tert-butyl(phenyl)diazomethane | 83922-79-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyl(phenyl)diazomethane
• 英文别名: t-butylphenyldiazomethane；(1-diazo-2,2-dimethylpropyl)benzene；1-phenyl-1'-tert-butyldiazomethane；(t-Bu)(Ph)CN2
• CAS: 83922-79-6
• 化学式: C₁₁H₁₄N₂
• 分子量: 174.246
• InChiKey: HOLNYRWKMZBZIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  tert-butyl(phenyl)diazomethane 在 nitric oxide 作用下， 以 various solvent(s) 为溶剂， 生成 anti-Pivalophenonoximradikal
  参考文献：
  名称：

  Forrester, Alexander R.; Sadd, John S., Journal of the Chemical Society. Perkin transactions II, 1982, p. 1273 - 1278

  摘要：

  DOI：
• 作为产物：
  描述：

  phenyl t-butyl ketoneone 2-naphthylethanone p-toluenesulfonylhydrazone 在 吡啶 、 sodium methylate 作用下， 生成 tert-butyl(phenyl)diazomethane
  参考文献：
  名称：

  The synthesis of silyl- and germyldiazoalkanes via tosylhydrazones

  摘要：

  从酰基硅烷和锗烷中制备了对甲苯磺酰肼。这些化合物可以在比类似碳化合物所需更温和的条件下，通过正丁基锂转化为金属型重氮烷，收率极高。这些重氮烷比它们的碳对应物更加稳定。这些结果，连同硅基和锗基化合物的光谱移位，被解释为重氮基团和金属型原子之间的dπ-pπ键合。

  DOI：

  10.1139/v69-720

文献信息

• Allene C(sp²)–H Activation and Alkenylation Catalyzed by Palladium
  作者：Benedikt S. Schreib、Mina Son、Françoise A. Aouane、Mu-Hyun Baik、Erick M. Carreira

  DOI：10.1021/jacs.1c11528

  日期：2021.12.29

  The selective transition-metal-mediated activation of C(sp2)–H bonds of allenes is a formidable challenge because of the competitive, intrinsic reactivity of cumulated double bonds. Herein, we report a Pd-catalyzed C–H alkenylation of electronically unbiased allenes, affording penta-1,2,4-triene products in up to 94% yield. A picolinamide directing group enables the formation of putative allenyl-palladacycles

  由于累积双键的竞争性、内在反应性，丙二烯的 C(sp 2 )-H 键的选择性过渡金属介导的活化是一项艰巨的挑战。在此，我们报道了电子无偏丙二烯的 Pd 催化 C-H 烯基化，以高达 94% 的产率提供五-1,2,4-三烯产物。吡啶酰胺导向基团能够形成假定的烯基-钯环，其随后与缺电子烯烃偶联伙伴参与限制周转的 Heck 型反应。这种机制提议与实验和计算研究一致。此外，我们首次报道了使用吡啶酰胺 N , O-缩醛作为 C-H 活化反应的易于去除的助剂，可以有效地进行烯基甲醇衍生物的烯基化。证明了在不影响产物的反应性五-1,2,4-三烯亚结构的情况下成功去除导向基团。
• 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
• New manganese-scaffolded organic triple-deckers based on quinoxaline, pyrazine and pyrimidine cores
  作者：Jean-Pierre Djukic、Christophe Michon、Zoran Ratkovic、Nathalie Kyritsakas-Gruber、André de Cian、Michel Pfeffer

  DOI：10.1039/b513322j

  日期：——

  The thermolytic coupling of Ph2CN2 and (t-Bu)(Ph)CN2 with doubly cyclomanganated 2,5-diphenylpyrazine and 4,6-diphenylpyrimidine afforded substantial amounts of new triple decker compounds of either Ci and C2 symmetry respectively containing, in both series, two η3-bonded Mn(CO)3 fragments which intervene as scaffolds sustaining the helical non-conjugated triaryl backbone. The molecular structures of two pyrazine derivatives show a typical non-parallel stacking of the aromatic rings and the encapsulation of the central pyrazyl fragment with interplanar centroid-to-centroid distances of ca. 3.5 Å. The stacking of the aromatics in the triple-decker pyrimidine derivatives has been assessed by 1H NMR experiments at low temperature. All the triple-decker-type compounds are electroactive. Pyrimidine triple-deckers can reversibly be electrochemically reduced to the corresponding anions.

  Ph2 和 (t-Bu)(Ph)CN2 与双环锰化 2,5-二苯基吡嗪和 4,6-二苯基嘧啶的热解偶联，产生了大量分别具有 Ci 和 C2 对称性的新型三层化合物，在这两个系列中，都含有两个 η3 键合的 Mn(CO)3 片段，它们作为支撑螺旋状非共轭三芳基骨架的支架而介入。两种吡嗪衍生物的分子结构显示出典型的芳香环非平行堆积和中心吡嗪片段的包裹，平面中心距约为 3.5 Å。所有三层甲板型化合物都具有电活性。嘧啶三层衍生物可逆地通过电化学还原成相应的阴离子。
• Solid-state photochemistry of crystalline pyrazolines: reliable generation and reactivity control of 1,3-biradicals and their potential for the green chemistry synthesis of substituted cyclopropanes
  作者：Saori Shiraki、Cortnie S. Vogelsberg、Miguel A. Garcia-Garibay

  DOI：10.1039/c2pp25263e

  日期：2012.12

  To expand on the limited number of examples that exist in the literature for the solid-state photodenitrogenation of azoalkanes, a series of crystalline 7-alkyl-2,3,7-triazabicyclo[3.3.0]oct-2-ene-6,8-diones with varying 4,4-substituents were prepared. Their photochemical behavior in solution and in the solid state was dependent on the 4,4-substitution of the 1-pyrazoline ring, with unsubstituted pyrazoline 12 giving a mixture of products both in solution and in the solid state. Diphenyl substituted pyrazolines 13 denitrogenate spontaneously in solution but require light exposure to react quantitatively in the solid state. t-Butyl-phenyl substituted pyrazolines 14 were shown to denitrogenate both chemo- and diastereoselectively in solution and in the solid state to yield a single product in quantitative yield.

  为了扩展文献中关于偶氮烷烃固态光脱氮反应的有限实例，我们制备了一系列具有不同4,4-取代基的7-烷基-2,3,7-三氮杂双环[3.3.0]辛-2-烯-6,8-二酮晶体。它们在溶液和固态下的光化学行为取决于1-吡唑啉环的4,4-取代基，未取代的吡唑啉12在溶液和固态下都会产生混合产物。二苯基取代吡唑啉13在溶液中自发脱氮，但在固态下需要光照才能定量反应。叔丁基苯基取代吡唑啉14在溶液和固态下均表现出化学和立体选择性脱氮，以定量产率产生单一产物。
• Formation and reactivity of .sigma.-radical cation intermediates in the carbon-carbon coupling reaction of phenyldiazomethanes by one-electron oxidation
  作者：Katsuya Ishiguro、Masatoshi Ikeda、Yasuhiko Sawaki

  DOI：10.1021/jo00037a021

  日期：1992.5

  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.