[15N]-(tert-butoxycarbonyl)aniline | 250330-16-6

• 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: [15N]-(tert-butoxycarbonyl)aniline
• 英文别名: (15)N-phenyl carbamic acid tert-butyl ester；tert-butyl N-phenylcarbamate
• CAS: 250330-16-6
• 化学式: C₁₁H₁₅NO₂
• 分子量: 194.239
• InChiKey: KZZHPWMVEVZEFG-HNHCFKFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [15N]-(tert-butoxycarbonyl)aniline 在 叔丁基锂 、 1,1-二碘乙烷 作用下， 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Enantioselective Synthesis of Six-Membered Palladacycles Having Metal-Bound Stereogenic Carbons:  Isolation and Reactivity of Palladacycles Containing Readily Accessible β-Hydrogens

  摘要：

  Five enantiopure palladacycles containing palladium bonded to a stereogenic carbon and an N-coordinated oxindole were synthesized by the reaction of alkenyl aryl triflates 2 and 9 with Pd(0) bisphosphine complexes. Two palladacyclic complexes, 3beta and 10alpha, were characterized by single-crystal X-ray crystallography. The reactivity of neutral palladacycles 3beta and 10beta was studied in detail. These unusual palladium alkyls, which have three accessible beta-hydrogens, are thermally stable at temperatures as high as 120 degreesC. At higher temperature, or at room temperature in the presence of weak acids, these complexes epimerize at the stereogenic carbon bonded to palladium. The mechanism of the acid-promoted epimerization was studied in detail. During this epimerization, cationic palladium alkyls 13/14 and 33 and cationic palladium hydride alkene complexes 31 and 32 are in rapid equilibrium.

  DOI：

  10.1021/ja045047p
• 作为产物：
  描述：

  二碳酸二叔丁酯 、 苯胺-15N 在 potassium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 19.0h， 以1.02 g的产率得到[15N]-(tert-butoxycarbonyl)aniline
  参考文献：
  名称：

  反式对还原消除率的影响。从具有不对称配位球的异构芳基钯酰胺中还原消除胺

  摘要：

  为了确定反式对芳基钯 (II) 酰胺配合物的还原消除速率的影响，研究了带有对称和不对称 DPPF（DPPF = 双（二苯基膦）二茂铁）衍生物的芳基钯酰胺配合物的反应。LPd(Ar)(NMeAr') 的 THF 溶液（L = DPPF、DPPF-OMe、DPPF-CF3、DPPF-OMe、Ph、DPPF-Ph、CF3 和 DPPF-OMe、CF3；Ar = C6H4-4-CF3 ;Ar' = C6H4-4-CH3、Ph 和 C6H4-4-OMe) 在 -15°C 进行 CN 键形成还原消除，以高产率形成相应的 N-甲基二芳基胺。由对称 DPPF 衍生物与 DPPF 芳基上的吸电子取代基连接的复合物比由对称 DPPF 衍生物与配体芳基上的给电子取代基连接的复合物更快地进行还原消除。对含有不对称 DPPF 配体的芳基钯酰胺配合物的研究揭示了几种趋势。首先，具有较弱的供体反式氮和较强的供体反式到钯

  DOI：

  10.1021/ja037425g

文献信息

• Trans Influence on the Rate of Reductive Elimination. Reductive Elimination of Amines from Isomeric Arylpalladium Amides with Unsymmetrical Coordination Spheres
  作者：Makoto Yamashita、Jose V. Cuevas Vicario、John F. Hartwig

  DOI：10.1021/ja037425g

  日期：2003.12.1

  forming reductive elimination at -15 C to form the corresponding N-methyldiarylamine in high yield. Complexes ligated by symmetrical DPPF derivatives with electron-withdrawing substituents on the DPPF aryl groups underwent reductive elimination faster than complexes ligated by symmetrical DPPF derivatives with electron-donating substituents on the ligand aryl groups. Studies of arylpalladium amido complexes

