geranyl 2,2,2-trichloroacetimidate | 51479-75-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: geranyl 2,2,2-trichloroacetimidate
• 英文别名: Geraniol-trichloracetimidat；[2,2,2-trichloro-1-[(2E)-3,7-dimethyl-octa-2,6-dienoxy]-ethylidene]-amine；[(2E)-3,7-dimethylocta-2,6-dienyl] 2,2,2-trichloroethanimidate
• CAS: 51479-75-5
• 化学式: C₁₂H₁₈Cl₃NO
• 分子量: 298.64
• InChiKey: RILLNXNDXDGILZ-GXMNMPHMSA-N

物化性质

• 沸点：
  302.2±52.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 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：

  geranyl 2,2,2-trichloroacetimidate 在 sodium hydroxide 、 mercury(II) trifluoroacetate 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 2.0h， 生成 N-[3,7-dimethyl-1,6-octadienyl]amine
  参考文献：
  名称：

  A general method for the synthesis of amines by the rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions

  摘要：

  DOI：

  10.1021/ja00426a038
• 作为产物：
  描述：

  香叶醇 、 三氯乙腈 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 正己烷 为溶剂， 反应 0.83h， 以94%的产率得到geranyl 2,2,2-trichloroacetimidate
  参考文献：
  名称：

  一种制备不锈高纯度三氯乙酰亚胺的简单方法

  摘要：

  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。

  DOI：

  10.1055/s-0037-1611551

文献信息

• Allyl, epoxy and glycosyl perfluoroimidates. One-pot preparation and reaction
  作者：Noriyuki Nakajima、Miho Saito、Masabumi Kudo、Makoto Ubukata

  DOI：10.1016/s0040-4020(02)00305-8

  日期：2002.4

  obtained trifluoroacetimidates were more stable than the trichloro analogue and were easily purified by SiO2 column chromatography and/or distillation. The 3,3-sigmatropic rearrangement of allylic analogues, acid-catalyzed cyclization of the epoxy analogues and glycosylation of sugar analogues were studied comparing with their corresponding trichloroacetimidates. The trifluoroacetimidates were considerably

  描述了烯丙基，环氧和糖基全氟亚氨酸的一锅法制备及其反应。挥发性全氟腈是在-78°C下由具有“活化”二甲基亚砜（DMSO）物种的全氟酰胺生成的。将醇和糖衍生物原位亲核加成腈后，可以制备44-92％的烯丙基，环氧和糖基全氟亚氨酸酯。所获得的三氟乙酰亚氨酸盐比三氯类似物更稳定，并且易于通过SiO 2纯化。柱色谱法和/或蒸馏。与它们相应的三氯乙酰亚胺比较，研究了烯丙基类似物的3,3-σ重排，环氧类似物的酸催化环化和糖类似物的糖基化。由于三氟乙酰基亚胺在亚氨酸酯碳上的吸电子取代基，因此它们的反应性明显低于三氯乙酰基亚胺。
• Alkylation of thiols with trichloroacetimidates under neutral conditions
  作者：Brian C. Duffy、Kyle T. Howard、John D. Chisholm

  DOI：10.1016/j.tetlet.2014.12.042

  日期：2015.6

  Trichloroacetimidates are displaced with thiols to form the corresponding sulfides without the need for an added acid or base by simply heating the reactants in refluxing THF. This operationally simple procedure provides the corresponding sulfides in excellent yields with only the formation of the neutral trichloroacetamide as the side product. The imidate may also be formed in situ, allowing for a direct method for the formation of sulfides from alcohols. This reaction provides a general method for the synthesis of a variety of sulfides from inexpensive and readily available alcohol starting materials. (C) 2014 Elsevier Ltd. All rights reserved.
• Synthesis of 2-deoxy-2-fluoro analogs of polyprenyl β-d-arabinofuranosyl phosphates
  作者：Maju Joe、Todd L. Lowary

  DOI：10.1016/j.carres.2006.08.020

  日期：2006.11

  Described is the synthesis of polyprenyl 2-deoxy-2-fluoro-beta-D-arabinofuranosyl phosphate derivatives, including an analog of decaprenyl P-D-arabinofuranosyl phosphate, the donor species used by the arabinosyltransferases involved in mycobacterial cell-wall biosynthesis. The targets were synthesized via a route involving the synthesis of a protected beta-D-arabinofuranosyl phosphate derivative, its coupling with a polyprenyl trichloroacetimidate, and then deprotection of the resulting product. The use of arabinofuranosyl phosphates with the monosaccharide hydroxyl groups protected as either silyl ethers or benzoate esters was explored. Although the coupling yields between the phosphate and polyprenyl trichloroacetimidates were comparable with either type of protecting group, access to the benzoyl-protected derivative was more efficient and therefore gave the products in higher overall yield. (c) 2006 Elsevier Ltd. All rights reserved.
• Improved Conditions for Facile Overman Rearrangement¹
  作者：Toshio Nishikawa、Masanori Asai、Norio Ohyabu、Minoru Isobe

  DOI：10.1021/jo9713924

  日期：1998.1.1
• A general method for the synthesis of amines by the rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions
  作者：Larry E. Overman

  DOI：10.1021/ja00426a038

  日期：1976.5