butyl 3-bromo-3H-diazirine-3-carboxylate | 792950-89-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: butyl 3-bromo-3H-diazirine-3-carboxylate
• 英文别名: butyl 3-bromodiazirine-3-carboxylate；3-bromo-3-carbobutoxyaziridine
• CAS: 792950-89-1
• 化学式: C₆H₉BrN₂O₂
• 分子量: 221.054
• InChiKey: FCNKGDYBDXUVDR-UHFFFAOYSA-N

物化性质

• 沸点：
  196.5±50.0 °C(Predicted)
• 密度：
  1.69±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  51
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  butyl 3-bromo-3H-diazirine-3-carboxylate 在 sodium methylate 作用下， 以 甲醇 、 水 为溶剂， 反应 18.0h， 以49%的产率得到3-bromodiazirine-3-carboxylic acid
  参考文献：
  名称：

  Evidence for the Cyclic CN₂ Carbene in the Gas Phase

  摘要：

  3-Halodiazirine-3-carboxylic acids (c-CN2XCOOH, X = Cl or Br) were prepared from their esters and converted to the corresponding sodium salts. Collision-induced dissociation (CID) of the carboxylate ions led exclusively to the loss of CO2 and the resulting c-CN2X(-) ions dissociated to c-CN2 carbene at low energies. The bond dissociation energy (BDE) for c-CN2Br(-) was found to be less than 8 kcal/mol using CID of the anion generated by electrospray ionization of the carboxylate. The analogous difluoro system (CF2XCOOH/CF2X(-)/CF2) exhibits similar dissociative behavior. All experimental BDEs are in very good agreement with MP4/aug-cc-pVTZ calculations.

  DOI：

  10.1021/ol5027602
• 作为产物：
  描述：

  carbobutoxy-N-chloroformamidine 在 次氯酸叔丁酯 、 lithium bromide 作用下， 以 乙腈 为溶剂， 反应 24.17h， 生成 butyl 3-bromo-3H-diazirine-3-carboxylate
  参考文献：
  名称：

  Synthesis of Carboalkoxychloro- and Bromodiazirines

  摘要：

  The first known 3H-diazirines bearing a carbonyl group and a halogen atom on C-3 have been prepared by a novel synthetic method. Carboalkoxychloro- and bromodiazirines 1a-d are formed in up to 45% yields by reductive dechlorination of carboalkoxy-N,N,N'-trichloroformamidines 9a,b using chloride or bromide ion. This method constitutes the first example of the use of N,N,N'-trichloroamidines as starting materials in organic synthesis.

  DOI：

  10.1021/jo040194r

文献信息

• Evidence for the Cyclic CN₂ Carbene in Solution
  作者：Eva Hanzlová、Rafael Navrátil、Jan Čejka、Stanislav Böhm、Tomáš Martinů

  DOI：10.1021/ol4036243

  日期：2014.2.7

  Diazirinylidene (c-CN2) is formally the simplest of the N-heterocyclic carbenes. The intermediacy of this elusive species in the fragmentation of butyl 3-bromodiazirine-3-carboxylate (1a) with pent-4-en-1-ols and their sodium alkoxides in DMF is supported by the formation of 2-oxabicyclo[4.1.0]heptanes and dipentenoxymethanes. These products result from an intramolecular [2 + 1] cycloaddition and O–H

  二叠氮基亚烷基（c -CN 2）在形式上是最简单的N杂环卡宾。通过2-氧杂双环的形成[4.1.0]支持了这种难以捉摸的物质在3-溴二氮杂-3-羧酸丁酯（1a）与戊-4-烯-1-醇及其烷醇钠在DMF中的裂解中的中介作用。庚烷和二戊氧基甲烷。这些产物分别来自戊二烯的分子内[2 +1]环加成反应和O–H插入，这表明它们是由亲电c -CN 2与烷氧基离子的反应产生的。1a与伯胺或仲胺在甲醇中的反应得到相应的3-溴二氮杂-3-甲酰胺。
• The Bromodiazirinyl Anion: A Weakly Bound Complex of Diazirinylidene and a Bromide Ion
  作者：Tomáš Martinů、Stanislav Böhm、Eva Hanzlová

