乙基1-氟-2-环己酮羧酸酯 | 1578-70-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 乙基1-氟-2-环己酮羧酸酯
• 英文名称: 1-fluoro-2-oxocyclohexanecarboxylic acid ethyl ester
• 英文别名: 2-Fluor-2-aethoxycarbonyl-cyclohexan-1-on；Ethyl 1-fluoro-2-oxocyclohexanecarboxylate；ethyl 1-fluoro-2-oxocyclohexane-1-carboxylate
• CAS: 1578-70-7
• 化学式: C₉H₁₃FO₃
• 分子量: 188.199
• InChiKey: WBRNDLRGLOAFCQ-UHFFFAOYSA-N

物化性质

• 沸点：
  66℃/0.35mm
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  乙基1-氟-2-环己酮羧酸酯 在 sodium hydroxide 作用下， 生成 2-氟环己酮
  参考文献：
  名称：

  α-单氟烷酸的合成

  摘要：

  α-单氟链烷酸是合成生物活性氟化合物的重要中间体。已根据以下三种试剂检查了一般制备方法： (a) 氟化氢 + N-溴乙酰胺；(b) 单氟丙二酸二乙酯；(c) 全氯酰氟。其中第一个是简单的未取代 α-氟酸的推荐程序；然而，氟丙二酸路线不太活跃，因此是那些含有不稳定官能团的 α-氟代酸的首选方法。

  DOI：

  10.1139/v65-224
• 作为产物：
  描述：

  2-环己酮甲酸乙酯 在 fluorine 作用下， 以 甲酸 为溶剂， 反应 2.0h， 以90%的产率得到乙基1-氟-2-环己酮羧酸酯
  参考文献：
  名称：

  Direct fluorination of 1,3-dicarbonyl compounds

  摘要：

  1,3-二酮类化合物，如1,3-二酮和1,3-酮酯，能在室温下与元素氟直接反应，生成对应的2-氟化合物，在某些情况下，还能生成2,2-二氟化合物，反应产率很高。

  DOI：

  10.1039/c39950000021

文献信息

• Halogen-containing compounds, herbicidal composition containing the same
  申请人：Mitsubishi Petrochemical Co., Ltd.

  公开号：US05262385A1

  公开（公告）日：1993-11-16

  A compounds represented by the formula ##STR1## wherein X represents a fluorine atom, W represents an oxygen atom, sulfur atom or group --OCH.sub.2 --, Z.sup.1 and Z .sup.2 each represent a nitrogen atom or group CH, but when Z.sup.1 is a nitrogen atom, Z.sup.2 represents a nitrogen atom or group CH and when Z.sup.1 is a group CH, Z.sup.2 represents a nitrogen atom, R.sup.1 and R.sup.2 each independently represent either a hydrogen atom, halogen atom or mono- or dilower alkyl-substituted amino, or a lower alkyl, lower alkoxy or lower alkylthio each of which may be substituted with a halogen atom, R.sup.3 and R.sup.4 form together with the carbon atoms to which they bind respectively a 5- to 8-membered carbon ring.

  一种由以下公式表示的化合物 ##STR1## 其中X代表氟原子，W代表氧原子、硫原子或基团--OCH.sub.2 --，Z.sup.1和Z .sup.2各自代表氮原子或基团CH，但当Z.sup.1是氮原子时，Z.sup.2代表氮原子或基团CH，当Z.sup.1是基团CH时，Z.sup.2代表氮原子，R.sup.1和R.sup.2各自独立地代表氢原子、卤素原子或单取代或双取代的较低烷基氨基，或较低烷基、较低烷氧基或较低烷基硫基，其中每个基团可能被卤素原子取代，R.sup.3和R.sup.4分别与它们结合的碳原子共同形成一个5-至8-成员碳环。
• Self‐Sustaining Fluorination of Active Methylene Compounds and High‐Yielding Fluorination of Highly Basic Aryl and Alkenyl Lithium Species with a Sterically Hindered <i>N</i> ‐Fluorosulfonamide Reagent
  作者：Yuhao Yang、Gerald B. Hammond、Teruo Umemoto

  DOI：10.1002/anie.202211688

  日期：2022.10.24

  By developing a sterically hindered fluorinating agent, N-fluoro-N-(tert-butyl)-tert-butanesulfonamide (NFBB), we discovered a conceptually novel base-catalyzed, self-sustaining fluorination of active methylene compounds and achieved an unprecedented high-yield fluorination of highly basic (hetero)aryl and alkenyl lithium species.

