三氟甲烷-D | 558-22-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 中文名称: 三氟甲烷-D
• 英文名称: deuterofluoroform
• 英文别名: d-trifluoromethane；fluoroform-d；deuterotrifluoromethan；deuterio-trifluoro-methane；Deuterio-trifluor-methan；Deuteriofluoroform；Methane-d, trifluoro-；deuterio(trifluoro)methane
• CAS: 558-22-5
• 化学式: CHF₃
• 分子量: 71.0062
• InChiKey: XPDWGBQVDMORPB-MICDWDOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  三氟甲烷-D 在 三氟甲烷 作用下， -79.1 ℃ 、4.0 kPa 条件下， 生成 二氟卡宾
  参考文献：
  名称：

  The effects of wavelength, temperature, and trifluoromethane‐H buffer gas pressure on the infrared multiphoton decomposition of trifluoromethane‐D

  摘要：

  The isotopically selective infrared multiphoton dissociation of trifluoromethane-d (CF3D) has been studied as a function of trifluoromethane-h (CF3H) buffer gas pressure at three temperatures and two wavelengths. The measurements revealed that the isotopic selectivity in dissociation (ratio of probabilities of CF3D and CF3H dissociation) was high even under conditions where many collisions took place between CF3D and CF3H molecules during the laser pulse. For example, this selectivity was >220 under conditions where approximately 50 gas kinetic collisions would occur. It was also found that the laser fluence required to cause CF3D dissociation was a relatively slow function of collision number. The number of collisions at room temperature required to double the fluence required for dissociation, calculated assuming a simple threshold model for the dependence of yield on fluence, was ∼60 and ∼140, respectively, at the CO2 laser transitions R(26) and R(12). The implications of these results on economic production of deuterium are discussed.

  DOI：

  10.1063/1.447855
• 作为产物：
  描述：

  potassium trifluoroacetate 在 dideuteroethylene glycol 作用下， 反应 4.0h， 生成 三氟甲烷-D
  参考文献：
  名称：

  Integrated infrared intensities and atomic polar tensors in fluoroform

  摘要：

  The integrated intensities of the fundamental modes in HCF3 and DCF3 have been measured by Wilson–Wells–Penner–Weber method, and the atomic polar tensors were derived. The effective atomic charge for fluorine was found to be χF/e=0.598±0.018, in good agreement with that in other fluorocarbons. The effective atomic charge for hydrogen was found to be χH/e=0.049±0.006, a value somewhat lower than that found in other hydrocarbons and their derivatives.

  DOI：

  10.1063/1.440079

文献信息

• Alkyl Substituent Effect in the Deprotonation of Unsymmetrical Ketones
  作者：Cris E. Johnson、Kristin A. Sannes、John I. Brauman

  DOI：10.1021/jp953249p

  日期：1996.1.1

  independent measurement of the kinetic isotope effect, allowed the kinetic effect of the alkyl environment on the relative proton transfer rates to be determined. The primary and secondary isotope effects are also estimated from the enolate ion product ratios. By examining the magnitude of the kinetic alkyl effect, the primary isotope effect, and the secondary isotope effect, we learn about the transition

  考察了不同程度的烷基取代对气相中几个不对称酮中两个不同位点的去质子化相对速率的影响。适当地氘标记的醇盐离子的红外多光子活化产生了离子分子复合物，用于烷基阴离子和不对称酮之间的双分子质子转移过程的半反应，其中一个去质子位被选择性地氘化。所得产物是通过去除氘核或质子而产生的烯醇酸根离子，因此可以通过质量区分。烯醇盐离子产物比率的测量，以及动力学同位素效应的独立测量，使得可以确定烷基环境对相对质子转移速率的动力学效应。初级和次级同位素效应也可以从烯醇盐离子产物比率估算出来。通过研究动力学烷基效应，初级同位素效应和次级同位素效应的大小，我们了解了质子转移的过渡态。
• Mechanistic studies on gas-phase negative ion unimolecular decompositions. Alkoxide anions
  作者：William. Tumas、Robert F. Foster、John I. Brauman

