1-叔-丁基氮丙啶 | 4017-38-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 1-叔-丁基氮丙啶
• 英文名称: N-n-Butylaziridin
• 英文别名: N-tert.-Butyl-ethylenimin；N-tert-butylaziridine；1-tert-butyl-aziridine；1-tert-Butyl-aziridin；tert.butylaziridine；AZIRIDINE, 1-tert-BUTYL-；1-tert-butylaziridine
• CAS: 4017-38-3
• 化学式: C₆H₁₃N
• 分子量: 99.1759
• InChiKey: BBFCEQFUUOTJPD-UHFFFAOYSA-N

物化性质

• 保留指数：
  699

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-叔-丁基氮丙啶 在 H₃PO₃S 作用下， 生成 Ethanethiol, 2-[(1,1-dimethylethyl)amino]-, dihydrogen phosphate(ester)
  参考文献：
  名称：

  Process for preparing 2-aminoethylthiophosphate salts

  摘要：

  公开号：

  US03501557A1
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 chlorosulphuric acid 作用下， 生成 1-叔-丁基氮丙啶
  参考文献：
  名称：

  核磁共振谱。N-取代氮丙啶（乙烯亚胺）1 的氮转化率

  摘要：

  已经检查了环大小从三到六不等的各种环亚胺的核磁共振谱。发现 N-取代的氮丙啶 (ethplenimine) 衍生物的光谱强烈地依赖于温度，如果氮原子和连接的基团不位于平面内并且反转发生相当缓慢，则可以预期。可以评估影响环状亚胺中非平面氮原子反转率的一些因素。正如预期的那样，不饱和基团与非平面氮的连接增加了转化率，这是与氮未共享电子对共轭的结果。无论是连接到氮还是连接到亚胺环的碳上的庞大基团也会增加速率。烷基取代一个氢或两个与碳相连的顺式氢似乎使分子呈现优选构型，其中N-取代基与环取代基反式。由于溶剂和亚氨基氮之间的氢键使分离构型稳定，因此羟基溶剂中的转化率最有可能降低。迄今为止获得的数据表明，由于三价氮而具有分子不对称性的取代氮丙啶可能只能在低于 - 50o 的温度下分解成相当稳定的光学对映体。N-取代的氮杂环丁烷（三亚甲基亚胺）和大环亚胺的氮转化率似乎太大而无法在高于 77o 的温度下通过核磁共振技术进行测量。

  DOI：

  10.1021/ja01552a048

文献信息

• Cycloaddition of tertiary aziridines and carbon dioxide using a recyclable organocatalyst, 1,3-di-tert-butylimidazolium-2-carboxylate: straightforward access to 3-substituted 2-oxazolidones
  作者：Atsushi Ueno、Yoshihito Kayaki、Takao Ikariya

  DOI：10.1039/c2gc36414j

  日期：——

  Imidazolium-2-carboxylates derived from N-heterocyclic carbenes (NHCs) and CO2 serve as efficient catalysts for CO2-carboxylation of tertiary aziridines bearing various substituents such as halogens, ether, olefin, ester, acetal, and nitro groups on the aziridine ring in 2-propanol, leading to 3-substituted-2-oxazolidones in good to excellent yields and with high selectivity. The NHC–CO2 adducts facilitate

  咪唑-2-羧酸盐衍生自 N-杂环卡宾（NHCs）和CO 2起到了有效的作用催化剂的CO 2-羧化氮丙啶 带有各种取代基，例如 卤素， 醚， 烯烃， 酯， 乙缩醛，以及氮丙啶环上的硝基 2-丙醇，从而以高至优异的收率和高选择性产生3-取代的-2-恶唑烷酮。NHC-CO 2加合物促进了CO 2部分对核素的亲核攻击。氮丙啶，其中取代基在羧化过程中是完整的。这催化剂 成功回收了五次，没有明显的活性损失。
• [3+2] Cross-Coupling Reactions of Aziridines with Isocyanates Catalyzed by Nickel(II) Iodide
  作者：Takeshi Munegumi、Isao Azumaya、Takako Kato、Hyuma Masu、Shinichi Saito

  DOI：10.1021/ol052417l

  日期：2006.2.1

  [reaction: see text]. Cycloaddition of aziridines with isocyanates proceeded smoothly in the presence of a nickel catalyst, and five iminooxazolidine derivatives were isolated in good yields. The best result was obtained when the reaction was carried out in the presence of NiI2, and a longer reaction time allowed the isomerization of the iminooxazolidine to the corresponding imidazolidinone derivatives

