2-methoxy-1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindole | 80037-95-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 2-methoxy-1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindole
• 英文别名: 2-methoxy-1,1,3,3-tetramethylisoindoline；2-Methoxy-1,1,3,3-tetramethylisoindole
• CAS: 80037-95-2
• 化学式: C₁₃H₁₉NO
• 分子量: 205.3
• InChiKey: KCXSGTUCAOGHIO-UHFFFAOYSA-N

物化性质

• 沸点：
  258.5±50.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,1,3,3-四甲基异吲哚啉 生成 2-methoxy-1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindole
  参考文献：
  名称：

  与清除剂1,1,3,3-四甲基异吲哚基-2-氧自由基反应的定量研究

  摘要：

  通过使用标题氮氧化物作为自由基清除剂的技术，发现了以前未曾观察到的对-丁氧基自由基攻击乙烯基单体的反应途径。

  DOI：

  10.1016/s0040-4039(00)87091-4

文献信息

• Reaction of Acyclic Hydrocarbons Towards t-Butoxy Radicals. A Study of Hydrogen Atom Abstraction by Using the Radical Trapping Technique
  作者：Peter Dokolas、Steven M. Loer、David H. Solomon

  DOI：10.1071/c98055

  日期：——

  The reaction of 3-methylpentane and 2,4-dimethylpentane toward t-butoxy radicals has been investigated, in neat and benzene solutions, by using the radical trapping technique. Abstraction occurs principally from the tertiary and secondary C-H reaction sites of 3-methylpentane and the tertiary position of 2,4-dimethylpentane. The tertiary and in particular secondary C-H reaction sites of 2,4-dimethylpentane are shown to be considerably less susceptible towards t-butoxy radical facilitated abstraction compared with the equivalent reaction sites of 3-methylpentane. As a result, the latter is three times as reactive as 2,4-dimethylpentane as a neat hydrocarbon solution and seven times as reactive in a diluted mixture of benzene. Diferences in selectivity and rate of hydrogen abstraction, between the substrates, are interpreted in terms of non-bonding interactions retarding t-butoxy radicals from approaching sterically demanding C-H reaction sites. The selectivity from 3-methylpentane is solvent-insensitive whereas abstraction from 2,4-dimethylpentane is modified in benzene. Further, the rate of hydrogen abstraction, from either substrate, to t-butoxy radical β-scission is considerably smaller in benzene. Both observations are interpreted in terms of t-butoxy radical solvation by the aromatic solvent.

  在纯净溶液和苯溶液中，通过使用化学方法研究了 3-甲基戊烷和 2,4-二甲基戊烷与 t-丁氧基自由基的反应。 自由基的反应进行了研究。 自由基捕获技术进行了研究。萃取主要发生在 3-甲基戊烷的三级和二级 C-H 反应位点上。 的三级和二级 C-H 反应位点以及 2,4-二甲基戊烷的三级位点发生萃取。 2,4-二甲基戊烷的叔位。2,4 二甲基戊烷的三级，特别是二级 C-H 反应位点 的叔位，特别是仲位 C-H 反应位点对 t-丁氧基自由基促进萃取的敏感性大大降低。 的反应位点相比，2,4-二甲基戊烷的三级，特别是二级 C-H 的反应位点相比，2,4-二甲基戊烷对 t-丁氧基自由基促进萃取的敏感性要低得多。因此，后者的反应活性是 2,4 二甲基戊烷的三倍。 是 2,4-二甲基戊烷在纯碳氢化合物溶液中反应活性的三倍，在稀释的苯混合物中反应活性的七倍。 在稀释的苯混合物中的反应活性是 2,4-二甲基戊烷的七倍。在选择性和 底物间氢抽取选择性和速率的差异可解释为 非键相互作用阻止叔丁氧自由基接近有立体要求的 C-H 反应位点。 有立体要求的 C-H 反应位点。对 3-甲基戊烷的选择性 的选择性对溶剂不敏感，而从 2,4-二甲基戊烷中萃取则在苯中发生改变。 在苯中发生改变。此外，从两种底物中的 底物的氢萃取到 t-丁氧基自由基 β 分裂的速率在苯中要小得多。 苯。这两项观察结果都可以解释为 t-丁氧基自由基 被芳香族溶剂溶解。
• The Reaction of Organophosphorus Radicals With Vinyl Acetate and Acrylonitrile in the Presence of an Aminoxyl Radical Scavenger
  作者：WK Busfield、ID Grice、ID Jenkins

  DOI：10.1071/ch9950625

  日期：——

  The radical-trapping technique employing 1,1,3,3-tetramethyl-1,3-dihydro-2H-isoindol-2-yloxyl (1) as a radical scavenger has been used to study the reaction of diphenylphosphinoyl (2) and dimethoxyphosphinoyl (3) radicals with vinyl acetate and acrylonitrile. The phosphorus- centred radicals were generated by hydrogen abstraction from diphenylphosphine oxide and dimethyl phosphite respectively. Diphenylphosphine oxide was approximately three times as reactive as dimethyl phosphite towards hydrogen abstraction by t- butoxyl radicals and four times as reactive as tetrahydrofuran (towards abstraction of an α-hydrogen). Diphenylphosphinoyl radicals were found to be relatively nucleophilic and, in competition experiments, reacted about an order of magnitude faster with acrylonitrile than with vinyl acetate. Dimethoxyphosphinoyl radicals were rather less nucleophilic and reacted only twice as fast with acrylonitrile as they did with vinyl acetate. In the presence of excess aminoxyl (1), both diphenylphosphinoyl and dimethoxyphosphinoyl radicals were efficiently scavenged to produce stable phosphinic and phosphate esters respectively. The rate of scavenging was close to diffusion-controlled (c. 1.8×109 1. mol-1 s-1).

