronaphthalene-1β,2α-diol；r,t-1,2-dihydroxy-t,t-3,4-epoxy-1,2,3,4-tetrahydronaphthalene；(+/-)-anti-naphthalene dihydrodiol epoxide；(+/-)-1β,2α-Dihydroxy-3α,4α-epoxy-1,2,3,4-tetrahydro-naphthalin；Naphthalene-1,2-diol-3,4-epoxide, anti；(1aS,2S,3R,7bR)-1a,2,3,7b-tetrahydronaphtho[3,4-b]oxirene-2,3-diol
• CAS: 69222-28-2
• 化学式: C₁₀H₁₀O₃
• 分子量: 178.188
• InChiKey: XDSJRQRRQDAPNL-RGOKHQFPSA-N

物化性质

• 沸点：
  382.5±42.0 °C(Predicted)
• 密度：
  1.484±0.06 g/cm3(Predicted)

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,2α,3β,7bα)-naphth<1,2-b>oxirene-2,3-diol 在 氨 、 三乙胺 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 55.0~70.0 ℃ 、2.03 MPa 条件下， 反应 189.0h， 生成 4-[9-((2R,4S,5R)-4-Hydroxy-5-hydroxymethyl-tetrahydro-furan-2-yl)-9H-purin-6-ylamino]-1,2,3,4-tetrahydro-naphthalene-1,2,3-triol
  参考文献：
  名称：

  致癌性多环芳烃脱氧腺苷加合物的非仿生途径

  摘要：

  氨基三醇是通过多环芳族烃的二醇环氧化物的直接氨解制备的，与文献方法相比有实质性的改进。氨基三醇与6-卤代嘌呤脱氧核糖核苷的缩合提供了脱氧腺苷N 6加合物的区域和立体特异性合成。

  DOI：

  10.1016/0040-4039(91)80756-v
• 作为产物：
  描述：

  (+/-)-trans-1,2-dihydroxy-1,2-dihydronaphthalene 在 间氯过氧苯甲酸 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (+/-)-1a,2,3,7b-tetrahydro-(1aα,2α,3β,7bα)-naphth<1,2-b>oxirene-2,3-diol
  参考文献：
  名称：

  Chemistry of anti- and syn-1,2:3,4-naphthalene dioxides and their potential relevance as metabolic intermediates

  摘要：

  DOI：

  10.1021/jo00148a021

文献信息

• A Mechanistic Study of the Dihydroflavin Reductive Cleavage of the Dihydroflavin–Tetrahydronaphthalene Epoxide Adducts
  作者：Yong T. Lee、Jed F. Fisher

  DOI：10.1006/bioo.2000.1171

  日期：2000.6

  covalent flavin-epoxide adduct formation) the products having a methylene group at the benzylic position. The reduction product yield was proportional to the yield of the N(5) flavin-epoxide adduct intermediate, and the rate of the reaction was proportional to the dihydroflavin concentration. These observations are consistent with these reduction products resulting from bimolecular reaction between the

  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
• Studies of the Mechanisms of Adduction of 2‘-Deoxyadenosine with Styrene Oxide and Polycyclic Aromatic Hydrocarbon Dihydrodiol Epoxides
  作者：Hye-Young H. Kim、Jari I. Finneman、Constance M. Harris、Thomas M. Harris

  DOI：10.1021/tx000054m

  日期：2000.7.1

  With the PAH dihydrodiol epoxides, only naphthalene dihydrodiol epoxide exhibited significant initial reaction at N1 (50%). No detectable rearranged product was seen in reactions with benzo[a]pyrene dihydrodiol epoxide or non-bay or bay region benz[a]anthracene dihydrodiol epoxide; interestingly, a small amount of N1 attack (5-7%) was seen in the case of benzo[c]phenanthrene dihydrodiol epoxide. It

  使用（15）N（6）标记的腺嘌呤核苷探索了氧化苯乙烯和多环芳烃二氢二醇环氧化物加成2'-脱氧腺苷的机理。在使Dimroth重排发生之后，通过N（6）加合物的（1）H NMR评估N1对N（6）的反应程度。在N1处发生攻击然后进行Dimroth重排而产生的产物表现出较小的两键（1）H-（15）N偶合常数（N1-H2 J约为13 Hz）。直接攻击产生的产物表现出更大的单键（1）H-（15）N耦合常数（J约为90 Hz）。在氧化苯乙烯的情况下，所有N（6）β加合物的起因是在N1处初次进攻，而N（6）α加合物的大部分（70-80％）来自直接进攻。还用含有九个（15）N（6）标记腺嘌呤残基的自互补寡聚脱氧核苷酸（24-聚体）研究了氧化苯乙烯反应。在对24-mer进行酶促降解后，分离出的N（6）α-和β-苯乙烯氧化物加合物的NMR检查给出了非常相似的结果，表明即使使用双链寡核苷酸，N1攻击也很容易发生。
• Synthesis of an aromatic hydrocarbon diol epoxide–cytosine adduct, 5′-O-(9-phenylxanthen-9-yl)-N⁴-[(±)-1β,2α,3α-triacetoxy-1,2,3,4-tetrahydro-4β-naphthyl]-2′-deoxycytidine, suitable for incorporation into synthetic oligodeoxyribonucleotides
  作者：Clive A. Smith、Andrea E. Harper、Maurice M. Coombs

  DOI：10.1039/p19880002745

  日期：——

  total synthesis of a model polyaromatic hydrocarbon diol epoxide–cytosine adduct is described, suitable for incorporation into oligodeoxyribonucleotide synthesis. An approach to control the relative stereochemistry of the diol epoxide–nucleoside adduct is discussed. This synthesis yields 5′-O-(9-phenylxanthen-9-yl)-N4-[(±)-1β,2α,3α-triacetoxy-1,2,3,4-tetrahydro-4β-naphthyl]-2′-deoxycytidine as a mixture

  描述了适用于掺入寡脱氧核糖核苷酸合成的模型聚芳烃二醇环氧-胞嘧啶加合物的第一个全合成。讨论了控制二醇环氧化物-核苷加合物的相对立体化学的方法。该合成产生5'- O-（9-苯基黄嘌呤-9-基）-N 4 -[（±）-1β，2α，3α-三乙酰氧基-1,2,3,4-四氢-4β-萘基] -2 ′-脱氧胞苷为非对映异构体的混合物。
• 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.
• 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