cyclohex-2-en-1-yl 2,2,2-trichloroacetimidate | 51479-76-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 甲亚胺酸及其衍生物
• 英文名称: cyclohex-2-en-1-yl 2,2,2-trichloroacetimidate
• 英文别名: cyclohex-2-en-1-yl 2,2,2-trichloroethanimidoate；Cyclohexen-3-yl-trichloracetimidat；Cyclohex-2-en-1-yl 2,2,2-trichloroethanimidate
• CAS: 51479-76-6
• 化学式: C₈H₁₀Cl₃NO
• 分子量: 242.532
• InChiKey: QHKIFWRELFFYID-UHFFFAOYSA-N

物化性质

• 沸点：
  223.5±50.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  33.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cyclohex-2-en-1-yl 2,2,2-trichloroacetimidate 在 18-冠醚-6 sodium hydride 作用下， 以 xylene 为溶剂， 反应 42.5h， 生成 N-cyclohex-2-en-1-yl-N-methyltrichloroacetamide
  参考文献：
  名称：

  Effects of temperature on atom transfer cyclization reactions of allylic .alpha.-iodo esters and amides

  摘要：

  Atom-transfer cyclizations of allyl iodoacetates and N-allyl-N-methyliodoacetamides are much more efficient at 80-degrees-C than at 25-degrees-C. At 80-degrees-C, beta-(iodomethyl) lactones and lactams are formed rapidly and in good yield under standard atom-transfer conditions (sunlamp irradiation of iodide and 10% hexabutylditin in benzene for 10-60 min). It is proposed that this temperature effect is responsible for some unusual observations by Jolly and Livinghouse in the cyclization of N-cyclohexenyl-N-methyliodoacetamide. The results suggest that the beneficial effect of temperature arises because an increase in the rate of rotation of the OC-O or OC-N bond in the intermediate radicals begins to convert syn radicals (which cannot cyclize) to anti radicals (which can cyclize). Consistent with this hypothesis, the radical derived from N,N-diallyliodoacetamide (which always has a favorable arrangement for cyclization) closes with excellent efficiency at 25-degrees-C.

  DOI：

  10.1021/jo00008a032
• 作为产物：
  描述：

  2-环己烯醇 、 三氯乙腈 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 cyclohex-2-en-1-yl 2,2,2-trichloroacetimidate
  参考文献：
  名称：

  通过相应的三氯乙酰亚胺将官能团区域选择性地引入烯丙基和均烯丙基醇的双键

  摘要：

  描述了从烯丙基和均烯丙基醇开始的新的区域选择性碘化胺化反应。通过相应的1，3-恶唑啉（1）和二氢-1，3-恶嗪（3）获得作为盐（2）和（4）的碘氨基醇。

  DOI：

  10.1039/c39820001308

文献信息

• A new α-amono acid synthesis via an acetimidate rearrangement
  作者：Seiichi Takano、Masashi Akiyama、Kunio Ogasawara

  DOI：10.1039/c39840000770

  日期：——

  A new efficient synthesis of α-amino acids from allyl alchol derivatives via an acetimidate rearrangement has been developed.

  已经开发了通过乙酰亚氨酸酯重排从烯丙基醇衍生物中有效合成α-氨基酸的新方法。
• Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions
  作者：Daniel R. Wallach、John D. Chisholm

  DOI：10.1021/acs.joc.6b01421

  日期：2016.9.2

  with trichloroacetimidates is reported. This transformation does not require an exogenous acid, base, or transition metal catalyst; instead the addition occurs in refluxing toluene without additives. The sulfonamide alkylation partner appears to be only limited by sterics, with unsubstituted sulfonamides providing better yields than more encumbered N-alkyl sulfonamides. The trichloroacetimidate alkylating

  据报道，磺酰胺与三氯乙酰亚胺的分子间烷基化。该转化不需要外源酸，碱或过渡金属催化剂；取而代之的是在没有添加剂的情况下在回流甲苯中进行添加。磺酰胺烷基化伙伴似乎仅受空间限制，未取代的磺酰胺比负担更大的N-烷基磺酰胺提供更好的产率。三氯乙酰亚胺酸酯烷基化剂必须是稳定的阳离子前体，才能在这些条件下进行取代反应。
• A Simple Method for the Preparation of Stainless and Highly Pure Trichloroacetimidates
  作者：Kazutada Ikeuchi、Kentaro Murasawa、Hidetoshi Yamada

  DOI：10.1055/s-0037-1611551

  日期：2019.7

  We describe a method for obtaining various allylic, benzylic, and glucosyl 2,2,2-trichloroacetimidates (TCAIs) as stainless liquids or solids at the crude stage. The general synthetic method for the preparation of TCAIs often leads to stained products, and further purification of crude TCAIs causes decomposition due to their instability. In the described method, we use a solvent that barely dissolves

  我们描述了一种在原油阶段以不锈钢液体或固体形式获得各种烯丙基、苄基和葡萄糖基 2,2,2-三氯乙酰亚胺 (TCAI) 的方法。制备 TCAI 的一般合成方法通常会导致产品染色，而粗 TCAI 的进一步纯化由于其不稳定性而导致分解。在所描述的方法中，我们使用几乎不溶解反应物的溶剂，提供不锈钢和足够纯的 TCAI，无需纯化步骤。此外，反应混合物在开始时是混浊的，在结束时是清澈的，这使我们能够直观地监测反应的进程。
• Brønsted Acid Catalyzed Monoalkylation of Anilines with Trichloroacetimidates
  作者：Daniel R. Wallach、Patrick C. Stege、Jigisha P. Shah、John D. Chisholm

  DOI：10.1021/jo5027222

  日期：2015.2.6

  under these conditions. Electron-poor anilines provide superior yields, with electron-rich anilines sometimes showing competitive Friedel–Crafts alkylation. A single flask protocol with formation of the imidate in situ is demonstrated, providing a convenient method for the direct substitution of alcohols with anilines. Reaction with a chiral imidate favors a mechanism that proceeds through a carbocation

  三氯乙酰亚胺酸酯是用于芳族胺的有用的烷基化剂，仅需要催化量的布朗斯台德酸即可促进反应。在这些条件下，单烷基化占主导。贫电子的苯胺具有较高的收率，富电子的苯胺有时显示出竞争性的Friedel-Crafts烷基化反应。演示了在原位形成亚氨酸酯的单瓶实验方案，为用苯胺直接取代醇提供了便利的方法。与手性亚氨酸酯的反应有利于通过碳正离子中间体进行的机理。
• [EN] NOVEL PHENYLAMINO ISONICOTINAMIDE COMPOUNDS<br/>[FR] NOUVEAUX COMPOSÉS PHÉNYLAMINO ISONICOTINAMIDES
  申请人：MERCK SERONO SA

  公开号：WO2010017051A1

  公开（公告）日：2010-02-11

  The invention provides novel compounds according to Formula (I), their manufacture and use for the treatment of hyperproliferative diseases, such as cancer, restenosis and inflammation.(Formula I)

  该发明提供了根据公式（I）的新化合物，它们的制备和用于治疗过度增殖性疾病，如癌症、再狭窄和炎症的用途。（公式I）