2-(溴甲基)-2-苯基环氧乙烷 | 64398-73-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-(溴甲基)-2-苯基环氧乙烷
• 英文名称: 2-(bromomethyl)-2-phenyloxirane
• 英文别名: 2-Brommethyl-2-phenyloxiran；Oxirane, 2-(bromomethyl)-2-phenyl-
• CAS: 64398-73-8
• 化学式: C₉H₉BrO
• 分子量: 213.074
• InChiKey: FXJKHQGPGQTYQZ-UHFFFAOYSA-N

物化性质

• 沸点：
  275.3±25.0 °C(Predicted)
• 密度：
  1.509±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  甲醇 、 2-(溴甲基)-2-苯基环氧乙烷 在 beta-胸苷 作用下， 反应 48.0h， 以100%的产率得到1-bromo-2-methoxy-2-phenylpropan-3-ol
  参考文献：
  名称：

  Oxidation of Acetylated Guanosine by 3,3-Disubstituted 1,2-Dioxetanes through Nucleophilic Attack on the Peroxide Bond: Model Studies on the Oxidative DNA Damage by Reactive Peroxides

  摘要：

  The reaction of the disubstituted 3-(methoxymethyl)-3-phenyl-1,2-dioxetane (1a) with the acetylated guanine nucleoside (2) in methanol affords 8-methoxyguanosine 5 as oxidation product, as well as guanine (6) and 1-methoxyribose 7 by deglycosylation (total yield ca. 30%). The dioxetane-derived reduction product constitutes the 1,2-diol 40, while the major dioxetane-derived product (85%) is omega-methoxyacetophenone (3a). A Grob-type fragmentation is made responsible for the exclusive formation of the dioxetane cleavage products in the reactions with the acetylated nucleosides 8-10 derived from adenine, cytosine, and thymine. Rather than redox chemistry, this guanosine oxidation, unprecedented for peroxides, is proposed to involve nucleophilic attack by the N-7 atom of the nucleosides on the peroxide bond of the dioxetane la electrophile to generate a zwitterionic intermediate. S(N)2 attack by methanol at the C-8 position of the guanine moiety in the zwitterionic intermediate leads to the 8-methoxyguanosine 5 and the diol 4a. Alternatively, heterolytic cleavage of the glycosidic bond affords the methoxylated ribose 7 (after methanol trapping) and the N-7-alkoxylated guanine. The latter, after protonation, subsequently undergoes Grob fragmentation into guanine (6) and the dioxetane decomposition products omega-methoxyacetophenone (3a) and formaldehyde. We propose that the present novel oxidation of guanosine is general for electrophilic peroxides and may constitute a prominent route of oxidative DNA damage. In contrast, the corresponding 3-(bromethyl)-3-phenyl- 1,2-dioxetane (1b) gave with the guanosine 2 an intractable, complex product mixture, for which presumably the bromo substituent is responsible on account of competitive alkylation chemistry. However, with the 2'-deoxythymidine 10, a novel acid-catalyzed ring-opening of the bromo-substituted dioxetane Ib to its beta-methoxy hydroperoxide 11b is observed, a reaction which does not take place for the methoxy-substituted dioxetane 1a. This unusual process for simple dioxetanes is rationalized in terms of stabilization of the intermediary benzylic cation by the adjacent beta-bromo substituent through neighboring group participation.

  DOI：

  10.1021/ja00115a002
• 作为产物：
  描述：

  3-(Bromomethyl)-3-phenyldioxetane 、 二苯基重氮甲烷 以7%的产率得到
  参考文献：
  名称：

  Adam Waldemar, Treiber Alexander, J. Org. Chem, 59 (1994) N 4, S 840-844

  摘要：

  DOI：

文献信息

• Reaction of 1,2-dioxetanes with heteroatom nucleophiles: adduct formation by nucleophilic attack at the peroxide bond
  作者：Waldemar Adam、Markus Heil

  DOI：10.1021/ja00040a017

  日期：1992.7

  The reactions of 3,3-disubstituted 1,2-dioxetanes 1 with numerous heteroatom nucleophiles, e.g., R 2 NH, R 3 N, RSH R 2 S, CN - , SCN - , Br - , Cl - , OH - , and O 2 .- , were investigated. Initial nucleophilic substitution at the sterically less hindered site of the dioxetane peroxide bond leads to addition, deoxygenation, and fragementation products. The observed S N 2 chemistry was substantiated

