N-氟代全氟哌啶 | 836-77-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: N-氟代全氟哌啶
• 英文名称: perfluoro-N-fluoropiperidine
• 英文别名: undecafluoropiperidine；Undecafluor-piperidin；N-fluoroperfluoropiperidine；1,2,2,3,3,4,4,5,5,6,6-undecafluoropiperidine
• CAS: 836-77-1
• 化学式: C₅F₁₁N
• mdl: MFCD00077545
• 分子量: 283.044
• InChiKey: VCEAGMYKGZNUFL-UHFFFAOYSA-N

物化性质

• 沸点：
  49.62°C (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  12

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S36
• 危险类别码：
  R36/37/38
• 海关编码：
  2933399090

反应信息

• 作为反应物：
  描述：

  N-氟代全氟哌啶 在 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以75%的产率得到nonafluoro-2,3,4,5-tetrahydropyridine
  参考文献：
  名称：

  N-halogeno compounds. Part 12 [1]. Site-specific fluorination of carbanions with perfluoro-N-fluoropiperidine [2]

  摘要：

  Perfluoro-N-fluoropiperidine (1) acts as a site-selective electrophilic fluorinating agent towards carbanionic substrates [Me2CNaNO2 --> Me2CFNO2; PhMgBr --> PhF; PhCNa(CO2Et)2 --> PhCF(CO2Et)2; EtCNa(CO2Et)2 --> EtCF(CO2Et)2; activated CH2(CH2)2COCNaCO2Et --> activated CH2(CH2)2COCFCO2Et], but in doing so is converted to perfluoro-l-azacyclohexene (2). Unfortunately, this imidoyl fluoride (2) is highly electrophilic and competes with the N-F compound (1) for carbanionic species, as exemplified by the formation of the 2-substituted octafluoro-l-azacyclohexenes activated CF2(CF2)3N = CR, where R = Ph, CEt(CO2Et)2, and activated C(CO2Et)CO(CH2)2CH2 in the respective cases of the last three sodio derivatives listed above.

  DOI：

  10.1016/s0022-1139(00)80353-x
• 作为产物：
  描述：

  二哌啶甲烷 在 氢氟酸 作用下， 生成 N-氟代全氟哌啶
  参考文献：
  名称：

  Fluorocarbon Derivatives. II. Cyclic Nitrides

  摘要：

  DOI：

  10.1021/ja01570a030
• 作为试剂：
  描述：

  苯基丙二酸二乙酯 在 N-氟代全氟哌啶 、 sodium hydride 、 cesium fluoride 作用下， 生成 diethyl 2-fluoro-2-phenylmalonate
  参考文献：
  名称：

  N-halogeno compounds. Part 12 [1]. Site-specific fluorination of carbanions with perfluoro-N-fluoropiperidine [2]

  摘要：

  Perfluoro-N-fluoropiperidine (1) acts as a site-selective electrophilic fluorinating agent towards carbanionic substrates [Me2CNaNO2 --> Me2CFNO2; PhMgBr --> PhF; PhCNa(CO2Et)2 --> PhCF(CO2Et)2; EtCNa(CO2Et)2 --> EtCF(CO2Et)2; activated CH2(CH2)2COCNaCO2Et --> activated CH2(CH2)2COCFCO2Et], but in doing so is converted to perfluoro-l-azacyclohexene (2). Unfortunately, this imidoyl fluoride (2) is highly electrophilic and competes with the N-F compound (1) for carbanionic species, as exemplified by the formation of the 2-substituted octafluoro-l-azacyclohexenes activated CF2(CF2)3N = CR, where R = Ph, CEt(CO2Et)2, and activated C(CO2Et)CO(CH2)2CH2 in the respective cases of the last three sodio derivatives listed above.

