过氧化,1,1-二甲基乙基1,2,3,4-四氢-1-萘基 | 106477-02-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 中文名称: 过氧化,1,1-二甲基乙基1,2,3,4-四氢-1-萘基
• 英文名称: 1-(tert-butylperoxy)tetralin
• 英文别名: 1-t-Butylperoxytetralin；1-tert-butylperoxy-1,2,3,4-tetrahydronaphthalene
• CAS: 106477-02-5
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: GCOSDHDWVLGLAL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  过氧化,1,1-二甲基乙基1,2,3,4-四氢-1-萘基 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 3,4-二氢-1(2H)-萘酮
  参考文献：
  名称：

  Copper catalyzed oxidation of tetralin to 1-(tert-butylperoxy)-tetralin by aqueous tert-butylhydroperoxide under phase transfer conditions

  摘要：

  Selective alpha-peroxidation of tetralin by TBHP is catalyzed by copper salts with the aid of quaternary ammonium compounds in an aqueous-organic biphasic system.

  DOI：

  10.1016/0040-4039(96)00192-x
• 作为产物：
  描述：

  溴代叔丁烷 、 1,2,3,4-四氢-1-萘基氢过氧化物 以40%的产率得到过氧化,1,1-二甲基乙基1,2,3,4-四氢-1-萘基
  参考文献：
  名称：

  Electronic Absorption Spectra of Some Alkoxyl Radicals. An Experimental and Theoretical Study

  摘要：

  The visible and UV absorptions of a variety of alkoxyl radicals have been examined by experiment and theory. In most solvents, the tert-butoxyl radical shows only a weak ''tail-end'' absorption in the UV region of the spectrum and no absorption in the visible region. However, a visible absorption band has been observed (lambda(max) = 440 nm) in the presence of 1,3,5-trimethoxybenzene. This absorption band provides the first unequivocal evidence for the existence of alkoxyl radical/electron-rich aromatic pi-complexes. By way of contrast, a solvent-independent absorption in the visible is observed for (arylcarbinyl)oxyl radicals, e.g., benzyloxyl (lambda(max) = 460 nm, epsilon = 1300 M(-1) cm(-1)) and cumyloxyl (lambda(max) = 485 nm, epsilon = 1300 M(-1) cm(-1)). Electron-donating substituents on the aromatic ring shift the visible absorption to the red by 25-30 nm for a 4-methyl group and by 100-105 nm for a 4-methoxy group. However, alpha-substitution has only a minor effect on lambda(max), e.g., 530 and 535 nm for diphenylmethoxyl and 1,1-diphenylethoxyl, respectively. The visible absorption appears to be virtually uninfluenced by the (calculated) magnitude of the dihedral angle, theta, between the C-O-. bond and the plane of the aromatic ring, e.g., indan-1-oxyl, theta - 51 degrees, lambda(max) = 530 nm, and Tetralin-1-oxyl, theta similar to 33 degrees (major conformer), lambda(max) = 520 nm, vs benzyloxyl and cumyloxyl, both of which have theta similar to 0 degrees. All of these experimental observations are well-matched by theory, which reveals that the visible absorptions of (arylcarbinyl)oxyl radicals are due to D-0(A '')-->D-2(A '') (pi-->pi*) transitions which increase the negative charge on the oxygen atom and have respectable oscillator strengths. The unpaired electron is largely localized in the oxygen 2p orbital which is perpendicular to the plane of the aromatic ring.

  DOI：

  10.1021/ja00115a005

文献信息

• Copper-catalyzed homolytic and heterolytic benzylic and allylic oxidation using tert-butyl hydroperoxide
  作者：Gadi Rothenberg、Liron Feldberg、Harold Wiener、Yoel Sasson

  DOI：10.1039/a805324c

  日期：——

  Allylic and benzylic alcohols were oxidized in good yields to the respective ketones by tert-butyl hydroperoxide (TBHP) in the presence of copper salts under phase-transfer catalysis conditions. This dehydrogenation was found to proceed via a heterolytic mechanism. CuCl2, CuCl, and even copper powder were equally facile as catalysts, as they were all transformed in situ to Cu(OH)Cl which was extracted

  在相转移催化条件下，在铜盐存在下，叔丁基氢过氧化物（TBHP）将烯丙醇和苄醇以良好的产率氧化为相应的酮。发现该脱氢是通过杂化机理进行的。CuCl 2，CuCl甚至铜粉同样容易用作催化剂，因为它们都可以原位转化得到Cu（OH）Cl，其被相转移催化剂（PTC）萃取到有机相中。氘标记实验证明了在速率测定步骤中苄基CH键的断裂。在醇底物的存在下未观察到非生产性TBHP分解。相反，发现在同一介质中的π-活化的亚甲基的氧合是一个自由基过程，主要产物是合适的叔丁基过氧化物。讨论了催化剂的失活，溶剂作用和萃取作用。通过应用的Minisci的关于TBHP分子朝着相对反应性的假定叔-质子和非质子环境中的-丁氧基自由基，可以解释均解和杂化途径的共存。提出了一种完整的反应机理，其中自由基氧化遵循高知的机理，并且杂合脱氢基于高价Cu IV O物种或[Cu（OH）Cl] 2物种。
• N-Heterocyclic Carbene Dirhodium(II) Complexes as Catalysts for Allylic and Benzylic Oxidations
  作者：Jaime A. S. Coelho、Alexandre F. Trindade、Riccardo Wanke、Bruno G. M. Rocha、Luis F. Veiros、Pedro M. P. Gois、Armando J. L. Pombeiro、Carlos A. M. Afonso

