3,3-d₂-3-chloro-1-propene | 37730-14-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: 3,3-d₂-3-chloro-1-propene
• 英文别名: 3-chloro-3,3-dideutero-1-propene；allyl chloride-d₂；3,3-dideuteroallyl chloride；2-propenyl-1,1-d2-chloride；3-chloro-3,3-d2-propene；3-chloro-3,3-dideuterio-propene；3-Chloro-3,3-dideuterioprop-1-ene
• CAS: 37730-14-6
• 化学式: C₃H₅Cl
• 分子量: 78.5098
• InChiKey: OSDWBNJEKMUWAV-SMZGMGDZSA-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：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  3,3-d₂-3-chloro-1-propene 在 四溴化碳 、 三苯基膦 作用下， 以 乙醚 为溶剂， 生成 1,1-[D]2-allyl bromide
  参考文献：
  名称：

  The case favoring direct C-alkylation of heteroatom-substituted enolates

  摘要：

  DOI：

  10.1021/jo00256a029
• 作为产物：
  描述：

  3,3-dideuterioallyl alcohol 在 吡啶 、 三氯化磷 作用下， 以64%的产率得到3,3-d₂-3-chloro-1-propene
  参考文献：
  名称：

  Mechanistic insights into the hydrosilylation of allyl compounds – Evidence for different coexisting reaction pathways

  摘要：

  The hydrosilylation of allyl compounds is often accompanied by the formation of high amounts of byproducts. The formation processes have not been fully understood so far. In this work, the allyl hydrosilylation mechanism is investigated in detail and experimental and theoretical evidence for multiple, coexisting reaction pathways is provided. Based on earlier reports and the observations during an extensive catalytic study, different pathways, leading to the observed byproducts, were identified and proven by labeling experiments and DFT calculations. Oxidative addition of the silane and the insertion of the allyl compound into the Pt-H bond turned out to be the crucial, selectivity-determining steps within the catalytic cycle. Based on these findings, it should be possible to systematically influence these steps and pave the way to a rational and straightforward design of more selective catalysts. (C) 2012 Published by Elsevier Inc.

  DOI：

  10.1016/j.jcat.2012.06.006

文献信息

• Investigations on the question of multiple mechanisms in the cope rearrangement
  作者：D.C. Wigfield、S. Feiner、G. Malbacho、K. Taymaz

  DOI：10.1016/s0040-4020(01)97471-x

  日期：1974.1

  occurrence of the ionic Cope rearrangement, and other non-concerted mechanisms is discussed. The synthesis of 2 - (1 - ethyl - 1 - propenyl) -2- (3 - p - methoxyphenylallyl)malononitrile (1b) and its clean thermal 1,3 rearrangement to (1 - ethyl - 5 - p - methoxyphenyl - 2 - methyl - 4 - pentenylidene)malononitrile (4) are reported. This result contrasts with the rearrangement of 2 - (1,1 - dideuterioallyl)

  讨论了离子对付重排的可能发生，以及其他不确定的机制。2-（1-乙基-1-丙烯基）-2-（3-对-甲氧基苯基烯丙基）丙二腈（1b）的合成及其1,3-净热重排生成（1-乙基-5-对-甲氧基苯基-2-报道了甲基-4-戊烯叉基）丙二腈（4）。该结果与2-（1,1-二氘代烯丙基）-2-（1-乙基-1-丙烯基）丙二腈（1c）的重排形成鲜明对比，后者在3,3的重排中干净地异构化。然而，2-（1-环己烯基）-2-（3-对甲氧基苯基烯丙基）丙二腈（11）的重排缓慢地导致[2-（-p -甲氧基- α -乙烯基苄基）环己基〕丙二腈（19）（3,3-移位）和2重排- （1 -异丙基- 2 -甲基- 1 -丙烯基） - 2 - （3 - p - methoxyphenylallyl）丙二腈（12）同样缓慢地导致（1-异丙基-5-对甲氧基苯基-2,2-二甲基-4-戊烯叉）丙二腈（14）（1.3位移）。在硼氢化钠存在下
• The preparation of HCF2CdX and HCF2ZnX via direct insertion into the carbon halogen bond of CF2HY (Y=Br, I)
  作者：Donald J. Burton、Greg A. Hartgraves

