2-(溴甲基)-3-苯基环氧乙烷 | 60633-79-6

• 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)-3-苯基环氧乙烷
• 英文名称: 2-(bromomethyl)-3-phenyloxirane
• CAS: 60633-79-6
• 化学式: C₉H₉BrO
• 分子量: 213.074
• InChiKey: CBGMFGUNEQKSGF-UHFFFAOYSA-N

物化性质

• 沸点：
  282.4±25.0 °C(Predicted)
• 密度：
  1.492±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 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：

  2-(溴甲基)-3-苯基环氧乙烷 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 1-苯基-2-丙醇
  参考文献：
  名称：

  Selective reductive cleavage of 2,3-epoxybromides by the InCl3–NaBH4 reagent system

  摘要：

  A combination of sodium borohydride and a catalytic amount of indium(Ill) chloride in acetonitrile reduces 2,3-epoxy-bromides to the corresponding allylic alcohols in good yields involving reduction of the bromo moiety followed by selective C-O bond cleavage through a radical process. Several aromatic, cyclic and open-chain bromoepoxides successfully participated in this reaction. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.09.120
• 作为产物：
  描述：

  Cinnamyl bromide 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 2-(溴甲基)-3-苯基环氧乙烷
  参考文献：
  名称：

  Irreversible Inhibition of the HIV-1 Protease:  Targeting Alkylating Agents to the Catalytic Aspartate Groups

  摘要：

  Irreversible inhibition of the HIV-1 protease by agents that specifically alkylate its catalytic aspartate residues is a potentially useful approach for circumventing the evolution of HIV strains that are resistant to protease inhibitors. Five haloperidol- and two FMOC-based epoxides of differing reactivities have been synthesized and tested as irreversible inhibitors of the HIV-1 protease (HIV-1 PR). Of these, two trisubstituted epoxides, a cis-1,2- disubstituted epoxide, a 1,1-disubstituted epoxide, and a monosubstituted epoxide function as irreversible inhibitors, but two trans-1,2-disubstituted epoxides do not. The most effective of the epoxides (6) inactivates HIV-1 PR with K-inact = 65 mu M and V-inact = 0.009 min(-1). 1,2-Epoxy-3-(p-nitrophenoxy)propane (EPNP), a nonspecific inactivating agent for aspartyl proteases, has been used to validate a protocol for establishing the stoichiometry and site of protein alkylation. Mass spectrometric analysis of the inactivated enzyme shows that one molecule of either EPNP or the cyclic 1,2-disubstituted epoxide 6 is covalently bound per HIV-1 PR dimer. Mass spectrometric sequencing of labeled proteolytic peptides shows that both inhibitors are covalently bound to a catalytic aspartate residue. The covalent binding of three alpha,beta-unsaturated ketone derivatives of haloperidol has been similarly examined. Analysis of HIV-1 PR inactivated by these agents establishes that they bind covalently to the two cysteines and the N-terminal amino group but not detectably to the catalytic aspartate residues. The results indicate that aspartate-targeted inactivation of HIV-1 PR depends on (a) matching the reactivity of the alkylating functionality to that of the aspartates, preferably by exploiting the two-aspartate catalytic motif of the protease to activate the alkylating agent, and (b) appropriate positioning of the alkylating functionality within the active site. These requirements are readily met by a monosubstituted, 1,1-disubstituted, or cyclic cis-1,2-disubstituted epoxide but not by trans-1,2-disubstituted epoxides or alpha,beta-unsaturated ketones.

  DOI：

  10.1021/ja954069w

文献信息

• Visible-Light-Induced Charge Transfer Enables C_sp3–H Functionalization of Glycine Derivatives: Access to 1,3-Oxazolidines
  作者：Xiaorong Yang、Yin Zhu、Zhixiang Xie、Ying Li、Yuan Zhang

  DOI：10.1021/acs.orglett.0c00234

  日期：2020.2.21

  visible-light-induced aerobic oxidative [2 + 3] cycloaddition reaction between glycine derivatives and styrene oxides has been disclosed that provides an efficient approach for the rapid synthesis of 1,3-oxazolidines under mild conditions. This photoinduced process is enabled by the formation of an electron donor-acceptor complex between glycine derivatives and benzyl iodides.