  以 1,1,3,3-四甲基-1,3-二氢-2H-异吲哚-2-基氧基（1）为自由基清除剂的自由基捕获技术被用于研究二苯基膦酰（2）和二甲氧基膦酰（3）自由基与醋酸乙烯酯和丙烯腈的反应。以磷为中心的自由基分别通过从二苯基氧化膦和亚磷酸二甲酯中抽取氢而生成。 二苯基氧化膦对 t-丁氧自由基析取氢的反应活性大约是亚磷酸二甲酯的三倍，是四氢呋喃（析取 α-氢）的四倍。研究发现，二苯基膦酰基具有较强的亲核性，在竞争实验中，与丙烯腈反应的速度比与醋酸乙烯反应的速度快一个数量级。 二甲氧基膦酰基的亲核性较弱，与丙烯腈反应的速度仅是与醋酸乙烯反应速度的两倍。在存在过量氨基己基（1）的情况下，二苯基膦酰和二甲氧基膦酰自由基都能被有效清除，分别生成稳定的膦酸酯和磷酸酯。清除速率接近于扩散控制（c. 1.8×109 1. mol-1 s-1）。
• Thermal Decomposition Mechanisms of <i>tert</i>-Alkyl Peroxypivalates Studied by the Nitroxide Radical Trapping Technique
  作者：Tomoyuki Nakamura、W. Ken Busfield、Ian D. Jenkins、Ezio Rizzardo、San H. Thang、Shuji Suyama

  DOI：10.1021/jo990680s

  日期：2000.1.1

  mechanism involving concerted two-bond scission within the solvent cage to generate the tert-butyl radical, CO(2), and an alkoxyl radical. The thermolysis rate constants of tert-alkyl peroxypivalates 1 were influenced by both inductive and steric effects [Taft-Ingold equation, log(rel k(d)) = (0.97 +/- 0. 14)Sigmasigma - (0.31 +/- 0.04)SigmaE(s)(c), was obtained].

  通过使用氮氧化物自由基捕获技术，研究了一系列枯烯中的叔烷基过氧新戊酸酯1的热解。由热分解产生的叔烷氧基经历了单分子反应，β断裂和1,5-H移位，与从枯烯中提取氢竞争。叔烷氧基自由基β-断裂的绝对速率常数（变化超过4个数量级）表明烷氧基自由基的行为截然不同。但是，自由基产生效率1仅有微小的变化，从53（R = Me）到63％（R = Bu（t）（）），支持了一种机制，该机制涉及溶剂笼中的双键双键断裂产生叔叔-丁基，CO（2）和烷氧基。
• Thermal Decomposition of 1-Cyclohexyl-1-methylethyl Peroxypivalate
  作者：Tomoyuki Nakamura、W. Ken Busfield、Ian D. Jenkins、Ezio Rizzardo、San H. Thang、Shuji Suyama

  DOI：10.1246/cl.1998.965

  日期：1998.10

  The thermal decomposition of a novel peroxyester, 1-cyclohexyl-1-methylethyl peroxypivalate 1a in cumene has been studied using the radical trapping technique employing 1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-2-yloxyl T, a stable aminoxyl radical, as the scavenger. Comparable amounts of cyclohexyl radicals and t-butyl radicals were generated from the thermolysis of 1a. Thus, 1-cyclohexyl-1-methylethoxyl

  使用采用 1,1,3,3-四甲基-2,3-二氢-1H-isoindol-2-的自由基捕获技术研究了新型过氧酯、1-环己基-1-甲基乙基过氧新戊酸酯 1a 在异丙苯中的热分解yloxyl T，一种稳定的氨氧基自由基，作为清除剂。1a 的热解产生了相当数量的环己基自由基和叔丁基自由基。因此，1-环己基-1-甲基乙氧基2a 仅经历β-断裂。1a 的自由基生成效率确定为 0.56，略高于过氧化新戊酸叔丁酯 (0.53)。
• Photolysis of dioxiranes in the presence of a nitroxide radical scavenger: the intermediacy of radical anion and diyl species in the production and trapping of methyl and trifluoromethyl radicals
  作者：Waldemar Adam、Steven E. Bottle、Rossella Mello

  DOI：10.1039/c39910000771

  日期：——

  Electron transfer between dioxiranes 1 and nitroxide 2 affords the dioxirane radical anion–oxoammonium cation pair, which generates methyl radicals that are trapped by the nitroxide.

  二环氧乙烷 1 和硝基氧 2 之间的电子转移提供了二环氧乙烷自由基阴离子-氧铵阳离子对，其产生被硝基氧捕获的甲基自由基。