  DOI：10.1002/ejoc.201201300

  日期：2013.3

  conditions (solvent, base, temperature and oxidant) for allylic and benzylic oxidation reactions catalyzed by dirhodium(II)/N-heterocyclic carbene (NHC) complexes were optimized for the first time in this work. The oxidations of cyclohexene and fluorene were used as model reactions. Two optimized experimental conditions for both types of oxidations were found, which resulted in their ketone [aerobic conditions

  在这项工作中首次优化了由二铑（II）/N-杂环卡宾（NHC）配合物催化的烯丙基和苄基氧化反应的实验条件（溶剂，碱，温度和氧化剂）。环己烯和芴的氧化用作模型反应。发现了两种氧化类型的两种优化实验条件，这导致了它们的酮 [有氧条件，40 °C，1 当量。tBuOOH (TBHP)] 或过氧化叔丁基衍生物（厌氧条件，25 °C，2 当量 TBHP）。通过循环伏安法在 CH2Cl2 中，二铑 (II) 配合物经历了单电子可逆氧化，这被指定为 Rh24+/Rh25+ 氧化还原对，氧化电位随着进一步配体与 Rh-Rh 中心的连续轴向配位而降低。
• Green Organic Solvent-Free Oxidation of Alkylarenes with tert-Butyl Hydroperoxide Catalyzed by Water-Soluble Copper Complex
  作者：Abdelaziz Nait Ajjou、Ateeq Rahman

  DOI：10.1515/chem-2020-0018

  日期：2020.3.24

  Abstract Different benzylic compounds were efficiently oxidized to the corresponding ketones with aqueous 70% tert-butyl hydroperoxide (TBHP) and the catalytic system composed of CuCl2.2H2O and 2,2’-biquinoline-4,4’-dicarboxylic acid dipotassium salt (BQC). The catalytic system CuCl2/BQC/TBHP allows obtaining high yields at room temperature under organic solvent-free conditions. The interest of this

  摘要 在 70% 叔丁基氢过氧化物 (TBHP) 水溶液和由 CuCl2·2H2O 和 2,2'-二喹啉-4,4'-二羧酸二钾盐 (BQC) 组成的催化体系中，不同的苄类化合物被有效氧化为相应的酮。 ）。CuCl2/BQC/TBHP 催化体系允许在室温下在无有机溶剂条件下获得高产率。该系统的利益在于其成本效益和对环境的良性性质。观察到苄基叔丁基过氧醚和苄醇作为反应中间体。通过原子吸收对有机产品的分析没有显示出任何铜金属污染。在效率方面，CuCl2/BQC 系统与文献中描述的大多数基于有毒有机溶剂的催化系统相当或更好。图形概要
• Rh₂(esp)₂-catalyzed allylic and benzylic oxidations
  作者：Yi Wang、Yi Kuang、Yuanhua Wang

  DOI：10.1039/c4cc10336j

  日期：——

  The dirhodium(ii) catalyst Rh₂(esp)₂ allows direct solvent-free allylic and benzylic oxidation by T-HYDRO with a remarkably low catalyst loading.

  二价二铑催化剂Rh₂(esp)₂可使T-HYDRO直接在无溶剂条件下对烯丙基和苄基进行氧化反应，且催化剂负载量极低。
• Structural Effects on the β-Scission Reaction of Alkoxyl Radicals. Direct Measurement of the Absolute Rate Constants for Ring Opening of Benzocycloalken-1-oxyl Radicals
  作者：Massimo Bietti、Osvaldo Lanzalunga、Michela Salamone

  DOI：10.1021/jo048026m

  日期：2005.2.1

  The absolute rate constants for β-scission of a series of benzocycloalken-1-oxyl radicals and of the 2-(4-methylphenyl)-2-butoxyl radical have been measured directly by laser flash photolysis. The benzocycloalken-1-oxyl radicals undergo ring opening with rates which parallel the ring strain of the corresponding cycloalkanes. In the 1-X-indan-1-oxyl radical series, ring opening is observed when X =

  通过激光闪光光解法直接测量了一系列苯并环烯-1-氧基和2-（4-甲基苯基）-2-丁氧基的β-断裂的绝对速率常数。苯并环烯-1-氧基自由基以与相应环烷烃的环应变平行的速率开环。在1-X-茚满-1-氧基自由基系列中，当X = H，Me时，观察到开环，而当X = Et时，发生独家CX键断裂。讨论了控制片段区域选择性的因素。