  DOI：

  10.1016/s0022-1139(00)80353-x

文献信息

• N-fluoro-compounds. Part II. Reaction of perfluoro-N-fluoropiperidine or perfluoro-N-fluoromorpholine with manganese pentacarbonyl hydride to give the corresponding N–H compounds
  作者：R. E. Banks、R. N. Haszeldine、R. Hatton

  DOI：10.1039/j39670000427

  日期：——

  Treatment of perfluoro-N-fluoropiperidine and perfluoro-N-fluoromorpholine with manganese pentacarbonyl hydride converts them into perfluoropiperidine and perfluoromorpholine, respectively. Perfluoromorpholine reacts with fuming nitric acid in trifluoroacetic anhydride to give perfluoro-N-nitromorpholine, and with anhydrous potassium fluoride to yield perfluoro-5,6-dihydro-2H-1,4-oxazine; thermal chlorination

  用五羰基锰氢化物处理全氟-N-氟哌啶和全氟-N-氟吗啉将它们分别转化为全氟哌啶和全氟吗啉。全氟吗啉在三氟乙酸酐中与发烟硝酸反应生成全氟N-硝基吗啉，与无水氟化钾反应生成全氟-5,6-二氢-2 H -1,4-恶嗪。在无水氟化钾存在下对全氟吗啉进行热氯化，除其他外，得到6-氯-八氟-5-氧杂-2-氮杂并-2-烯。
• N-fluoro-compounds. Part IV. Photochemical and fluoride-initiated reactions between perfluoro-N-fluoropiperidine and perfluoropropene
  作者：R. E. Banks、K. Mullen、W. J. Nicholson、C. Oppenheim、A. Prakash

  DOI：10.1039/p19720001098

  日期：——

  Photolysis of perfluoro-N-fluoropiperidine in the presence of perfluoropropene gives perfluoro-(2-methylpentane), perfluoro-(2,3-dimethylbutane), perfluoro-(N-propylpiperidine). perfluoro-(N-isopropylpiperidine), perfluoro-[N-(1,3-dimethylbutyl)piperidine], a 2:2 adduct (2C5F10NF:2C3F6), and perfluoro-NN′-bipiperidyl. Thermal reaction of perfluoro-N-fluoropiperidine with perfluoropropene in stainless

  在全氟丙烯存在下，全氟-N-氟哌啶的光解得到全氟-（2-甲基戊烷），全氟-（2,3-二甲基丁烷），全氟-（N-丙基哌啶）。全氟- （Ñ -isopropylpiperidine），全氟[ Ñ - （1,3-二甲基丁基）哌啶]，2：2加合物（2C 5 ˚F 10 NF：2C 3 ˚F 6），全氟-和NN '-bipiperidyl。在氟化铯存在下，全氟-N-氟哌啶与全氟丙烯在不锈钢中的热反应，尤其是，全氟-（2-异丙基-3,4,5,6-四氢吡啶）和全氟-（2-异丙基吡啶）; 该转化被认为涉及将哌啶脱氟成全氟-2,3,4,5-四氢吡啶，然后被全氟异丙基阴离子侵蚀该产物，随后将全氟-（2-异丙基-3,4,5,6-芳构化由此形成四氢吡啶）。全氟-（2-异丙基吡啶）可以根据该方案在三个单独的阶段中由全氟-N-氟哌啶制备，其举例说明了制备2-取代的四氟吡啶的可能的有用途径。
• Perfluoro [2(e),6(e)-dimethylpiperidin-N-oxyl]
  作者：Mahmood Nickkho-Amiry、R.Eric Banks、Antony J. Parker、Maxwell J. Parrott

  DOI：10.1016/0022-1139(95)03311-2

  日期：1995.12

  UV irradiation of solutions of perfluoro [N-fluoro-2(e),6(e)-dimethylpiperidine] (8) in the presence of oxygen and silica creates a persistent free radical with ESR spectroscopic parameters consistent with perfluoro [2(e),6(e)-dimethylpiperidin-N-oxyl] (7). Attempts to isolate this new oxyl from products of preparative experiments in which the corresponding NON compound presumed to be formed initially