  3,3-二取代的 1,2-二氧杂环丁烷 1 与许多杂原子亲核试剂的反应，例如 R 2 NH、R 3 N、RSH R 2 S、CN - 、SCN - 、Br - 、Cl - 、OH - 和O 2 .- ，进行了调查。在二氧杂环丁烷过氧化物键的空间位阻较小的位点处的初始亲核取代导致加成、脱氧和断裂产物。观察到的 SN 2 化学反应得到二氧杂环丁烷 1c 的证实，因为溴离子被邻近的醇盐离子位点置换得到环氧化物产物
• Adam, Waldemar; Andler, Simone; Heil, Markus, Angewandte Chemie, 1991, vol. 103, # 10, p. 1395 - 1396
  作者：Adam, Waldemar、Andler, Simone、Heil, Markus

  DOI：——

  日期：——
• 1,3-Dioxolane Formation by Nucleophilic Attack of Diazoalkanes on the Peroxide Bond of 1,2-Dioxetanes
  作者：Waldemar Adam、Alexander Treiber

  DOI：10.1021/jo00083a027

  日期：1994.2

  The reaction of the 1,2-dioxetanes 1a-d with the diazoalkanes 2 alpha-eta was investigated. The two 3,3-disubstituted (3,3-dimethyl- and 3-(bromomethyl)-3-phenyl) dioxetanes (1a and 1b), trimethyldioxetane (1c), and tetramethyldioxetane (1d) gave with the various diazoalkanes 2 the corresponding 1,3-dioxolanes 3 (insertion products) and/or the dioxetane-derived ketones 4 (fragmentation). Nucleophilic attack by the negatively charged carbon pole of the diazoalkane on the sterically less hindered site of the dioxetane peroxide bond affords the 1,3-dioxolane 3 after cyclization with denitrogenation of the resulting O,N dipole. The O,C dipole, formed by the nucleophilic attack of the negatively charged nitrogen pole on the dioxetane, is proposed as precursor to the ketones 4 through Grob-type fragmentation with regeneration of the diazoalkane.
• Oxidation of Acetylated Guanosine by 3,3-Disubstituted 1,2-Dioxetanes through Nucleophilic Attack on the Peroxide Bond: Model Studies on the Oxidative DNA Damage by Reactive Peroxides
  作者：Waldemar Adam、Alexander Treiber

  DOI：10.1021/ja00115a002

  日期：1995.3

  The reaction of the disubstituted 3-(methoxymethyl)-3-phenyl-1,2-dioxetane (1a) with the acetylated guanine nucleoside (2) in methanol affords 8-methoxyguanosine 5 as oxidation product, as well as guanine (6) and 1-methoxyribose 7 by deglycosylation (total yield ca. 30%). The dioxetane-derived reduction product constitutes the 1,2-diol 40, while the major dioxetane-derived product (85%) is omega-methoxyacetophenone (3a). A Grob-type fragmentation is made responsible for the exclusive formation of the dioxetane cleavage products in the reactions with the acetylated nucleosides 8-10 derived from adenine, cytosine, and thymine. Rather than redox chemistry, this guanosine oxidation, unprecedented for peroxides, is proposed to involve nucleophilic attack by the N-7 atom of the nucleosides on the peroxide bond of the dioxetane la electrophile to generate a zwitterionic intermediate. S(N)2 attack by methanol at the C-8 position of the guanine moiety in the zwitterionic intermediate leads to the 8-methoxyguanosine 5 and the diol 4a. Alternatively, heterolytic cleavage of the glycosidic bond affords the methoxylated ribose 7 (after methanol trapping) and the N-7-alkoxylated guanine. The latter, after protonation, subsequently undergoes Grob fragmentation into guanine (6) and the dioxetane decomposition products omega-methoxyacetophenone (3a) and formaldehyde. We propose that the present novel oxidation of guanosine is general for electrophilic peroxides and may constitute a prominent route of oxidative DNA damage. In contrast, the corresponding 3-(bromethyl)-3-phenyl- 1,2-dioxetane (1b) gave with the guanosine 2 an intractable, complex product mixture, for which presumably the bromo substituent is responsible on account of competitive alkylation chemistry. However, with the 2'-deoxythymidine 10, a novel acid-catalyzed ring-opening of the bromo-substituted dioxetane Ib to its beta-methoxy hydroperoxide 11b is observed, a reaction which does not take place for the methoxy-substituted dioxetane 1a. This unusual process for simple dioxetanes is rationalized in terms of stabilization of the intermediary benzylic cation by the adjacent beta-bromo substituent through neighboring group participation.
• Adam Waldemar, Treiber Alexander, J. Org. Chem, 59 (1994) N 4, S 840-844
  作者：Adam Waldemar, Treiber Alexander

  DOI：——

  日期：——