  [反应：请参见文字]。在镍催化剂的存在下，氮丙啶与异氰酸酯的环加成反应顺利进行，并且以高收率分离出五种亚氨基恶唑烷衍生物。当在NiI2存在下进行反应时，可获得最佳结果，更长的反应时间使亚氨基恶唑烷异构化为相应的咪唑烷酮衍生物。
• Palladium Terminal Imido Complexes with Nitrene Character
  作者：Annette Grünwald、Bhupendra Goswami、Kevin Breitwieser、Bernd Morgenstern、Martí Gimferrer、Frank W. Heinemann、Dajana M. Momper、Christopher W. M. Kay、Dominik Munz

  DOI：10.1021/jacs.2c02818

  日期：2022.5.25

  Whereas triplet-nitrene complexes of the late transition metals are isolable and key intermediates in catalysis, singlet-nitrene ligands remain elusive. Herein we communicate three such palladium terminal imido complexes with singlet ground states. UV–vis–NIR electronic spectroscopy with broad bands up to 1400 nm as well as high-level computations (DFT, STEOM-CCSD, CASSCF/NEVPT2, EOS analysis) and

  尽管晚期过渡金属的三线态-氮烯配合物是可分离的并且是催化中的关键中间体，但单线态-氮烯配体仍然难以捉摸。在这里，我们交流了三种具有单线态基态的钯末端亚氨基配合物。具有高达 1400 nm 的宽带的紫外-可见-近红外电子光谱以及高级计算（DFT、STEOM-CCSD、CASSCF/NEVPT2、EOS 分析）和反应性研究表明钯 (0) 单线态氮烯具有显着的特征。尽管由于异丁烯的消除，脂肪族氮烯配合物被证明过于活泼，无法以分析纯形式分离，但芳基同系物可以通过 SC-XRD、元素分析、IR-、NMR 光谱和 HRMS 进行表征。配合物独特的两亲性使其能够活化六氟苯、三苯基膦和频哪醇硼烷，,尽管晚期过渡金属的三线态-氮烯配合物是可分离的并且是催化中的关键中间体，但单线态-氮烯配体仍然难以捉摸。在这里，我们交流了三种具有单线态基态的钯末端亚氨基配合物。具有高达 1400 nm 的宽带的紫外-可见-近
• Danzer, Wolfgang; Hoefer, Roland; Menzel, Hartmut, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1984, vol. 39, # 2, p. 167 - 179
  作者：Danzer, Wolfgang、Hoefer, Roland、Menzel, Hartmut、Olgemoeller, Bernhard、Beck, Wolfgang

  DOI：——

  日期：——
• Acid-catalyzed decomposition of 1-alkyltriazolines: a mechanistic study
  作者：Richard H. Smith、Brian D. Wladkowski、Jesse E. Taylor、Erin J. Thompson、Brunon Pruski、John R. Klose、A. W. Andrews、Christopher J. Michejda

  DOI：10.1021/jo00060a027

  日期：1993.4

  1-Alkyltriazolines are five-membered cyclic triazenes containing the unusual Z-configuration for the triazene moiety. The hydrolytic decomposition of these compounds in aqueous or mixed acetonitrile-aqueous buffers leads predominantly to the formation of the corresponding 1-alkylaziridines and lesser amounts of 2-(alkylamino)ethanols, alkylamines, and acetaldehyde. The latter two products presumably result from hydrolysis of a rearrangement product, N-ethylidenealkylamine. Neither the nature of the 1-alkyl group nor the pH of the medium greatly influences the product distribution, although decomposition in purely aqueous buffers slightly reduces the aziridine yields. The rate of hydrolysis of 1-alkyltriazolines is about twice as fast as that of the analogous acyclic 1,3,3-trialkyltriazenes and varies in the order tert-butyl > isopropyl > ethyl > butyl > methyl > propyl > benzyl. The mechanism of the decomposition is specific acid-catalyzed (A1) involving rapid reversible protonation followed by rate-limiting formation of a 2-(alkylamino)ethyldiazonium ion. The slopes of the log k(obs) versus pH plots are near -1.0. The solvent deuterium isotope effect, k(H2O)/k(D2O), is in all cases <1.0 and ranges from 0.58 for 1-methyltriazoline to 0.86 for 1-benzyltriazoline. The rate of decomposition shows no significant dependence on the concentration of the buffer acid. The proposed mechanism involves rate-limiting formation of a 2-(alkylamino)ethyldiazonium ion, which is then partitioned among several competing product formation pathways. 1-Alkyltriazolines are potent direct-acting mutagens in the alkylation-sensitive TA 1535 strain of Salmonella typhimurium. A clear, dose-dependent mutagenicity is observed. At the highest dose level, various 1-alkyltriazolines have activities roughly equivalent to that of the potent methylating agent, 1,3-dimethyltriazene. At low levels of substrate, 1-alkyltriazolines are significantly more active than 1,3-dimethyltriazene, with mutagenicity following the order benzyl > methyl > ethyl.