dimethyl 2,2-di(nona-2,4-diyn-1-yl)malonate | 1574693-32-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: dimethyl 2,2-di(nona-2,4-diyn-1-yl)malonate
• 英文别名: Dimethyl 2,2-bis(nona-2,4-diynyl)propanedioate；dimethyl 2,2-bis(nona-2,4-diynyl)propanedioate
• CAS: 1574693-32-5
• 化学式: C₂₃H₂₈O₄
• 分子量: 368.473
• InChiKey: OMZFKVVZAJJLQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  27
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl 2,2-di(nona-2,4-diyn-1-yl)malonate 在 dilithium tetrachlorocuprate 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以70%的产率得到dimethyl 5-butyl-6,7-dichloro-4-(hex-1-yn-1-yl)-1,3-dihydro-2H-indene-2,2-dicarboxylate
  参考文献：
  名称：

  Dichlorination of (Hexadehydro-Diels–Alder Generated) Benzynes and a Protocol for Interrogating the Kinetic Order of Bimolecular Aryne Trapping Reactions

  摘要：

  The efficient dichlorination of benzynes prepared by the hexadehydro-Diels-Alder (HDDA) reaction is reported. Cycloisomerization of a triyne substrate in the presence of dilithium tetrachlorocuprate is shown to provide dichlorinated products A by capture of the benzyne intermediate. A general strategy for discerning the kinetic order of an external aryne trapping agent is presented. It merely requires measurement of the competition between bimolecular vs unimolecular trapping events (here, dichlorination vs intramolecular Diels-Alder (IMDA) reaction to give A vs B, respectively) as a function of the concentration of the trapping agent.

  DOI：

  10.1021/ol403258c
• 作为产物：
  描述：

  丙二酸二甲酯 在 盐酸羟胺 、 sodium hydride 、 copper(l) chloride 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成 dimethyl 2,2-di(nona-2,4-diyn-1-yl)malonate
  参考文献：
  名称：

  通过HDDA联轴器获得苯并ze氮平和完全取代的吲哚。

  摘要：

  基于苯并炔与C═N双键的加成反应，恶唑啉可捕获HDDA衍生的苯并炔中间体。一步合成苯并a庚因衍生物，稠合的苯并x庚因衍生物和完全取代的吲哚。该反应不需要任何催化剂或添加剂。提出了可能的反应机理。

  DOI：

  10.1021/acs.orglett.9b04499

文献信息

• Synthesis of Imides, Imidates, Amidines, and Amides by Intercepting the Aryne–Isocyanide Adduct with Weak Nucleophiles
  作者：Sourav Ghorai、Daesung Lee

  DOI：10.1021/acs.orglett.9b02711

  日期：2019.9.20

  have been developed. Arynes generated from triynes or tetraynes through the hexadehydro Diels-Alder reaction readily react with isocyanide to generate nitrilium intermediate. Intercepting this nitrilium species with various weak nucleophile including carboxylic acids, alcohols, sulfonamides, or water generated the corresponding imides, imidates, amidines, or amides. The high regioselectivity of these

  已经开发出新的基于芳烃的多组分偶联反应，用于形成官能化的芳族化合物。通过六氢Diels-Alder反应由三炔或四炔生成的芳烃容易与异氰化物反应生成腈中间体。用各种弱亲核试剂（包括羧酸，醇，磺酰胺或水）拦截该腈物种，生成相应的酰亚胺，酰亚胺基、,或酰胺。这些转化的高区域选择性主要由芳烃的取代基控制。
• Synthesis of Phenolic Compounds by Trapping Arynes with a Hydroxy Surrogate
  作者：Rajdip Karmakar、Sourav Ghorai、Yuanzhi Xia、Daesung Lee

  DOI：10.3390/molecules200915862

  日期：——

  Trapping of arynes with various nucleophiles provides a range of heteroatom-functionalized arene derivatives, but the corresponding reaction with water does not provide phenol derivatives. Silver trifluroacetate (AgO2CCF3) can nicely solve this problem. It was found that in typical organic solvent, AgO2CCF3 readily reacts with arynes to generate trifluoroacetoxy organosilver arene intermediate, which, upon treating with silica gel, provides phenolic products. This protocol can be extended to the synthesis of α-halofunctionalized phenol derivatives by simply adding NBS (N-bromosuccinimides) or NIS (N-iodosuccinimides) to the reaction along with silver trifluroacetate, which provided α-bromo or α-iodophenol derivatives in good yield. However, the similar reactions with NCS (N-chlorosuccinimides) afforded only the protonated product instead of the expected α-chlorophenols derivatives. Interestingly, substrates containing silyl substituents on 1,3-diynes resulted in α-halotrifluoroacetates rather than their hydrolyzed product. Additionally, trapping the same arynes with other oxygen-based nucleophiles containing silver counter cation, along with NXS (N-halosuccinimides), generated α-halooxyfunctionalized products.

