丙酰氯-3,3,3-D3 | 75695-44-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 中文名称: 丙酰氯-3,3,3-D3
• 英文名称: <3,3,3-2H3>propionyl chloride
• 英文别名: 3,3,3-Trideuterio-propionylchlorid；Propionyl-3,3,3-D3 chloride；3,3,3-trideuteriopropanoyl chloride
• CAS: 75695-44-2
• 化学式: C₃H₅ClO
• 分子量: 95.5013
• InChiKey: RZWZRACFZGVKFM-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  5
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  丙酰氯-3,3,3-D3 在 lithium aluminium tetrahydride 、 三缩四乙二醇 作用下， 以 various solvent(s) 为溶剂， 生成 丙醇-D3
  参考文献：
  名称：

  Unimolecular reactions of isolated organic ions: The chemistry of the oxonium ions CH3CH2CH2CH2+O = CH2 and CH3CH2CH2CH = O+CH3

  摘要：

  AbstractThe reactions of the metastable oxonium ions CH3CH2CH2CH2+O = CH2 and CH3CH2CH2 = O+ CH3 are reported and discussed. Both these isomers of C5H11O+ expel predominantly CH2O (75–90% of the metastable ion current), a moderate amount of C3H6 (5–15%), a minor amount of CH3OH (2–8%) and a very small proportion of H2O (0.5–3%). All these processes give rise to Gaussian metastable peaks. The kinetic energy releases associated with fragmentation of these oxonium ions are similar, but slightly larger for dissociation of CH3CH2CH2CH = O+CH3. The behaviour of labelled analogues confirm that the reactions of CH3CH2CH2CH = O+CH3 are closely related, but subtly different. Elimination of CH2O and C3H6 is intelligible by means of mechanisms involving CH3CH+CH2CH2OCH3. This open‐chain cation is accessible to CH3CH2CH2 +O = CH2 by a 1,5‐H shift and to CH3CH2CH2‐CH = O+CH3 by two consecutive 1,2‐H shifts (or, possibly, a direct 1,3‐H shift). The rates of these 1,2‐, 1,3‐ and 1,5‐H shifts are compared with one another and also with the rates of CH2O and C3H6 loss from each of the two oxonium ions. The 1,5‐H shift that converts CH3CH+CH2CH2OCH3 formed from CH3CH2CH2CH = O+ CH3 into CH3CH2CH2+O = CH2 prior to CH2O elimination is essentially unidirectional. In contrast, the corresponding step converting C5H11O+ ions generated as CH3CH2CH2CH2+O = CH2 into CH3CH+ CH2CH2OCH3 competes effectively with expulsion of CH2O and C3H6. The implications of the latter finding for the degree of concert in the hydrogen transfer and carbon‐carbon bond fission steps in alkene losses from oxonium ions via routes that are formally isoelectronic with the retro ‘ene’ pericyclic process are emphasized.

  DOI：

  10.1002/oms.1210281035
• 作为产物：
  描述：

  丙酸-D3 在 苯甲酰氯 作用下， 以75%的产率得到丙酰氯-3,3,3-D3
  参考文献：
  名称：

  膦酸酯催化的烯丙酸酯与醛的[3 + 2]环化：2-炔基四氢呋喃的一种简单有效的合成方法

  摘要：

  叶立德是关键：的膦催化的[3 + 2]环2一个与芳香醛1以形成四氢呋喃3在中度至良好的产率被描述（参见方案）。该反应代表了构建四氢呋喃的一种有效且收敛的一步法，并且证明了γ-取代的烯丙酸酯与醛的独特反应性模式。

  DOI：

  10.1002/chem.200901276

文献信息

• Unimolecular reactions of isolated organic ions: reactions of the immonium ions CH₂N⁺(CH₃)CH(CH₃)₂, CH₂N⁺(CH₃)CH₂CH₂CH₃and CH₂N⁺(CH₂CH₂CH₃)₂
  作者：Richard D. Bowen、Alex W. Colburn、Peter J. Derrick

  DOI：10.1039/p29930002363

  日期：——

  The reactions of metastable CH2N+(CH3)C3H7 immonium ions have been investigated by means of 2H-labelling experiments and kinetic energy release measurements. Loss of C3H6, with specific β-H transfer, is the sole channel for dissociation of CH2N+(CH3)CH(CH3)2. This process gives rise to a Gaussian metastable peak. The isomeric ion, CH2N+(CH3)CH2CH2CH3, also expels C3H6; however, both α-H and γ-H as