  为了确定反式对芳基钯 (II) 酰胺配合物的还原消除速率的影响，研究了带有对称和不对称 DPPF（DPPF = 双（二苯基膦）二茂铁）衍生物的芳基钯酰胺配合物的反应。LPd(Ar)(NMeAr') 的 THF 溶液（L = DPPF、DPPF-OMe、DPPF-CF3、DPPF-OMe、Ph、DPPF-Ph、CF3 和 DPPF-OMe、CF3；Ar = C6H4-4-CF3 ;Ar' = C6H4-4-CH3、Ph 和 C6H4-4-OMe) 在 -15°C 进行 CN 键形成还原消除，以高产率形成相应的 N-甲基二芳基胺。由对称 DPPF 衍生物与 DPPF 芳基上的吸电子取代基连接的复合物比由对称 DPPF 衍生物与配体芳基上的给电子取代基连接的复合物更快地进行还原消除。对含有不对称 DPPF 配体的芳基钯酰胺配合物的研究揭示了几种趋势。首先，具有较弱的供体反式氮和较强的供体反式到钯
• An Efficient Synthesis of [¹⁵N]-Carbazole from [¹⁵N]-Aniline
  作者：Matt A. Peterson、Bradley L. Nilsson

  DOI：10.1080/00397919908086022

  日期：1999.11

  A reaction sequence involving ortho-lithiation of [N-15]-(tert-Butoxycarbonyl)aniline, quenching with Bu3SnCl, palladium catalyzed coupling with bromobenzene, and deprotection provides efficient access to [N-15]-2-aminobiphenyl (4). Compound 4 is converted to [N-15]-carbazole via diazotization, treatment with NaN3, and heating to promote intramolecular nitrene insertion.
• H and ¹⁵N Dynamic Nuclear Polarization Studies of Carbazole
  作者：Jian Z. Hu、Mark S. Solum、Robert A. Wind、Brad L. Nilsson、Matt A. Peterson、Ronald J. Pugmire、David M. Grant

  DOI：10.1021/jp9938011

  日期：2000.5.1

  N-15 NMR experiments, combined with dynamic nuclear polarization (DNP), are reported on carbazole doped with the stable free radical 1,3 bisdiphenylene-2-phenylallyl (BDPA). Doping shortens the nuclear relaxation times and provides paramagnetic centers that can be used to enhance the nuclear signal by means of DNP so that N-15 NMR experiments can be done in minutes. The factors were measured in a 1.4 T external field, using both unlabeled and 98% N-15 labeled carbazole with doping levels varying between 0.65 and 5.0 wt % BDPA. A doping level of approximately 1 wt % produced optimal results. DNP enhancement factors of 35 and 930 were obtained for H-1 and N-15, respectively making it possible to perform N-15 DNP NMR experiments at the natural abundance level.
• Enantioselective Synthesis of Six-Membered Palladacycles Having Metal-Bound Stereogenic Carbons:  Isolation and Reactivity of Palladacycles Containing Readily Accessible β-Hydrogens
  作者：Brenda J. Burke、Larry E. Overman

  DOI：10.1021/ja045047p

  日期：2004.12.1

  Five enantiopure palladacycles containing palladium bonded to a stereogenic carbon and an N-coordinated oxindole were synthesized by the reaction of alkenyl aryl triflates 2 and 9 with Pd(0) bisphosphine complexes. Two palladacyclic complexes, 3beta and 10alpha, were characterized by single-crystal X-ray crystallography. The reactivity of neutral palladacycles 3beta and 10beta was studied in detail. These unusual palladium alkyls, which have three accessible beta-hydrogens, are thermally stable at temperatures as high as 120 degreesC. At higher temperature, or at room temperature in the presence of weak acids, these complexes epimerize at the stereogenic carbon bonded to palladium. The mechanism of the acid-promoted epimerization was studied in detail. During this epimerization, cationic palladium alkyls 13/14 and 33 and cationic palladium hydride alkene complexes 31 and 32 are in rapid equilibrium.