7,8,9,10-四羟基四氢苯并(a)芘 | 59957-91-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 中文名称: 7,8,9,10-四羟基四氢苯并(a)芘
• 中文别名: 3-吡啶羧酸,1,2-二氢-4,6-二羟基-5-[2-(4-甲基-3-硝基苯基)二氮烯基]-2-羰基-1-苯基-,甲基酯
• 英文名称: 7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzopyrene
• 英文别名: benzopyrene-r-7,t-8,t-9,c-10-tetrahydrotetrol；benzopyrene-trans-7,8,9,10-tetrahydrotetraol；benzopyrene-r-7,t-8,9,10-tetrahydrotetrol；7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzo[a]pyrene；1,2,3,4-tetrahydroxy-1,2,3,4-tetrahydro-benzo[a]pyrene；7,8,9,10-tetrahydroxytetrahydrobenzo[a]pyrene；7,8,9,10-Tetrahydrobenzo(a)pyrene-7,8,9,10-tetrol；7,8,9,10-tetrahydrobenzo[a]pyrene-7,8,9,10-tetrol
• CAS: 59957-91-4
• 化学式: C₂₀H₁₆O₄
• 分子量: 320.345
• InChiKey: KWFVZAJQUSRMCC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

SDS

反应信息

• 作为反应物：
  描述：

  7,8,9,10-四羟基四氢苯并(a)芘 、 α-溴-2,3,4,5,6-五氟甲基苯酸酯 在 18-冠醚-6 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 26.0h， 以43%的产率得到2,3-bis(pentafluorobenzyl)pyrenedicarboxylate
  参考文献：
  名称：

  Polar Forms of Benzo[a]pyrene May Be Ubiquitous in the Environment

  摘要：

  Previously, we reported that polar polycyclic aromatic compounds (polar PAC) can be detected by first oxidizing them with KO2/O-2 and then detecting the carboxylic acid products, after pentafluorobenzylation, by gas chromatography electron capture mass spectrometry (Allam et at. Anal. Chem. 1992, 65, 1723-1727). For example, we used the method in the cited study to detect a benzo[a]pyrene tetrahydrotetraol hydrolysis product derived from benzo[a]pyrene-exposed lymphocytes after isolation of the DNA. However,the method was limited in its sensitivity by the presence of an interfering, analyte-like peak in the final mass chromatograms. Now, the results of our current work strong ly suggest that the contamination leading to the unwanted peak is ubiquitous in the urban environment. Results from the analysis of a standard reference sample of urban particulate matter (SRM 1649) yielded a level of 10 ng of contaminant in a 5-mg sample (2 mu g/g). The concentration of this polar contaminant is comparable to the certified value for benzo[a]pyrene of 14.5 ng (2.9 mu g/g). Furthermore, our mass spectral data show evidence for the presence of many other polar PAC in the sample. These observations add to the concern raised by related environmental health studies focused on the potential impact of airborne polar PAC on human health.

  DOI：

  10.1021/es9710722
• 作为产物：
  描述：

  苯并[a]芘 生成 7,8,9,10-四羟基四氢苯并(a)芘
  参考文献：
  名称：

  GIBSON T. L.; SMITH L. L., J. ORG. CHEM., 1979, 44, NO 11, 1842-1846

  摘要：

  DOI：

文献信息

• Influence of Na⁺ on DNA Reactions with Aromatic Epoxides and Diol Epoxides:  Evidence That DNA Catalyzes the Formation of Benzo[<i>a</i>]pyrene and Benz[<i>a</i>]anthracene Adducts at Intercalation Sites
  作者：Harshica Fernando、Chao-Ran Huang、Ann Milliman、Luchuan Shu、Pierre R. LeBreton

  DOI：10.1021/tx960134j

  日期：1996.1.1

  BP metabolites. DNA adducts, which account for less than 10% of the yields, also form. For BPDE in 0.20 mM ctDNA, k decreases 5.1 times as the Na+ concentration increases from 2.0 to 100 mM. Nevertheless, the DNA adduct level remains constant over the range of Na+ concentrations examined. These results provide evidence that, for BPDE in 0.20 mM DNA and 2.0 mM Na+, ctDNA adduct formation follows a mechanism