  已通过2 H标记实验和动能释放测量研究了亚稳态CH 2 N +（CH 3）C 3 H 7铵离子的反应。具有特定的β-H转移的C 3 H 6的损失是CH 2 N +（CH 3）CH（CH 3）2分解的唯一通道。该过程产生了高斯亚稳峰。异构离子CH 2 N +（CH 3）CH 2 CH 2 CH 3，也排出C 3 H 6 ; 但是，在这种情况下，会同时发生α-H和γ-H以及β-H的转移，并且反应的动能释放增加。讨论了离子中性络合物在C 3 H 6中的作用，以及CH 2 N +（CH 3）C 3 H 7离子的损失。另外，CH 2 N +（CH 3）CH 2 CH 2 CH 3消除了C 2 H 4。这种分裂产生了广泛的菜平顶亚稳峰，对应于非常大的动能释放（Ť ½〜73千焦耳摩尔-1），它涉及特定和单向γ-H传输。构造了概述CH 2 N +（CH 3）CH 2 CH 2 CH 3和CH 2 N +（CH
• Wasserstoff/Deuterium-Isotopeneffekte bei Europium-Verschiebungsexperimenten and Allencarbonsäureestern
  作者：Robert W. Lang、Hans-Jürgen Hansen

  DOI：10.1002/hlca.19800630513

  日期：1980.7.9

  Hydrogen/Deuterium Isotope Effects on Europium Induced Chemical Shifts of Allenic Esters

  氢/氘同位素对Euro诱导的烯丙基酯化学位移的影响
• Avermectin biosynthesis. Intact incorporation of a diketide chain-assembly intermediate into the polyketide macrocyclic ring
  作者：Christopher J. Dutton、Antony M. Hooper、Peter F. Leadlay、James Staunton

  DOI：10.1016/s0040-4039(00)76544-0

  日期：1994.1

  Incorporation experiments in Streptomyces avermitilis with synthetic analogues of the proposed diketide intermediate support the processive mechanism of chain assembly in the biosynthesis of the polyketide core of the avermectin structure. Specific incorporation of a 13C labelled precursor was established by 13C NMR; intact incorporation of two deuterium-labelled analogues was established by electrospray

  阿维链霉菌与拟定的二酮化合物中间体的合成类似物的掺入实验支持阿维菌素结构聚酮化合物核心生物合成中链组装的过程机理。通过13 C NMR确定了13 C标记的前体的特异性结合。通过电喷雾质谱（ESMS）建立了两个氘标记的类似物的完整整合。
• Mechanism of propene and water elimination from the oxonium ion CH₃CHO⁺CH₂CH₂CH₃
  作者：Richard D. Bowen、Dennis Suh、Johan K. Terlouw

  DOI：10.1039/p29950000119

  日期：——

  The site-selectivity in the hydrogen transfer step(s) which result in propene and water loss from metastable oxonium ions generated as CH3CH=O+CH2CH2CH3 have been investigated by deuterium-labelling experiments. Propene elimination proceeds predominantly by transfer of a hydrogen atom from the initial propyl-substituent to oxygen. However, the site-selectivity for this process is inconsistent with beta-hydrogen transfer involving a four-centre transition state. The preference for apparent alpha- or gamma-hydrogen transfer is interpreted by a mechanism in which the initial propyl cation accessible by stretching the appropriate bond in CH3CH=O+CH2CH2CH3 isomerizes unidirectionally to an isopropyl cation, which then undergoes proton abstraction-from either methyl group CH3CH=O+CH2CH2CH3 --> CH3CH=O--- (CH2CH2CH3)-C-+ --> [CH3CH-O (CH)-C-+(CH3)(2)] --> [CH3CH=OH+ CH3CH=CH2]}. This mechanism involving ion-neutral complexes can be elaborated to accommodate the minor contribution of expulsion of propene containing hydrogen atoms originally located on the two-carbon chain. Water elimination resembles propene loss insofar as there is a strong preference for selecting the hydrogen atoms from the alpha- and gamma-positions of the initial propyl group. The bulk of water loss is explicable by an extension of the mechanism for propene loss, with the result that one hydrogen atom is eventually transferred to oxygen from each of the two methyl groups in the complex [CH3CH=O- (CH)-C-+(CH3)(2)]. This site-selectivity is strikingly different from that (almost random participation of the seven hydrogen atoms of the propyl substituent) encountered in the corresponding fragmentation of the lower homologue CH2O+CH2CH2CH(3). This contrast is explained in terms of the differences in the relative energetics and associated rates of the cation rearrangement and hydrogen transfer steps.
• Clezy, Peter S.; Ravi,B. N.; Thuc, Le van, Australian Journal of Chemistry, 1986, vol. 39, # 3, p. 419 - 432
  作者：Clezy, Peter S.、Ravi,B. N.、Thuc, Le van

  DOI：——

  日期：——