乙基苯基重氮甲烷 | 52686-70-1

• 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: 乙基苯基重氮甲烷
• 英文名称: triethylamine-1-(2-naphthylethyl)borane
• 英文别名: ethyl phenyl diazomethane；ethylphenyldiazomethane；(1-diazopropyl)benzene；(1-diazo-propyl)-benzene；1-phenyl-diazo-propane；[(1Z)-1-diazopropyl]benzene
• CAS: 52686-70-1
• 化学式: C₉H₁₀N₂
• 分子量: 146.192
• InChiKey: LJTFEHMRMWNEIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  乙基苯基重氮甲烷 在 tetrabutylammonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Formation and reactivity of .sigma.-radical cation intermediates in the carbon-carbon coupling reaction of phenyldiazomethanes by one-electron oxidation

  摘要：

  One-electron oxidation of phenyldiazomethanes afforded cis-stilbene predominantly. The reaction was independent of the oxidation methods, e.g., electrolysis, copper(II), triarylaminium salts, or photosensitized one-electron oxidations. The C-C coupling reaction was retarded by introducing alpha-substituents on phenyldiazomethane. The ESR spectra of diazoalkane radical cations could be obtained during the electrolysis at low temperature and the resulting spectra revealed their unique electronic structure as sigma-radicals for most cases. When a bulky tert-butyl group was substituted, the corresponding pi-radical cation was observed, but the C-C coupling reaction did not occur. The novel HOMO-LUMO switching by one-electron removal from the HOMO pi-orbital of diazomethane is explained by the interaction of phenyl group with the C-N-N sigma-radical moiety. The C-C coupling reaction proceeds via facile [4 + 2] cycloaddition between the diazomethane and sigma-radical cation, and the preferential formation of cis-olefins is based on the secondary orbital interaction between the two phenyl groups. The structure and the stability of radical cation intermediates are rationalized on the basis of ab initio calculations.

  DOI：

  10.1021/jo00037a021
• 作为产物：
  描述：

  1-苯基亚丙基肼 生成 乙基苯基重氮甲烷
  参考文献：
  名称：

  通过催化碳插入甲酰基CH键中形成不同的烷酮。方便地获得天然的Achyrofuran

  摘要：

  一个多世纪前，重氮甲烷与醛的首次反应生成了甲基酮。在此期间，醛很少与三甲基甲硅烷基重氮甲烷，重氮乙酸酯和芳基重氮甲烷发生同系化反应。这项工作描述了一种由不稳定的重氮烷烃聚合酮组装的温和方法，包括使用双取代（内部）亲核试剂进行手性酮合成的实例。该方法对空间拥挤具有显着的耐受性，这是通过对复杂的二苯并呋喃呋喃呋喃进行的简单处理得到证实的。

  DOI：

  10.1021/ol9010932

文献信息

• The phenylcarbene rearrangement as a source of real carbenes.
  作者：Joseph M. Fox、Jennifer E. Gillen Scacheri、K.Gwyn L. Jones、Maitland Jones、Philip B. Shevlin、Brian Armstrong、Renata Sztyrbicka

  DOI：10.1016/s0040-4039(00)61178-4

  日期：1992.8

  The phonylcarbene rearrangement is used to produce carbenes that are compared to the intermediates formed on photolysis and pyrolysis of diazo compounds.

  苯甲酰基卡宾重排用于生产与重氮化合物的光解和热解过程中形成的中间体相比的卡宾。
• Decomposition of toluene-p-sulphonylhydrazones by alkali. Part II
  作者：R. K. Bartlett、T. S. Stevens

  DOI：10.1039/j39670001964

  日期：——

  Hydrazones of further mono- and especially di-carbonyl compounds have been studied. That of acetonylacetone gave hexa-2,5-diene, and that of biphenacyl gave diphenylbutadiene with much 3,6-diphenylpyridazine. Hydrazones of αβ-unsaturated aldehydes and ketones gave pyrazoles, also obtained under the same conditions from 1-toluenesulphonylpyrazolines. Hydrazones of ω-substituted acetophenones, PhCO·CH2X

  已经研究了其他单羰基化合物，尤其是二羰基化合物的dra。丙酮基丙酮的化合物得到六-2，5-二烯，而联苯酰基基的化合物得到具有大量3，6-二苯基哒嗪的二苯基丁二烯。αβ-不饱和醛和酮的gave得到吡唑，也以相同条件从1-甲苯磺酰基吡唑啉获得吡唑。ω-取代的苯乙酮的CO（PhCO·CH 2 X）产生苯乙酮以及PhCH·CHX（X = OR或Ts）。
• 1,2-Hydrogen migration and alkene formation in the photoexcited states of alkylphenyldiazomethanes
  作者：Sol Celebi、Soccoro Leyva、David A. Modarelli、Matthew S. Platz

  DOI：10.1021/ja00072a014

  日期：1993.9

  Laser flash photolysis of alkylphenyldiazomethanes in the presence of pyridine produces easily detected ylides. The data indicate that photolysis of alkylphenyldiazomethanes leads to both carbene formation and direct formation of rearrangement products which do not derive from relaxed carbene intermediates

  在吡啶存在下，烷基苯基重氮甲烷的激光闪光光解产生易于检测的叶立德。数据表明，烷基苯基重氮甲烷的光解导致卡宾的形成和重排产物的直接形成，这些产物不是来自松弛的卡宾中间体
• Synthesis of Acyclic Ketones by Catalytic, Bidirectional Homologation of Formaldehyde with Nonstabilized Diazoalkanes. Application of a Chiral Diazomethyl(pyrrolidine) in Total Syntheses of Erythroxylon Alkaloids
  作者：Andrew J. Wommack、Jason S. Kingsbury

  DOI：10.1021/jo401377a

  日期：2013.11.1

  This work offers a catalytic approach to convergent ketone assembly based upon formal and tandem C–H insertion of diazoalkanes in the presence of limiting amounts of monomeric formaldehyde, which is easily generated as a gas by thermolysis of the inexpensive and abundant paraformaldehyde (∼30 USD/kg). The method forms di-, tri-, and even tetrasubstituted acetones with high efficiency, and it has streamlined

  这项工作为在有限量的单体甲醛存在下，通过重氮的正式和串联C–H重氮插入而提供了一种催化酮聚合的催化方法，该单体甲醛很容易通过热解廉价而丰富的多聚甲醛而作为气体产生（约30美元/公斤）。该方法高效地形成二，三，甚至四取代的丙酮，并且简化了（-）-二氢cuscohygrine的合成过程，其中保留了脯氨酸基原料的绝对立体化学。在氧化新方案的问世帮助下，我们还提供了处理非羰基稳定的重氮化合物的完整细节。
• Diazomethane Radical Cations as a Dipolarophile in the Dimeric Olefin Formation from Diazo-compounds
  作者：Katsuya Ishiguro、Yasuhiko Sawaki、Hiizu Iwamura

  DOI：10.1246/cl.1987.1853

  日期：1987.9.5

  A novel cycloaddition mechanism involving diazomethane radical cations is proposed for the dimeric olefin formation by the one-electron oxidation of diazo-compounds. The preference of cis-stilbene formation from phenyldiazomethane is understood by a secondary orbital interaction of phenyl groups on the cycloaddition step.

  提出了一种涉及重氮甲烷自由基阳离子的新型环加成机制，用于通过重氮化合物的单电子氧化形成二聚烯烃。通过苯基在环加成步骤中的次级轨道相互作用来理解从苯基重氮甲烷形成顺式二苯乙烯的优选性。

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