  芳炔与各种亲核物的捕获反应可提供一系列杂原子官能化的炔衍生物，但与水的相应反应却不能提供苯酚衍生物。三氟乙酸银（AgO2CCF3）可以很好地解决这个问题。研究发现，在典型的有机溶剂中，AgO2CCF3 很容易与芳香烃反应生成三氟乙酰氧基有机银炔中间体，用硅胶处理后可得到酚类产物。只需在反应中加入 NBS（N-溴代琥珀酰亚胺）或 NIS（N-碘代琥珀酰亚胺）以及三氟乙酸银，即可将此方案扩展到 α-半官能化苯酚衍生物的合成，从而以良好的收率获得 α-溴或 α-碘苯酚衍生物。然而，与 NCS（N-氯代丁二酰亚胺）的类似反应只能得到质子化产物，而不是预期的 α-氯苯酚衍生物。有趣的是，1,3-二炔上含有硅基取代基的底物会产生 α-卤代三氟乙酸酯，而不是其水解产物。此外，用其他含银反阳离子的氧基亲核物和 NXS（N-卤代丁二酰亚胺）捕获相同的芳烃，也会产生 α-卤氧基官能化产物。
• Fused multifunctionalized bridge aromatic hydrocarbons from in situ-generated arynes and anthracene derivatives
  作者：Baohua Liu、Qiong Hu、Feihu Yang、Xiaojie Zheng、Yimin Hu

  DOI：10.1016/j.cclet.2019.10.003

  日期：2020.5

  for the formation of highly substituted butterfly 1,4-adducts/9,10-adducts via the Diels–Alder reaction of benzyne intermediates. The method achieves very good to excellent yields of the respective anthracene derivatives under mild conditions. This practical protocol is compatible with a variety of sensitive functional groups and provides access to difunctionalized bridge 1,4-adducts/9,10-adducts.

  摘要这项研究提出了一种简便的策略，可通过苯炔中间体的Diels-Alder反应形成高度取代的蝶形1,4-加合物/ 9,10-加合物。在温和条件下，该方法可以很好地获得各自的蒽衍生物。该实用协议与各种敏感的官能团兼容，并提供了双功能桥1,4-加合物/ 9,10-加合物的访问途径。
• Access to Fully Substituted Dihydroindazoles Via Hexadehydro-Diels–Alder/[3 + 2] Cycloaddition
  作者：Weigang Xu、Xiuhuan Li、Luyao Zou、Xiaoli Li、Zhiqiang Zhang、Sajjad Ali、Zhengshen Wang、Pengfei Li、Huaiji Zheng

  DOI：10.1021/acs.joc.3c01901

  日期：2023.10.20

  A cascade hexadehydro-Diels–Alder (HDDA)/[3 + 2] cycloaddition reaction between tetrayne and N,N′-cyclic acylhydrazone is described. This strategy allows the efficient construction of fully substituted 2,3-dihydro-1H-indazole scaffolds which have insecticidal activity against the third instar larvae of Mythimna separata.

  描述了四炔和N , N'-环状酰腙之间的级联六氢-Diels-Alder (HDDA)/[3 + 2]环加成反应。该策略允许有效构建完全取代的2,3-二氢-1H-吲唑支架，该支架对粘虫三龄幼虫具有杀虫活性。
• Access to Benzoxazepines and Fully Substituted Indoles via HDDA Coupling
  作者：Xiaojie Zheng、Baohua Liu、Feihu Yang、Qiong Hu、Liangliang Yao、Yimin Hu

  DOI：10.1021/acs.orglett.9b04499

  日期：2020.2.7

  The HDDA-derived benzyne intermediate was captured by oxazolines based on the addition reaction of benzyne to the C═N double bond. Benzoxazepine derivatives, fused benzoxazepine derivatives, and fully substituted indoles are synthesized in one step. The reaction does not require any catalyst or additives. Possible reaction mechanisms are presented.

  基于苯并炔与C═N双键的加成反应，恶唑啉可捕获HDDA衍生的苯并炔中间体。一步合成苯并a庚因衍生物，稠合的苯并x庚因衍生物和完全取代的吲哚。该反应不需要任何催化剂或添加剂。提出了可能的反应机理。