  苯并[a] py（BP）和苯并[a]蒽（BA）代谢产物，（+/-）-trans-7 8-二羟基-抗-9、10-环氧-7、8、9、10的反应-四氢-BP（BPDE），（+/-）-trans-3，4-二羟基-反-1,2-环氧-1,2,3,4-四氢-BA（BADE），（+/-）在伪一阶条件下，在变化的Na +（2.0-100 Mm）和天然浓度下，检查了-BP-4,5-氧化物（BPO）和（+/-）-BA-5、6-氧化物（BAO）小牛胸腺DNA（ctDNA）浓度。在0.2 mM的ctDNA和2.0 mM的Na +中，pH值为7.3时，大多数BPDE，BADE，BPO和BAO（87-95％）都会经历DNA催化的水解或重排。对于BPDE和BPO，2.0 mM Na +和0.2 mM ctDNA中的总体伪一级速率常数k比不使用DNA获得的值大21-72倍。对于BADE和BAO，速率常数受DNA的影响较小。k值为0。2
• Fluorinated Alcohol Mediated Displacement of the C₁₀ Acetoxy Group of Benzo[<i>a</i>]pyrene-7,8,9,10-tetrahydrotetraol Tetraacetates:  A New Route to Diol Epoxide−Deoxyguanosine Adducts
  作者：Haruhiko Yagi、Donald M. Jerina

  DOI：10.1021/jo701705c

  日期：2007.12.1

  via an SN1 mechanism involving a carbocation intermediate that is common to the cis and trans tetraacetates. Since it is likely that the cis and trans products from 3 arise from different conformations of the carbocation, its lifetime must be sufficiently long to permit conformational equilibration before its capture by the purine nucleophile. The corresponding reaction of (±)-9α-bromo-7β,8α,10β-triacetoxy-7

  我们描述了在四个立体异构体7,8,9,10-tetraacetoxy-7,8,9,10-中的海湾区域C 10乙酰氧基的新型三氟乙醇（TFE）或六氟丙烷-2-醇（HFP）介导的取代反应四氢苯并[一个]芘（四元醇四乙酸盐中，两对顺式和反式异构体在9,10位的）通过环外ñ 2的氨基ö 6 -烯丙基-3' ，5'-二- ö - （叔-丁基二甲基甲硅烷基）-2'-脱氧鸟苷（3）。四乙酸酯衍生自（±）-7β，8α-二羟基-9β，10β-环氧-7,8,9,10-四氢苯并[ a ]（（B [ a] P DE-1）和（±）-7β，8α-二羟基-9α，10α-环氧-7,8,9,10-四氢苯并[ a ] py（B [ a ] P DE-2）在C- 10，然后乙酰化。观察到优异的产率和高的区域选择性。在HFP中，从DE-1（〜75/25）和DE-2（〜67/33）衍生出的每组顺式和反式四醇四乙酸酯观察到相似的顺式/反式产物比率。这强烈表明取代是通过S
• Proton-coupled electron transfer in the oxidation of guanines by an aromatic pyrenyl radical cation in aqueous solutions
  作者：Vladimir A. Kuzmin、Alexander Dourandin、Vladimir Shafirovich、Nicholas E. Geacintov

  DOI：10.1039/b000212g

  日期：——

  factor of only ∽3. The dGMP(-H)• neutral radicals formed on time scales of a few microseconds, were identified by their characteristic transient absorption spectrum (λmax∽310 mn). The rate constant of electron transfer from dGMP to BPT•+ was smaller in D2O by a factor of ∽1.5 than in H2O. This kinetic isotope effect indicates that the electron transfer reaction from dGMP to BPT•+ is accompanied by the deprotonation

  DNA 中的核酸残基与强氧化剂之间的电子转移反应通常是引发氧化性、不可逆 DNA 损伤的关键初始步骤。采用激光闪光光解瞬态吸收光谱技术，我们研究了 2'-脱氧核苷 5'-单磷酸盐、dGMP、dAMP、dCMP 和 dTMP 与代表性单电子氧化剂在水溶液中的电子转移反应特征。后者是具有增强水溶性的芘衍生物的自由基阳离子，即 7,8,9,10-四羟基四氢苯并[a]芘 (BPT)。BPT 自由基阳离子 BPT•+ 是由强纳秒激光脉冲（308 或 355 nm，50-70 mJ 脉冲-1 cm-2）通过非线性连续双光子吸收过程产生的。dAMP、dTMP 和 dCMP 未观察到电子转移反应，与其不利的氧化还原电位相一致。然而，BPT•+ 以速率常数 kb=1.7±0.1)×109 M-1 s-1 有效地氧化 dGMP，比扩散控制值小仅 ∽3 倍。dGMP(-H)• 在几微秒的时间尺度上形成的中性自由
• Photoemission probes of hydrocarbon-DNA interactions: a comparison of DNA influences on the reactivities of (.+-.)-trans-7,8-dihydroxy-anti-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene, benzo[a]pyrene 4,5-oxide, and benz[a]anthracene 5,6-oxide
  作者：Shigeyuki Urano、Harry L. Price、Sharon M. Fetzer、Anita V. Briedis、Ann Milliman、Pierre R. LeBreton

