(1-tert-butyl-2-methyldiaziridin-3-ylidene)(methyl)amine | 1026091-68-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1-tert-butyl-2-methyldiaziridin-3-ylidene)(methyl)amine
• CAS: 1026091-68-8
• 化学式: C₇H₁₅N₃
• 分子量: 141.216
• InChiKey: HZWYANUHZLDWPT-VURMDHGXSA-N

反应信息

• 作为产物：
  描述：

  N,N',N"-trimethyl-N-hydroxyguanidine O-sulfonic acid 在 potassium hydroxide 作用下， 以 水 、 正戊烷 为溶剂， 反应 1.0h， 生成 (1-tert-butyl-2-methyldiaziridin-3-ylidene)(methyl)amine 、 (1-tert-butyl-2-methyldiaziridin-3-ylidene)(methyl)amine
  参考文献：
  名称：

  Iminodiaziridines 的合成和 15N NMR 谱 - 1-Aryl-3-iminodiaziridines 的环扩展为 1H-和 3aH-Benzimidazoles、2H-Indazoles 和 5H-Dibenzo[d,f][1,3]diazepines

  摘要：

  亚氨基二氮丙啶是通过 (i) 用 N-氯胍的叔丁醇钾进行 1,3-脱氯化氢合成的，由 N,N',N"-取代的胍与次氯酸叔丁酯原位生成，以及 (ii) 碱介导的 1 ,3-从 N,N',N"-取代的羟基胍 O-磺酸中消除硫酸。在升高的温度下，（烷基亚氨基）二氮丙啶通过 1,3-移位、[2+1] 环消去反应得到异氰化物和二氮烯，以及开环消除反应得到亚烷基胍。N'-芳基-N-羟基胍O-磺酸提供（N-芳基亚氨基）二氮丙啶，但不提供1-芳基-3-亚氨基二氮丙啶，而是提供重排的异构体。含有全氘化叔丁基的前体得到重排产物，显示完全混乱。这表明 1-芳基-3-亚氨基二氮丙啶是中间体，可进行非常快速的简并价异构化。如果邻芳基位置被取代，则可获得高产率的（芳基亚氨基）二氮丙啶以及 2-亚氨基-2,3-二氢-3aH-苯​​并咪唑。否则，2-氨基-1H-苯并咪唑和强荧光 3-氨基-2H-吲唑，源自难以捉摸的 1-

  DOI：

  10.1002/ejoc.200900350

文献信息

• Iminodiaziridines by Regio- and Stereoselective Cyclization of Diastereomeric Singlet Triazatrimethylenemethane Diradicals Generated Through Photolysis of 5-Imino-4,5-dihydro-1<i>H</i>-tetrazoles
  作者：Helmut Quast、Lothar W. Bieber

  DOI：10.1021/jo702697f

  日期：2008.5.1

  1,4-Dialkyl-5-(N-alkylimino)-4,5-dihydro-1H-tetrazoles were prepared in high yields by deprotonation with sodium hydride of 1,4-dialkyl-5-(N-alkylamino)tetrazolium salts that were adorned with two or three different alkyl groups, including methyl, trideuteriomethyl, and tert-butyl groups. Direct irradiation (lambda > 255 nm) at -60 degrees C yielded molecular nitrogen and mixtures of 1,2-dialkyl-3-(N-alkylimino)diaziridines (83-87%) along with carbodiimides (13-17%) arising by 1,3-dipolar cycloreversion. The missing 1,3-dipoles, alkyl azides, did not survive photolysis. Each member of a pair of isotopomers and of a pair of isomers, and an iminodihydrotetrazole, whose three nitrogens were tagged, yielded a characteristic mixture of three isomeric iminodiaziridines that allowed the mode of formation to be deduced. The results are interpreted in terms of photodenitrogenation of the iminodihydrotetrazoles to furnish diastereomeric singlet triazatrimethylenemethane diradicals that retain the inherited configurations before ring closure to iminodiaziridines, presumably in two steps via mono-orthogonal diradicals.