(2,3-二甲基-2-丁烯-1,4-二基)镁 | 95251-09-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 中文名称: (2,3-二甲基-2-丁烯-1,4-二基)镁
• 英文名称: (2,3-dimethyl-2-butene-1,4-diyl)magnesium
• CAS: 95251-09-5
• 化学式: C₆H₁₀Mg
• 分子量: 106.45
• InChiKey: RTTXHSHMXXHQAE-YSMBQZINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.88
• 重原子数：
  7.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (2,3-二甲基-2-丁烯-1,4-二基)镁 以 四氢呋喃 为溶剂， 反应 0.83h， 生成
  参考文献：
  名称：

  Direct synthesis of spiro δ-lactones from conjugated dienes and epoxides

  摘要：

  Stepwise reactions of conjugated diene-magnesium reagents with an epoxide followed by carbon dioxide provide a direct method for a one-pot synthesis of spiro delta-lactones accommodating a vinyl moiety at the beta-position.

  DOI：

  10.1016/s0040-4039(00)61713-6
• 作为产物：
  描述：

  1,1-diphenyl-3,4-dimethyl-1-germacyclopent-3-ene 在 萘 、 lithium 、 magnesium 、 1,2-二溴乙烷 作用下， 以 四氢呋喃 、 全氘代环己烷 为溶剂， 反应 8.0h， 生成 (2,3-二甲基-2-丁烯-1,4-二基)镁
  参考文献：
  名称：

  溶液中锡烷环戊-3-烯的光解直接检测，二聚化和化学捕集二甲基锡和二苯基锡

  摘要：

  Dimethyl- and diphenylstannylene (SnMe2 and SnPh2, respectively) have been successfully detected and characterized in solution. The stannylenes were generated by photolysis of 1,1,3trimethy1-4-phenyl- (2) and 3,4-dimethy1-1,1-diphenylstannacydopent-3-ene (3), respectively, which have been shown to extrude the species cleanly and in high (0.6 < Phi <0.8) quantum yields through trapping studies using dichlorodimethylstannane (Me2SnCl2) as the stannylene substrate. Laser flash photolysis of 2 and 3 in deoxygenated hexanes affords promptly formed transient absorptions assigned to SnMe2 (lambda(max) = 500 nm; epsilon(500) = 1800 +/- 600 M-1 cm(-1)) and SnPh2 (lambda(max) = 290, 505 nm; 8500 = 2500 +/- 600 M-1 cm(-1)), respectively, which decay with absolute second-order rate constants within a factor of 2 of the diffusional limit in both cases. The decay of the stannylenes is accompanied by the growth of new transient absorptions ascribable to the corresponding dimers, the structures of which are assigned with the aid of DFT and time-dependent (TD) DFT calculations at the (TD)omega B97XD/6-31+G(d,p)(C,H,O)-LANL2DZdp(sn) level of theory. Dimerization of SnMe2 affords a species exhibiting lambda(max) = 465 nm, which is assigned to the expected Sn=Sn doubly bonded dimer, tetramethyldistannene (Me2Sn=SnMe2, 16a), in agreement with earlier work. In contrast, the spectrum of the dimer formed from SnPh2 exhibits strong absorptions in the 280-380 nm range and a very weak absorption at 650 nm, on the basis of which it is assigned to phenyl(triphenylstanny)stannylene (17b). The calculations suggest that 17b is formed via ultrafast rearrangement of a novel phenyl-bridged stannylidenestannylene intermediate (20), which can be formed either directly by "endo" dimerization of SnPh2 or by isomerization of the "exo" dimer, tetraphenyldistannene (16b); the predicted barriers for these rearrangements are consistent with the experimental finding that the observed product is formed at close to the diffusion-controlled rate. Absolute rate and equilibrium constants are reported for the reactions of SnMe2 and SnPh2 with Me2SnCl2 and methanol (MeOH), respectively, in hexanes at 25 degrees C.

  DOI：

  10.1021/acs.organomet.5b00615

文献信息

• Preparation of alcohols and 1,2-diols from epoxides and 1,3-dienes
  作者：Mathew S. Sell、Heping Xiong、Reuben D. Rieke

  DOI：10.1016/s0040-4039(00)61714-8

  日期：1993.9

  Formation of both alcohols and 1,2-diols containing a quaternary carbon center can be achieved in high yields in a one-pot synthesis utilizing active magnesium, epoxides, and 1,3-dienes.

