methyl (2-chloroethylamino)carbonyldiazenecarboxylate | 367965-97-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methyl (2-chloroethylamino)carbonyldiazenecarboxylate
• 英文别名: Methyl [(2-chloroethyl)carbamoyl]diazene-1-carboxylate；methyl N-(2-chloroethylcarbamoylimino)carbamate
• CAS: 367965-97-7
• 化学式: C₅H₈ClN₃O₃
• 分子量: 193.59
• InChiKey: BWQZQRDVPZJLCH-UHFFFAOYSA-N

物化性质

• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  80.1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (2-chloroethylamino)carbonyldiazenecarboxylate 在 Dowex(R) 50WX₂-100 、 sodium acetate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 methyl 5-acetyl-3-(2-chlorethyl)-4-methyl-2-oxo-2,3-dihydro-1H-imidazol-1-ylcarbamate
  参考文献：
  名称：

  A simple and efficient synthesis of 2-imidazolin-2-ones

  摘要：

  我们报道了重氮化合物1和2与1,3-二羰基化合物的反应。第一步涉及重氮化合物选择性地攻击活性亚甲基，形成迈克尔加合物3或4，可以在醋酸钠或DBN（1,5-二氮双环[4.3.0]壬-5-烯）的存在下进行。迈克尔加合物经过环闭合反应，生成了2-咪唑啉酮5或6，某些情况下可以分离得到。我们发现5或6在酸性条件下容易脱水，生成最终产物咪唑啉-2-酮7或8。刚才提到的这一最后步骤的速率决定步骤取决于初始2-咪唑啉酮在C4和C5的立体化学。我们还描述了一个一步法程序，直接从重氮化合物与适当的二羰基化合物生成7或8。

  DOI：

  10.1039/b502719e
• 作为产物：
  描述：

  Methyl 2-{[(2-chloroethyl)amino]carbonyl}hydrazinecarboxylate 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以74%的产率得到methyl (2-chloroethylamino)carbonyldiazenecarboxylate
  参考文献：
  名称：

  Electrophilic Amination of 4-Fluorophenol with Diazenes:  A Complete Removal of the Fluorine Atom

  摘要：

  The electrophilic amination of 2-fluorophenol, 4-fluorophenol, and 2-chlorophenol was observed to occur as a result of their treatment with diazenes 1-4 under mild reaction conditions in the presence of ZrCl4. The products originating from the 2-fluorophenol or 2-chlorophenol can be considered as "normal" products of amination. On the other hand, the 2-chloro-4-amino-substituted phenols obtained from the 4-fluorophenol seem to be formed in a process that involves an ipso amination, the complete removal of the fluorine atom, and the introduction of the chlorine atom.

  DOI：

  10.1021/jo035856b

文献信息

• A New and Straightforward Approach to Highly Functionalized 2-Imidazolin-2-ones
  作者：Sergeja Bombek、Roman Lenaršič、Marijan Kočevar、Slovenko Polanc

  DOI：10.1055/s-2001-16053

  日期：——

  Substituted aminocarbonyldiazenecarboxylates reacted with 1,3-diketones or β-ketoesters under mild reaction conditions in the presence of ZrCl4 to give highly functionalized imidazolin-2-ones via the corresponding Michael adducts. Reaction of unsymmetrical precursors resulted in the formation of only one regioisomer.

  取代氨基甲酰二氮烯羧酸盐在ZrCl4存在的温和条件下与1,3-二酮或β-酮酯反应，通过相应的Michael加合物生成高度官能化的咪唑啉-2-酮。不对称前体的反应只形成了唯一的区域异构体。
• EP1889831
  申请人：——

  公开号：——

  公开（公告）日：——
• A simple and efficient synthesis of 2-imidazolin-2-ones
  作者：Sergeja Bombek、Franc Požgan、Marijan Kočevar、Slovenko Polanc

  DOI：10.1039/b502719e

  日期：——

  We report on the reactions of diazenes 1 and 2 with 1,3-dicarbonyl compounds. The first step involves a regioselective attack of the diazene on the active methylene group, giving the Michael adducts 3 or 4, and can be performed either in the presence of sodium acetate or DBN (1,5-diazabicyclo[4.3.0]non-5-ene). The Michael adducts underwent ring-closure leading to 2-imidazolidinones 5 or 6 which were isolated in some cases. We found that 5 or 6 easily eliminated water in the presence of an acid to give imidazolin-2-ones 7 or 8 as the final products. The rate-determining step of this last mentioned process depends on the stereochemistry at C4 and C5 of the initial 2-imidazolidinone. A one-pot procedure to produce 7 or 8 directly from the diazene and the appropriate dicarbonyl partner is also described.

  我们报道了重氮化合物1和2与1,3-二羰基化合物的反应。第一步涉及重氮化合物选择性地攻击活性亚甲基，形成迈克尔加合物3或4，可以在醋酸钠或DBN（1,5-二氮双环[4.3.0]壬-5-烯）的存在下进行。迈克尔加合物经过环闭合反应，生成了2-咪唑啉酮5或6，某些情况下可以分离得到。我们发现5或6在酸性条件下容易脱水，生成最终产物咪唑啉-2-酮7或8。刚才提到的这一最后步骤的速率决定步骤取决于初始2-咪唑啉酮在C4和C5的立体化学。我们还描述了一个一步法程序，直接从重氮化合物与适当的二羰基化合物生成7或8。
• Electrophilic Amination of 4-Fluorophenol with Diazenes:  A Complete Removal of the Fluorine Atom
  作者：Sergeja Bombek、Franc Požgan、Marijan Kočevar、Slovenko Polanc

  DOI：10.1021/jo035856b

  日期：2004.3.1

  The electrophilic amination of 2-fluorophenol, 4-fluorophenol, and 2-chlorophenol was observed to occur as a result of their treatment with diazenes 1-4 under mild reaction conditions in the presence of ZrCl4. The products originating from the 2-fluorophenol or 2-chlorophenol can be considered as "normal" products of amination. On the other hand, the 2-chloro-4-amino-substituted phenols obtained from the 4-fluorophenol seem to be formed in a process that involves an ipso amination, the complete removal of the fluorine atom, and the introduction of the chlorine atom.