1,1-difluoro-2-(N,N-diethylcarbamoyloxy)ethene | 143366-90-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,1-difluoro-2-(N,N-diethylcarbamoyloxy)ethene
• 英文别名: 2,2-Difluorovinyl N,N-diethylcarbamate；2,2-difluoroethenyl N,N-diethylcarbamate；2,2-difluoro-1-(N,N-diethylcarbamoyloxy)ethene；Diethylcarbamic acid 2,2-difluorovinyl ester
• CAS: 143366-90-9
• 化学式: C₇H₁₁F₂NO₂
• 分子量: 179.167
• InChiKey: FLOPJCARDFFPIX-UHFFFAOYSA-N

物化性质

• 沸点：
  146.4±40.0 °C(Predicted)
• 密度：
  1.125±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-difluoro-2-(N,N-diethylcarbamoyloxy)ethene 在 盐酸 、 sodium periodate 、 过氧化苯甲酰 作用下， 以 甲醇 为溶剂， 生成 2,2-difluoro-3-(N,N-diethylcarbamoyloxy)-1-propanol
  参考文献：
  名称：

  通过含氧自由基光化学和热加成到 2,2-二氟乙烯基氨基甲酸酯中制备掩蔽的 2,2-二氟-1,3-二醇和 2,2-二氟-1,3,4-丁三醇

  摘要：

  除甲醇外的某些醇中，二氟乙烯基碳酸酯的光反会生成自由基加成产物，这些产物以2,2-二氟-1,3-二醇的隐匿形式存在。1,3-二恶烷在偶氮二甲酰胺过氧化物引发的热自由基反应中也能生成自由基产物。2,2-二甲基-1,3-二恶烷的自由基产物可转化为隐匿形式的2,2-二氟-1,3-丙二醇。

  DOI：

  10.1055/s-2001-16809
• 作为产物：
  描述：

  2,2-diflouoro-1-(N,N-diethylcarbamoyloxy)-1-(trimethylsilyl)ethene 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到1,1-difluoro-2-(N,N-diethylcarbamoyloxy)ethene
  参考文献：
  名称：

  Fluorinated vinyl carbamates and carbamoyloxy allylsilanes. α-Metalation, organolithium addition-elimination, and fluoride. Mediated electrophilic reactivity patterns

  摘要：

  LiTMP or LDA-mediated in situ generation of alpha-lithio difluorovinyl carbamate 1b allows the preparation of silylated derivatives 4a and 2b which undergo organolithium addition-elimination and fluoride-mediated condensation reactions respectively to give new functionalized organofluorine derivatives 5a-d (Table 2) and 11a-c (Table 3).

  DOI：

  10.1016/0040-4039(93)85090-j

文献信息

• Highly-functionalised difluorinated (hydroxymethyl)conduritol analogues via the Diels–Alder reactions of a difluorinated dienophile
  作者：Andrea Arany、Patrick J. Crowley、John Fawcett、Michael B. Hursthouse、Benson M. Kariuki、Mark E. Light、Andrew C. Moralee、Jonathan M. Percy、Vittoria Salafia

  DOI：10.1039/b314314g

  日期：——

  A difluorodienophile, synthesised using a Stille coupling reaction underwent tin(IV)-catalysed cycloaddition with three furans to afford oxa[2.2.1]bicycloheptenes in good yield. Reduction of ester and carbamate carbonyl groups and diol protection as the acetonide set the stage for palladium-catalysed hydrostannylation in two cases. Treatment of the stannanes with methyllithium triggered ring-opening to afford highly-functionalised difluorinated cyclohexenols which could be deprotected to afford (hydroxymethyl)conduritol analogues.