  已经公开了甘氨酸衍生物和苯乙烯氧化物之间无光氧化还原催化剂的可见光诱导的需氧氧化[2 + 3]环加成反应，该反应为在温和条件下快速合成1,3-恶唑烷提供了一种有效的方法。通过在甘氨酸衍生物和苄基碘之间形成电子供体-受体复合物，可以实现这种光诱导过程。
• Cleavage of 2,3-epoxyalkylhalides by the sonochemical zinc–copper couple
  作者：Luis A. Sarandeses、Antonio Mouriño、Jean-Louis Luche

  DOI：10.1039/c39910000818

  日期：——

  2,3-Epoxyalkylhalides are readily transformed into allylic alcohols when sonicated in the presence of a zinc–copper couple in aqueous ethanol.

  2,3-环氧烷基卤化物在水醇溶液中与锌-铜耦合物共同超声处理时，易于转化为烯丙醇。
• Trimethyl Phosphite as a Trap for Alkoxy Radicals Formed from the Ring Opening of Oxiranylcarbinyl Radicals. Conversion to Alkenes. Mechanistic Applications to the Study of C−C versus C−O Ring Cleavage
  作者：Bangwei Ding、Wesley G. Bentrude

  DOI：10.1021/ja020761x

  日期：2003.3.1

  and C-C (k(2)) cleavages of intermediate oxiranylcarbinyl radical 2 and their reverse (k(-1), k(-2)). Diversion by (MeO)(3)P of allyloxy radicals (3) from haloepoxides 11 and 12 fulfills a prior prediction that under conditions closer to kinetic control, products of C-O scission, not just those of C-C scission, may result. Thus, for oxiranylcarbinyl radicals from haloepoxides 11, 12, and 13, C-O scission

  亚磷酸三甲酯 (MeO)(3)P 作为有效和选择性陷阱引入环氧乙烷基自由基 (2) 系统中，该系统由卤代环氧化物 8-13 在约 80 摄氏度的热 AIBN/n-Bu(3)SnH 条件下形成最初，在不存在亚磷酸酯的情况下，8-13 向烯丙醇 7 和/或乙烯基醚 5 的转化被定量测量（表 1）。中间体环氧乙烷基 (2)、烯丙氧基 (3) 和乙烯基氧基羰基 (4) 自由基的结构变化涉及 CO (2 --> 3, k(1)) 和 CC (2 --> 4, k(2)) 自由基断裂过程，并且很容易解释形成的产物乙烯基醚 (5) 和烯丙醇 (7) 的量的变化。添加的 (MeO)(3)P 对乙烯基氧羰基自由基 4 呈惰性，并选择性地快速捕获烯丙氧基自由基 3，将其转移到磷酸三甲酯和烯丙基 6。烯丙基 (6) 二聚化或被 n-Bu(3)SnH 捕获以产生烯烃，由卤代环氧化物 8、9 和 13 形成，产率为
• A new and efficient methodology for olefin epoxidation catalyzed by supported cobalt nanoparticles
  作者：Lucía Rossi-Fernández、Viviana Dorn、Gabriel Radivoy

  DOI：10.3762/bjoc.17.46

  日期：——

  A new heterogeneous catalytic system consisting of cobalt nanoparticles (CoNPs) supported on MgO and tert-butyl hydroperoxide (TBHP) as oxidant is presented. This CoNPs@MgO/t-BuOOH catalytic combination allowed the epoxidation of a variety of olefins with good to excellent yield and high selectivity. The catalyst preparation is simple and straightforward from commercially available starting materials

  提出了一种新型多相催化体系，由负载在 MgO 上的钴纳米粒子 (CoNP) 和作为氧化剂的叔丁基过氧化氢 (TBHP) 组成。这种 CoNPs@MgO/ t -BuOOH 催化组合可以实现多种烯烃的环氧化，具有良好至优异的产率和高选择性。该催化剂的制备过程简单直接，采用市售起始原料，可以回收和重复使用，保持其高活性不变。
• Novel Reductive Cleavage Reaction of <i>α</i>-Halo Epoxides with SMI₂: Synthesis of Cyclopropanols
  作者：Heui Sul Park、So Hee Chung、Yong Hae Kim

  DOI：10.1055/s-1998-1889

  日期：1998.10

  Aryl substituted α-halo epoxide reacted with SmI2 to give the cyclopropanols in the presence of HMPA, while allyl alcohols were yielded in the absence of HMPA.

  在 HMPA 存在的情况下，芳基取代的 δ-halo 环氧化物与 SmI2 反应生成环丙醇，而在 HMPA 不存在的情况下生成烯丙醇。