  通过开发空间位阻氟化剂N-氟-N- (叔丁基)-叔丁磺酰胺(NFBB)，我们发现了一种概念性新颖的碱催化、活性亚甲基化合物自持氟化反应，并实现了前所未有的高产率。产生高碱性（杂）芳基和烯基锂物种的氟化。
• Halogen-containing compounds, herbicidal composition containing the same as an active ingredient, and intermediary compounds therefor
  申请人：Mitsubishi Chemical Corporation

  公开号：EP0468766A1

  公开（公告）日：1992-01-29

  Halogen-containing compounds represented by the formula wherein    X represents a halogen atom,    W represents an oxygen atom, sulfur atom or group -OCH₂-,    Z¹ and Z² each represent a nitrogen atom or group CH, but when Z¹ is a nitrogen atom, Z² represents nitrogen atom or group CH and when Z¹ is a group CH, Z² represents a nitrogen atom,    R¹ and R² each independently represent either a hydrogen atom, halogen atom or mono- or dilower alkyl-substituted amino, or a lower alkyl, lower alkoxy or lower alkylthio each of which may be substituted with a halogen atom,    R³ and R⁴ each independently represent a hydrogen atom, halogen atom, hydroxycarbonyl, lower alkoxycarbonyl, lower alkyl, lower alkenyl, lower alkynyl, aryl or aralkyl, or R³ and R⁴ form together with the carbon atoms to which they bind respectively a 5- to 8-membered carbon ring or heterocycle and these rings may optionally be substituted with one or the same or different two of hydroxy, lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, lower alkoxycarbonyl, lower alkylcarbonyloxy and a group = 0, and may have unsaturated bond(s) therein,    R⁵ represents a hydrogen atom or lower alkyl group, or may form together with part of R³ a double bond,    A represents an oxygen atom, sulfur atom or group = N-B wherein B represents hydroxy or lower alkylcarbonyloxy, or lower alkoxy optionally substituted with hydroxycarbonyl or lower alkoxycarbonyl, and    Y either represents a hydrogen atom, a hydroxy, a mercapto, or    a lower alkoxy, lower alkenoxy, lower alkynoxy, lower alkylthio, aryloxy, aralkyloxy, arylthio, aralkylthio, lower cycloalkoxy, lower cycloalkenyloxy, pyridylthio, furylmethyloxy, furylthio or thienyloxy each optionally substituted with a halogen atom, hydroxy, lower alkyl, lower alkoxy, lower alkylthio, lower alkoxycarbonyl, lower alkylcarbonyl, cyano, nitro or azido, or    an azido, a trilower alkyl-substituted silyloxy or an imidooxy, or represents a group [wherein    R⁶ and R⁷ each independently represent a hydrogen atom, lower alkyl, lower alkoxy, aryl or aralkyl, or R⁶ and R⁷ may form together with the carbon atom to which they bind a lower cycloalkane ring, and    R⁸ and R⁹ each independently represent a hydrogen atom, a hydroxy, a lower alkyl, a lower alkenyl, a lower alkynyl, a lower alkoxy, a lower alkylcarbonyloxy, a cyano, a lower alkylsulfonyl optionally substituted with a halogen atom, a lower alkyl substituted with lower alkoxycarbonyl, a lower alkyl substituted with hydroxycarbonyl, a lower alkoxy substituted with lower alkoxycarbonyl, a lower alkoxy substituted with hydroxycarbonyl, or    an aryl, aralkyl, aryloxy, aralkyloxy, arylcarbonyloxy, pyridyl, (wherein Z³ represents an oxygen atom, group CH or sulfur atom, Z⁴ represents a nitrogen atom or group CH, Z¹ and Z² are as defined above, and m represents an integer of 0 or 1) each optionally substituted with a halogen atom, hydroxy, lower alkyl, lower alkoxy, lower alkyl substituted with halogen atoms, cyano, nitro, amino, mono- or dilower-alkyl-substituted amino or lower alkoxycarbonyl, (wherein R¹⁰ and R¹¹ each represent a hydrogen atom, a lower alkyl, a lower alkoxycarbonyl, a lower alkyl substituted with lower alkoxycarbonyl, a lower alkyl substituted with hydroxycarbonyl, or an aryl, aralkyl, pyridyl or benzothiazolyl each optionally substituted with a halogen atom, lower alkyl, lower alkyl substituted with a halogen atom, lower alkoxy, cyano, amino or nitro)), and salts thereof, are herbicidally active.