  使用活性镁，环氧化物和1,3-二烯的一锅法合成可以高收率地形成包含季碳中心的醇和1,2-二醇。
• Yamamoto, Hitoshi; Yasuda, Hajime; Tatsumi, Kazuyuki, Organometallics, 1989, vol. 8, # 1, p. 105 - 119
  作者：Yamamoto, Hitoshi、Yasuda, Hajime、Tatsumi, Kazuyuki、Lee, Keonil、Nakamura, Akira、Chen, Jie、Kai, Yasushi、Kasai, Nobutami

  DOI：——

  日期：——
• Synthesis of 1-Stannacyclopent-3-enes and Their Pyrolysis to Stannylenes
  作者：Dong Zhou、Clemens Reiche、Mrinmoy Nag、John A. Soderquist、Peter P. Gaspar

  DOI：10.1021/om800541f

  日期：2009.4.27

  1,1-Diorgano-1-stannacyclopent-3-enes have been synthesized by condensation in THF of magnesium complexes of 1,3-dienes and dichlorodiorganostannanes. 1, 1-Dimethyl-, 1, 1-di-n-butyl-,1, 1-di-tert-butyl-, and 1,1-diphenyl-1-stannacyclopent-3-enes and 1,1,3,4-tetramethyl-, 1,1-di-tert-butyl-3,4-dimethyl-, and 3,4-dimethyl-1,1-diphenyl-1-stannacyclopent-3-enes were prepared. Kinetic studies of the pyrolysis. at temperatures as low as 75 degrees C of several of these stannacyclopent-3-enes resulted in their first-order disappearance, consistent with a unimolecular dissociation to the corresponding stannylene and diene. Activation parameters are reported. Trapping of dimethylstannylene by dienes was overwhelmed by oligomerization of Me2Sn::, but for t-Bu2Sn: a high yield of diene adduct was obtained. The dimethylstannylene oligomer(s) functioned as stannylenoids and were responsible for several reactions previously attributed to free Me2Sn:. cyclo-(t-Bu2Sn)(4) may also function as a stannylenoid.
• Okamoto, Takuji; Yasuda, Hajime; Nakamura, Akira, Organometallics, 1988, vol. 7, # 11, p. 2266 - 2273
  作者：Okamoto, Takuji、Yasuda, Hajime、Nakamura, Akira、Kai、Kanehisa、Kasai, Nobutami

  DOI：——

  日期：——
• Reaction of Cp*₂Zr(2,3-dimethylbutadiene) with Isonitriles and CO
  作者：Travis N. Valadez、Jack R. Norton、Michelle C. Neary、Patrick J. Quinlivan

  DOI：10.1021/acs.organomet.6b00522

  日期：2016.9.26

  We have investigated the reaction of isonitriles with a permethylzirconocene complex of 2,3-dimethylbutadiene. Cp*Zr-2(2,3-dimethylbutadiene) (1) reacts with tert-alkyl isonitriles to give eta(2)-iminoacyl complexes Cp*Zr-2[CH2C(CH3)C(CH3)CH2C(NR)](2) (R = Bu-t) and 3 (R = 1- adamantyl). Treatment of 2 with excess isopropyl isonitrile gives the eta(1),eta(2)-bis(iminoacyl) complex Cp*Zr-2[C((NPr)-Pr-i)CH2C(CH3)C(CH3)CH2C(((NPr)-Pr-i)] (4) and free tert-butyl isonitrile. The reaction of 1 with 2 equiv of isopropyl isonitrile also affords 4, through the intermediate Cp*Zr-2[CH2C(CH3)C(CH3)CH2C((NPr)-Pr-i)] (5). Carbonylation of 2 affords the Zr formimidoyl cyclopentadienolate 6. Treatment of a Zr hydride cyclopentadienolate (7), obtained from the carbonylation of 1, with tert-butyl isonitrile also affords 6. Isotopic labeling shows that the insertion of tert-butyl isonitrile into 1 and 7 is reversible. All complexes were characterized by spectroscopic and crystallographic methods.