  一种二氟二烯亲核体，通过Stille偶联反应合成，经过锡(IV)催化的环加成与三种呋喃反应，良好产率地生成了oxa[2.2.1]双环庚烯。酯和氨基甲酸酯的酮基还原以及二醇保护为在两种情况下进行的钯催化氢锡化反应奠定了基础。将锡烷与甲基锂处理引发开环，生成高度功能化的二氟化环己烯醇，这些化合物可以去保护，得到(hydroxymethyl)conduritol类似物。
• Molecular Design and Synthesis of Fluorinated Polyethers toward Organic Materials with High Dielectric Constants and Ferroelectricity
  作者：Takashi Okano、Makiko Hiraishi、Tomonori Mizutani

  DOI：10.1246/bcsj.80.752

  日期：2007.4.15

  Molecular design and synthesis of organic ferroelectric materials with a -OCH2CF2CH2O- moiety as the basic molecular structure were conducted in order to improve the high coercive field value of poly(vinylidene fluoride) (PVDF). The synthesis of the designed molecules were based on the half ester 2,2-difluoro-l,3-propanediol N,N-diethylcarbamamic acid. The sequence of alkylation of alcohol, deprotection

  为了提高聚偏二氟乙烯（PVDF）的高矫顽场值，进行了以-OCH2CF2CH2O-部分为基本分子结构的有机铁电材料的分子设计和合成。设计分子的合成基于半酯 2,2-二氟-1,3-丙二醇 N,N-二乙基氨基甲酸。醇的烷基化、脱保护和第二次烷基化的顺序有效地产生了所需的聚醚，但威廉姆森醚合成的情况除外，该合成发生在氟化醇和氟化甲苯磺酸酯之间。制备的聚醚在室温下的介电常数相对较高，但未观察到铁电性能。另一种方法在分子末端具有用于分子间相互作用的官能团。
• Vinylic CF bond activation with low-valent zirconocene: the generation and cross-coupling reactions of 1-fluorovinylzirconocene
  作者：Masaki Fujiwara、Junji Ichikawa、Tatsuo Okauchi、Toru Minami

  DOI：10.1016/s0040-4039(99)01491-4

  日期：1999.10

  is treated with zirconocene equivalent ‘Cp2Zr’ to generate thermostable 1-fluorovinylzirconocene via a CF bond cleavage. This 1-fluorovinylzirconocene can be used for CC bond formation through the cross-coupling with aryl iodides in the presence of palladium catalyst and zinc iodide, leading to (Z)-1-aryl-2-(p-dimethylaminophenoxy)-1-fluoroolefins in good yields.

  易于从2,2,2-三氟乙醇制得的（p -2,2-二氟乙烯基氧基苯基）二甲基胺经锆茂等效物'Cp 2 Zr'处理，通过CF键断裂生成热稳定的1-氟乙烯基锆茂。通过在钯催化剂和碘化锌存在下与芳基碘化物交叉偶联，可将这种1-氟乙烯基锆茂合金用于CC键的形成，从而生成（Z）-1-芳基-2-（对-二甲基氨基苯氧基）-1 -氟代烯烃收率高。
• Suzuki–Miyaura Coupling Reactions of Iodo(difluoroenol) Derivatives, Fluorinated Building Blocks Accessible at Near-Ambient Temperatures
  作者：Peter G. Wilson、Jonathan M. Percy、Joanna M. Redmond、Adam W. McCarter

  DOI：10.1021/jo3011705

  日期：2012.8.3

  A recently developed method for the near-ambient generation of difluorovinylzinc reagents has facilitated the preparation of 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro1-iodoethene and 2,2-difluoro-1-iodo-1-(2'-methoxyethoxymethoxy)ethene. The utility of these reagents has been investigated in Suzuki-Miyaura couplings with a range of potassium trifluoroborate coupling partners, with the scope of successful couplings proving wide. Deiodinated species appeared as significant side products, but a solvent change from i-PrOH to t-BuOH suppressed the pathway to these species and improved coupling yields.
• New fluorine-containing building blocks from trifluoroethanol. 2.
  作者：Judith A. Howarth、W. Martin Owton、Jonathan M. Percy、Michael H. Rock

  DOI：10.1016/0040-4020(95)00588-y

  日期：1995.9

  A new fluorine containing acyl anion equivalent 1,1 -difluoro-2-lithio-2-[(N,N-diethylcarbamato)-ethene 9 has been prepared and trapped with a number of electrophiles in good yields. Transacylation of the first formed lithium alkoxides releases a difluoroenolate, affording difluoromethylketones upon work-up.