  DOI：10.1021/ja00217a003

  日期：1988.4

  Les ions alcoolates subissent une elimination de molecules neutres pour donner des ions enolates

  Les ion alcoolates subissent une demoles neutres pour donner des ions enolates
• Simple, Stable, and Easily Accessible Well-Defined CuCF3 Aromatic Trifluoromethylating Agents
  作者：Olesya A. Tomashenko、Eduardo C. Escudero-Adán、Marta Martínez Belmonte、Vladimir V. Grushin

  DOI：10.1002/anie.201101577

  日期：2011.8.8

  Give me an F: Exceptionally easy to make in over 90 % yield (see scheme) and air‐stable in the solid state, [(Ph3P)3Cu(CF3)] is a remarkable example of a rarely encountered well‐defined Cu(I) trifluoromethylating agent and a convenient starting material for the synthesis of other CuCF3 complexes, such as [(phen)Cu(PPh3)(CF3)].

  给我一个F：[90（90％）的产率非常容易（参见方案）并且在固态下是空气稳定的，[（Ph 3 P）3 Cu（CF 3）]是一个罕见的例子，很少遇到井井有条的情况。定义的三氟甲基化Cu（I）试剂和方便的起始原料，用于合成其他CuCF 3配合物，例如[（phen）Cu（PPh 3）（CF 3）]。
• Trifluoromethide as a Strong Base: [CF₃^–] Mediates Dichloromethylation of Nitrones by Proton Abstraction from the Solvent
  作者：Jean-Bernard Behr、Dani Chavaria、Richard Plantier-Royon

  DOI：10.1021/jo402028r

  日期：2013.11.15

  An unprecedented reactivity of CF3-TMS has been revealed, which exploits the basic character of the generated [CF3–] capable of delivering dichloromethide from dichloromethane with subsequent transfer to nitrones under smooth conditions. The proton-abstraction pathway was demonstrated through isotopic labeling experiments in CD2Cl2. The same reaction was achieved in acetonitrile with the introduction

  CF的前所未有的反应3 -TMS已经揭示，其利用的基本特征所生成的[CF 3 - ]能够与后续的光滑的条件下转移到硝酮从二氯甲烷递送dichloromethide的。通过CD 2 Cl 2中的同位素标记实验证明了质子吸收途径。在氰基上引入氰基甲基后，在乙腈中完成了相同的反应。
• Reactions of Thorium Atoms with Polyhalomethanes: Infrared Spectra of the CH ₂ =ThX ₂ , HC÷ThX ₃ , and XC÷ThX ₃ Molecules
  作者：Jonathan T. Lyon、Lester Andrews

  DOI：10.1002/ejic.200701048

  日期：2008.3

  and density functional theoretical calculations confirm the identity of these methylidene and methylidyne complexes. Parallels with the analogous chloromethane and Group 4 metal reaction products are discussed. Structure calculations show that the C=Th bond lengths decrease and the agostic distortion increases from CH2=ThF2 to CH2=ThFCl to CH2=ThCl2 for the methylidene complexes. The triplet-state HC÷ThF3

  激光烧蚀的钍原子与亚甲基氟化物反应形成单线态 CH2=ThF2，与氟形成三线态 HC÷ThF3，与 CF4 产生三线态 FC÷ThF3 分子作为固体氩气中的主要产物。红外光谱、同位素取代和密度泛函理论计算证实了这些亚甲基和亚甲基配合物的身份。讨论了与类似的氯甲烷和第 4 族金属反应产物的相似之处。结构计算表明，对于亚甲基配合物，C=Th 键长减少，前向畸变从 =ThF2 到 =ThFCl 再到 =ThCl2。三重态 HC÷ThF3 和 FC÷ThF3 缺电子甲基化炔配合物表现出离域键合，这由与类似锆配合物计算的自旋密度相当的自旋密度证明。氯取代氟支持更强的 C÷Th 键。因此，钍似乎作为早期的过渡金属原子与氟甲烷和氯甲烷反应。然而，除了 SOMO 中的 6d 之外，Th 5f 轨道也有很大的贡献，在这些缺电子的甲基炔配合物中形成弱 π 键。（© Wiley-VCH Verlag