2,2,7,7-Tetramethyl-4-octyne | 16344-02-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2,2,7,7-Tetramethyl-4-octyne
• 英文别名: dineopentylacetylene；2,2,7,7-tetramethyl-oct-4-yne；2,2,7,7-Tetramethyloct-4-in；Dineopentylacetylen；4-Octyne, 2,2,7,7-tetramethyl；2,2,7,7-tetramethyloct-4-yne
• CAS: 16344-02-8
• 化学式: C₁₂H₂₂
• 分子量: 166.307
• InChiKey: XUMLVUIECTXEPJ-UHFFFAOYSA-N

物化性质

• 沸点：
  176.4±8.0 °C(Predicted)
• 密度：
  0.791±0.06 g/cm3(Predicted)
• 保留指数：
  1003

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  2,2,7,7-Tetramethyl-4-octyne 在 palladium on activated charcoal 氢气 作用下， 以 异辛烷 为溶剂， 生成 2,2,7,7-四甲基辛烷
  参考文献：
  名称：

  Roth, Wolfgang R.; Hopf, Henning; Horn, Carina, Chemische Berichte, 1994, vol. 127, # 9, p. 1781 - 1796

  摘要：

  DOI：
• 作为产物：
  描述：

  3,3'-dimethyl-3,3'-but-2-yne-1,4-diyl-bis-thietane 在 镍 氢气 作用下， 以 甲醇 为溶剂， 生成 2,2,7,7-Tetramethyl-4-octyne
  参考文献：
  名称：

  Steric Effect of Neopentyl Groups in the Reaction of Olefins with Peracids

  摘要：

  DOI：

  10.1021/ja00985a016

文献信息

• Kinetic Stabilization of the [1.1]Paracyclophane System: Isolation and X-ray Structural Analysis of a [1.1]Paracyclophane Derivative and Its Interconversion with the Transannular Adduct
  作者：Hidetoshi Kawai、Takanori Suzuki、Masakazu Ohkita、Takashi Tsuji

  DOI：10.1002/1521-3765(20001117)6:22<4177::aid-chem4177>3.0.co;2-v

  日期：2000.11.17

  Substituted [1.1]paracyclophane (2a), photochemically generated from the precursor, is indefinitely stable at 50 degrees C and suffers decomposition only by 8 % after 2 h at 100 degrees C in degassed n-decane, demonstrating its greatly improved kinetic stability compared to previous [1.1]paracyclophanes. Since 2a undergoes efficient photochemical transformation into the transannular addition product

  通过用三甲基甲硅烷基甲基和N，N-二甲基-氨基甲酰基对芳环进行多次取代，可以实现[1.1]对环环烷骨架的有意设计的动力学稳定化，这可以保护其他桥头碳原子在空间上不受其他试剂的影响。双（杜瓦瓶）苯前体（1a）的制备方法与以前的衍生物基本相同-从1,4-双（三甲基甲硅烷基）-2-丁炔的光环加成到八氢茚并-1,5-二酮开始-除了文字中描述的一些重要修改。由前体以光化学方式生成的取代的[1.1]对环环烷（2a）在50摄氏度下无限稳定，在100摄氏度的2 h脱气正癸烷中仅分解8％，证明了与以前的[1.1]对环烷相比，它的动力学稳定性大大提高。由于2a经历了有效的光化学转化为跨环加成产物3a，因此1a的辐照倾向于产生主要由3a组成的产物的混合物。但是，化合物3a在55摄氏度下的40分钟半衰期过程中会热还原为2a；此过程的激活参数为deltaH（不等于）= 21.1 +/- 0.8 kcalmol（-1）和deltaS（不等于）=
• Towards persistent cyclobutadiene radical cations? The tetra-1-adamantyl-, and tetraneopentylcyclobutadiene radical cations.
  作者：Q.B. Broxterman、H. Hogeveen、R.F. Kingma

  DOI：10.1016/s0040-4039(01)90108-x

  日期：1984.1

  The persistence of alkyl substituted cyclobutadiene radical cations strongly depends on the method of generation and the size of the alkyl substituents used. Hindered rotation, the consequence of bulky substituents, is observed in the title compounds.