  DOI：10.1016/j.jfluchem.2007.05.015

  日期：2007.10

  The difluoromethylcadmium and zinc reagents have been prepared in DMF via direct insertion of Cd-0 into the carbon halogen bond of CF2HY (Y = Br, I). These reagents are stable at 65-75 degrees C and exhibit prolonged stability and activity at room temperature. Metathesis of the difluoromethylcadmium reagents with Cu(I)X (X = Br, Cl) at -55 degrees C rapidly produces difluoromethylcopper. The copper reagent is significantly less stable than the cadmium or zinc reagent and rapidly decomposes at room temperature. The difluoromethylcadmium and copper reagents exhibit good reactivity with allylic halides, propargylic derivatives and 1-iodoalkynes to provide good yields of the corresponding difluoromethylalkenes, difluoromethylallenes and difluoromethyl-2-alkynes. Alkylation is successful only with reactive alkyl halides. Generally, the difluoromethylcopper reagent is more reactive than the difluoromethylcadmium reagent and generally exhibits higher regioselectivity in reactions that can occur by either alpha- or -gamma-attack. (C) 2007 Elsevier B.V. All rights reserved.
• Mechanistic insights into the iridium-catalyzed hydrosilylation of allyl compounds
  作者：Korbinian Riener、Teresa K. Meister、Peter Gigler、Wolfgang A. Herrmann、Fritz E. Kühn

  DOI：10.1016/j.jcat.2015.09.003

  日期：2015.11

  The hydrosilylation of allyl compounds is very important for the industrial production of gamma-substituted propylsilanes; however, it is also a process known to suffer from either substantial selectivity issues or short catalyst lifetimes. While there are reports on the platinum-catalyzed variant, this study is the first comprehensive work on the more recently employed iridium-catalyzed process. A combination of stoichiometric and catalytic experiments as well as reactions with isotope-labeled compounds is used to elucidate the critical parameters influencing the catalytic performance and to identify the main deactivation pathways. This report is intended to pave the way toward the optimization of current iridium-catalyzed processes and the design and synthesis of improved catalyst structures. (C) 2015 Elsevier Inc. All rights reserved.
• Palladium-catalyzed polyhetero-Claisen rearrangement of 2-(allylthio)pyrimidin-4(3H)-ones
  作者：Masato Mizutani、Yuzuru Sanemitsu、Yoshinao Tamaru、Zenichi Yoshida

  DOI：10.1021/jo00206a007

  日期：1985.3
• Unimolecular reactions of ionized methyl allyl ether
  作者：Richard D. Bowen、Andrew D. Wright、Peter J. Derrick

  DOI：10.1002/oms.1210270812

  日期：1992.8

  AbstractThe fragmentation of CH2CHCH2OCH3+· cation‐radicals has been investigated by means of 2H‐ and 13C‐labelling experiments and by analysis of collision‐induced dissociation spectra. Metastable C4H8O+· species decompose via one of three main channels which involve loss of (a) a hydrogen atom, (b) a methyl radical or (c) a formaldehyde molecule. Extensive, but not complete, exchange of the hydrogen and deuterium atoms in specifically labelled C4H8‐nDnO+· analogues precedes each of the three fragmentation pathways. The role of distonic ions in the rearrangement steps which bring about hydrogen exchange is discussed. The influence of isotope effects on the relative rates of the major reactions and the associated kinetic energy releases is examined. Only loss of a hydrogen atom is subject to a substantial isotope effect. Elimination of a methyl radical releases a large amount of kinetic energy, as is shown by the broad and dish‐topped appearance of the corresponding metastable peak (T1/2 ≈ 42 kJ mol−1). The carbon atom of the original methoxy group is specifically expelled in this process. Both the large T1/2 value and the unusual site selectivity are atypical of methyl and other alkyl radical losses from ionized alkenyl methyl ethers. The carbon atom of the methoxy group also participates specifically in formaldehyde elimination, but the two hydrogen atoms are not always selected from the three contained in the initial methoxy group. The implications of these labelling results for the synchronicity of concert of formaldehyde loss, which can be formu lated as a pericyclic process, is analysed.