乙烯-D | 2680-00-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 中文名称: 乙烯-D
• 中文别名: 乙烯-D1
• 英文名称: ethylene-d1
• 英文别名: deuterioethene
• CAS: 2680-00-4
• 化学式: C₂H₄
• 分子量: 29.0458
• InChiKey: VGGSQFUCUMXWEO-MICDWDOJSA-N

物化性质

• 熔点：
  -169 °C(lit.)
• 沸点：
  -104 °C(lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  乙烯-D 在 溴 作用下， 生成 1,2-二溴-1-氘代乙烷
  参考文献：
  名称：

  Microwave spectrum and molecular structure ofgauche‐1,2‐difluoroethane

  摘要：

  The microwave spectra of four isotopic species of gauche-1,2-difluoroethane have been observed. Having combined the rotational constants obtained with those of the normal species, all the structural parameters have been determined as follows; r(C–C)=1.493(8) Å, r(C–F) =1.390(3) Å, r(C–Hg)=1.099(2) Å, r(C–Ht)=1.093(5) Å, ∠CCF=110.6(5)°, ∠CCHg=108.4(6)°, ∠CCHt=111.3(6)°, ∠HCH=109.1(5)°, ∠FCHg=109.6(3)°, ∠FCHt=107.8(6)°, and FCCF (dihedral angle)=71.0(3)°. The spectra of normal species in the excited torsional states have also been observed up to vt=4, and the results of the analysis indicate that the gauche-gauche barrier should be higher than the value, 468.6 cm−1, reported by the analysis of vibrational spectra.

  DOI：

  10.1063/1.450042
• 作为产物：
  描述：

  溴乙烯 在 重水 、 magnesium 作用下， 生成 乙烯-D
  参考文献：
  名称：

  The Synthesis of [2-2H1]Thiirane-1-oxide and [2,2-2H2]Thiirane-1-oxide and the Diastereoselective Infrared Laser Chemistry of [2-2H1]Thiirane-1-oxide

  摘要：

  We report the synthesis of the title compounds CH2CHDSO and CH2CD2SO and their characterization by infrared spectroscopy. The monodeuterated species occurs in two isotopically diastereomeric forms with the D atom either cis or trans oriented to the O atom, The SO infrared chromophore in these diastereomers has a strong absorption centered near 1114 and 1116 cm(-1), respectively, with an integrated band strength G = 2.8 pm(2), which renders it very suitable for infrared multiphoton excitation with a CO2 laser, leading to the laser chemical dissociation of the reactants into deuterated ethylene and SO((3) Sigma(-)). We have established the first successful laser chemical separation of such a diastereomer pair, with a small but significant separation factor based on the small frequency difference of the v(4) (SO stretching) fundamental mentioned above; the analysis used high-resolution FTIR spectroscopy in the region of the Q branches of v(4). Our results are discussed in relation to various aspects of stereochemical reaction dynamics in chiral and achiral sulfoxides.

  DOI：

  10.1002/(sici)1521-3765(19980310)4:3<441::aid-chem441>3.0.co;2-3

文献信息

• Mechanism of the Iron(II)-Catalyzed Hydrosilylation of Ketones: Activation of Iron Carboxylate Precatalysts and Reaction Pathways of the Active Catalyst
  作者：Tim Bleith、Lutz H. Gade

  DOI：10.1021/jacs.6b02173

  日期：2016.4.13

  isolation of the catalytically active alkoxide intermediate, and DFT-modeling of the whole reaction sequence. The proposed reaction mechanism is characterized by a rate-determining σ-bond metathesis of an alkoxide complex with the silane, subsequent coordination of the ketone to the iron hydride complex, and insertion of the ketone into the Fe-H bond to regenerate the alkoxide complex.

  使用高活性和对映选择性铁 (II) boxmi 配合物作为催化剂（高达 > 99% ee）对酮的催化氢化硅烷化进行了详细的机理研究，以阐明预催化剂活化的途径和铁催化的机理。氢化硅烷化。发现羧酸盐预催化剂通过将羧酸盐配体还原为相应的醇盐然后进入铁催化氢化硅烷化的催化循环而被活化。对映体比率的温度依赖性的 Eyring 型分析建立了 ln(S/R) 和 T(-1) 的线性关系，表明在 -40 到 +65° 的整个温度范围内有一个单一的选择性决定步骤C (ΔΔG(‡)sel, 233 K = 9 ± 1 kJ/mol)。速率定律以及速率决定步骤的活化参数由哈米特分析、自由基时钟实验、动力学同位素效应 (KIE) 测量 (kH/kD = 3.0 ± 0.2)、催化活性分离醇盐中间体，以及整个反应序列的 DFT 建模。所提出的反应机制的特点是醇盐络合物与硅烷的速率决定 σ 键复分解，随后酮与氢化铁络合物配位，以及酮插入
• Metal-Free Catalytic Reductive Cleavage of Enol Ethers
  作者：Karina Chulsky、Roman Dobrovetsky

  DOI：10.1021/acs.orglett.8b02932

  日期：2018.11.2

  In contrast to the well-known reductive cleavage of the alkyl–O bond, the cleavage of the alkenyl–O bond is much more challenging especially using metal-free approaches. Unexpectedly, alkenyl–O bonds were reductively cleaved when enol ethers were reacted with Et3SiH and a catalytic amount of B(C6F5)3. Supposedly, this reaction is the result of a B(C6F5)3-catalyzed tandem hydrosilylation reaction and