  式所代表的含卤化合物 其中 X 代表卤素原子 W 代表氧原子、硫原子或基团 -OCH₂-、 Z¹ 和 Z² 各自代表氮原子或基团 CH，但当 Z¹ 为氮原子时，Z² 代表氮原子或基团 CH；当 Z¹ 为基团 CH 时，Z² 代表氮原子、 R¹ 和 R² 各自独立地代表氢原子、卤素原子或单烷基或稀烷基取代的氨基，或低级烷基、低级烷氧基或低级烷硫基，其中每个基团均可被卤素原子取代、 R³ 和 R⁴ 各自独立地代表氢原子、卤素原子、羟基羰基、低级烷氧基羰基、低级烷基、低级烯基、低级炔基、芳基或芳烷基、或 R³ 和 R⁴ 与它们分别结合的碳原子一起形成 5 至 8 元碳环或杂环，这些环可任选被羟基、低级烷基、低级烯基、低级炔基、低级烷氧基、低级烷氧羰基、低级烷基羰氧基和基团 = 0 中的一个或相同或不同的两个取代，并且其中可能有不饱和键、 R⁵ 代表氢原子或低级烷基，或可与部分 R³ 形成双键、 A 代表氧原子、硫原子或基团 = N-B，其中 B 代表羟基或低级烷基羰氧基，或任选被羟基羰基或低级烷氧基羰基取代的低级烷氧基，以及 Y 代表氢原子、羟基、巯基，或 低级烷氧基、低级烯氧基、低级炔氧基、低级烷硫基、芳氧基、芳烷氧基、芳硫基、芳烷硫基、低级环烷氧基、低级环烯氧基、吡啶硫基、呋喃甲氧基、呋喃硫基或噻吩氧基，它们各自任选被卤原子、羟基、低级烷基、低级烷氧基、低级烷硫基、低级烷氧羰基、低级烷羰基、氰基、硝基或叠氮取代，或 叠氮、三阶梯烷基取代的硅氧基或亚氨基氧基，或代表一个基团 其中 R⁶ 和 R⁷ 各自独立地代表氢原子、低级烷基、低级烷氧基、芳基或芳烷基，或 R⁶ 和 R⁷ 可与它们结合的碳原子一起形成低级环烷环，以及 R⁸和 R⁹ 各自独立地代表氢原子、羟基、低级烷基、低级烯基、低级炔基、低级烷氧基、低级烷基羰氧基、氰基、任选被卤素原子取代的低级烷磺酰基、被低级烷氧基羰基取代的低级烷基、被羟基羰基取代的低级烷氧基、被羟基羰基取代的低级烷氧基，或 芳基、芳烷基、芳氧基、芳烷氧基、芳羰氧基、吡啶基、 (其中 Z³ 代表氧原子、基团 CH 或硫原子，Z⁴ 代表氮原子或基团 CH，Z¹ 和 Z² 如上文所定义，且 m 代表 0 或 1 的整数）各自任选被卤素原子、羟基、低级烷基、低级烷氧基、被卤素原子取代的低级烷基、氰基、硝基、氨基、单烷基或稀释烷基取代的氨基或低级烷氧基羰基取代、 (其中 R¹⁰ 和 R¹¹ 分别代表氢原子、低级烷基、低级烷氧基羰基、被低级烷氧基羰基取代的低级烷基、被羟基羰基取代的低级烷基，或芳基、芳烷基、吡啶基或苯并噻唑基，每个基团可任选被卤素原子、低级烷基、被卤素原子取代的低级烷基、低级烷氧基、氰基、氨基或硝基取代））及其盐具有除草活性。
• Highly Selective Fluorinating Agents: a Counteranion-Bound N-Fluoropyridinium Salt System
  作者：Teruo Umemoto、Ginjiro Tomizawa