  烷基取代的环丁二烯自由基阳离子的持久性在很大程度上取决于生成方法和所用烷基取代基的大小。在标题化合物中观察到笨重的取代基导致的旋转受阻。
• Klusik, Hartmut; Pues, Christine; Berndt, Armin, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1984, vol. 39, # 8, p. 1042 - 1045
  作者：Klusik, Hartmut、Pues, Christine、Berndt, Armin

  DOI：——

  日期：——
• Synthesis and reactivity of a series of analogous rhenium tris(imido), bis(imido) alkyne, and imido bis(alkyne) complexes
  作者：Darryl S. Williams、Richard R. Schrock

  DOI：10.1021/om00028a032

  日期：1993.4

  A reaction between Re2O7, ArNH2 (Ar = 2,6-C6H3-i-Pr2), NEt3, and Me3SiCl yields Re(NAr)3Cl. Reduction of Re(NAr)3Cl in THF by 1 equiv of sodium amalgam gives Hg[Re(NAr)s]2 in ca. 50% yield. An X-ray study showed Hg[Re(NAr)3]2 to be composed of molecular units of (ArN)3Re-Hg-Re(NAr)3 having a linear Re-Hg-Re bond and nearly trigonal planar staggered Re(NAr)3 units. Reduction of either Hg[Re(NAr)3]2 or Re(NAr)3Cl by 2 equiv of sodium amalgam in THF affords Na(THF)2Re(NAr)3 in high yield. An X-ray structure of [N(PPh3)2][Re(NAr)3] showed that the [Re(NAr)3]- ion is a trigonal planar species in which the Re-N-C angles all are essentially linear. Compounds that contain the [Re(NAr)3]- ion can be alkylated to give compounds of the type Re(NAr)3R and protonated to give Re(NAr)3H. Reactions between Re(NAr)3H and pi-acceptor ligands yield pseudotetrahedral compounds of the type Re(NAr)2(NHAr)(eta2-L) [L = C2H2, C2Me2, OCHCMe3, C2H4, or norbornene]. Addition of 2 equiv of pyHCl to Re(NAr)3Cl yields Re(NAr)2Cl3(PY). Reduction of Re(NAr)2Cl3(PY) with sodium amalgam in THF in the presence of MeC=CMe or NpC=CNp (Np = neopentyl) yields complexes of the type Re(NAr)2(eta2-C2R2)Cl. Reduction of Re(NAr)2(eta2-C2NP2)Cl by 1 equiv of sodium amalgam yields Hg[Re(NAr)2(eta2-C2NP2)]2, while reduction by 2 equiv of sodium amalgam yields pentane-soluble Na(THF)2Re(NAr)2(eta2-C2Np2). Na(THF)2Re(NAr)2(eta2-C2Np2)reacts with MeI or ClCH2-2,4,6-C6H2Me3 to yield Re(NAr)2(eta2-C2NP2)R or with [Et2NH2][OTf] in THF to give Re(NAr)2(eta2-C2NP2)H. Addition of excess PMe2Ph to Re(NAr)2(eta2-C2NP2)H yields Re(NAr)2(PMe2Ph)2H. Addition of 4 equiv of pyridinium chloride in a 1:5 mixture of THF and pyridine to Na(THF)2Re(NAr)3 affords Re(NAr)Cl3(PY)2 in high yield. Re(NAr)Cl3(PY)2 is reduced by excess Zn dust in the presence of 2 equiv of dineopentylacetylene in refluxing THF to afford Re(NAr)(eta2-C2NP2)2Cl. Reduction of Re(NAr)(eta2-C2NP2)2Cl by 1 or 2 equiv of sodium amalgam in THF yields Hg[Re(NAr)(eta2-C2NP2)2]2 or Na(THF)2Re(NAr)(eta2-C2NP2)2, respectively. The molecular structure of Na(THF)2Re(NAr)(eta2-C2Np2)2 shows that [Na(THF)2]+ is bound to the imido nitrogen atom (2.464(9) angstrom), not to rhenium (Re-Na = 3.17 angstrom), and the coordination about the rhenium center is distorted from the pseudotrigonal planar geometry expected for [Re(NAr)(eta2-C2NP2)2]-. Na(THF)2Re(NAr)(eta2-C2NP2)2 is alkylated smoothly by MeI or ClCH2-2,4,6-C6H2Me3 to afford Re(NAr)(eta2-C2NP2)2R, while addition of [Et2NH2][OTf] yields pale yellow Re(NAr)(eta2-C2NP2)2H. Cyclic voltammograms (200 mV s-1) were obtained for the chloride derivatives and sodium salts of the tris-, bis-, and mono(imido) complexes in a solution of 0.5 M[NBu4][PF6] in THF. Extended Huckel calculations on [Re(NH)3]-, [Re(NH)2(C2H2)]-, and Re(NH)(C2H2)2]- all clearly show that a 20-electron count on the metal is avoided by filling a ligand-centered nonbonding orbital.
• Van Der Heijden, Harry; Gal, Anton W.; Pasman, Peter, Organometallics, 1985, vol. 4, # 10, p. 1847 - 1853
  作者：Van Der Heijden, Harry、Gal, Anton W.、Pasman, Peter、Orpen, A. Guy

  DOI：——

  日期：——