  DOI：10.1021/ja00010a033

  日期：1991.5

  Time-resolved fluorescence and UV photoelectron measurements have been employed to examine the influence of calf thymus DNA on the reactivities of epoxides derived from benzo[a]pyrene (BP) and benz[a]anthracene (BA). By monitoring the increase in fluorescence intensity, which accompanies reaction at 23-degrees-C, overall, pseudo-first-order rate constants have been measured for reactions of the highly carcinogenic bay region epoxide (+/-)-trans-7,8-dihydroxy-anti-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE) and of two less carcinogenic K region epoxides benzo[a]pyrene 4,5-oxide (BPO) and benz[a]anthracene 5,6-oxide (BAO). Overall rate constants for hydrolysis and rearrangement reactions have been measured for BPDE, BPO, and BAO in buffer alone (1.0 mM sodium cacodylate, pH 7.1). The rate constants increase in the order BPO ((3.8 +/- 0.1) x 10(-6) s-1) < BAO ((5.7 +/- 2.6) x 10(-5) s-1) < BPDE ((7.2 +/- 1.0) x 10(-4) s-1). These results have been compared with overall rate constants for reactions, carried out in calf thymus DNA, which result in catalyzed hydrolysis and rearrangement, as well as DNA adduct formation. In DNA, the ordering of the rate constants for BPO and BAO changes from that observed in buffer alone. The rate constants increase in the order BAO ((2.8 +/- 0.1) x 10(-3) s-1) < BPO ((1.2 +/- 0.2) x 10(-2) s-1) < BPDE (approximately 1 x 10(-1) s-1). This ordering is the same as the ordering of association constants for the reversible binding to DNA of the fluorescent diols trans-7,8-dihydroxy-7,8-dihydro-BP (BP78D), trans-4,5-dihydroxy-4,5-dihydro-BP (BP45D) and cis-5,6-dihydroxy-5,6-dihydro-BA (BAD), which are model compounds of BPDE, BPO, and BAO, respectively. For the model compounds, the association constants for intercalation increase in the order BAD ((3.6 +/- 0.9( x 10(2) M-1) < BP45D ((9.6 +/- 0.5) x 10(3) M-1) < BP78D ((3.4 +/- 0.1) x 10(4) M-1). This ordering is consistent with the ordering of the association constants of BPDE ((2.5 +/- 0.3) x 10(4) M-1) and of BPO ((6.0 +/- 1.0) x 10(3) M-1). The temperature dependence of the association constants of the model compounds demonstrates that, for the intercalation of the BP diols into DNA, differences in the enthalpy of binding contribute significantly to differences in the free energy of binding. UV photoelectron data and results from ab initio molecular orbital calculations on BPDE, BPO, and BAO indicate that, for these three epoxides, the association constants increase as the ionization potentials decrease and the polarizabilities increase. The percentage of epoxide reaction that yields DNA adducts has been compared under varying conditions. For long reaction times (> 1 h) in systems containing native, calf thymus DNA at low salt concentrations, the ordering of adduct yields is BPO (14.9 +/- 1.1%) > BPDE (10.1 +/- 3.0%) > BAO (3.6 +/- 0.4%). For short reaction times (10 min) in systems containing native DNA stabilized with 0.10 mM Mg2+, the ordering of adduct yields is BPDE (7.3 +/- 1.9%) > BPO (1.3 +/- 0.1%) > BAO (0.1 +/- 0.1%). These results suggest that the ability of an epoxide to form adducts with exposed DNA during long reaction times is less indicative of the genotoxic potency of the epoxide than its ability to form adducts with stabilized DNA during short reaction times.
• Laser-Induced Room-Temperature Phosphorescence Detection of Benzo[a]pyrene-DNA Adducts
  作者：Tuan. Vo-Dinh、Mayo. Uziel

  DOI：10.1021/ac00135a006

  日期：1987.4.15