  DOI：10.1002/ejoc.201100529

  日期：2011.11

  3-bromodiazirine-3-carboxylates by sodium n-butoxide in DMF, affording high yields of dibutyl carbonates, may proceed by nucleophilic acyl displacement of the bromodiazirinyl anion, a weakly bound complex of a cyclic carbene c-CN2 (diazirinylidene) and a bromide ion. We explain the formation of substantial amounts of di-n-butoxymethane in the presence of n-butanol by a sequence of O–H insertion and denitrogenation

  实验和计算证据表明，正丁醇钠在 DMF 中裂解 3-溴二氮嗪-3-羧酸正丁酯和叔丁酯，得到高产率的碳酸二丁酯，可以通过溴二氮杂环丙烷阴离子的亲核酰基置换来进行。环状卡宾 c-CN2（二氮丙啶）和溴离子的弱结合复合物。我们通过假定的 c-CN2 卡宾的一系列 O-H 插入和脱氮反应来解释在正丁醇存在下大量二正丁氧基甲烷的形成。这种基态单线态物质是 CN2 反应中间体家族的最后一个未描述的成员。它与经典的 N-杂环卡宾的不同之处在于其高电离电位和电子亲和力。
• Nitrenic reactivity of diazirines
  作者：Petra Kolářová、Václav Čmolík、Igor Linhart、Ignacio Álvarez Martínez、Tomáš Martinů

  DOI：10.1016/j.tetlet.2013.10.001

  日期：2013.12

  possessing a singlet imidoylnitrene character at the N2 atom. Most notably, the reaction of 7 with PhMgBr in diethyl ether affords 2-hydroxy-2,2,N-triphenylacetamidine (9) and 2-methyl-5,5-diphenyl-4-phenylamino-2,5-dihydrooxazole (10) as products derived from nitrene insertion to the ether α-C–H bond.

  3-溴-3 H-重氮基-3-羧酸丁酯（7）和3-溴-3-苯基-3 H-重氮基（17）与苯基溴化镁或氰化四丁基铵表现出硝化反应性。几个N，N′-二取代的idine的形成归因于在N 2原子上具有单线亚氨基酰亚胺基亚硝烯特性的1-苯基或1-氰基-1 H-二嗪。最值得注意的是，7与PhMgBr在乙醚中的反应得到2-羟基-2,2，N-三苯基乙am（9）和2-甲基-5,5-二苯基-4-苯基氨基-2,5-二氢恶唑（10）是由于氮醚插入醚α-C–H键而衍生的产物。
• Synthesis of Carboalkoxychloro- and Bromodiazirines
  作者：Tomas Martinu、William P. Dailey

  DOI：10.1021/jo040194r

  日期：2004.10.1

  The first known 3H-diazirines bearing a carbonyl group and a halogen atom on C-3 have been prepared by a novel synthetic method. Carboalkoxychloro- and bromodiazirines 1a-d are formed in up to 45% yields by reductive dechlorination of carboalkoxy-N,N,N'-trichloroformamidines 9a,b using chloride or bromide ion. This method constitutes the first example of the use of N,N,N'-trichloroamidines as starting materials in organic synthesis.
• Evidence for the Cyclic CN₂ Carbene in the Gas Phase
  作者：Eva Hanzlová、Jiří Váňa、Christopher J. Shaffer、Jana Roithová、Tomáš Martinů

  DOI：10.1021/ol5027602

  日期：2014.10.17

  3-Halodiazirine-3-carboxylic acids (c-CN2XCOOH, X = Cl or Br) were prepared from their esters and converted to the corresponding sodium salts. Collision-induced dissociation (CID) of the carboxylate ions led exclusively to the loss of CO2 and the resulting c-CN2X(-) ions dissociated to c-CN2 carbene at low energies. The bond dissociation energy (BDE) for c-CN2Br(-) was found to be less than 8 kcal/mol using CID of the anion generated by electrospray ionization of the carboxylate. The analogous difluoro system (CF2XCOOH/CF2X(-)/CF2) exhibits similar dissociative behavior. All experimental BDEs are in very good agreement with MP4/aug-cc-pVTZ calculations.