碘代丙烷-D2 | 25493-15-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 中文名称: 碘代丙烷-D2
• 英文名称: 2,2-d2-1-Iodopropane
• 英文别名: 1-iodopropane-2,2-d₂；Propyljodid-2,2-d2；1-Iod-2,2-dideutero-propan；2,2-dideuterio-1-iodo-propane；1-Iodopropane-2,2-D2；2,2-dideuterio-1-iodopropane
• CAS: 25493-15-6
• 化学式: C₃H₇I
• 分子量: 171.977
• InChiKey: PVWOIHVRPOBWPI-CBTSVUPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  4
• 可旋转键数：
  1
• 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：
  0

反应信息

• 作为反应物：
  描述：

  碘代丙烷-D2 在 铜 作用下， 生成 三聚丙烯 、 丙烯-2-D1
  参考文献：
  名称：

  Effects of surface defects and coadsorbed iodine on the chemistry of alkyl groups on copper surfaces: evidence for a cage effect

  摘要：

  The effects of defect sites and coadsorbed iodine atoms on the chemistry of alkyl groups with two to four carbon atoms on copper surfaces have been studied by temperature-programmed reaction (TPR). The primary reaction pathway for the adsorbed alkyl group both in the presence and absence of defects and iodine atoms is beta-hydride elimination. Because desorption is not (under most conditions) the rate-determining step in the evolution of the product from the surface, the rate of the surface beta-hydride elimination reaction could be monitored by TPR. Neither surface defects nor low coverages of coadsorbed iodine significantly affect the beta-elimination rate. For high coverages of iodine, however, the rate of beta-elimination by 5-10% of the adsorbed alkyl groups is decreased by over five orders of magnitude (T-rxn = 385 K versus 230 K). The reaction kinetics together with observations from low-energy electron diffraction studies suggest that the dramatic inhibition of the beta-elimination rate for high iodine coverages is due to cages of immobile iodine atoms that surround the alkyl groups and prohibit hydrogen transfer to the surface.

  DOI：

  10.1021/j100053a036
• 作为产物：
  描述：

  丙醇-D2 在 磷化氢 、 碘 作用下， 生成 碘代丙烷-D2
  参考文献：
  名称：

  分离的有机离子的单分子反应：铵离子CH 2 N +（CH 3）CH（CH 3）2，CH 2 N +（CH 3）CH 2 CH 2 CH 3和CH 2 N +（CH 2 CH 2 CH 3）2

  摘要：

  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

  DOI：

  10.1039/p29930002363

文献信息

• Bowen, Richard D.; Derrick, Peter J., Journal of the Chemical Society. Perkin transactions II, 1992, # 7, p. 1041 - 1047
  作者：Bowen, Richard D.、Derrick, Peter J.

  DOI：——

  日期：——
• Low-Temperature Decomposition of Alkyl Iodides on Ni(100) Surfaces: Evidence for the Formation of Alkyl Free Radicals
  作者：Francisco Zaera、Sariwan Tjandra

  DOI：10.1021/j100062a049

  日期：1994.3

  Previous studies have shown that alkyl iodides dissociate on metal substrates around 200 K to produce iodine atoms and alkyl moieties on the surface; here we report a new low-temperature decomposition pathway for those compounds on Ni(100) that leads to the formation of a close to 1:1 alkane-alkene mixture below 150 K. This latter reaction is proposed to occur via a mechanism where alkyl iodide dissociation results in the direct formation of free radicals. A combination of thermal desorption experiments with isotope labeling and hydrogen coadsorption was used to establish the importance of the nickel surface in the overall process and to rule out either surface disproportionation or gas-phase reactions as the source of the low-temperature products. Evidence was also obtained for a possible rearrangement of the adsorbed alkyl iodide molecules from a fat geometry into an upright configuration at high coverages, a change that would explain the ease with which the radicals formed after C-I bond scission are released into the gas phase instead of being left on the surface as adsorbed alkyl surface moieties. A comparison with other systems is also presented.
• 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.
• Reactions of ionized dibutyl ether
  作者：Richard D. Bowen、Dennis Suh、Johan K. Terlouw

  DOI：10.1002/oms.1210291211

  日期：1994.12

  AbstractThe reactions of ionized di‐n‐butyl ether are reported and compared with those of ionized n‐butyl sec‐butyl and di‐sec‐butyl ether. The main fragmentation of metastable (CH3CH2CH2CH2)2O+. is C2H5⋅ loss (˜85%), but minor amounts (2–4%) of CH3⋅, C4H7⋅, C4H9⋅, C4H10 and C4H10O are also eliminated. In contrast, C2H5⋅ elimination is of much lower abundance (20 and 4%, respectively) from metastable CH3CH2CH2CH2OCH(CH3)CH2CH3+. and [CH3CH2(CH3)CH]2O+., which expel mainly C2H6 and CH3⋅ (35–55%). Studies on collisional activation spectra of the C6H13O+ oxonium ions reveal that C2H5⋅ loss from (CH3CH2CH2CH2)2O+. gives the same product, (CH3CH2CH2CH2 +OCHCH3) as that formed by direct cleavage of CH3CH2CH2CH2OCH(CH3)CH2CH3+.. Elimination of C2H5⋅ from (CH3CH2CH2CH2)2O+. is interpreted by means of a mechanism in which a 1,4‐H shift to the oxygen atom initiates a unidirectional skeletal rearrangement to CH3CH2CH2CH2OCH(CH3)CH2CH3+., which then undergoes cleavage to CH3CH2CH2CH2+OCHCH3 and C2H5⋅. Further support for this mechanism is obtained from considering the collisional activation and neutralization‐reionization mass spectra of the (C4H9)2O+. species and the behaviour of labelled analogues of (CH3CH2CH2CH2)2O+.. The rate of ethyl radical loss is suppressed relative to those of alternative dissociations by deuteriation at the γ‐position of either or both butyl substituents. Moreover, C2H5⋅ loss via skeletal rearrangement and fragmentation of the unlabelled butyl group in CH3CH2CH2CH2OCH2CH2CD2CH3+. occurs approximately five times more rapidly than C2H4D⋅ expulsion via isomerization and fission of the labelled butyl substituent. These findings indicate that the initial 1,4‐hydrogen shift is influenced by a significant isotope effect, as would be expected if this step is rate limiting in ethyl radical loss.
• Unimolecular reactions of isolated organic ions: The chemistry of the oxonium ions CH3CH2CH2CH2+O = CH2 and CH3CH2CH2CH = O+CH3
  作者：Richard D. Bowen、Peter J. Derrick

  DOI：10.1002/oms.1210281035

  日期：1993.10

  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.