  在氧气和二氧化硅的存在下，对全氟[ N-氟-2（e），6（e）-二甲基哌啶]（8）溶液进行紫外线照射会产生持久的自由基，该自由基的ESR光谱参数与全氟[2（e）一致，6（e）-二甲基哌啶-N-氧基]（7）。试图从制备实验的产物中分离出这种新的羟基的尝试是失败的：制备的实验中假定最初形成的相应NOinitiallyN化合物已被热解：仅在（主要）其羟基中稀释了该羟基的溶液（约1％的收率）。获得NF前体（8）。
• Fluorinated sulfonamide derivatives
  申请人：Air Products and Chemicals, Inc.

  公开号：US05227493A1

  公开（公告）日：1993-07-13

  N-fluoro perfluoroheterocyclic sulfonamides of the following Formula I ##STR1## wherein Het.sub.f represents an aromatic perfluoroheterocyclic radical of valency n and each R independently represents a substituted or unsubstituted C.sub.1 -C.sub.30 alkyl, C.sub.6 -C.sub.14 aryl substituted C.sub.1 -C.sub.10 alkyl, C.sub.6 -C.sub.14 aryl, or C.sub.1 -C.sub.10 alkyl substituted C.sub.6 -C.sub.14 aryl group, are novel electrophilic fluorinating agents. Preferably Het.sub.f is a perfluorinated nitrogen-containing aromatic group, especially pyridyl, pyrimidinyl, pyrazinyl or 1,3,5-triazinyl; n is 1; and R is perfluorinated, especially trifluoromethyl.

  下列式子I中的N-氟过渡金属杂环磺酰胺为新颖的亲电性氟化试剂，其中： ##STR1## 其中，Het.sub.f代表一个价数为n的芳香全氟杂环基团，每个R独立地代表取代或未取代的C.sub.1-C.sub.30烷基、C.sub.6-C.sub.14芳基取代的C.sub.1-C.sub.10烷基、C.sub.6-C.sub.14芳基或C.sub.1-C.sub.10烷基取代的C.sub.6-C.sub.14芳基基团。最好的情况是，Het.sub.f是全氟氮含量芳香基团，特别是吡啶基、嘧啶基、吡嗪基或1,3,5-三嗪基；n为1；R为全氟基，特别是三氟甲基。
• Process for selectively ortho-fluorinating substituted aromatic compounds
  申请人：Air Products and Chemicals, Inc.

  公开号：US05233074A1

  公开（公告）日：1993-08-03

  The invention describes a process for selectively preparing ortho-fluorinated substituted aromatic compounds wherein an aromatic compound containing a substituent capable of directing ortho metalation is contacted with a metalating reagent under reaction conditions sufficient to form an ortho-metalated substituted aromatic compound. The ortho-metalated substituted aromatic compound is reacted with an electrophilic fluorinating reagent under reaction conditions sufficient to form the desired ortho-fluorinated substituted aromatic compound which is then recovered from the reaction mixture. The process which utilizes a metalation intermediate prior to effecting the electrophilic fluorination step overcomes problems associated with prior art electrophilic fluorination processes which do not proceed through a regiospecifically controlled intermediate.

  本发明描述了一种选择性制备邻-氟代取代芳香化合物的方法，其中将含有能够引导邻位金属化的取代基的芳香化合物与金属化试剂在反应条件下接触，以形成邻位金属化的取代芳香化合物。然后，在足以形成所需的邻-氟代取代芳香化合物的反应条件下，将邻位金属化的取代芳香化合物与亲电性氟化试剂反应，然后从反应混合物中回收所得的产物。该方法利用金属化中间体在进行亲电性氟化步骤之前，克服了与先前艺术亲电性氟化过程相关的问题，这些问题不通过区域特异性控制的中间体进行。