  DOI：10.1021/jo00125a049

  日期：1995.10

  A series of alkyl- or (trifluoromethyl)-substituted N-fluoropyridinium-2-sulfonates 2a-h, differing in fluorinating power, were synthesized, and assessment was made of the effectiveness of each selective fluorinating agent. N-Fluoropyridinium-3- and -4-sulfonates 3 and 4 were also synthesized. Power-variables 2a-h were found to be highly selective fluorinating agents for a wide range of nucleophilic substrates such as activated aromatics, enol trialkylsilyl and alkyl ethers, active methylene compounds, activated olefins, and sulfides. Thus, phenol, naphthol, phenylurethane, and the trimethylsilyl ether of phenol were exclusively or highly selectively fluorinated at the o-position with 2f-h. Conjugated enol trialkylsilyl ethers of a steroid were regioselectively fluorinated at the 6-position with moderately powerful 2b-e. This regioselectivity increased with the bulkiness of the silyl part, and with the most bulky triisopropylsilyl group exclusive B-fluorination was achieved. Preferential beta-stereoselective fluorination at the 6-position was observed. N-Fluoropyridinium-2-sulfonates were activated with an acid. This acid-catalyzed fluorination led to the preferential p-fluorination of anisole. The present results can be explained based on the capacity of the 2-sulfonate anion to interact with the hydroxy group of phenol or naphthol, NH group of phenylurethane, silicon atoms of silyl ethers, or protons of acids.
• Synthesis, Properties, and Reactivity of <i>N,N</i>‘-Difluorobipyridinium and Related Salts and Their Applications as Reactive and Easy-To-Handle Electrophilic Fluorinating Agents with High Effective Fluorine Content¹
  作者：Teruo Umemoto、Masayuki Nagayoshi、Kenji Adachi、Ginjiro Tomizawa

  DOI：10.1021/jo972338q

  日期：1998.5.1

  N,N'-Difluoro-2,2'-, -2,4'-, -3,3'-, -4,4'-bipyridinium and substituted N,N'-difluoro-2,2'-bipyridinium bis(triflates), bis(tetrafluoroborates), bis(hexafluorophosphates), and bis(hexafluoroantimonates) 1-9 were synthesized in high yields by the direct fluorination of a mixture of a bipyridyl and a Lewis acid, a Bronsted acid, or the alkali metal salt of an acid. The higher homologues, trimer 10 and polymer II, were also synthesized. Unsubstituted or electron-donating group-substituted N,N'-difluorobipyridinium salts are stable nonhygroscopic crystals, while the electron-withdrawing group-substituted N,N'-diflurobipyridinium salts 3, 5, and 6 are moisture-sensitive crystals. Hydrolysis of Ib in boiling water gave 3,3'-dihydroxy-2,2'-bipyridyl. The reactivity determination indicated that the fluorinating capability decreased in the order 2,2'- much greater than 2,4' > 3,3'- approximate to 4,4'-isomer much greater than N-fluoropyridinium salt and that the two N-F moieties in a molecule mere effective for fluorination. This fluorination occurred in a step-by-step manner, and the reactivity difference between the first and second fluorinations was very small. N,N'-Difluoro-2,2'-bipyridinium bis(tetrafluoroborate) (Ib) is thus shown to be a highly reactive and easy-to-handle electrophilic fluorinating agent with the high effective fluorine content (103.3 g/kg) for preparing many fluoro organic compounds.