  与众所周知的烷基-O键的还原裂解相反，烯基-O键的裂解更具挑战性，尤其是使用无金属方法时。出乎意料的是，当烯醇醚与Et 3 SiH和催化量的B（C 6 F 5）3反应时，烯基-O键被还原性裂解。据推测，该反应是B（C 6 F 5）3催化的串联氢化硅烷化反应和硅辅助的β-消除的结果。基于实验和密度泛函理论（DFT）计算，提出了这种裂解反应的机理。
• Gas-phase studies of alkane oxidation by transition-metal oxides. Selective oxidation by CrO+
  作者：H. Kang、J. L. Beauchamp

  DOI：10.1021/ja00284a011

  日期：1986.11

  of alkenes and alkanes occur. In reactions with cyclic alkanes, cyclopropane and cyclobutane yield products characteristic of C-C bond cleavage. In contrast, reactions with cyclopentane and cyclohexane mainly involve dehydrogenation and elimination of H/sub 2/O. A series of hydrogen abstraction reactions are examined to determine the bond dissociation energy D/sup 0/ (CrO/sup +/-H) = 89 +/- 5 kcal

  已经通过使用离子束反应散射技术研究了 CrO/sup +/ 与烷烃的气相反应。CrO/sup +/ 与大于甲烷的烷烃发生容易的反应。CrO/sup +/ 选择性氧化乙烷以形成乙醇。除了可能形成醇外，与较大烷烃的反应更为复杂，产生的产物会发生脱氢和烯烃和烷烃的损失。在与环状烷烃的反应中，环丙烷和环丁烷产生具有 CC 键断裂特征的产物。相比之下，环戊烷和环己烷的反应主要涉及脱氢和消除H/sub 2/O。检查一系列夺氢反应以确定键离解能 D/sup 0/ (CrO/sup +/-H) = 89 +/- 5 kcal mol/sup -1/。这种键能对 CrO/sup +/ 与烷烃的反应机制有影响，导致提出多中心反应中间体的建议，其中烷基 CH 键添加到 Cr/sup +/-O 键作为初始步骤。这得到了对 Cr/sup +/ 与醇反应的检验的支持。
• Decomposition of 1,1-dimethyl-1-silacyclobutane on a tungsten filament-evidence of both ring CC and ring SiC bond cleavages
  作者：L. Tong、Y. J. Shi

  DOI：10.1002/jms.1712

  日期：2010.2

  W filament to form ethene and 1,1‐dimethylsilene is a catalytic process. In addition, two other decomposition channels exist to produce methyl radicals via the SiCH3 bond cleavage and to form propene (or cyclopropane)/dimethylsilylene. It has been demonstrated that both the formation of ethene and that of propene are stepwise processes initiated by the cleavage of a ring CC bond and a ring SiC bond

  使用真空紫外激光单光子电离飞行时间质谱技术研究了加热的钨丝上1,1–二甲基-1-硅油基环丁烷（DMSCB）的分解。发现W丝上DMSCB的分解形成乙烯和1,1-二甲基硅烷是一个催化过程。此外，另两个通道分解存在通过在Si，以产生甲基自由基 CH 3键断裂，并形成丙烯（或环丙烷）/二甲基亚甲硅基。已经证明，乙烯和丙烯的形成都是由环CC键和环Si裂解引发的逐步过程。C键分别形成双自由基中间体，然后破坏双自由基中剩余的中心键。通过环C的初始裂解乙烯的形成 C键通过环Si的初始裂解是在该丙烯的主导 C键。当无碰撞条件无效时，气相中的次级反应会产生各种甲基取代的1,3-二硅杂环丁烷分子。发现所有物质中最主要的是1,1,3,3-四甲基-1,3-二硅环丁烷，其源自1,1-二甲基硅的二聚作用。版权所有©2010 John Wiley＆Sons，Ltd.
• Hydrocarbon activation by gas-phase lanthanide cations: interaction of praseodymium (Pr+), europium (Eu+), and gadolinium (Gd+) with small alkanes, cycloalkanes, and alkenes
  作者：J. Bruce. Schilling、J. L. Beauchamp

  DOI：10.1021/ja00209a002

  日期：1988.1

  reactivity. Gd/sup +/ can be thought of as having two valence electrons, and indeed it reacts similarly to Sc/sup +/ and the other group 3 metal ions Y/sup +/ and La/sup +/, yielding products corresponding to elimination of hydrogen, alkanes, and alkenes. The elimination of neutral alkenes in the reaction of Gd/sup +/ with alkanes results in the formation of metal dialkyl or hydrido-alkyl complexes. This finding

  作者描述了气相镧系元素离子、镨 (Pr/sup +/)、铕 (Eu/sup +/) 和钆 (Gd/sup +/) 与小烷烃、环烷烃、烯烃和几种含氧化合物。只有 Gd/sup +/ 可以激活烷烃的 CH 和 CC 键。Gd/sup +/ (4f/sup 7/5d/sup 1/6s/sup 1/)的基态电子构型与Pr/sup +/- (4f/sup 3/6s/sup 1/)不同和 Eu/sup +/- (4f/sup 7/6s/sup 1/)，得出的结论是 f 电子在金属离子反应性中的作用很小。Gd/sup +/ 可以认为有两个价电子，实际上它与Sc/sup +/ 和其他第3 族金属离子Y/sup +/ 和La/sup +/ 的反应类似，产生对应于消除的产物氢、烷烃和烯烃。在 Gd/sup +/ 与烷烃的反应中中性烯烃的消除导致金属二烷基或氢化烷基配合物的形成。该发现导致对介于 110 和 130